Surfaces and Interfaces 36 (2023) 102534

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Surfaces and Interfaces

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Photoelectrocatalytic degradation of sulfamethoxazole over S–Scheme

Co3Se4/BiVO4 heterojunction photoanode: An experimental and density
functional theory investigations
Tunde Lewis Yusuf a, Segun Ajibola Ogundare b, Francis Opoku c, Nonhlagabezo Mabuba a, d, *
a
Department of Chemical Sciences, Faculty of Science, University of Johannesburg, 9 Lewes Road, Johannesburg 2092, South Africa
b
Department of Chemical Sciences, Olabisi Onabanjo University, P. M. B. 2002, Ago–Iwoye, Nigeria
c
Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana
d
Centre for Nanomaterials Science Research, University of Johannesburg, South Africa

A R T I C L E I N F O A B S T R A C T

Keywords: We have carried out comprehensive experimental and density functional theory simulations of Co3Se4/BiVO4
Photoanode heterojunction to understand the relationship between interface and enhanced photocatalytic activity. This study
S-Scheme demonstrates the photoelectrochemical degradation of sulfamethoxazole (SMX) with a photoanode developed
Heterojunction
based on S–Scheme heterojunction. The difference in the energy levels of the band gaps and conduction bands of
Sulfamethoxazole
DFT
BiVO4 and Co3Se4 makes them suitable semiconductors for the fabrication of an S–Scheme heterojunction. The
Photoelectrocatalysis BiVo4/Co3Se4 composite is prepared by solvothermal method and characterized using X–ray diffraction (XRD),
field emission–scanning electron microscopy (FE–SEM), transmission electron microscopy (TEM), Energy
Dispersive X–Ray Analysis (EDX), Ultraviolet–Visible Diffuse Reflectance Spectroscopy (UV–DRS). The photo­
electrochemical properties of the fabricated photoanode are studied using Electrochemical impedance spec­
troscopