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Cite this: Chem. Sci., 2025, 16, 2980

Magnéli phase titanium oxides for energy storage
and environmental remediation
Open Access Article. Published on 20 2025. Downloaded on 2025/2/20 0:50:17.

S. Amanda Ekanayake, a Haoxin Mai, a

Dehong Chen ab

and Rachel A. Caruso *a

High-temperature reduction of TiO2 causes the gradual formation of structural defects, leading to oxygen
vacancy planar defects and giving rise to Magnéli phases, which are substoichiometric titanium oxides that
follow the formula TinO2n−1, with 4 # n # 9. A high concentration of defects provides several possible
configurations for Ti4+ and Ti3+ within the crystal, with the variation in charge ordered states changing
the electronic structure of the material. The changes in crystal and electronic structures of Magnéli
phases introduce unique properties absent in TiO2, facilitating their diverse applications. Their
exceptional electrical conductivity, stability in harsh chemical environments and capability to generate
hydroxyl radicals make them highly valuable in electrochemical applications. Additionally, their high
specific capacity and corrosion resistance make them ideal for energy storage facilities. These properties,
combined with excellent solar light absorption, have led to their widespread use in electrochemical,
photochemical, photothermal, catalytic and energy storage applications. To provide a complete
overview of the formation, properties, and environmental- and energy-related applications of Magnéli
phase titanium suboxides, this review initially highlights the crystal structure and the physical,
thermoelectrical and optical properties of these materials. The conventional and novel strategies
developed to synthesise these materials are then discussed, along with potential approaches to
overcome challenges associated with current issues and future low-energy fabrication methods. Finally,
we provide a comprehensive overview of their applications across various fields, including environmental
remediation, energy storage, and thermoelectric and optoelectronic technologies. We also discuss
promising new directions for the use of Magnéli phase titanium suboxides and solutions to challenges in
Received 6th July 2024
Accepted 9th January 2025
energy and environment-related applications, and provide guidance on how these materials can be
developed and utilised to meet diverse research application needs. By making use of control measures
DOI: 10.1039/d4sc04477k
to mitigate the potential hazards associated with their nanoparticles, Magnéli phases can be considered
rsc.li/chemical-science as versatile materials with potential for next generation energy needs.

potential to be used in many other applications.5 Various

1. Introduction approaches have been investigated to extend the light absorp-
Titanium dioxide (TiO2) is one of the most widely used semi- tion of TiO2 into the visible region, including surface modi-
conductors in industry owing to its high abundance, low cost, cation using organic materials, semiconductor coupling,
non-toxicity, chemical stability and biocompatibility.1–4 These creation of surface defects and oxygen vacancies (VO), non-
properties have made TiO2 an excellent candidate for utilisation metal doping and transition metal doping.6–8 Recent studies
in a variety of diverse applications including optics, cosmetics, on defective titania have shown that the changes in physical and
photovoltaic devices, photocatalysis and photoelectrochemical chemical properties of TiO2 such as electrical, thermal, optical
cells.2,4 However, the large bandgap of TiO2 (3.2 eV for anatase), and tribological properties can enhance its performance
which connes its light absorbance to the UV region and the towards electrocatalytic and photocatalytic applications.9,10
high rate of electron–hole recombination, greatly limits its The introduction of defects in the lattice structure of TiO2
serves as a platform to tune its physicochemical and surface
properties, making it useful in a wider range of applications.
a
Applied Chemistry and Environmental Science, School of Science, STEM College, These defects can be produced by thermal annealing, electron
RMIT University, Melbourne, Victoria 3000, Australia. E-mail: rachel.caruso@rmit.
bombardment, sputtering and via the inclusion of impurities
edu.au
b
Current Address College of Materials Science and Engineering, Qingdao University of
such as Ca and H.11 Thermal annealing of TiO2 produces its
Science and Technology, Qingdao 266042, P. R. China reduced oxide form, due to the formation of VO and Ti

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interstitials. Low amounts of these vacancies (<10−4) are a range of areas, including for environmental remediation,
considered as point defects within the structure, whereas energy generation or in optoelectronic devices. These aspects as
higher degrees of reduction form interstitial defects along with well as the changes in TiO2 surface upon defect creation and
VO. Increasing the amount of VO during defect creation changes their effect in catalytic applications have been previously
the O/Ti ratio in the TiO2 crystal structure, leading to the reviewed.11,14,31–33 Although several reviews have focused on the
generation of titanium suboxides.12 At elevated temperatures, literature related to titanium suboxides and defective (or
these VO arrange into planar defects known as crystallographic “black”) TiO2,31,34–37 only a few have specically addressed the
shear planes (CSPs). As the concentration of CSPs increases, the synthesis and potential applications of Magnéli phase titanium
planes arrange into regular arrays known as Magnéli phases, suboxides.33,38,39 Some of these reviews not only discuss the
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with chemical formula TinO2n−1, where n can range from 4 to ‘Magnéli phases’ but also provide a comprehensive overview of
9.12–14 Hence, the structure of Magnéli phases can be visualised the synthesis and properties of all titanium oxides up to TiO,
as rutile chains, consisting of n number of unmodied octa- describing their structure, synthesis and performance.
hedral blocks, interrupted by a CSP.15–17 However, these reviews primarily focus on either the environ-
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Formation of VO, or its singly (VO+) or doubly (VO2+) charged mental remediation or electrochemical applications of Magnéli
components, result in delocalised electrons within the crystal phase titanium suboxides, leaving their broader potential in
structure that improve the electrical conductivity of the defec- areas such as thermoelectric and energy storage applications
tive material.12 Hence, since their discovery by Arne Magnéli in underexplored. To address this gap, this review provides
1957,18 Magnéli phase titanium suboxides have been widely a comprehensive overview of the literature on Magnéli phase
used in the elds of electronics, photocatalysis, tribology, titanium suboxides. We discuss the formation, synthesis and
optoelectronics and thermomechanics due to their desirable properties of the lower Magnéli phases (TinO2n−1, 4 # n # 9),
features including excellent electrical and thermal conductivity, along with recent advances (within the timeframe 2015–2024) in
visible light absorptivity and chemical inertness.14,19–21 Magnéli various elds, including environmental remediation, thermo-
phase titanium suboxides are used in various applications due electric applications, energy storage and catalysis. In discussing
to their unique structure, which imparts exceptional properties the use of these materials across diverse applications, we
such as high electrical conductivity and strong corrosion explore the fundamental principles and mechanisms that
resistance. For instance, Ti4O7, the most studied Magnéli phase, underlie their performance, drawing connections among
has an electrical conductivity of ∼1000 S cm−1, surpassing that applications to guide readers in tailoring Magnéli phase tita-
of graphitic carbon (∼727 S cm−1).22 This high conductivity, nium suboxides for specic uses. This review also highlights the
combined with their oxygen evolution potential, makes Magnéli challenges associated with their application in various elds,
phases ideal for electrochemical applications like water split- offering insights into potential future developments in the
ting and cathodic protection.22 Additionally, Magnéli phases (n lesser-explored areas of Magnéli phase titanium suboxides.
= 4–6) have been commercialised under the trade name Ebo-
nex® and are utilised as electrode substrates in batteries and as
catalyst supports in fuel cells and water treatment systems.23,24 2. Structure and properties of
Their stability in harsh chemical environments, such as Magnéli phase titanium suboxides
uoride-based etchants, hydrochloric acid and aqua regia,
further expands their versatility in diverse electrochemical 2.1 Crystal structure
environments.25 Applications such as reactive electrochemical 2.1.1 Types of defects on the crystal structure of TiO2. TiO2
membranes (REMs) also take advantage of the material's ability crystallises in three main phases: anatase (tetragonal, D4h19-I41/
to generate hydroxyl radicals (OHc) through water oxidation.26 amd, a = b = 3.782 Å, c = 9.502 Å), rutile (tetragonal, D4h14-P42/
In battery applications, Magnéli phases are highly valued due to mnm, a = b = 4.584 Å, c = 2.953 Å) and brookite (rhombohedral,
their excellent electrical conductivity and high specic capacity, D2h15-Pbca, a = 5.436 Å, b = 3.782 Å, c = 5.135 Å).11 Anatase and
allowing for signicant energy storage and release. Their rutile phases have been the most investigated phases of TiO2. In
stability, corrosion resistance, and durability make them reli- both crystals, the building blocks of their unit cells are made of
able materials for rechargeable batteries.27,28 In optics and slightly distorted octahedra, composed of a titanium atom
photosensitivity-related applications, these suboxides are used surrounded by six oxygen atoms (Fig. 1). Additionally, cotunn-
for their visible light and near-infrared (NIR) photosensitivity, ite, a high-pressure phase of TiO2, prepared at high temperature
which results from VO created during the phase transformation and pressure has also been reported and is considered as one of
from rutile to Magnéli.29 Furthermore, their high solar-to- the hardest polycrystalline materials.40 However, rutile is iden-
vapour efficiency makes them suitable for photothermal appli- tied as the thermodynamically stable phase of TiO2, stable at
cations, such as solar steam generation.30 These properties all temperatures, while other phases are considered
make Magnéli phases highly versatile, supporting their use in metastable.11,41
diverse elds, including energy storage, water treatment and Intentional creation of defects in TiO2 with precise control of
solar energy harvesting. their position, concentration and distribution tailors the
Throughout the last few decades, studies have been con- materials physicochemical properties and reactivity. Different
ducted on various synthesis approaches to produce different types of defects introduced into TiO2 can be classied as
types of titanium suboxides and examine their application in follows.31,42,43

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1
MO2 /MO2
x þ xO2ðgÞ (1)
2

VO are the most common point defects in semiconducting

metal oxides. This is due to their lowest formation energy
among various types of defects that act as donors.47,48 Density
functional theory (DFT) calculations indicate that the formation
of VO introduces a defect level near the Fermi level, enhancing
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photoabsorption and electronic conductivity while reducing

electron–hole recombination, which in turn extends the life-
times of charge carriers. Additionally, VO can create unsaturated
coordination that are more reactive, facilitating processes such
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as H2 evolution and CO2 reduction.46

By modifying the local atomic and electronic structures, VO
act as centres for charge carrier separation, enhancing carrier
separation efficiency. They can also adjust light absorption,
inuence the conductivity, and impact separation and surface
Fig. 1 Bulk structures of rutile and anatase TiO2. Reproduced with reactions in semiconducting metal oxides.46,49 This results in
permission from ref. 11. Copyright 2003, Elsevier. changes in their chemical and physical properties including
photocatalytic and photoelectrochemical effects, superconduc-
(I) Zero dimensional defects (point defects: oxygen and tita- tivity, ferromagnetism, piezoelectric effect, redox activity and
nium vacancies and interstitials and substitutional impurities). phase transitions.48 In addition, research has shown that these
(II) One dimensional defects (line defects: edge or screw vacancies are involved in reactive oxygen species generation and
dislocations). acting as crucial adsorption and active sites in different
(III) Two dimensional defects (planar defects: grain and twin applications.50
boundaries and stacking faults). 2.1.2 Formation of titanium suboxides
(IV) Three dimensional defects (volume defects: aggregates 2.1.2.1 Structural changes occurring during defect creation. As
of atoms or vacancies to form precipitates or voids). shown in Fig. 2, in the rutile crystal lattice structure, each Ti
Defects in the TiO2 lattice can be introduced either by atom is surrounded by six O neighbours and four Ti next-
changing the O/Ti ratio or through the incorporation of high nearest neighbours while each O atom is bonded to 3 Ti
and low valence ions into the lattice to form donors and atoms. Within rutile TiO2, the (110) surface is the most stable
acceptors. These defects in titania can be generated during crystal surface, characterised by rows of titanium and oxygen
synthesis or post synthesis of the material.31,44 Some approaches atoms along the [001] direction.52 The titanium atoms on the
used to induce defects in the TiO2 lattice include thermal surface exhibit ve-fold coordination with one dangling bond
annealing, electron bombardment, prolonged oxidation, partial
oxidation, reducing agents (H2, C, metals), UV irradiation, high
energy particle bombardment and vacuum activation.11 Calcu-
lated formation energies of point defects have shown that Ti-
rich conditions favour the formation of VO and Ti interstitials,
which behave as weak donors, whereas O-rich conditions lead
to Ti vacancies that act as acceptors.45 Defect disorder in TiO2 as
a variation of oxygen partial pressure was elucidated by Now-
otny and co-workers. These ndings suggested that Ti intersti-
tials and electrons are formed at low oxygen partial pressures
due to reduction of TiO2, whereas prolonged oxidation forms Ti
vacancies and holes. In addition, due to the low formation
enthalpy of VO and their prevalence across a broad range of
stoichiometry in both reducing and oxidizing conditions, VO
can be regarded as the dominant type of defect in TiO2.44
VO in metal oxides can be generated through various
processes, such as thermal treatment in a vacuum or inert
environment, chemical reduction at elevated temperatures, ion
doping or interfacial engineering. When metal oxides undergo Fig. 2 Ball and stick model of the rutile TiO2 (110) surface. Large grey
high-temperature treatment, lattice oxygen atoms may either balls represent oxygen atoms and small black balls represent titanium
desorb to release O2 (eqn (1)) or react with H2 or CO, forming atoms. Two types of point defects that are prevalent in rutile TiO2,
H2O and CO2, respectively.46 oxygen vacancies (Ovac) and Ti interstitials, are shown. Reprinted with
permission from ref. 51. Copyright 2003, Springer Nature.

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and those in the bulk, six-fold coordination. Oxygen atoms can number of defects increases defect interaction and leads to
be present in-plane (bulk) or in bridging positions. Those in defect ordering and structural transformation. Thereby, new
bulk are three-fold coordinated whereas the oxygen atoms in compounds with different crystallographic structures are
bridging positions are two-fold coordinated. Due to less coor- formed.
dination at the surface, these oxygen atoms are prone to When the nonstoichiometry x in TiO2−x reaches a critical
removal during high-temperature treatments, leading to the value of x = 10−3 it causes VO to arrange into planar defects
formation of point defects.51 known as CSPs.31,60 Formation of this shear structure can be
During defect creation, surface oxygen atoms in the TiO2 considered as a way of eliminating point defects, forming
lattice can be removed as a H2O molecule by a hydrogen regularly arranged extended planar defects.60 At CSPs, lattice
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reductant or O2 molecule by a non-hydrogen reductant, leading planes move relative to each other, causing a collapse in the
to the formation of surface VO.53,54 These VO can cause recon- lattice structure. Such CSPs are common for d0 oxides including
struction within the TiO2 lattice or if the concentration of VO is Ti, V, Mo and W.17 The structure of titanium suboxides with
very high it can eventually lead to lattice disorder.55 An oxygen CSPs is described as a chain of rutile-like TiO6 octahedra
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vacancy is a double donor, where the position of the absent interrupted every nth octahedron by a shear plane, where the
oxygen atom in the lattice can be occupied by two electrons octahedra share faces at the shear plane instead of usual edges
leading to a neutral oxygen vacancy. Resonant photoemission and corners within the structure.32
spectroscopy conrms that these electrons have the ability to When the x value in TiO2−x falls between 0.027 and 0.001,
partially occupy the Ti 3d state, resulting in the creation of an new Ti37O73–TiO1.999 structures are formed. In these structures,
energy state approximately 0.8 eV below the Fermi level.56 the CSPs are oriented in the (132) direction.31,60 When x reaches
Furthermore, these electrons can also interact with neigh- 0.0625–0.027, Magnéli phases from Ti16O31–Ti37O73 are formed.
bouring Ti4+ giving Ti3+ centres and VO+ or VO2+. Ti3+ formed on In these structures, the shear planes oriented in (132) are
the lattice surface could react with adsorbed H2O and O2 grouped in bands.62 When x in TiO2−x = 0.1–0.0625, higher
molecules giving rise to –OH groups and O2− centres.57,58 The Magnéli phases from Ti10O19 to Ti16O31 are formed. In these
rearrangement of atomic positions within the lattice structure crystal structures, the shear plane orientation continuously
induced by VO can ultimately result in the reduction in Ti–O changes from (132) direction to (121). When the x in TiO2−x falls
bond length. This in turn, can create a strain on the TiO6 between 0.25 and 0.1 (for Ti4O7–Ti9O17), CSPs are oriented in
octahedra leading to the formation of Ti–O systems with the (121) plane equidistantly, forming ordered arrays of VO.
different octahedral packing.59 2.1.2.3 Magnéli phases (TinO2n−1, 4 # n # 37). Titanium
2.1.2.2 Formation of crystallographic shear planes and struc- suboxides with CSPs in their structure are known as Magnéli
tural changes in TiO2−x. Defective TiO2 (TiO2−x) and titanium phases and can be denoted by the formula TinO2n−1, where 4 #
suboxides are formed because of VO and ionisation of these VO n # 37.32 Based on the concentration of CSPs (value of n), these
which at the same time correspond to the reduction of Ti4+ to Magnéli phases can be classied into two groups: in the series
Ti3+.60 Depending on the value of x in TiO2−x, the types of of suboxides with 10 # n # 37 (higher Magnéli phases), the CSP
defects present in TiO2−x varies, along with their crystallo- is introduced in the (132) plane in the structure of rutile TiO2,
graphic structure, see Fig. 3. Slightly reduced TiO2 (TiO2−x, x < whereas the direction of the CSP changes to the (121) plane
10−4) is considered to only have point defects distributed in the when 4 # n # 9 (Fig. 4). In all Magnéli phase suboxides, across
matrix, where VO and Ti interstitials coexist in low concentra- the CSPs, rutile slabs are displaced relative to each other by the
tions.61 When the x value in TiO2−x falls between 0.001 and 1
½011 vector, also known as the displacement vector.63 Such
0.0001, these are known as Wadsley defects. The increasing 2

Fig. 3 Formation of different defect induced TiO2 and phases with increasing x in TiO2−x.

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Ti3+ and one Ti4+ sites.65 The presence of two types of metallic
ions within the unit cell causes a distorted octahedron due to
different Ti–O distances.66 Ti2O3 is reported to have the
corundum (a-Al2O3) structure, with its stoichiometry extending
from TiO1.49 to TiO1.51.18,66 Its fundamental unit cell comprises
of pairs of Ti3+ ions situated in octahedral sites. TiO possesses
a defective NaCl crystal structure (space group Fm3 m), wherein
there are an equivalent number of vacancies distributed
randomly on both the cation and anion sites, with its homo-
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geneity ranging from TiO0.64 to TiO1.26.14,18

2.1.3 Structure of Magnéli phase titanium suboxides. The
crystal structure of TiO2 typically contains point defects known
as Wadsley defects. However, the formation of additional VO, as
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described earlier, results in the reorganisation of the crystal

structure into new crystallographic phases and congurations.67
Fig. 4 Crystallographic shear structure of Magnéli phase titanium
As mentioned in the previous section, when the n value in
suboxides showing the shear plane formation along the (a) (121) plane
and (b) (132) plane. Reprinted with permission from ref. 63. Copyright TinO2n−1 falls between 10 and 16, the orientation of the CSP
2010, AIP Publishing. changes from (132) to the (121) plane. Pure (121) plane CSP rst
appears for the TinO2n−1 Magnéli phase series when n = 9 and
continues in the same plane for all suboxides where 4 # n # 9.68
displacement requires the removal of an oxygen plane, thereby Padilha et al. reports that the model for these oxygen decient
making the CSP oxygen decient in comparison with rutile phases can be derived from rutile phase through a shear oper-
TiO2.16 Considering the nonstoichiometry of these Magnéli ation that involves the successive displacement of atoms within
phases, the y value of TiOy in higher Magnéli phases can range the rutile crystal. Specically, all atoms located above each (121)
from 1.933 # y # 1.972 whereas for the lower Magnéli phases it plane are shied n times along the c vector from the origin and
are subsequently dislocated in the [01 1] direction of the rutile
ranges from 1.750 # y # 1.889.64
2.1.2.4 Lower titanium suboxides. In the octahedral unit cell structure. This direction aligns with a lattice vector of the
of Ti3O5 (space group C2/m), Ti atoms are surrounded by O oxygen subnet—namely, the vector [011] that connects two
atoms and are located at three distinct sites in the crystal, two oxygen atoms in the rutile crystal. This allows mapping of the

Fig. 5 (a) Edge, corner and face sharing orientations of TiO2 octahedra in Magnéli phase titanium suboxides. Reproduced with permission from
ref. 23. Copyright 2010, Elsevier. (b) Corundum Ti2O3 viewed parallel to the c axis and (c) structure of Ti4O7, showing four-unit rutile chains along
the c direction bounded by corundum structures restricted in the (001) planes. Blue spheres represent the Ti atoms while the smaller red spheres
represent O atoms.67

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dislocated atoms of that species onto atoms of the same species, TiO2−x. Hence, the electrical conductivity (s) of such an n-type
while leaving the lattice positions of the oxygen atoms semiconductor can be related to the electronic charge (e),
unchanged.67 carrier concentration (n) and carrier mobility (m) as given in eqn
The rutile phase features an ordered arrangement of both (2):77,78
oxygen and titanium atoms along the [001] direction. In
contrast, the Magnéli phase maintains an ordered arrangement s = enm (2)
of oxygen atoms along the [001] direction but exhibits a tita-
nium atomic mismatch along the (121) plane.69 The lattice Excellent electrical conductivity demonstrated by Magnéli
structure of lower Magnéli phases can therefore be understood phase titanium suboxides is attributed to the presence of shear
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as a repeated pattern (block) of edge- and corner-sharing TiO6 planes and Ti3+, which serve as platforms for electron delocal-
rutile octahedra (as illustrated in Fig. 5(a)) that extend in two isation.79 Formation of CSPs increases the carrier density and
directions. However, in the third direction these blocks are reduces the carrier mobility. This makes the electron mobility
disrupted by a plane of VO in the (121) direction at every nth hopping-driven, where the electron hops between cation sites.71
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octahedra.15,16,69 This plane is formed of face sharing TiO6 The change in conductivity from electron conduction in Ti to
octahedra, resembling a corundum (Ti2O3) structure (Fig. 5(b)). a hopping driven mechanism in Magnéli phase titanium sub-
The boundaries created by the corundum structures in Magnéli oxides is attributed to the presence of oxygen and to the pres-
phases are known as shear planes as illustrated in Fig. 5(c).67 ence of both Ti3+ and Ti4+ in its structure.15,80 With the reduction
This layer of face sharing octahedra serves both as the last layer in oxygen, Ti atoms in the lattice interact electronically leading
of one block and the rst layer of the adjacent one. This causes to higher conductivity. As shown in Fig. 6(a), variation in elec-
titanium atoms of one block to relate to the unoccupied or tron conductivity in different n Magnéli phases is related to the
interstitial positions of the adjacent block. As a result, the difference in oxygen vacancy content.23,81,82 Ti oxides in the
symmetry of the structure changes from tetragonal to triclinic TinO2n−1 homologous series are mixed valence compounds,
as the size of the unit cell increases.21 Parallel rutile blocks with two Ti3+ and (n-2) Ti4+ ions per formula unit. Furthermore,
containing n number of octahedra (referred to as pseudorutile based on electron paramagnetic resonance spectra studied
chains) link together through the terminal face sharing octa- between 90 and 150 K in Magnéli phase single crystals, Fair-
hedron,41,67,70 leading to electronic interactions between the hurst and co-workers reported that the intrinsic components in
corresponding titanium atoms.41,71 Hence, in Magnéli phase, the crystal structure of TinO2n−1 (n = 5–8) are Ti27+ oxygen-
there is an ordered arrangement of oxygen atoms along the bridged dimers.41,59,83
[001] direction, while a titanium atomic mismatch occurs on the Magnéli phase titanium suboxides have highest conductivity
(121) plane.69 for lowest n values (n = 4, 5) and exhibit phase transitions with
Based on crystal structures previously reported for Magnéli temperature. Such transitions have been attributed to the
phase titanium suboxides,70,72,73 Bowden et al. calculated X-ray presence of both Ti3+ and Ti4+, which provide possibilities for
powder diffraction patterns and compared them with experi- electron localisation at these cation sites, leading to different
mental diffraction patterns.74 Calculated patterns for n = 4, 5 charge ordered states.84 Ti4O7, the most conductive Magnéli
have shown good representation of the reported crystal data, phase titanium suboxide, is reported to undergo two phase
though experimental patterns for n > 5 patterns were not pre- transitions with temperature. At 130 K it undergoes a semi-
sented due to the difficulty in obtaining their single phases.74 conductor–semiconductor transition and a semiconductor–
Crystal structure parameters for these Magnéli phase suboxides metal transition at 150 K.15,85 Similar observations had previ-
are given in Table 1.74 ously been made by Bartholomew et al. in their electrical
property measurement of some titanium oxide Magnéli phases.
They reported that Ti4O7 showed metallic behaviour at room
2.2 Physical properties of Magnéli phase titanium suboxides
temperature and undergoes a phase transition at 149 ± 2 K to
2.2.1 Electrical conductivity. TiO2 is recognised as an n- a semiconducting phase, with a reduction in conductivity, fol-
type semiconductor, and its conductivity is primarily attrib- lowed by a signicant decrease in magnetic susceptibility. A
uted to donor-type defects, such as VO and titanium intersti- second transition has been observed at 125 K with three-orders
tials.76 These defects contribute to the nonstoichiometry of of magnitude decrease in conductivity, but with no change in
TiO2, leading to an apparent deciency of oxygen in the form of

Table 1 Crystal structure parameters of Magnéli phase (TinO2n−1) titanium suboxides (4 # n # 9)

Space group a (Å) b (Å) c (Å) a (Å) b (Å) g (Å) Reference

Ti4O7 
A1 5.593 7.125 12.456 95.02 95.21 108.87 72
Ti5O9 
P1 5.569 7.120 8.865 97.55 112.34 108.50 73
Ti6O11 
I1 5.552 7.126 32.233 66.94 57.08 108.51 75
Ti7O13 
I1 5.537 7.132 38.151 66.70 57.12 108.50 75
Ti8O15 
I1 5.526 7.133 44.059 66.54 57.17 108.51 75
Ti9O17 
I1 5.524 7.142 50.03 66.41 57.20 108.53 75

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However, conductance measurements carried out for Ti8O15

and Ti9O17 have not shown any clear steps between 4 K < T < 295
K. But a discontinuous change in the rst derivative has been
observed at 120 K, which was more evidently observed in
Ti7O13.15 Bartholomew et al. reported that higher titanium
suboxides (Ti8O15) were found to be semiconducting over the
temperature range 78–295 K.21
Fan et al. compared the electrical conductivities of Ti4O7 and
Ti9O17 samples prepared via hydrogen reduction. The study
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revealed that Ti4O7 has an electrical conductivity of 9.92 × 104 S

m−1 at room temperature (RT), which decreases as temperature
rises. This metallic behaviour further conrmed that Ti4O7
becomes a highly paramagnetic metal following a semi-
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conductor-to-metal transition above 150 K, due to the delocal-

isation of 3d electrons from Ti3+ ions. On the other hand, Ti9O17
exhibited typical semiconductor characteristics from RT to 817
K, with electrical conductivity nearly an order of magnitude
lower than that of Ti4O7 at RT, reecting a lower level of electron
doping. Furthermore, the carrier concentration of Ti4O7 was an
order of magnitude higher than that of Ti9O17, with values of
17.2 × 1021 cm−3 for Ti4O7 and 1.83 × 1021 cm−3 for Ti9O17.
These ndings suggested that CSPs do not act as sources of
Fig. 6 (a) Phase diagram of Magnéli phase titanium suboxides showing electron diffraction, since the concentration of CSPs is higher in
the variation of log of conductivity with oxygen stoichiometry. (b) Ti4O7 compared to Ti9O17.77 Backhaus-Ricoult and co-workers
Schematic representation of Ti4O7, showing the presence of Ti3+, reported changes in electrical conductivity as a function of
Ti3.5+ and Ti4+ arranged in chains, interrupted by CSPs. At low temperature for ceramic powders (TiO2−x, x = oxygen de-
temperature, Ti4O7 is non-metallic and clearly distinguishable Ti3+ and
Ti4+ oxidation states are present. Reprinted with permission from ref.
ciency) containing mixtures of Magnéli phases. TiO1.75 was
32. Copyright 2022, Taylor & Francis. (c) Electrical conductivity as composed of n = 4–5 (in TinO2n−1) phases with Ti2O3, TiO1.80
a function of temperature for rutile single crystals (sc), nano-rutile, with n = 4–6 phases and Ti2O3, TiO1.87 with n = 6–8 phases and
anatase and different Magnéli phases. Reprinted with permission from TiO1.91 composed of other (possibly higher) Magnéli phases.
ref. 86. Copyright 2012, Springer Nature. Their observations showed that the electrical conductivity
increased with increasing oxygen deciency (Fig. 6(c)).
Ceramics with lower deciency demonstrated semiconducting
susceptibility.21 At low temperatures, the Ti3+ in Ti4O7 covalently behaviour with increasing conductivity with temperature while
bond with each other, forming bipolarons (Ti3+–Ti3+ pairs) and those with Ti4O7 and Ti5O9 phases showed metallic behaviour
occupy alternate pseudorutile chains to form a low temperature with decreasing conductivity with increasing temperature.86
(LT) semiconducting phase. A reordering of these Ti3+–Ti3+ Adamaki et al. measured the AC electrical properties of Magnéli
pairs occurs during semiconductor–semiconductor transition phase titanium suboxides up to 375 °C and compared them
from LT to intermediate temperature (IT). At high temperature with those obtained for TiO2. Low frequency (100 Hz) electrical
(HT) all Ti cations are present as Ti3.5+ with no apparent pairing conductivities of Magnéli phase titanium suboxide bres
leading to highly conductive metallic behaviour (Fig. 6(b)).72,85,87 reduced at 800–1100 °C showed increased conductivity between
Watanabe et al. measured the Raman spectra of Ti4O7 as 10−1 and 10 S m−1 in contrast to the insulating behaviour of
a function of temperature and observed a stable charge ordered rutile TiO2. Samples reduced at 1200–1300 °C demonstrated
state across the electronic phase transition temperatures.88,89 metallic behaviour with 103–104 S m−1 conductivity at low
Magnetic susceptibility measurements conducted for the frequency measurements. When the measurements were con-
material showed a strong increase in paramagnetic suscepti- ducted at a wider range of frequencies (1–105 Hz), bres
bility at 150 K where the semiconductor–metal transition takes reduced at 1200 and 1300 °C behaved as conductors showing
place. However, at temperatures below 150 K, it is that their conductivity was frequency independent across the
antiferromagnetic.90,91 frequency range examined.92 The conductivity of titanium sub-
Such phase transitions have also been observed in Ti5O9, at oxides is reported to be signicantly higher than that of TiO2, in
128 K and 139 K. Although LT and IT phases are semi- a wider range of frequencies from 0.1 Hz to 1 kHz.93
conducting, the conductivity of the HT phase increases with 2.2.2 Thermal conductivity. Thermoelectric efficiency of
increasing temperature, making it difficult to be classied as a material is evaluated by a dimensionless gure of merit, ZT,
a true metal.15,21,84 Electrical conductance measured for higher n and is related to three physical properties of the material, See-
Magnéli phases have shown that two transitions occur for beck coefficient (a), electrical resistivity (r) and thermal
Ti6O11 at 147 K and 119 K and one transition for Ti7O11 at 120 K conductivity (l). The dependence of ZT on these physical
separating regions showing non-metallic behaviour.15,21

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properties and absolute temperature (T) is given as follows (eqn materials with good thermoelectric performance demonstrate
(3)): low lattice thermal conductivity.
Harada et al. measured the variation in thermoelectric
a2
ZT ¼ T (3) properties of a series of hot pressed Magnéli phase TiO2−x
rl
powders with change in the x value (Fig. 7(a)). From the results
obtained for TiO2−x powders (x = 0.05, 0.10, 0.15 and 0.20), it
Thermal conductivity is a combination of two components: was noted that the value of electrical resistivity and thermal
phonon (lattice) contribution (kl) and carrier concentration (ke). conductivity decrease when the value of x increases, and the
Lattice imperfections help in scattering of phonons with absolute value of the Seebeck coefficient decreases with an
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different wavelengths leading to a reduction in kl. Point defects, increase in x. However, the value of lattice thermal conductivity
grain boundaries, phase boundaries, interfaces and disloca- decreased with increasing oxygen deciency (x) (Fig. 7(b)).
tions are some crystal imperfections that act as phonon scat- Based on the dependence of electrical resistivity and lattice
tering sources.94 Thereby, a reduction in lattice thermal thermal conductivity on oxygen deciency, it was concluded
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conductivity is reported to exhibit enhanced thermoelectric that CSPs act as sources for phonon scattering but not carrier
performance in the material.63,95 The large number of VO scattering.63
present in Magnéli phase titanium suboxides (in CSPs) serve as Reduced rutile TiO2 and highly decient Magnéli phase
phonon scattering centres that can reduce the mean free path of TiO2−x powders demonstrated a decrease in thermal conduc-
phonons.96 This reduction reduces the lattice thermal conduc- tivity with decreasing O/Ti ratio (i.e., increasing x). Furthermore,
tivity, which in turn can affect the total thermal conductivity it was also determined that phonon scattering was mostly
and thermopower.97,98The ke is estimated from electrical affected by planar defects compared to point defects and hence
conductivity (s) through the Wiedemann–Franz law, ke = sLT, planar defects play a critical role in the thermal conductivity of
where L is the Lorentz number and T is temperature. Although TiO2−x materials.69 Thermoelectric studies conducted by Fan
the Lorentz number is constant in metals, in semiconductors, it et al. showed that the thermal conductivity of Ti9O17 was lower
slightly depends on the carrier concentration.99 However, than that of Ti4O7, demonstrating better overall thermoelectric
carrier concentration does not affect kl, suggesting that performance compared to the latter (Fig. 7(c) and (d)).77 In

Fig. 7 (a) Variation of electrical resistivity (top) and Seebeck coefficient (bottom) with temperature for hot pressed TiO2−x specimens. (b)
Variation of lattice thermal conductivity with the density of CSPs (reciprocals of the spacing of CSPs) at RT and 500 °C. Reprinted with permission
from ref. 63. Copyright 2010, AIP publishing. (c) Variation of thermal conductivity (k), (d) electron thermal conductivity (ke) (top) and lattice
thermal conductivity (kl) with temperature for Ti4O7 and Ti9O17. Reprinted with permission from ref. 77. Copyright 2018, Elsevier.

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measurement of thermoelectric properties of plasma spray- long wavelength side, reectance decreases with increasing
synthesised TiO2−x deposits, Lee et al. found the introduction oxygen non stoichiometry.19,101 Based on the ionisation state of
of VO into substoichiometric titanium oxides with the resultant VO in rutile, they can act as single or double electron donors.
formation of Ti4O7 increases electrical conductivity but reduces Hence, the decrease in reectance with increasing VO is related
the Seebeck coefficient. It was further observed that the pres- to sample conductivity, which increases when the number of
ence of a porous, defective structure with interfaces in these free electrons in the lattice increases.101 Furthermore, studies
deposits caused a signicant reduction in through-thickness have also reported a less intense broad band at 500–600 nm,
thermal conductivities.100 caused by reduction. This band is attributed to the presence of
2.2.3 Optical properties. The optical properties of a mate- two-electron centred VO.102
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rial, such as its refractive index and absorption coefficient, can The linear region of the slope in the reectivity vs. wave-
be determined by examining the spectral dependence of length plot (Fig. 8(a)) was absent for highly reduced non-
transmittance and reectance. The spectral dependence of the stoichiometric samples. This is because the additional states
absorption coefficient can be used to determine the bandgap created during reduction absorb light related to photon ener-
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energy, which represents the energy of the fundamental optical gies within the forbidden bandgap.19 Because of this, all
transitions from the valence band (VB) to the conduction band Magnéli phases are known to be highly active under visible
(CB).19 light, extending their absorbance from visible to the near IR
As shown in Fig. 8(a), stoichiometric TiO2 shows a dramatic region.29,103,104
rise in reectance, in the range 390–420 nm. The change in the Liu et al. made similar observations in the optical properties
optical reectance that occurs in this range is associated with of hydrogen reduced rutile TiO2 annealed at different temper-
the beginning of the tail of the absorption curve of TiO2. The atures (Fig. 8(b)). The absorbance of UV light in the l < 400 nm
optical bandgap of the material is determined from the wave- region was similar for both pristine and hydrogen reduced TiO2.
length of the inection point of the absorption curve (edge). This similarity implies that the presence of VO on the surface of
Due to the surface reectivity of TiO2, the shorter wavelength the particles has minimal impact on UV absorption. However,
region (l < 400 nm) of its reectance curve consists of a region of increasing reduction temperature resulted in higher absorption
constant reectivity. This is because if the particles are all in the longer wavelength region (l > 400 nm), attributed to the
absorbing, the absorption coefficient has minimal impact until creation of oxygen defects that form mid gap states between the
it approaches the centre of the main absorption band. However, VB and CB. The sample reduced at the highest temperature (800
the particles become relatively transparent with reducing °C), comprising a mixture of Ti9O17 with rutile TiO2, showed the
absorption coefficient at longer wavelengths (l > 450 nm). This highest visible light absorbance, owing to the presence of the
in turn increases the net diffuse reectivity of the sample, due to highest amount of oxygen defects (Fig. 8(c)).105
numerous reections and refractions occurring in the bulk of 2.2.4 Electronic structure and properties. In the normal-
the material. Hence, when the value of the absorption coeffi- ised electron density of states (DOS) for both rutile and anatase,
cient is very low, diffuse reectivity reaches 1.19 as reported by Malik et al., CB is predominantly composed of Ti
As explained in the previous paragraph, rutile based TiO2 3d states, while the VB is comprised of O 2p electrons
samples show the most signicant variation in reectance (Fig. 9(a)).106 Similar observations were made by Niu and
between 390 and 420 nm related to their fundamental absorp- coworkers in the total DOS calculated for anatase TiO2, and the
tion edge. Reectance on the shorter wavelength side of this is Fermi level is located just above the VB maximum, conrming
independent of the oxygen stoichiometry in TiO2, while on the its semiconducting nature.107 But in Magnéli phase TinO2n−1 (n

Fig. 8 (a) Diffuse reflectance spectra of TiO2 and reduced TiO2−x showing the variation in light absorbance with changes in oxygen stoichi-
ometry. Reprinted with permission from ref. 19. Copyright 2007, Elsevier. (b) Digital images of untreated and reduced rutile TiO2 and (c) UV-vis
absorption (percentage scale) spectra of untreated and reduced TiO2 hydrogenated at 500–800 °C. Reprinted with permission from ref. 105.
Copyright 2019, American Chemical Society.

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Fig. 9 (a) Normalised DOS diagram for rutile, anatase, Ti4O7 and Ti5O9 (ref. 106) and (b) Calculated total DOS of Magnéli phase TinO2n−1 (5 # n # 9).30

= 4–9), the Fermi level shis into the CB, indicating the pres- Ekanayake et al. used DFT simulations to explore the elec-
ence of free electrons, thus imparting metallic characteristics tronic and optical properties of Magnéli phase TinO2n−1 (n = 5–
and excellent electrical conductivity.107 When studying the 9). Their total DOS analysis (Fig. 9(b)) conrmed that the CB
electronic structure of Ti4O7 and Ti5O9, Malik et al. also showed minimum is largely composed of Ti d orbitals, while the VB
that for these two suboxides, VO introduce an intermediate consists of O 2p orbitals. Their ndings also indicated strong d–
band formed by pseudo-point defects. This intermediate band d correlation effects in these titanium suboxides, which led to
emerges under reduced atmospheric conditions when Ti4+ the emergence of new bands within the Ti–O gap, thus reducing
interstitials in the CB are converted into Ti3+, which act as the bandgaps from the 3.2 eV observed in TiO2. Spin–orbit
shallow donor states below the CB minimum. As shown in coupling introduced additional bands derived from Ti 3d and O
Fig. 9(a), for both Ti4O7 and Ti5O9, the intermediate band 2p orbitals, especially in Ti9O17 and Ti5O9, creating high-energy
formed by Ti3+ pseudo-defects lowers the energy of the CB below mid-gap states near the Fermi level. This in turn led to further
the Fermi level, conrming the semi-metallic states of these narrowing of the bandgaps of these phases contributing to
Magnéli phases, where electron behaviour resembles that of metallic behaviour.30
metals.106
Padilha et al. demonstrated that DFT-based calculations
could identify defect levels within the bandgap region for all
3. Methods to synthesise Magnéli
TinO2n−1 phases (where 2 < n < 5). These defects, similar to those phase titanium suboxides
in rutile TiO2, primarily involve Ti 3d orbitals and arise due to
Synthesis approaches used to prepare Magnéli phase titanium
the presence of intrinsic VO. Improved descriptions of Ti 3d
oxides can be divided into two groups: partial reduction from
orbitals were obtained using either the Hubbard U parameter or
TiO2 and incomplete oxidation from low valence titania
hybrid functionals, which shied these defect levels away from
species.54 Reduction approaches include hydrogen reduction,
the CB minimum, depicting them as either shallow or deep
argon annealing, metal reduction, reduction with organic
levels.67 Slipukhina et al. conducted rst-principles calculations
reductants, high energy particle reduction and electrochemical
on Ti5O9 to investigate its electronic and magnetic properties.
reduction. Oxidation approaches involve the use of raw Ti
They identied several quasi-degenerate magnetic solutions for
materials including metallic titanium, organotitanium and
all phases—low, intermediate and high temperatures—making
inorganotitanium to generate TiO2−x in an oxygen containing
it challenging to determine the precise charge distribution at
environment.33 Fig. 10 summarises the fate of different Ti
various temperatures. They noted that the charge and orbital
sources and the typical strategies employed in each of the
orders across all three phases were non-unique, and the
synthesis methods.
formation of Ti3+–Ti3+ bipolaronic states was less likely than in
Ti4O7, though not impossible. Additionally, they concluded that
phase transitions in Ti5O9 result from complex interrelations 3.1 Hydrogen reduction
between electronic correlations, electron–lattice and spin– One of the most commonly used approaches to form Magnéli
lattice coupling, rather than structural changes alone.84 phase titanium suboxides is hydrogen reduction, which makes
use of either pure H2 gas under low or high pressure, mixtures

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Fig. 10 Different synthesis approaches for Magnéli phase titanium suboxides (TTIP is titanium(IV) isopropoxide and Tx indicates functional
groups) and a typical process for each method.
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of H2/Ar or H2/N2 or the use of hydrides such as NaBH4 or however, their study did not explore the effect of varying the
CaH2.108–112 The reduction reaction occurring in the presence of water-to-isopropanol ratio on the formation of Magnéli pha-
hydrogen can be written as shown in eqn (4).33 ses.131 Furthermore, while many studies employed a specic H2
stream ow rate, none have discussed its impact on particle size
nTiO2(s) + H2(g) / TinO2n−1(s) + H2O(g) (4) or the types of Magnéli phases formed. Therefore, the synthesis
temperature, as well as the use of dispersants and solvents, are
In a typical synthesis, the TiO2 source (such as amorphous or crucial design considerations for H2-based reduction methods
crystalline powders, pellets or membranes) is rst placed inside to achieve the desired phase and particle size.
the reactor, typically a tube furnace. The furnace is then heated As shown in Table 2, hydrogen reduction is a popular
to a high temperature, usually between 900 and 1200 °C, under method for synthesising Magnéli phases due to its ability to
a stream of pure H2 or a mixture of H2 and an inert gas. operate at lower temperatures (as low as 800 °C)126 and shorter
The reaction is maintained for a specic duration (typically reduction times (such as 1 h)129,130, thereby saving both time and
2–8 h), aer which the resulting product—whether in powder, energy. This method also offers the potential to obtain Magnéli
pellet, or membrane form—is collected for further testing and phase titanium suboxide nanoparticles, depending on the
characterisation. When different precursors, such as hydrox- precursor used. Despite these advantages, hydrogen reduction
ides, alkoxides, nitrates or MXenes, are used as the Ti source, has signicant drawbacks, primarily due to the high risk of
they are rst converted into TiO2 through methods like hydro- explosion associated with working with hydrogen, as well as the
lysis or hydrothermal treatment. In some cases, these precursor higher costs involved in the H2 storage and transportation.132 As
forms can be directly subjected to a hydrogen stream to form a result, alternative methods have been developed for synthe-
the desired Magnéli phases. sising Magnéli phase titanium suboxides.
Table 2 summarises various studies that have made use of
hydrogen reduction to prepare Magnéli phase titanium sub-
oxides using different titanium precursors. 3.2 Carbothermal reduction
The types of Magnéli phases obtained from each method
Reduction of TiO2 using carbon or an organic polymer under an
indicate that the key factor in hydrogen reduction is the
inert atmosphere is termed carbothermal reduction and occurs
temperature at which these phases are generated. Generally,
according to the following reaction (eqn (5)).33
higher temperatures and/or longer heating times result in Ti4O7
and other lower-n TinO2n−1 phases, whereas mixed phases tend nTiO2(s) + C(s) / TinO2n−1(s) + CO(g) (5)
to appear at lower temperatures or with shorter heating times.
Additionally, some studies have explored the mixing of different Carbothermal reduction has been widely used in recent
Ti sources, solvents and carbon sources before H2 reduction. studies owing to the safety and low cost of the method
For example, Krishnan et al. examined the inuence of poly(- compared to other approaches. Furthermore, contact between
vinyl alcohol) (PVA) on Magnéli phase formation. They investi- the reactant and the reductant has shown an increased reaction
gated mixtures of TiO2 and PVA (25–75% PVA by weight) and rate compared to gas–solid reactions.133 It is reported that
subsequently annealed the samples under a hydrogen atmo- during carbothermal reduction, VO in the TiO2 lattice are
sphere. PVA was utilised to reduce the agglomeration of initially increased followed by lattice reconstruction in the nal
TinO2n−1 and enhance the surface area. Their ndings showed stage.133 The ratio between TiO2 : carbon plays a critical role in
that the highest reduction in agglomeration and the largest the phase of the nal product, since an over stoichiometric ratio
surface area (25.3 m2 g−1) were achieved with 75 wt% PVA.130 can lead to the formation of TiC or TiOxCy.134–136 Furthermore,
You et al. mixed TiO2 powder with water and isopropanol (1 : 1, the kinetics of the TiO2 carbothermal reduction depends heavily
v/v) before hydrogen treatment to reduce the capillary force on the reaction temperature, initial bulk density, gas atmo-
within the powder. The resulting sample consisted of Ti4O7; sphere and TiO2 grain size.134,137

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Table 2 Magnéli phase titanium suboxides synthesised via hydrogen reduction using different starting materials and reduction conditions

Ti precursor Synthesis/treatment of the precursor Reduction conditions Product composition Ref.

Review

Amorphous TiOx Addition of H2O2 to a mixture of TiCl4 and 5 g of amorphous TiOx was heated in a quartz Mixture of Ti9O17 and Ti6O11 113
ethylenediaminetetraacetic acid caused the tubular reactor at 1050 °C for 2 h with a heating rate
decomposition of the Ti complex into colloidal of 5 °C min−1 under 10% H2 (Ar) stream fed at 20
TiOx. The resulting mixture aer precipitating cm3 min−1
and ltering yielded amorphous TiOx
Anatase TiO2 — Reducing anatase TiO2 powder at 950 °C for 4 h Ti4O7 powder/Ti4O7 pellet 114
under pure H2 ow of 200 mL min−1. Ti4O7 pellet
formed by reducing TiO2 pellet at 1050 °C for 2 h
TiO2 pellets were initially formed by uniaxial Reduction of TiO2 pellets was conducted in a 7% H2 Combinations of TiO2 and Ti4O7 obtained at 19
pressing followed by sintering at 1327 °C for 5 h (Ar) atmosphere for 3.5 h from 947 to 1147 °C 997 °C and 1067 °C and a mixture of Ti9O17
in air and Ti8O15 obtained at 1147 °C
TiO2 was mixed with MilliQ water, Reduced in a tube furnace from 850 to 1050 °C (5 ° Ti4O7/Al2O3 membrane 115
triethanolamine and polyethylene oxide C min−1 heating rate) under 30% H2 (N2)
solution to form a suspension. This mixture was atmosphere for 2–7 h
dip-coated on a tubular a-Al2O3 support, dried at
RT and at 100 °C followed by sintering in air at
800 °C
Anatase TiO2 Electrostatic deposition of TiO2 nanosheets on Annealing at 950 °C for 7 h under 200 mL min−1 H2 SiO2@Ti4O7 116
nanosheets SiO2 beads ow
Rutile TiO2 Rutile TiO2 powders mixed with water : Annealing at 1050 °C for 4 h under H2 atmosphere Monolithic porous Ti4O7 22

© 2025 The Author(s). Published by the Royal Society of Chemistry

isopropanol (1 : 1, v/v) and 5 wt% (w/w)
polyethylene oxide binder and compressed at
20 MPa to form a plate
Rutile TiO2 mixed with different weight Annealed at 1100 °C for 1 h at a heating rate of 3 ° A mixture of Ti4O7 and Ti5O9 was obtained 117
percentages of PVA C min−1 under 5% H2 (Ar) atmosphere when 75 wt% PVA and 25 wt% TiO2 was used
— Reduced at 800 °C heated at a rate of 10 °C min−1 Mixture of rutile TiO2 and Ti9O17 105
under pure H2 gas at 1.0 L min−1
TiO2 (Degussa, P25) P25 was oxidised (800 °C, 2 h) to remove any Reduced in a 4% H2 (Ar) atmosphere at 1000 °C, A mixture of Ti9O17/Ti6O11 was obtained at 118
organic contaminants 1100 °C and 1180 °C for 2 h at a heating rate of 1 ° 1000 °C and Ti4O7/Ti5O9 at 1100 °C
C min−1
Co ions deposited on TiO2 powders obtained by Annealed under H2 atmosphere with a ow rate of Ti8O15 119
dispersion of CoCl6$6H2O in TiO2 powder in 100 mL min−1 and heated at 400–800 °C for 3 h
ethanol followed by stirring at RT, solvent
evaporation at 65 °C and drying at 50 °C for 12 h
Commercial pigment Mixtures of TiO2/polyethylene glycol solution Reduced at 1050 °C for 4 h Monophasic Ti4O7 electrodes 120
TiO2 compacted in a uniaxial press followed by
sintering in air at 1050 °C for 1 day
TiO2 powder — Reduced at 1050 °C for 6 h under H2 ow in a tube Ti4O7/Ti6O11 121 and
furnace 122
Reduced in a tube furnace at 1050 °C for 5 h in 0.5 g of the formed Ti4O7 powder was mixed with Ti4O7 electrode 123
the presence of 1.0 atm H2 ow the binder, paraffin oil and pelletised using
a hydraulic press and further reduced at 1050 °C for
6 h under H2 ow to remove the binder
TiO2 membrane — Reduced in a tube furnace at 1050 °C for 30 h in Ti4O7/Ti6O11 REM 124
a H2 atmosphere
26
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Table 2 (Contd. )

Ti precursor Synthesis/treatment of the precursor Reduction conditions Product composition Ref.

TiO2 reactive REMs were synthesised in a tubular TiO2 REMs reduced in a tube furnace at 1050 °C under 1 Ti6O11 membrane when treated for 30 h,
electrochemical ultraltration membrane (50 kDa), followed by atm H2 ow for 30–50 h mixture of Ti6O11 and Ti4O7 at 40 h and Ti4O7
membrane (REM) cutting the membrane to 10 cm in length membrane at 50 h
Titanium(IV) Decomposition of TTIP vapour inside TiO2 was reduced by the H2 stream between 500 and 100% Ti4O7 at 1100 °C, 60% Ti4O7 and 21% 125
Chemical Science

isopropoxide (TTIP) a hydrogen stream thermal aerosol hot wall 1100 °C at 100 mbar Ti5O9 with 5.5% anatase TiO2 at 1000 °C and
reactor formed TiO2 aerosol 24% Ti4O7, 19% Ti5O9 with 31.4% anatase
TiO2 formed at 900 °C
TTIP solution is converted to Ti(OH)2 in water, Heated under H2 ow with a ow rate of 200 Mesoporous Ti6O11 with trace amounts of 126
which is further converted to titanium nitrate mL min−1 in a tube furnace at 800 °C for 5 h anatase TiO2
using HNO3. A colloidal crystal template formed

2992 | Chem. Sci., 2025, 16, 2980–3018

of silica nanoparticles was added into the above
solution followed by drying at 120 °C and
further at 200 °C for 3 h
TiO(NO3)2 Nitric acid added to a mixture of Ti(OC4H9)4)/ TiO(NO3)2 was then annealed in a tube furnace at Ti4O7 nanoparticles 127
distilled water so that Ti(OC4H9)4 would 1000 °C for 6 h at a 5 °C min−1 heating rate under
undergo hydrolysis and react with HNO3 to form 200 sccm H2 ow
TiO(NO3)2 as follows:106
Ti(OC4H9)4 + 3H2O / TiO(OH)2 + 4C4H9OH
TiO(OH)2 + 2HNO3 / TiO(NO3)2 + 2H2O
H2Ti3O7 nanorods Anatase TiO2 nanoparticles hydrothermally H2Ti3O7 nanorods are heated under a H2 Ti8O15 nanorods were obtained at 850 °C and 103
treated with NaOH at 150–180 °C for 2–5 days to atmosphere between 800 and 1050 °C for 1–4 h Ti4O7 bres at 1050 °C
form H2Ti3O7
Ti(OH)2 and anatase Ti(OH)2 was precipitated from H2TiCl6 and was Reduced in a Tamman furnace under H2 Reduction of Ti(OH)2 and anatase TiO2 at 128
TiO2 thoroughly washed followed by drying at 100 °C. atmosphere (ow rate of 5 L min−1) at 800, 900 and 1000 °C for 1 h: Ti9O17
To form anatase TiO2, Ti(OH)2 was 1000 °C for 1, 5.5 and 27.5 h Reduction of anatase TiO2 at 1000 °C for
hydrothermally treated at 200–300 °C for 3 h 5.5 h: mixture of Ti9O17, Ti8O15 and Ti5O9
MXenes (Ti3C2Tx) Peroxo titanic acid gel, formed by a mixture of Annealed at 800–1000 °C under H2 atmosphere for Magnéli phase exible lm (Ti4O7/Ti5O9 at 129
Ti3C2Tx and H2O2) was dropped on to an etched 1h 1000 °C and Ti6O11/Ti7O13 at 900 °C)
quartz glass followed by oven drying at 60 °C
(where Tx indicates fucntional groups)
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Table 3 Magnéli phase titanium suboxides synthesised via carbothermal reduction using different starting materials and reduction conditions

Ti precursor Synthesis/treatment of the precursor Reduction conditions Product composition Ref.

Review

Anatase TiO2 Anatase TiO2 mixed with carbon black was ball Dried powders were heated in a tube furnace Anatase/Rutile/Ti9O17 at 1100 °C 133
milled for 24 h at 200 rpm, dried at 80 °C to from 1000 to 1300 °C for 3 h under Ar ow with Ti5O9/Ti4O7/l-Ti3O5 at 1200 °C
remove the solvent a ow rate of 300 mL min−1
Anatase TiO2 and polydopamine (PDA) mixed in Heated in a tube furnace from 900 to 1200 °C Anatase/Ti4O7/l-Ti3O5 at 900 °C 133
1 : 1 mass ratio, the mixture dipped in tris– under Ar ow (300 mL min−1 ow rate) for 1 h Ti4O7/l-Ti3O5 at 1000 °C
buffer solution and stirred for 48 h. TiO2@PDA
composites obtained by centrifugation were
washed with water and ethanol and oven dried
at 80 °C for 12 h
TiO2 and synthetic graphite mixed with distilled Reduction was conducted under H2, Ar and He Under H2 ow: mixtures of TiO2/Ti8O15/Ti4O7 134
water and carboxymethyl cellulose and dried atmospheres (1.00 NL min−1) in a xed bed Under Ar ow: mixtures of TiO2/Ti9O17/Ti8O15/
overnight at 120 °C. The mixture was formed reactor in a vertical tube furnace for 5 h Ti5O9/Ti4O7
into pellets by uniaxial hydraulic press
Mixtures of TiO2/carbon black were ball milled Heated in vacuum furnace from 800 to 1100 °C At 1000 °C: Ti9O17/Ti7O13/Ti6O11 135
using 4.0 wt% carbon content for 2 h At 1025 °C: Ti4O7/Ti5O9
A paste formed with TiO2, carbon black, water Sintering at 1300 °C for 2 h under Ar Ti4O7/Ti5O9 138
and organic binders was air oxidised at 350 °C atmosphere
for 2 h
— Inside the tube of a tube furnace, a crucible At 6 h: >90% Ti9O17 30
containing anatase TiO2 is positioned between 7–8 h: mixtures of Ti9O17/Ti8O15/Ti7O13/Ti6O11

© 2025 The Author(s). Published by the Royal Society of Chemistry

two crucibles containing activated charcoal. 9 h: mixture of Ti9O17/Ti8O15/Ti7O13/Ti6O11/
Then the samples are reduced at 1100 °C for 2– Ti5O9
12 h 10–12 h: phase reversal resulting in mixtures of
Ti9O17/Ti8O15/Ti7O13/Ti6O11
Rutile TiO2 TiO2, polyvinylpyrrolidone and water were Heated at 950 °C for 30 min by 2.45 GHz Ti4O7 nanoparticles (60 nm) 139
mixed with ultrasonic radiation followed by microwave irradiation under Ar atmosphere
drying and placing in a silica tube surrounded introduced into the furnace at 0.5 L min−1
by carbon
TiO2 and PVA were mixed 50/50 mass ratio Heated at a rate of 5 °C min−1 at 1100 °C for 1 h Ti4O7 29
under N2 atmosphere with a ow rate of 50
mL min−1
TiO2 powder Green-body pellets were formed via uniaxial TiO2 tablets were covered with carbon black in Ti4O7/Ti5O9/Ti6O11 and residual TiO2 93
pressing of a ball-milled mixture of TiO2, alumina crucibles and heated at 1300 °C (120 °C
polyethylene glycol and distilled water. These h−1) for 4–6 h under Ar ow
pellets were then sintered at 1300 °C for 4 h in
air
TiO2 powder TiO2 bres were formed via thermoplastic TiO2 bres embedded in carbon black powder Mixture of Ti10O19, Ti9O17, Ti8O15, Ti6O11, Ti5O9, 92
extrusion using stearic acid as the pre-coating were reduced at 1200 °C and 1300 °C from 1 to Ti4O7, Ti3O5 and TiO2
material and polyethylene as the binder 24 h in an Ar atmosphere
TTIP Ti hydroxy oxide (Ti(OH)xOy was formed by the Calcined at 1000 °C for 2.5 h in a vacuum Ti4O7 140
reaction between TTIP with HCl vapour. This chamber (slow cooling to 500 °C followed by
precipitate was dispersed in glucose (C/Ti ratio quenching)
= 1.07)) and dried at 50 °C
Amorphous TiO2 is precipitated via TTIP and Heated from 700 to 1000 °C for 1 h under N2 Ti4O7 with trace amounts of anatase and rutile 141
mixed with PVA powder atmosphere with a ow rate of 40 mL min−1
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In a typical synthesis, TiO2, in the form of powder or pellets,

Ref. is mixed with a carbon-based reductant such as carbon black,

142
80
activated charcoal, or a polymer like PVA or polyethylene glycol
(PEG). The mixing of the TiO2 and the carbon source is usually
a physical process involving techniques such as ball milling,
ultrasonication or manual mixing. The resulting mixtures are
then heated in a tube furnace under an inert atmosphere at
temperatures ranging from 850 to 1300 °C for 1 to 24 h,
producing a series of products with various combinations of
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Magnéli phases. Table 3 summarises some research conducted

PEI/Ti (1000 °C): Ti6O11/Ti5O9

on synthesising Magnéli phase titanium suboxides using the

PEG/Ti (800 °C): Ti4O7/TiN

carbothermal reduction. The overall trend indicated that

PEI/Ti (900 °C): Ti8O15
Product composition

increasing the treatment/reduction time resulted in a higher

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proportion of lower Magnéli phases being formed.

The main trend in the materials formed via carbothermal
reduction is that lower Magnéli phases are more prevalent when
higher temperatures and longer durations are used for the
Ti4O7

reduction. However, for carbothermal reduction, the next most

important consideration is the ratio between the Ti source and
the carbon source. Toyoda et al. synthesised carbon-coated
Heated at 950 °C under Ar stream with a heating

Magnéli phase titanium suboxides by heat-treating mixtures

Heated from 700 to 1000 °C for 4 h under N2

of rutile TiO2 and PVA.29 A 95/5 ratio of TiO2/PVA at 1100 °C for

atmosphere at a heating rate of 5 °C min−1

1 h resulted in a mixture of rutile and Ti9O17. However, upon

reducing this ratio, lower Magnéli phases were obtained,
including Ti5O9 and Ti6O11 at an 80/20 ratio, and complete
Ti4O7 was achieved at a 50/50 ratio. Further reducing this ratio
resulted in lower titanium oxides, including Ti2O3 and Ti3O5,
implying the ability to control the generated titanium suboxide
Reduction conditions

phase with the reductant ratio. Similar studies were conducted

rate of 4 °C min−1

by Huang et al., where glucose was used as the carbon source to

reduce titanium hydroxy oxide (Ti(OH)xOy).140 The C/Ti ratio was
varied from 6.49 to 1.07. At the highest C/Ti ratio, TiO was ob-
tained in the product heat-treated at 1000 °C for 4 h; at a 2.17
ratio, TiO2 was obtained as the product aer annealing at 1000 °
C for 2.5 h; and at a 1.07 ratio, Ti4O7 was obtained as the
product under the same conditions. These studies demonstrate
to form a gel followed by heating at 100 °C for 4–
Titanium ethoxide and PEG mixed with ethanol

that in carbothermal reduction, the temperature of heat treat-

absolute dry ethanol) mixed with polyethylene
imine (PEI) or polyethylene glycol (PEG) were

ment, time of annealing and the C/Ti ratio are the most
Hybrid solutions of titanium ethoxide (in

prepared followed by electrospinning the

important design considerations for obtaining a desired

Synthesis/treatment of the precursor

product. However, similar to hydrogen reduction, no studies

have been conducted on the effect of gas ow rate, highlighting
further research opportunities in this area.
As mentioned earlier, carbothermal reduction addresses
many concerns associated with hydrogen reduction, particu-
larly the high costs and safety risks related to the use and
storage of hydrogen gas. However, the main drawback of car-
bothermal reduction is the extensive pretreatment required,
solutions

involving time-consuming mixing of the TiO2 source with the

carbon reductant. In addition, direct contact between TiO2 and
6h

the carbon source could also yield in unwanted byproducts such

as TiC and TiOxCy, which need to be separated from Magnéli
phases prior to their use. To address these issues, our group
(Contd. )

introduced a novel carbothermal reduction method that elimi-

Ti precursor

nates the need for pretreatment or mixing with a carbon source.

Titanium

Instead, this method relies on CO(g) generated under low-

ethoxide
Table 3

oxygen conditions to reduce TiO2 and form Magnéli phases.30

While the method successfully produces the desired Magnéli

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phases, the resulting particle sizes were in the micrometre (Ti4O7 and Ti8O15), lower titanium suboxides (TiO, Ti2O3 and
range, limiting their potential applications. Therefore, further Ti3O5) and metallic Ti, in solid phase reaction of rutile TiO2 with
development of a carbothermal reduction approach that TiH2 using varied TiO2/TiH2 ratios, treatment times and
requires less/no precursor pretreatment while achieving nano- temperatures (Fig. 11(a)).143 The presence of TiH2 causes the
particulate Magnéli phases remains an area of opportunity. generation of metallic Ti by evolving H2 at higher temperatures
(∼500 °C) (eqn (6)). This metallic Ti then rapidly reacts with
3.3 Metallothermic reduction TiO2 in the mixture to give titanium suboxides of varied de-
ciencies (eqn (7)).
To eliminate post-synthesis purication steps for the removal of
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any unreacted metal oxides or carbonaceous by-products TiH2 / Ti + H2 (6)

resulting from conventional reduction methodologies, metal-
lothermic reduction has been used to synthesise titanium Ti + (2n − 1)TiO2 / 2TinO2n−1 (7)
suboxides. This method makes use of metals or metal hydrides
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to reduce TiO2 at high temperatures.143 In this method, TiO2 is

mixed with a reductant (either a metal or metal hydride) and the Using these conditions, Ti4O7 has been prepared with a TiO2/
resulting mixture is heat-treated at high temperatures (typically TiH2 ratio of 3, by treating at 600 °C for 48 h, whereas for Ti8O15,
500 °C or above) for a certain duration, usually under an inert a ratio of 5 has been used at 600 °C for 72 h.143 Geng et al.
atmosphere, to obtain Magnéli phases. While metallothermic synthesised Ti4O7 through in situ hot-pressed sintering of Ti
reduction minimises most of the post-synthesis purication and TiO2 in a single-step process. A mixture of anatase TiO2,
compared to carbothermal reduction, the byproducts vary nano P25 and Ti powders in various ratios was prepared using
depending on the reductant used. When metal hydrides are ethanol as the solvent. Aer ball milling, a ceramic slurry was
used, H2 is evolved as a byproduct during the reaction. However, obtained, which, upon drying, yielded ceramic powders. These
when metals are used as reductants, metal oxides are formed as powders were compacted into green bodies through uniaxial
byproducts along with the Magnéli phases. Additionally, metals pressing to ensure proper loading into graphite molds. The
like Ti and Zr, though effective as reductants, are expensive, green bodies were then hot-press sintered under a 30 MPa load
making them unsuitable for large-scale synthesis due to the at varying temperatures (900–1200 °C) for 2 h under vacuum
high associated costs. Therefore, there is still room for (Fig. 11(b)). The optimal sample, with a Ti/TiO2 weight ratio of
improvement in metallothermic reduction methods that do not 0.09, sintered at 1000 °C, exhibited superior mechanical prop-
rely on costly metals as reductants. erties and an excellent electrical conductivity of 1129 S cm−1.144
Strobel et al. obtained Ti9O17 crystals and smaller crystals of Anatase TiO2 monoliths have been reduced using a zirco-
Ti8O15 and Ti6O11 upon the reaction of TiO2 with Ti powders in nium getter to form single phase Ti6O11, Ti4O7, Ti3O5 and Ti2O3
a two-zone furnace using Cl2 as the transporting agent. Here it with varied amounts of Zr between 1000 and 1180 °C at a heat-
was observed that the oxygen pressure is a critical parameter in ing rate of 100 °C h−1 for 1 day reaction time (Fig. 12(a)–(c)).81
crystal growth and the temperature gradient not only inuences The formation of porous TinO2n−1 monoliths is expressed in eqn
the growth rate but also the nature of the growing phase.75 (8).
Nagao et al. reported the synthesis of Magnéli phase titania

Fig. 11 (a) Schematic representation of the experimental route for the synthesis of titanium suboxides in an electric furnace under vacuum and
(b) schematic diagram of the in situ hot press sintering technique used to synthesise Ti4O7.

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Fig. 12 (a) Digital image of anatase TiO2, Ti6O11, Ti4O7, Ti3O5 and Ti2O3 monoliths (left to right) prepared using a sol–gel approach. SEM images
of macroporous monoliths of (b) anatase TiO2 and (c) Ti4O7. Reprinted with permission from ref. 81. Copyright 2012, American Chemical Society.
(d) SEM images (top left and bottom left) and TEM images (top right and bottom right) of TiO2 and Ti4O7 microspheres, respectively. Reprinted
with permission from ref. 145. Copyright 2021, Elsevier. (e) Schematic illustration of the vapour–solid mechanism used for the growth of Ti8O15
nanowires and (f) SEM image of the cross section of the Ti8O15 nanowires. Reprinted with permission from ref. 146. Copyright 2015, Royal Society
of Chemistry.

2nTiO2 + Zr / 2TinO2n−1 + ZrO2 (8) of N2 and H2 gases (obtained from instantaneously decomposed
NH3) at temperatures between 1000 and 1100 °C.149 Further-
more, Gou et al. reports the identication of Ti9O17 as a by-
Liu et al. made use of a mixture of mesoporous TiO2 and Ti product in reducing TiO2 powders under an NH3 atmosphere
powder (7 : 1 mol%) to synthesise Ti4O7 microspheres by heat at 1000 °C.150
treating at 850 °C for 3 h under Ar (Fig. 12(d)).145 A mixture of 3.4.2 Using plasma as the energy source. Zhang et al. used
anatase TiO2 and Ti4O7 was obtained when CaH2 was used as spark plasma sintering (SPS) to densify 1–2 mm sized Ti4O7
the reductant to reduce P25 TiO2 (Degussa) when reacted at powdered particles to full density.151 Ti4O7 electrodes with
500 °C for 5 h.147 Gusev et al. prepared single and multi-phase a relative density of 70.3% were synthesised using spark plasma
Ti4O7 and Ti6O11 oxides by reacting rutile TiO2 with Ti. Ball sintering at 700 °C and 30 MPa.152 Complete densication of
milling was used for mechanical activation of the starting Magnéli phase titania using ash spark plasma sintering (FSPS)
materials followed by annealing under Ar atmosphere at 1060– was performed on titanium suboxide powders with agglomer-
1080 °C for 4 h to obtain highly conducting ceramics.148 He et al. ates of 50–500 mm size. Results revealed that compared to
reduced TiO2 powders with the use of chemically polished Ti conventional spark plasma sintering, FSPS was more reliable for
foil. The Ti foil substrate was placed 6 cm away from the quartz densication since rapid sintering contributed to the retention
reactor containing TiO2 in a tube furnace followed by heating at of original phases Ti4O7, Ti5O9 and Ti6O11 without any oxidation
1050 °C under H2 ow for 2 h. During the reaction, reduction of aerwards. The XRD pattern of the FSPS sample (Fig. 13(a)) was
TiO2 by H2 forms H2O (g), which together with H2 (g) react with similar to that of the raw powder, whereas in the patterns of the
Ti to form a layer of compact Ti8O15 nanoparticles on the SPS samples, the characteristic Ti4O7 peak at 2q = 20.7° had
substrate (Fig. 12(e) and (f)).146 disappeared.153
Wang et al. also used SPS to fabricate Magnéli phase tita-
nium oxides via in situ reduction with carbon powder and
3.4 Other synthesis approaches observed that the reduction can be easily achieved at low pres-
3.4.1 Using NH3. Decomposed NH3 was used as the sure and temperatures above 1200 °C and pointed out that
reducing agent to synthesise a series of multi-phased Magnéli a stable sintering environment without any pressure change
titania by using rutile TiO2 as the starting material. It has been due to gas reaction is vital for the reaction.154 SPS has been used
observed that highly conductive Ti4O7, Ti5O9 and Ti6O11 have as a densication method for Ti4O7 and Ti8O15 nano-powders by
been obtained when the reactant was reduced under a mixture Conze and co-workers, in which the samples were heated at

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Fig. 13 (a) XRD patterns of raw powder, FSPS sample and samples prepared by conventional SPS at different temperatures.153 (b) Preparation of
TiOx nanoparticles using radiofrequency (RF) induction thermal plasma method (left) and heat treatment of the samples after synthesis to
improve their electrical conductivity (right).13

1300 °C for 5 min at a heating rate of 100 °C min−1 under 700 °C for a duration of 3 h, and then heating it to a temperature
60 MPa pressure using graphite dies lined with carbon foil.155 of 900 °C without any intervening period of rest under an
Lee et al. made use of an atmospheric plasma spray process to oxygen partial pressure of 1.0 × 10−10 atm. This resulted in
fabricate Magnéli phase titanium oxide deposits (n = 4–9), a Ti4O7 lm on a Ti metal foil, capable of absorbing visible and
using TiO1.9 as the feedstock powder and by varying the near IR light.159 Sun et al. introduced controlled amounts of
hydrogen gas ratio to allow the tunability in nonstoichiometry Magnéli phase suboxides (Ti8O15 and Ti6O11) and lower oxides
and phase content.100 Xu et al. synthesised Magnéli phase tita- (Ti3O5) into titania nanotubes by anodizing Ti sheets in a two-
nium suboxides and lower suboxides (n = 2, 3) using ash electrode system followed by annealing at 450 °C in a N2
synthesis by thermal plasma by varying the input power, feeding atmosphere. Formation and existence of Magnéli phases at
rate of the precursor H2TiO3, and the H2/Ar ratios in the gas such low temperatures have been ascribed to two potential
mixture, which was used as the carrier gas.156 A radiofrequency reasons. Firstly, the annealing process in N2 atmosphere, which
(RF) induction plasma method was used by Arif and co-workers is considered more favourable for Ti4+ reduction over an Ar
to form nanoparticles composed of TiO2, Ti8O15, Ti4O7 and atmosphere. Secondly, the presence of nonstoichiometric tita-
lower titanium oxide phases. In their synthesis, a mixture of nium oxides during anodisation is another plausible explana-
rutile TiO2 and water-isopropyl alcohol mixture was fed into the tion, as these oxides may retain their structure during
plasma reactor that made use of Ar both as the plasma and the subsequent thermal treatment.160
carrier gas. To improve the conductivity of these samples, the as
synthesised samples were pelletised and annealed in a vacuum
furnace under 3% H2 (Ar) atmosphere (Fig. 13(b)).13 4. Potential applications of Magnéli
3.4.3 Further synthesis approaches. Ertekin et al. used phase titanium suboxides
cathodic electrochemical deposition to form a Magnéli phase
titanium oxide lm on indium tin oxide glass. Deposition was Magnéli phase titanium suboxides have been studied for their
conducted using a peroxo-titanium solution bath containing potential application in a variety of elds: as electrocatalysts
TiOSO4 and 30% H2O2 in acetonitrile at different temperatures, and photocatalysts for environmental remediation, electrodes
ranging from −10 to 40 °C.157 Langlade et al. made use of UV for oxygen and hydrogen evolution and as support materials in
laser irradiation to form titanium oxide lms with Magnéli electronic and optoelectronic devices Fig. 14, as will be dis-
structure. In a typical synthesis, a pure Ti substrate was dipped cussed in the following sections. Ebonex® is the registered
in a solution of titanium(IV) isopropoxide (which was used as the trademark for a range of electrically conducting and corrosion
metal precursor) in isopropanol and heated at 850 °C for 1 or 4 h resistant suboxides of titanium, mainly Ti4O7 and Ti5O9. Ever
aer deposition. These coated materials were then moved in since its discovery and commercialisation, Ebonex® has been
front of a frequency tripled Nd:YAG laser, emitting 355 nm, at widely used in applications that require high electrical
different speeds to form Magnéli phase titanium suboxide conductivity, corrosion resistance and oxidation resistance.27
coated metallic surfaces.158 Matsuda et al. made use of an Due to the presence of highly conducting Magnéli phases, its
oxidation approach to synthesise Magnéli titanium oxide lms electrical conductivity reaches up to 300 S cm−1, comparable
using Ti metal as the precursor. The method they used involved with that of carbon. It is projected that at room temperature in
heating a thick foil of titanium metal in air at a temperature of a 4 mol dm−3 H2SO4 solution, the half-life of Ebonex® is 50
years.20 Due to the unique structure of Magnéli phase titanium

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Fig. 14 Potential applications of Magnéli phase titanium suboxides in environmental remediation and energy storage.

suboxides, the TiO plane at the edges connect with the TiO2 In alkaline solution:
plane via sharing faces, producing a conductive band that is
enclosed by TiO2. Hence, the conductivity in Ebonex® is as Cathode: 2H2O + 2e− / H2 + 2OH−
a result of the TiO layers while the chemical resistance is
attributed to the TiO2 planes that shield the TiO layer.27 Ebo- Anode: 2OH−/ H2O+ + 12O2 + 2e−
nex® is widely used as an electrode owing to its electrochemical
stability in both acidic and basic media, high electrical
Hence, in photoelectrocatalytic water splitting, electrons
conductivity and high overpotentials for O2 and H2 evolu-
facilitate the reduction of water molecules, leading to the
tion.161,162 However, Ebonex® itself possesses several disadvan-
formation of H2, while holes participate in the oxidation of
tages that make it impractical for use without alteration. One of
water, resulting in the formation of O2 simultaneously.166
the drawbacks is its tendency to undergo passivation through
Conventional catalysts used in water splitting in acidic
anodic polarisation, leading to an increase in the oxygen
medium include iridium and ruthenium-based catalysts for
content beyond the stoichiometric value, forming titanium(IV)
oxygen evolution and Pt based materials for hydrogen evolution.
oxide over time. Furthermore, the material demonstrates slow
Due to the scarcity and high cost of these materials, attention has
transfer kinetics, necessitating surface modication or deposi-
been drawn to the development of cost effective alternatives.165 In
tion of foreign materials such as noble metals and conductive
all catalysts involved in oxygen and hydrogen evolution, the
oxides, for it to be used as an efficient catalyst support.142,163
supporting material must have high electric conductivity and
corrosion resistance. While carbon or graphite are commonly
4.1 Oxygen evolution and hydrogen evolution reactions employed as catalyst support materials, there is emerging
interest in considering Magnéli phase titanium suboxides such
Photoelectrochemical water splitting is regarded as a highly as Ebonex®, as catalyst supports. This is due to their notable
desirable approach for generating sustainable hydrogen fuel, as properties including excellent oxidation resistance, high elec-
it allows for the direct decomposition of water into hydrogen trical conductivity (approximately 103 U−1 cm−1), high over-
and oxygen through the absorption of sunlight.164 Electro- potentials for oxygen and hydrogen evolution in both acidic and
chemical or photoelectrochemical water splitting occurs basic environments, and remarkable electrochemical stability.
through two half reactions: oxygen evolution reaction and These physicochemical properties make Magnéli phase titanium
hydrogen evolution reaction occurring at the anode and suboxides promising candidates for catalytic applications.27,161
cathode, respectively. Depending on the reaction conditions, 4.1.1 Oxygen evolution reaction. The oxygen evolution
these two half reactions are as follows.165 reaction is the anodic reaction of water electrolysis. Studies
In acidic solution: have shown that the presence of VO in transition metal oxides
could favour the oxygen evolution reaction due to changed
Cathode: 2H+ + 2e− / H22 + 2e-
surface and bulk electronic structures that can in turn, change
Anode: H2O / 2H+ + 12O2 + 2e− the surface adsorption properties and bulk conductivity.47
Owing to the presence of VO in its structure, Magnéli phase
In neutral solution: titanium suboxides (or its commercial form, Ebonex®) have
been used as a common candidate in these reactions.
Cathode: 2H2O + 2e− / H2 + 2OH− Slavcheva et al. showed that PtCo/Ebonex® synthesised via
a borohydride reduction method demonstrated better
Anode: H2O / 2H+ + 12O2 + 2e−

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performance in the oxygen evolution reaction in alkaline a Co/Ebonex® catalyst and tested it for oxygen and hydrogen
medium, compared to Pt/Ebonex® and unsupported PtCo. The evolution. The activity of the catalyst for hydrogen evolution was
catalytic efficiency of these three electrodes was demonstrated less than that of other electrocatalysts such as Vulcan XC-72 +
by normalising the anodic current relative to the Pt content in TiO2 or activated multi-walled carbon nanotubes, due to the low
the active layer, presented as mass activity (mA mgPt−1). The surface area of the Magnéli phase titanium suboxides in Ebo-
curves showed that the electrochemical behaviour of PtCo/ nex®. However, the Co/Ebonex® electrode showed better
Ebonex was signicantly superior to the other two electrodes, performance for oxygen evolution compared to CoPt/Ebonex®
despite containing the lowest amount of Pt (0.83 mg cm−2). This catalytic systems. The observed improvement is attributed to
facilitated the oxygen evolution reaction to a greater extent the formation of oxides on the surface of the catalyst and metal–
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compared to pure Pt/Ebonex (5 mg cm−2) and unsupported support interaction, causing Ebonex® to act as the support
PtCo (3.3 mg cm−2), proving the positive inuence of the material and as an active oxide electrode.170 Jović et al. studied
support on catalytic activity. The enhanced activity of the the use of electrodeposited Ni-(Ebonex®/Ir) coatings as anode
bimetallic catalyst was attributed to surface oxide formation materials for the oxygen evolution reaction in alkaline solution.
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and electronic interactions between the metals and the catalyst They observed that the pure Ni coating exhibited a drastic loss
support material.167 Similarly, compared to polycrystalline Pt, of activity aer 24 h of continuous oxygen evolution at j = 50 mA
a Pt/Ebonex® thin lm loaded Au disk showed enhanced cata- cm−2 (DE = 395 mV), despite initially showing higher intrinsic
lytic activity for the oxygen reduction reaction in acidic solution, catalytic activity for the oxygen evolution reaction compared to
due to the interaction of O2 with the active sites on the surface the composite coatings. In contrast, the oxygen evolution reac-
of the catalyst.161 They conducted rotating disk electrode tion overpotential of the Ni-(Ebonex/Ir) coatings showed only
measurements to compare the behaviour of Ebonex/Pt and pure negligible changes aer the stability test (DE = 22 mV). The OH
Pt electrodes during the oxygen reduction reaction in 0.5 mol species that were adsorbed by the active sites in Ni were trans-
dm−3 HClO4 solution. The obtained polarisation curves showed ferred to the less active IrO2 particles, causing both the inherent
that the onset of O2 reduction and the half-wave potentials were activity and improved retention of catalytic activity of Ni-(Ebo-
signicantly shied to more positive potentials in the case of nex®/Ir) coatings.171 An amorphous TiO2−x layer containing
the Ebonex/Pt electrodes, indicating higher catalytic activity for Ti4O7 and lower titanium oxides (Ti2O3) was employed to
O2 reduction compared to pure Pt. Stoyanova et al. measured fabricate a photoanode of black BiVO4@amorphous TiO2−x that
the water splitting electrocatalytic activity of Pt–Fe/Ebonex® showed a remarkable photocurrent density of 6.12 mA cm−2 at
and Pt–Co/Ebonex® catalysts using cyclic voltammetry and 1.23 VRHE for water oxidation and 2.5% applied bias photon-to-
steady state polarisation. Results revealed that these two cata- current efficiency for solar water splitting. The ability of the
lysts show enhanced performance for the oxygen evolution TiO2−x layer to act as an oxygen evolution catalyst, a protection
reaction in polymer electrolyte membrane water electrolysis layer to catalyse the water oxidation reaction and to prevent
compared to pure Pt. Best catalytic properties were observed in dissolution of BiVO4, promotes the efficient water splitting
the 2Pt : 3Co/Ebonex® (2 : 3 = weight ratios of precursors) with demonstrated by the BiVO4/TiO2−x photoanode (Fig. 15(a)-
the oxygen evolution reaction reaching current densities of 230 (c)).172
mA cm−2 at 1.9 V. Higher activity for bimetallic-Ebonex® cata- Huang et al. synthesised a series of titanium suboxides
lysts is attributed to the solid solution formed between the two (Ti2O3, Ti3O5, Ti4O7) with high surface areas (between 260 and
metals causing changes in the electron density in the atoms and 120 m2 g−1) via a combined sol–gel and carbothermic processes.
surface intermediate bond strength and stability of Ebonex® at The highest specic capacitance of 140 F g−1 was observed for
high anodic potentials.168 Won et al. developed a bifunctional the Ti4O7 electrode, with a high oxygen oxidation current above
oxygen catalyst using Ti4O7 capable of both oxygen reduction 0.5 V (Fig. 15(d) and (e)). A higher specic capacitance
reaction and oxygen evolution, to enhance the efficiency of demonstrated the outstanding pseudocapacitance behaviour of
a unitised regenerative fuel cell. The optimised oxygen catalyst, Ti4O7, making it a promising electrochemical electrode mate-
synthesised by depositing PtIr on a Ti4O7 support (60 wt% metal rial.140 Kolbrecka et al. studied the effect of porosity on the
catalysts on Ti4O7) using the borohydride reduction method, properties of Ti4O7 electrodes. Results revealed that the porosity
showed the highest specic activity of 1.50 mA cm−2 at 1.5 V, of the electrodes affects the anodic current densities and the
compared to Pt/Ti4O7 and Pt/C, which exhibited specic activ- course of oxygen evolution, which is irreversible on Magnéli
ities of 0.26 and 0.15 mA cm−2, respectively. Moreover, PtIr/ phase titanium suboxide electrodes. Furthermore, they also
Ti4O7 demonstrated the lowest Tafel slope of 82.3 mV dec−1, observed that the more reproducible results and high anodic
compared to 104.5 and 107.3 mV dec−1 for Pt/Ti4O7 and Pt/C, current densities are obtained for the ceramic electrodes that
respectively, highlighting its signicantly superior oxygen have a high number of large pores.120
evolution reaction activity. The enhanced performance was 4.1.2 Hydrogen evolution reaction. Similar to other evolu-
attributed to the synergistic effect of the PtIr phase that had tion reactions, the hydrogen evolution reaction requires
a suitable composition for both oxygen evolution and oxygen a signicant overpotential, making it crucial to identify suitable
reduction reactions and high stability of the Ti4O7 support in electrocatalysts to maximise efficiency. Noble metals like Pt, Pd
acidic medium.169 and Ru are among the most effective electrocatalysts for
With the intention of developing non-platinum electro- hydrogen evolution due to their low overpotential. Out of these,
catalysts for water splitting, Paunović and co-workers developed Pt is currently regarded as the best material, due to its ability to

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Fig. 15 (a) Energy diagram for the transit and transfer of photogenerated charges on the b-BiVO4/TiO2−x photoanode. (b) H2 and O2 generated
by the b-BiVO4/TiO2−x photoanode at 1.23 VRHE and calculated H2 and O2 amounts evolved from the photocurrent assuming 100% faradaic
efficiency. (c) Applied bias-to photocurrent efficiency (APBE) of the b-BiVO4/TiO2−x photoanode obtained for solar water splitting. Reprinted
with permission from ref. 172. Copyright 2019, John Wiley and Sons. (d) Specific capacitance vs. scan rate for the Ti4O7 electrode and Black Pearls
2000 carbon black electrode (BP 2000). (e) Linear sweep voltammetry curve for Ti4O7 electrodes in 0.1 M KOH solution. Reprinted with
permission from ref. 140. Copyright 2018, American Chemical Society. (f) Photocatalytic hydrogen evolution from powders synthesised at
temperatures 500–1000 °C under 365 nm LED and AM 1.5 solar simulator illumination. Inset: experiment conducted for anatase and powders
obtained by the same synthesis method but without Pt. (g) Schematic diagram showing the band alignment between TiO2, Magnéli phase
titanium suboxides and Pt. Reprinted with permission from ref. 173. Copyright 2019, American Chemical Society.

optimally adsorb hydrogen, which facilitates both the adsorp- irradiation and UV light (l = 365 nm) was attributed to the
tion of active hydrogen species and the desorption of hydrogen synergy of charge carrier formation by anatase and charge
molecules. However, the high cost and limited catalytic stability carrier separation and mobility by Magnéli phase titania
of these materials in acidic and alkaline electrolytes have (Fig. 15(f) and (g)).173 Nanoscopic inserts of Magnéli phase
prompted the search for alternative catalysts.174,175 titanium suboxides in anatase TiO2 nanocrystals have shown to
Weirzbicka et al. reported the use of anatase TiO2 and work as efficient cocatalysts in H2 generation when suspensions
Magnéli phase titanium suboxides loaded with Pt nanoparticles of these nanoparticles were used in H2O/methanol solutions.
for photocatalytic H2 evolution. The optimal mixed-phase The mixed-phase particles optimised at 900 °C, consisting of
particles, containing 32% anatase, 11% rutile and 57% 30% anatase, 25% Ti4O7 and 20% Ti5O9, achieved a direct
Magnéli phases, loaded with 290 ppm of Pt, exhibited a highly photocatalytic H2 evolution rate of 145 mmol h−1 g−1 under AM
efficient photocatalytic H2 evolution rate of ∼5432 mmol h−1 g−1 1.5 solar-simulated light, without the use of a cocatalyst. In
under UV light and 1670 mmol h−1 g−1 under AM 1.5 conditions. comparison, pure anatase or Magnéli phases exhibited signi-
This was approximately 50–100 times more efficient than cantly lower photocatalytic H2 evolution performance. The
anatase with similar Pt loading. The enhanced photocatalytic researchers further elaborate that the activity in these mixed
performance of the optimised nanoparticles under both solar particles is due to the synergistic effect of anatase TiO2 acting as

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the light absorber and Ti4O7 as the mediator for charge sepa- the chemical oxygen demand (COD) and dissolved organic
ration, transport and transfer, leading to signicant H2 gener- carbon (DOC) by 66.5% and 46.7% respectively, at 8 mA cm−2
ation without the need of an external cocatalyst.125 A Au(111) current density aer 2 h of reaction. Furthermore, the
@Ti6O11 heterostructure synthesised via photoreduction bioavailability of wastewater was improved, with the ratio
showed excellent hydrogen evolution activity with a low over- between the ve-day biological oxygen demand: COD increasing
potential of 49 mV at 10 mA cm−2 current density. Furthermore, from 0.029 to 0.28 aer treatment, making it a more cost
it also showed 18 times higher mass activity (9.25 A mgAu−1 vs. effective and environment friendly material for electrode prep-
0.51 A mgPt−1) and similar stability in acidic media compared to aration compared to PbO2 and SnO2 based electrodes.22 Wang
commercial Pt/C (20 wt%). Successful heterostructure forma- et al. investigated the successful degradation and deactivation
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tion enabling Au nanoparticles to better adsorb H+, increasing of antibiotics, antibiotic resistant bacteria and antibiotic resis-
the number of active sites on the catalyst and the conductive tance genes present in raw wastewater via electrooxidation
Ti6O11 support material were determined as factors that lead to using a Magnéli phase Ti4O7 anode. Multidrug-resistant
better performance in the Au(111)@Ti6O11 catalyst.176 Salmonella enterica serotype Typhimurium DT104 was fully
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inactivated, achieving a 6.2 log reduction within 15 minutes at

4.2 Wastewater purication a current density of 10.0 mA cm−2. Additionally, antibiotic
resistance genes such as TetG, oR and sul1, along with the class
4.2.1 Electrooxidation of organic pollutants. Electro- 1 integron gene (intI1) and virulence genes (invA and spvC)
oxidation, an advanced oxidation method, has emerged as within the pathogen, were reduced by 99.65% to 99.94%. In the
a promising approach for degrading organic contaminants in same electrochemical oxidation treatment system, the model
wastewater due to its high mineralisation efficiency, mild antibiotics tetracycline and sulfadimethoxine were degraded by
treatment conditions, relatively simple equipment and envi- 97.95% and 93.42%, respectively, within 3 h.185 When used for
ronmentally friendly nature.177 In electrooxidation, organic electrochemical oxidation of peruorooctanesulfonic acid
contaminants are removed in a two-step process. First, a direct (PFOS), the nano-Ti4O7 anode showed a better PFOS degrada-
electron transfer occurs from the contaminant (R) to the anode tion rate and energy efficiency in both batch and REM opera-
(eqn (9)) followed by generation of high amounts of highly tions compared to a micro-Ti4O7 anode and commercial
active OHc through water discharge at the surface of the anode Ebonex® (Ti9O17) anode due to its favourable pore size distri-
material (M), which has a high O2 overpotential (eqn (10)). bution and composition. The study found that the electroactive
Generated OHc actively participate in degrading a diverse range surface area of the anodes is linked to pores larger than 1.03
of organic compounds, as given in eqn (11).178,179 mm, suggesting a pore size threshold that limits electrochemical
accessibility in Magnéli phase porous titanium suboxide
R / (Rc)+ + e− (9)
materials. As a result, anodes with pore sizes just over 1 mm are
M + H2O / M (OHc) + H+ + e− (10) likely to offer the most effective surface area for electrochemical
reactions.186
R + M (OHc) / degradation by-products (11) A Ti4O7 anode was also used for the effective removal of
tetracycline by electrochemical oxidation, due to the high
Boron doped diamond (BDD) has been a common anode conductivity and chemical stability of the material. For tetra-
material in such reactions but has high fabrication cost. This cycline removal, applying current densities between 0.5 and 3
has moved attention to the use of materials such as Magnéli mA cm−2 achieved over 90% removal across initial concentra-
phase titanium suboxides, which have low fabrication costs, tions ranging from 1 to 50 ppm, with half-lives of 28 to 75
high oxygen evolution potential (>2.5 V vs. standard hydrogen minutes. They further found that hydroxyl radicals generated
electrode (SHE)) and chemical inertness.179,180 Magnéli titania- on Ti4O7, at a rate of 2 × 10−9 mol cm−2 min−1 under 0.5 mA
based electrodes have been used to successfully degrade and cm−2, contributed to at least 40% of the total tetracycline
inactivate various organic compounds including per- and pol- removal. Tests on Escherichia coli (E. coli) cultures conrmed
yuoroalkyl substances (PFASs), peruorooctanoic acid (PFOA), that electrooxidation by the Ti4O7 anode reduced tetracycline's
phenol, N-nitrosodimethylamine, antibiotics and antimicrobial activity to undetectable levels.182 A lm contain-
pathogens.181–183 However, studies have shown that the yield of ing a 1 : 1 TiO2 : Ti4O7 mixture prepared on polymethyl-meta-
OHc radicals generated by Magnéli phase titania-based elec- acrylate spectroscopy cuvettes showed effective photoanodic
trodes is lower compared to that by conventional electrodes performance in decolourising methylene orange dye compared
such as BDD and PbO2, due to its low interfacial charge transfer to TiO2 and Ti4O7 separately. The photoelectrochemical dye
rate. To overcome this issue and to gain better performance, degradation tests indicated that TiO2 and Ti4O7 achieved
pure phase titanium suboxides such as Ti4O7 were introduced decolourisation values of 35% and 46% respectively, while the
with the inclusion of varying amounts of foreign elements such TiO2/Ti4O7 mixed lm achieved 53% decolourisation. The
as C, amorphous Pd clusters and Ce3+ (Fig. 16(a)–(c)).181,184 enhancement in composite lm performance is attributed to
You et al. studied the use of monolithic porous Ti4O7 elec- the synergistic effect of photocatalytic and electrochemical
trodes for the electrochemical oxidation (degradation) of activities shown by TiO2 and Ti4O7, respectively.187 Geng et al.
organic pollutants in industrial dyeing and nishing waste- synthesised highly ordered Ti4O7 nanotube arrays and exam-
water. Their results conrmed that the Ti4O7 electrode removed ined their electrooxidation ability. In electrooxidizing phenol,

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Fig. 16 (a) Hydroxyl radical yield at different potentials and (b) oxidation of oxalate under anode polarisation at 2.0 V vs. saturated calomel
electrode by Ti4O7 and (Ti(1−x)Cex)4O7 electrodes. Reprinted with permission from ref. 181. Copyright 2021, American Chemical Society. (c)
Pseudo first order kinetics of PFOA degradation with pristine Ti4O7, Ti4O7/amorphous Pd and Ti4O7/crystalline Pd electrodes. Reprinted with
permission from ref. 184. Copyright 2020, American Chemical Society. (d) High resolution TEM (HRTEM) image, (e) high-angle annular dark-field
scanning transmission electron microscopy (HAADF-STEM) image, (f) and (g) HRTEM-STEM energy dispersive X-ray spectroscopy (EDS) mapping
images of Pt/Ti8O15 nanowires. Reprinted with permission from ref. 146. Copyright 2015, Royal Society of Chemistry.

Ti4O7 nanotube arrays showed a 1.7 times higher degradation trichloroethylene and observed that CO2 was primarily formed
coefficient compared to BDD, demonstrating their suitability with traces of CO, and no other carbon containing products.190
for electrooxidation applications.180 Ti4O7 nanotube arrays Under an anodic potential (Ea) of 2.5 to 4.3 V vs. silver-silver
achieved a 95.3% removal of phenol chemical oxygen demand, chloride electrode, trichloroethylene degradation followed rst-
outperforming Ti4O7 particles (79.4%). This enhanced perfor- order kinetics with respect to its concentration. The oxidation
mance was attributed to the presence of Ti4O7 particulates in rate was pH-independent between pH 1.6 and 11. Trichloro-
the nanotube arrays and their higher surface area (11.7 m2 g−1) ethylene oxidation occurred exclusively on the anodic surface
compared to Ti4O7 particles (4.7 m2 g−1). When used for the and became mass transport-limited at higher potentials (Ea >
electrochemical methanol oxidation reaction, Pt loaded Ti8O15 4.0 V). Despite the strong anodic performance of Magnéli phase
nanowires prepared by an electrodeposition method showed electrodes, Jing et al.191 observed a decline in the electro-
a peak current density of 28.2 mA cm−2 compared to 20.5 mA chemical activity of TinO2n−1 electrodes during anodic polar-
cm−2 and 17.2 mA cm−2 for Pt/C and Pt/TiO2 electrodes, isation. This was attributed to be dependent on the type of
respectively, demonstrating the best performance for the electrolyte, either due to the formation of a surface TiOSO4
Magnéli titania supported electrocatalysts (Fig. 16(d)–(g)).146 A passivating layer or by the loss of charge carriers. Though this
Sc2O3-Magnéli phase titanium composite electrode was surface deactivation can be reversed during the discharge
prepared by Bai and co-workers using a sintering-pressing process, the associated ohmic drop requires pre-conditioning of
technique that demonstrated 90.16% degradation of methyl the cell.191,192
orange aer 120 min of electrolysis. Optimal electrocatalytic 4.2.2 Photocatalytic degradation of wastewater pollutants.
activity was determined with a current density of 10 mA cm−2, Semiconductors have been widely used in the photocatalytic
solution pH 3 and temperature of 25 °C.188 degradation of wastewater pollutants, including waterborne
The interaction of Ebonex® with the deposited metal could pathogens, antibiotics, pharmaceuticals, dyes and other
alter the activity or nature of the metal electrocatalyst, as industrial effluents. This is due to the low cost of semiconductor
studied by Dieckmann and Langer. When tested for electro- materials, their high pollutant degradation rate, low toxicity
generative oxidation of aliphatic and aromatic alcohols and and the ability to completely mineralise organic contaminants
formaldehyde, Pt/Ebonex® showed higher activity for methanol into non-toxic products such as H2O and O2. In semiconductor
oxidation compared to Ni/Ebonex®, while the latter showed photocatalysis, when light with energy greater than the bandgap
signicant activity for formaldehyde oxidation and was slightly of the semiconductor is absorbed, it excites electrons from the
more polarised for benzyl alcohol.189 Chen et al. investigated the VB to the CB, generating electron–hole pairs. These electrons
use of an Ebonex® ceramic anode for electrolytic oxidation of and holes participate in a series of oxidation and reduction

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reactions, producing reactive oxygen species, which degrade the absorption, a large specic surface area and enhanced charge
organic contaminants in wastewater.193,194 TiO2 is a regularly carrier separation efficiency.196 Carbon-coated Magnéli phase
used semiconductor in photocatalytic wastewater purication titanium suboxides, prepared by heat-treating rutile TiO2 with
due to its high abundance, non-toxicity, strong oxidising ability, PVA at 1100 °C under N2 ow, were studied for the photo-
low cost and chemical stability. Photocatalytic degradation of catalytic decomposition of iminoctadine triacetate and phenol
organic contaminants occurs with absorption of UV light by under visible light (l > 400 nm). However, results showed that
TiO2, which eventually leads to the formation of highly active lower titanium suboxides, Ti2O3 and Ti3O5, had better photo-
superoxide (O2c−) and hydroxyl (OHc) radicals. These radicals catalytic activity compared to higher n Magnéli phases (n = 4, 5,
along with photogenerated holes oxidise organic contaminants 6, 9), implying that the presence of a higher concentration of VO
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resulting in less toxic by-products.41,195 Unlike UV light-active is favourable for the photocatalytic activity under visible light.29
TiO2, Magnéli phase titanium suboxides demonstrate visible
light photosensitivity, due to the VO induced during phase
transformation from rutile to Magnéli.29 However, as described 4.3 Reactive electrochemical membranes
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above, most Magnéli phase titanium suboxides synthesis Traditional membrane ltration faces several challenges, such
approaches require high temperature annealing, resulting in as relying solely on physical separation for removing toxic
micrometre-sized particles with poor surface area having less pollutants, membrane fouling, decreased permeate ux,
adsorption capacity, thus limiting its photocatalytic activity.33,196 chemical usage and high energy consumption. In contrast,
To address this issue, Magnéli titania has been combined with reactive electrochemical membranes (REMs) integrate electro-
different materials such as C, Pt or g-C3N4 to improve the chemical advanced oxidation processes (EAOPs) with physical
surface properties.29,196 ltration, creating a single, multifunctional water treatment
Si et al. synthesised gradient titanium oxide nanowire lms system. REMs generate reactive oxygen species through EAOPs
composed of TinO2n−1 (composed of Ti5O9, Ti4O7 and Ti3O5) and to disinfect organic contaminants without producing harmful
TiO2−x (anatase TiO2 with traces of rutile TiO2) (Fig. 17(a)) by an by-products.178 Similar to the electrooxidation of organic
electrostatic spinning method and gradient temperature pollutants discussed in Section 4.2.1, water in reactive electro-
annealing, which showed excellent photothermal conversion chemical membranes is oxidised to produce OHc radicals on the
efficiency and high photodegradation ability against simulated anode surface, as shown in eqn (12) below.
sewage (Fig. 17(b)). The lm completely degraded 0.02 g L−1
methylene blue dye in 90 min under 2 suns and achieved H2O /OḢ + H+ + e− (12)
a water evaporation rate of 1.833 kg m−2 h−1 under 1 sun.197
Similarly, Fujiwara et al. showed that TiO2 nanostructures These OHc engage in oxidative reactions with various organic
containing layers of Ti4O7 and lower titanium suboxides (Ti3O5) contaminants, leading to their complete degradation or
with different Ag loadings demonstrated high photoactivity in conversion to different byproducts. However, for certain recal-
Cr6+ reduction and methylene blue degradation under visible citrant compounds that exhibit low activity towards OHc (such
light (l > 400 nm) (Fig. 17(c)). The improved performance as uorinated organics), direct oxidation can also take place
compared to pristine materials has been attributed to the strong during anodic oxidation. In this process, an electron is trans-
visible light activity of the composite due to the sub-bandgap ferred from the contaminant (R) to the anode, as was shown in
energy tails generated from the suboxides.198 Li and co- eqn (9).200
workers synthesised TiO2–Ti5O9 nanostructures via a one-step REMs can effectively remove waterborne pathogens and
laser ablation in liquids approach, using varying pulse energy heavy metals from drinking water. Their use minimises the
densities during synthesis. The optimised Ti5O9–TiO2 hetero- need for pretreatment, simplies operation, reduces chemical
junction formed between the metal oxide phases exhibited consumption and lowers both process and operational costs.201
enhanced visible light photocatalytic degradation of rhodamine By combining EAOPs and microltration, REMs also mitigate
B dye (l $ 420 nm), nearly completely removing the dye within membrane fouling during ltration or backwashing, enhancing
three hours of light irradiation. This improved performance was ux recovery.26
attributed to efficient charge separation at the phase junction Given the similarity in the working principles of anodic
and increased light absorption across a broader wavelength oxidation for organic pollutants, as discussed in Section 4.2.1,
range.199 and REMs, the types of materials commonly employed are also
Zhao et al. synthesised a high surface area carbon layer similar. The efficiency of the process is highly dependent on the
coated Ti4O7 and g-C3N4 composite via a wet chemical and high choice of anode material. Several anode materials, such as BDD,
temperature treatment route (C@Ti4O7/g-C3N4), with its surface Ti/RuO2, SnO2 and PbO2, have been extensively explored for
area 5 times higher (72.97 m2 g−1) than pristine Ti4O7 (14.83 m2 REMs. Among these, BDD has demonstrated the highest effi-
g−1). Photocatalytic degradation studies on rhodamine B, ciency and lowest energy consumption (65 kW h kg per COD1).
methylene blue and methyl orange under visible light showed However, due to the high production costs involved with BDD,
that the activity and cyclability of C@Ti4O7/g-C3N4 out- there has been a search for alternative anode materials for
performed that of pristine Ti4O7, C@Ti4O7 and anatase TiO2/g- REMs.202 Magnéli phases, particularly Ti4O7, have attracted
C3N4 catalysts. The superior activity of the core–shell structured attention in this regard due to their excellent stability, high
composite catalyst was attributed to inherent VO, efficient light oxygen evolution potential and superior electrical conductivity.

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Fig. 17 (a) Digital images of the (i) prepared pristine TiO2 and (ii) gradient titanium oxide films and (b) photographs of the change in simulated
sewage with time with the treatment of gradient titanium oxide films. Reprinted with permission from ref. 197. Copyright 2022, American
Chemical Society. (c) Photocatalytic reduction of Cr6+ ions (left) and methylene blue degradation (right) under visible light irradiation by TiO2
(commercial P25) and 20Ag/TiO2 prepared by flame spray pyrolysis (FSP) at X/Y = 3/5 and X/Y = 8/5. X is the rate at which the precursor solution
containing TTIP, silver acetate and acetonitrile was fed through the FSP nozzle, which was then dispersed to a fine spray by Y = 5 mL min−1
oxygen. Reprinted with permission from ref. 198. Copyright 2014, Elsevier.

Zaky and Chaplin demonstrated the potential use of porous membrane without the need for any chemical reagents
and tubular Ti4O7 as REMs through the removal of a series of p- (Fig. 18(a) and (b)).124 Degradation of sulfamethoxazole using
substituted phenolic pollutants. Their studies showed that electrochemical reduction and oxidation in single pass, ow
these REMs were effective for both anodic oxidation and OHc through mode using Ti4O7 REMs and Pd–Cu doped Ti4O7 REMs
generation, facilitating efficient removal of the phenolic were studied by Misal and co-workers. An impressive 96.1 ±
compounds. Their cross-ow ltration studies, supported by 3.9% of sulfamethoxazole was removed by the Pd–Cu/Ti4O7
DFT calculations, revealed that p-benzoquinone was mainly REM via electrochemical reduction at −1.14 V/SHE, higher than
removed through reactions with electrochemically produced that observed for Ti4O7 and Pd/Ti4O7 REMs. However, in elec-
OHc. In contrast, the removal of p-nitrophenol and p-methox- trochemical oxidation, the Ti4O7 REM showed the highest
yphenol was mainly inuenced by the anodic potential applied removal, removing 95.7 ± 1.0% sulfamethoxazole at 2.03 V/
during the process.203,204 To improve the exibility of REMs, SHE.122 Adsorption and electrochemical reduction of N-nitro-
Santos et al. used an electrospinning and electrospraying sodimethylamine by carbon–Ti4O7 composite REMs was
method that resulted in highly porous and exible REMs, studied by Almassi and co-workers. Upon the addition of multi-
composed of polysulfone bres and Ti4O7 particles. Membrane walled carbon nanotubes or activated carbon to the REM, the
ltration experiments showed that the observed rst order rate residence times of N-nitrosodimethylamine in the REM
constant for phenol oxidation was 2.6 times higher in ltration increased by a factor of 3.8 to 5.4, leading to higher degrada-
mode compared to cross ow mode at a 1.0 mA cm−2 current tion.183 To study the electrochemical inactivation of E. coli at
density.205 Studies have shown that the use of REMs as cathodes different current densities, Liang et al. studied a REM system
prevents the formation of halogenated organic compounds that with two highly conductive, stable and porous Ti4O7 membrane
are typically produced during electrochemical oxidation and electrodes, working in dead-end ltration mode (Fig. 18(c)).
advanced oxidation processes. Magnéli phase titania samples Their studies showed that as the current density increased, the
have been investigated as suitable candidates for this purpose bacterial concentration decreased, with severe damage to the
because of the low cost of porous monolithic structure forma- cells. Moreover, it is reported that the E. coli concentration
tion and their ability to form OHc via water oxidation.26 decreased from 6.46 to 0.18 log CFU mL−1 aer passing through
As discussed above, Ti4O7 is the most conductive Magnéli the membrane lter (Fig. 18(d)).207 To treat agriculturally
phase, generating the highest amount of OHc.206 However, to contaminated water, Gayen and co-workers modied Ti4O7
further improve OHc generation, many studies have focussed on REMs by depositing B-doped SnO2 to provide high overpotential
modifying Ti4O7 either by increasing the electrochemical in oxygen evolution. When atrazine and clothianidin were used
surface area or by doping or forming composites with other as the model contaminants and terephthalic acid as the OHc
electrocatalysts.123 Jing et al. synthesised a ceramic, asymmetric, probe, complete mineralisation of all compounds was achieved
ultraltration REM composed of Ti4O7 and Ti6O11 Magnéli at 3.5 V/SHE in a single pass in the reactor with a 3.6 s residence
phases and tested their activity using humic acid and poly- time.121
styrene beads as model foulants. Membrane fouling was char-
acterised using an electrochemical impedance spectroscopy
technique. A backwash mode chemical-free electrochemical 4.4 Electronic and optoelectronic applications
regeneration process was developed based on the results of the The operation of resistive random-access memory (ReRAM) is
above analyses and enabled complete recovery of a fouled based on the dielectric breakdown of an insulator, mostly metal

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Fig. 18 (a) Normalised permeate flux under different operational conditions for the anodic chemical-free electrochemical regeneration in
backwash mode of 150 mg L−1 humic acid fouled REM and (b) electron impedance spectra obtained in the complete frequency range. Reprinted
with permission from ref. 124. Copyright 2016, Elsevier. (c) REM system containing Ti4O7 ceramic membrane design and setup. (d) Effect of
different current densities on the removal of E. coli by the Ti4O7 membrane filtration system. Reprinted with permission from ref. 207. Copyright
2018, Elsevier.

oxides, which shows resistive switching phenomena. In the Banerjee et al. demonstrated the resistive switching and
structure of a ReRAM, the insulator/semiconducting material is complementary resistive switching behaviours in a TiOx/Al2O3-
sandwiched between two metal electrodes. In the resistive based 3D vertical crossbar ReRAM device. Stable resistive
switching process of an ReRAM, by applying pulsed voltages, switching mechanisms in these devices were conrmed and
the resistance of the cell can be changed signicantly.208,209 attributed to the observation of Ti5O9 nanolaments by
Hence, devices in which the resistive switching mechanism HRTEM.213 As observed in these studies, formation of titanium
occurs demonstrate bipolar behaviour, wherein the conducting suboxide Magnéli phases via generation of shear planes in TiO2
and insulating states are alternated by applying opposite bias is related to the valence-change memory effect, which states
polarities. that the reduction of transition metal ions is caused by migra-
Kwon and co-workers probed the nanolaments in a Pt/TiO2/ tion of VO driven by the electrochemical potential gradient of
Pt system during resistive switching directly by HRTEM. They VO.62,210–214
observed that Ti4O7 conducting laments formed in TiO2
implying that the formation of Magnéli phase laments
induced the observed switching (Fig. 19(a)).210 Similarly, Stra- 4.5 Batteries
chan et al. observed a Ti4O7 crystallite in the TiO2 matrix, Rechargeable batteries, a type of electrochemical energy
showing that the resistance switching demonstrated by a Pt/ storage, have garnered signicant attention over the past few
TiO2/Pt memristor is due to TiO2 reduction and crystallisation decades due to their higher energy efficiency compared to
of a metallic conducting network. They further explained that mechanical and chemical storage systems.215 Among various
within a TiO2 matrix, the formation of Magnéli phases is ther- rechargeable batteries, commercial lithium-ion batteries have
modynamically favoured over a high concentration of randomly become particularly popular thanks to their high energy
distributed vacancies in the material, depending on the elec- density, cyclic stability and energy efficiency. Recently, sodium
trochemical potential within the device (Fig. 19(b) and (c)).211 and potassium have also gained similar interest as potential
Kim et al. prepared a cross-bar type Pt/TiO2/Pt structure with alternatives, due to their comparable chemical properties to
improved electrical endurance characteristics and uniform low lithium.216 Magnéli phase titanium suboxides are used in
resistance state and high resistance state distribution in la- batteries as electrodes because of their unique electronic and
mentary resistive switching. Ti4O7 and Ti5O9 conducting la- electrochemical properties. These materials have high electrical
ments were observed in the TiO2 thin lm that lead to a stable conductivity and high specic capacity, suggesting that they can
memory window.212 store and release a signicant amount of energy per unit mass.

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Fig. 19 (a) HRTEM image of a nanocrystalline Ti4O7 filament (outlined in blue) in a Pt/TiO2/Pt system used in a resistive switching device.
Open Access Article. Published on 20 2025. Downloaded on 2025/2/20 0:50:17.

Reprinted with permission from ref. 217. Copyright 2020, Springer Nature. (b) Scanning Transmission X-ray Microscopy image of the device
junction area, showing absorption contrast within the junction and (c) chemical and structural mapping of the three observed phases in the
junction. Region (i) corresponds to amorphous TiO2, Region (ii) is anatase TiO2 and Region (iii) is reduced titanium suboxides TiO2−x. Reprinted
with permission from ref. 211. Copyright 2010, John Wiley and Sons.

In addition, Magnéli phase titanium suboxides are highly with a capacity fading rate of 0.07% per cycle at 0.5C.220 Han and
stable, corrosion resistant and durable, making them excellent Wang reported the use of graphitic carbon coated Ti9O17 as
candidates in rechargeable batteries.27,28 They have also anodes for Li-ion batteries and in hybrid electrochemical cells.
demonstrated excellent cyclability, enabling them to undergo These materials have shown excellent cyclic stability giving
many charge–discharge cycles without a decline in electro- a pseudocapacitive lithium-storage behaviour with a reversible
chemical performance. Furthermore, their high thermal capacity of 182 mA h g−1.221 Additionally, Lee et al. presented the
stability allows these materials to withstand high temperature, Ti6O11/carbon nanotube composite electrode as a promising
improving the safety and reliability of batteries and preventing anode material for K-ion batteries. This electrode exhibited an
overheating and short circuiting.23,24,218 As discussed in Section extended cycling life of over 500 cycles at a current rate of
4.1, Magnéli phase titanium suboxides are commonly used as 200 mA g−1, with a capacity retention of 76% and an impressive
catalyst supports for oxygen and hydrogen evolution reactions, coulombic efficiency of 99.9%.222
primarily due to their high electrical conductivity and excep- Wei et al. developed a sulfur cathode hosted on mesoporous
tional corrosion resistance, which ensure stability in both Ti4O7 microspheres (70 wt% sulfur) that exhibited a high
highly acidic and basic environments and provide signicant discharge capacity of 1317.6 mA h g−1 at moderate current
electrochemical durability. Given that similar properties are density, with 88% capacity retention aer 400 cycles, exhibiting
desirable for battery applications, it is likely that Magnéli phase excellent cyclability. Excellent stability attributed to the Ti–S
titanium suboxides developed for catalytic purposes could be interactions between low-coordinated Ti4O7 and lithium poly-
adapted and optimised for use in battery technologies as well. suldes, facilitated sulfur redeposition during the charging
Ti4O7 has been investigated as a suitable host material for phase. Additionally, the porosity and the high electronic
sulfur loading in lithium sulfur batteries due to its high conductivity of the electrodes contributed to the high perfor-
conductivity and high binding affinity towards lithium poly- mance of the material.223 Furthermore, Li et al. successfully
sulde.145 In lithium sulfur batteries, the shuttle effect and the studied the feasibility of Ti4O7 for use as air–cathodes in zinc–
uncontrollable deposition of lithium suldes have been iden- air batteries under strong alkaline conditions due to its elec-
tied as factors that can result in low coulombic efficiency and trochemical durability and stability. The stability of the Ti4O7
capacity decay. To nd a solution to this challenge, Tao et al. electrode was evaluated in an O2-saturated alkaline solution
used a sublimation and deposition method to fabricate a high through cyclic voltammetry within a potential range of −0.7 to
performance Ti4O7–S cathode composite by thermal diffusion +0.7 V vs. Hg/HgO. The Ti4O7 electrode successfully survived
of S into the Ti4O7 matrix. Results revealed higher cycling 5000 cycles without any signicant loss in the oxygen reduction
performance and reversible capacity compared to the TiO2–S reaction peak current.114 Yao et al. used Ti4O7 as the conductive
cathode, due to more effective binding of Ti4O7 with S species. additive in a sulfur electrode and showed that sulfur/Ti4O7 had
The Ti4O7–S cathode demonstrated high specic capacities at improved electrochemical properties compared to a sulfur/
different C rates, achieving 1342, 1044 and 623 mA h g−1 at 0.02, acetylene black electrode, in both its polysulde absorption
0.1 and 0.5C, respectively, along with impressive capacity and its catalytic activity towards the Li/S redox reaction.127
retention of 99% at 100C and 0.1C (Fig. 20(a) and (b)).219 Sab- Franko and co-workers utilised Ti4O7 as a stabilising additive
baghi and co-workers developed highly conductive Magnéli for simple carbon paper cathodes to limit NaO2 degradation in
Ti4O7 nanotube arrays supported by a carbon-coated separator, sodium–oxygen batteries. Results revealed that Ti4O7 serves as
to enhance the energy density and enable rapid charging and a stable nucleation point for NaO2 formed in the solution,
discharging in Li–S batteries. The battery demonstrated resulting in a reduced rate of NaO2 degradation. Consequently,
a reversible discharge capacity of 723 mA h g−1 aer 500 cycles Ti4O7-coated cathodes exhibited signicantly longer cell

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Fig. 20 (a) Initial charge–discharge curves of composite cathodes formed with TiO2, Ti4O7 and Ti6O11 at a rate of 0.02C. (b) Cyclic performance
and coulombic efficiency of the cathodes for 100 cycles at 0.1C rate. Reprinted with permission from ref. 219. Copyright 2014, American
Chemical Society. (c) Rate performance from C/10 to 2C of rutile TiO2 microspheres infiltrated with S (RM/S) and Ti4O7 microspheres infiltrated
with S (MM-x/S) (The molar ratio of TiO2 : C during synthesis varied across the samples, with a ratio of approximately 3 : 2 for MM-1, and 3 : 4 for
MM-2, depending on the volume of resol solution used) and (d) cyclability with calculated coulombic efficiency of RM/S and MM-1/S at C/5.
Reprinted with permission from ref. 223. Copyright 2017, John Wiley and Sons.

lifetimes over many cycles compared to cathodes cast with low cost.228 Magnéli phase titanium suboxides, with their
commercial SuperP carbon black. When the Ti4O7 content in excellent light absorbance across the solar spectrum and
the cathode slurry (comprising Ti4O7, poly(vinylidene uoride) desirable thermal conductivity, have demonstrated high solar-
and SuperP carbon in acetone) was increased to up to 90%, the to-vapour efficiency, making them suitable photothermal
cell lifetime signicantly improved to 37 cycles before any materials for solar steam generation.30
notable degradation was observed.224 To evaluate the possibility The ability for Magnéli phase titanium suboxides to absorb
of replacing carbon in electrodes, Lee et al. synthesised solar light has been used in solar steam generation via a self-
RuO2@Ti4O7 nanospheres that could enhance the performance oating Ti4O7/yttrium stabilised zirconia (YSZ) membrane
of Li–O2 batteries. With Ti4O7 supporting the activation of (Fig. 21(a)). While the insulating YSZ layer is conducive to water
catalytic performance of RuO2 nanoparticles during discharge– transportation, the upper Ti4O7 layer was used for photothermal
charge processes, these carbon-free RuO2@Ti4O7 nanosphere conversion, so that the bilayered membrane showed a remark-
electrodes are considered as potential candidates for superior able water evaporation rate of 1.86 kg m−2 h−1 under one sun
oxygen reduction and oxygenation reactions.225 (Fig. 21(b) and (c)).229 Si et al. synthesised gradient titanium
oxide nanowire lms composed of TiO2−x and TinO2n−1, which
exhibit both photocatalytic and photothermal properties. The
4.6 Photothermal applications TinO2n−1 component of the lm (containing Ti4O7 and Ti3O5)
Solar-driven steam generation is becoming an important demonstrated a water evaporation rate of 1.833 kg m−2 h−1
approach for harnessing solar energy, as it directly converts under one sun irradiation, with an energy conversion efficiency
solar energy into heat for water evaporation and facilitates of 88.96%.197 Xu et al. prepared Ti4O7-PVA nanocomposite
energy storage.226 The photothermal materials used in solar hydrogels that exhibit a narrow bandgap of approximately
steam evaporators can effectively capture solar energy and 0.81 eV for highly efficient solar steam generation. Under one
generate heat, which is then transferred to bulk water for water sun irradiation, this hydrogel achieved an evaporation rate of
vapour generation.227 The performance of a solar steam evapo- approximately 4.45 kg m−2 h−1 with an energy efficiency of
rator partially depends on the photothermal material employed. around 90.69%. Additionally, the hydrogel demonstrated
Among the various types of photothermal materials, such as impressive stability, maintaining an evaporation rate of up to
plasmonic nanoparticles, carbon-based materials, polymers approximately 4.03 kg m−2 h−1 until day 20. Further experi-
and inorganic semiconductors, semiconductors are increas- ments conducted on seawater desalination revealed negligible
ingly being modied and utilised due to their abundance and salt accumulation on the hydrogel's surface, enabling its use in

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power generation in a material used in hydrovoltaics, its interac-

tion with water needs to be improved with a reduction in its
internal resistance. Since VO increase the carrier concentration and
attract cations, Si et al. used Magnéli phase nanocrystal lm as the
active material for hydrovoltaic power generation. They observed
that the open circuit voltage (VOC) and short circuit current (ISC)
increased with increasing oxygen vacancy concentration (which
correlated to increasing annealing temperature during material
synthesis). They demonstrated the use of their energy generation
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devices by capturing rainwater and observed that a ∼600 mV VOC

was maintained for over 2.5 h (Fig. 22(a)–(c)).129
Qing et al. synthesised a Ti4O7/polyimide composite using
a heat pressing technique, which exhibited tunable dielectric
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properties and excellent absorbance in the high-frequency

range of the GHz band. In addition, the study also demon-
strated the potential of these composites as exible absorbing
coating materials. When the polyimide matrix was backlled
Fig. 21 (a) SEM image of fibrous Ti4O7 membrane after calcination. (b) with 60 wt% Ti4O7 particles, the minimal reection loss reached
Rate of water evaporation from the Ti4O7 membrane with and without
−49.3 dB at 13.7 GHz with a thickness of 1.25 mm. This nding
YSZ. (c) Temperatures on the surface of water recorded for TiO2, Ti4O7
and Ti4O7/YSZ membranes by an IR thermometer. Reprinted with further conrmed that the tunable and unique dielectric
permission from ref. 229. Copyright 2022, American Chemical Society. properties of Ti4O7 make it an excellent candidate for designing
absorbers and for other electromagnetic applications.231 The
gas sensing behaviour of a Magnéli phase containing a metal
stable purication of sewage or desalination of seawater con-
oxide layer (rutile TiO2, Ti9O17 and Ti8O15) coated on a exible
taining multiple organic contaminants.228 Since most Magnéli
polymeric thin lm was tested using NH3(g) at 12.5–100 ppm.
phase titanium suboxides used in solar steam evaporators are
Positive results observed in the sensing experiments were
based on Ti4O7, in one of our previous studies, we investigated
attributed to the high concentration of VO and porosity of the
Magnéli phases other than Ti4O7 in a solar steam evaporator
active layer, which can increase gas adsorption capacity and the
and monitored its performance. We utilised a graphene oxide-
surface for interaction.232 Fan et al. demonstrated the possibility
based aerogel and incorporated Magnéli phase titanium sub-
of using Ti9O17 as a non-toxic n-type thermoelectric material,77
oxides (comprising 2.8% Ti5O9, 81.8% Ti6O11, 30.7% Ti7O13,
while Canillas et al. explored the use of Ti5O9 as a candidate
3.8% Ti8O15 and 0.9% Ti9O17) to form a solar steam evaporator.
electrode material in neuron growth stimulation due to its low
The composite aerogel (radius 2.25 cm) demonstrated a water
impedance and high chemical stability.233
evaporation rate of 0.832 kg m−2 h−1 under 1.0 sun with an
optimised weight of 50 mg of Magnéli phase titanium suboxide
particles. The calculated energy conversion efficiency for the 5. Challenges and prospects
optimised aerogel was 56.5%, which is over three times that of
water without the aerogel under the same conditions.30 5.1 Stability and durability
Magnéli phases are well known for their excellent chemical and
electrochemical stability, making them appealing to electro-
4.7 Other applications chemists and electrochemical engineers. Because of these
Hydrovoltaics is a novel electricity generating technology that properties, Ebonex® materials have been employed both as
harnesses the ability of nanomaterials to respond to waves or the standalone electrode materials and as substrates for various
ow, dropping or evaporation of water.230 To enhance the electric electrocatalysts.

Fig. 22 (a) Measured open circuit voltage (VOC) and (b) short circuit current (ISC) for Magnéli phase nanocrystal films prepared at different
temperatures (800–1000 °C) and (c) average peak values of VOC and ISC. Reprinted with permission from ref. 129. Copyright 2021, American
Chemical Society.

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Research conducted by Smith et al. explored the stability of environments over time. Instead of instability, they exhibit
titanium suboxides in the Magnéli phase under harsh condi- remarkable stability and durability across diverse chemical
tions. The study found these materials to be more durable than conditions, reaffirming their suitability for various applications.
traditional electrodes used in large-scale electrochemical
processes, including both Ti and TiO2. Magnéli phases 5.2 Cost–benet analysis
remained stable when exposed to aggressive chemicals like
As detailed in the synthesis section, TiO2 is the primary feed-
uoride-based etchants, hydrochloric acid and aqua regia.
stock for many synthesis methods of Magnéli phases.
However, they experienced some degradation in more extreme
Depending on the method, different reducing agents such as
environments, such as boiling phosphoric acid, concentrated
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hydrogen gas, carbon or metals are used. Since these reduction

HF and highly concentrated NaOH solutions (concentration >
processes typically require high temperatures over extended
12 M).25 Liu et al. investigated the electrochemical stability
periods, cost considerations largely depend on the choice of raw
windows of Ti4O7 electrodes across acidic, neutral and alkaline
materials and reductants, assuming operational and energy
aqueous solutions. Their ndings demonstrate that the stability
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costs remain comparable.

windows in all three types of solutions exceed 3.5 V, enabling
In most reduction methods for forming Magnéli phases,
the production of signicant amounts of cOH radicals. Notably,
TiO2 is the primary raw material, priced at approximately USD 3/
the Ti4O7 electrode exhibited its widest stability window of
kg globally in 2022.235 Considering the various reduction
4.19 V in a 1 M NaCl solution, while the narrowest window,
methods used to form Magnéli phases, the high cost of metals
3.53 V, was observed in a 1 M H2SO4 solution.234
such as Ti (over USD 10/kg)236 and Zr (with an average import
Magnéli phase titanium suboxides show better stability in
price of USD 28/kg in the United States in 2023) makes large-
various aspects compared to carbon-based materials. Ceramics
scale synthesis via metallothermic reduction highly impractical.
produced at high temperatures tend to be in their most stable
Due to the high costs associated with the storage and
and fully oxidised state, meaning they are less likely to oxidise
transportation of hydrogen, carbothermal reduction emerges as
further, unlike metals and carbon. In addition, in applications
a more cost-effective method for large-scale synthesis of
like electrolysis, Ebonex® electrodes demonstrate greater
Magnéli phase titanium suboxides, including commercial
stability than carbon electrodes, particularly at high pH levels,
Ebonex®. This approach is particularly advantageous as it uses
where carbon materials tend to decompose.25 Li et al. investi-
activated charcoal as the reductant, which is priced at around
gated the stability of Magnéli phase Ti4O7 electrodes for oxygen
USD 5.6/kg, based on both literature and commercial sources.237
reduction in zinc–air rechargeable batteries, as carbon mate-
Consequently, the relatively low cost of raw materials for
rials tend to degrade due to corrosion from O2 and H2O2, and at
producing Magnéli phase titanium suboxides offers these
high electrode potentials. Ti4O7, with its excellent conductivity
materials a signicant cost-benet advantage over more
and electrochemical stability, emerged as a strong candidate for
commonly used electrode materials like BDD in electro-
air–cathodes in these batteries. Cyclic voltammetry and chro-
chemical applications.
nopotentiometric tests conrmed its stability. Raman and XPS
analysis before and aer testing revealed the formation of a thin
TiO2 layer on the Ti4O7 surface, which likely protects the bulk 5.3 Challenges related to the synthesis and use of Magnéli
material from further oxidation, enhancing its long-term phase titanium suboxides
stability.114 In the last decade, Ti3+ self-doped Magnéli phase titanium
Krishnan et al. describe the use of Magnéli phase titanium suboxides have attracted much interest in diverse elds due to
suboxides as durable catalyst supports capable of withstanding their outstanding optoelectronic, photochemical and photo-
high potentials in PEM fuel cells. These materials demonstrate catalytic properties. The main current issues in the synthesis
remarkable corrosion resistance, even under very high potential and use of Magnéli phase titanium suboxides are the high
conditions. The electrochemical stability of the Pt/TinO2n−1 temperatures and extensive sintering required, which lead to
catalyst (with Ti4O7 as the dominant phase in TinO2n−1) was particle coalescence and the formation of microparticles that
investigated through cyclic voltammetry at a scan rate of 50 mV are unsuitable for applications requiring high surface areas.
s−1. Their research highlighted that TinO2n−1 exhibits excellent Issues related to microparticle formation have been resolved by
stability over the potential range of −0.25 to 2.75 V vs. SHE.130 using diverse titanium precursors, such as Ti(NO3)2, and
Owing to their resistance to corrosion and resilience against various polymeric reducing agents combined with microwave
polarity reversal, Ebonex® electrodes are also used in electro- irradiation, leading to the synthesis of nanoscale Ti4O7.127,238
phoresis. Their chemical inertness, especially in the presence of However, these methods still require expensive, extensive and
organic electrolytes, provides exibility in the choice of gel types time-consuming precursor treatments and high-temperature
. Their large surface area allows for efficient voltage and current synthesis. To address this, several novel techniques have been
distribution, and they perform exceptionally well in reverse or developed to synthesise titanium suboxides without the need
pulsed electrophoresis, due to their high stability under polarity for such intense sintering. One such approach, described by Arif
reversal.25 and co-workers, involves a thermally induced plasma process.239
These ndings suggest that, despite being synthesised While this method successfully produces Magnéli phase tita-
through the creation of VO, Magnéli phase titanium suboxides nium suboxides with relatively higher surface area (52.9 m2 g−1)
remain stable at room temperature and in oxygen-rich the use of plasma is expensive and limits its scalability.

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Moderate-temperature synthesis methods for Magnéli phase were considered as non-hazardous, with no increase in intra-
titanium suboxides have also been explored, but these oen rely cellular reactive oxygen species levels upon exposure.244 Jemec
on costly reductants, such as metals and metal hydrides, Kokalj et al. conducted a study on hazard characterisation of
making them impractical for large-scale production.143 This Magnéli TiOx using a set of ecotoxicological test organisms and
indicates that none of the current synthesis approaches fully human lung and liver cell lines. Since exposure to these test
meet all criteria, including nanoparticle formation, the use of organisms and cell lines did not induce any biological response,
low cost reductants/raw materials and the elimination of sin- Magnéli TiOx particles were considered as acutely non-
tering. Therefore, there is a clear opportunity to develop inno- hazardous.245 To mitigate the harmful effects of these nano-
vative methods for synthesising nanostructured Magnéli phases particles, some countries use particle traps to capture these
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at moderate temperatures without relying on costly raw nanoparticles before nal emission of the exhaust gas. Further
materials. assessment regarding the impact of Magnéli phase titanium
Recently, Ma et al. made use of 3D printing technique to suboxide particles is required to determine the feasibility of
synthesise a porous Magnéli phase electrode composed of using them in large scale applications.
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Ti5O9, Ti6O11 and traces of Ti7O13, from a TiOx powder mixture

and aqueous binder (Fig. 23(a) and (b)). This 3D TiOx electrode
showed enhanced degradation kinetics for the probe molecules 5.4 Potential improvement strategies and prospects
oxalic acid, terephthalic acid and paracetamol, lower accumu- As previously discussed, the 3D printing of Magnéli phase
lation of toxic by-products (hydroquinone and benzoquinone) titanium suboxide electrodes offers a promising synthesis route
and higher mineralisation yield compared to commercial BDD due to its relatively low cost and time efficiency compared to
and Ti/TiOx plate anodes.240 This study demonstrates the conventional approaches, which oen require signicant
potential of 3D printing for creating low-energy, feasible energy and extensive processing time. To date, there has been
approaches for TinO2n−1 preparation, offering an alternative to only one documented instance of Magnéli phases being syn-
conventional methods requiring high temperatures or expen- thesised through additive manufacturing. This represents
sive raw materials. a signicant opportunity for further research and development,
In addition to the challenges associated with the synthesis of particularly in the creation of Magnéli phase electrodes for
Magnéli phase titanium suboxides, a lesser-known aspect is the various electrochemical applications. Advancing this area could
potential health risks and concerns related to these materials. It lead to more sustainable and scalable production methods for
is reported that Magnéli phase materials are generated as energy storage and conversion technologies.
incidental nanoparticles during industrial coal combustion Due to the high production costs of BDD for electrochemical
causing these nanomaterials to be widespread in the environ- applications, Magnéli phase titanium suboxides and their
ment.241,242 Analyses of coal ash samples obtained from power- doped counterparts are actively being investigated as alternative
plants in USA and China have shown that all Magnéli phases (n anode materials for the electrooxidation of organic pollutants
= 4–9) are generated during coal burning with Ti6O11 being the and in REMs. While their use in these applications is currently
most frequent.243 mostly limited to the laboratory scale, we believe that electro-
Toxicity tests on Magnéli phase nanomaterials report that chemical applications will soon present a promising direction
they have potential toxicity pathways that are biologically active for Magnéli phase titanium suboxides.
without photostimulation.241 These studies report that exposure The authors of this review identied several areas related to
and accumulation of Magnéli phases cause abnormalities in these materials that offer signicant opportunities for further
macrophages due to increased oxidative stress and mitochon- development and clarication. As discussed in Section 4, pho-
drial dysfunction and also result in reduced lung function tocatalytic pollutant degradation using Magnéli phase titanium
impacting airway resistance and elastance.242 Kononenko et al. suboxides has been investigated in numerous studies, with
studied the hazard potential of Magnéli phase titanium sub- most approaches focusing on heterojunction formation
oxides on A549 human lung cells. Although some potentially between Magnéli phase TinO2n−1 and other materials. However,
adverse effects of Magnéli phase nanoparticles were observed comprehensive studies on heterojunctions involving both
due to their cellular internalisation and biopersistance, they organic and inorganic semiconductors are limited, revealing an
evident research gap. Moreover, the charge transfer mecha-
nisms in these heterojunctions, which are currently understood
in terms of Z-scheme or semiconductor-to-metal charge transfer
mechanisms, require deeper investigation. Integrating these
experimental studies with theoretical insights could provide
a broader understanding of charge transfer dynamics and open
new avenues for utilising these materials in photocatalysis.
Further research could also explore the potential of Magnéli
phases as standalone catalysts in photocatalytic water puri-
Fig. 23 (a) Porous structure and pore size of 3D printed TiOx electrode
cation or with dye sensitisation. A key challenge in these
and (b) morphology of 3D TiOx as observed from SEM. Reprinted with applications is the narrow bandgap of Magnéli phases, which
permission from ref. 240. Copyright 2023, Elsevier. may limit their ability to generate reactive oxygen species.

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Additionally, the low surface area of these materials may hinder Author contributions
dye adsorption, thus reducing their efficacy. Our research has
demonstrated the possibility of bandgap tuning to overcome S. Amanda Ekanayake: investigation, validation, formal anal-
this limitation, allowing Magnéli phases to reach the potentials ysis, writing – original dra. Haoxin Mai: investigation, writing
required for the formation of superoxide and hydroxyl radicals, – review and editing. Dehong Chen: conceptualisation, visual-
thereby enabling them to participate in photocatalytic reac- isation, supervision. Rachel A. Caruso: conceptualisation,
tions. Developing Magnéli phases with higher surface areas funding acquisition, writing – review & editing, supervision.
could further expand their applications, enhancing their utility
in environmental and energy-related technologies. Implement-
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ing in situ characterisation could offer critical insights into the Conflicts of interest
catalytic and oxidation mechanisms occurring on the surface or
interface of the material across various applications. This There are no conicts to declare.
approach may clarify real-time structural and chemical
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changes, thereby advancing our understanding of how Magnéli

phase titanium suboxides perform under operational Acknowledgements
conditions. The authors acknowledge funding support from the Australian
Two lesser-explored applications of Magnéli phase titanium Research Council through the Discovery Project scheme,
suboxides are gas sensing and hydrovoltaics. These areas hold DP180108315.
considerable potential for industrial applications and sustain-
able energy generation, particularly using low-cost raw mate-
rials. Further investigation into these applications could References
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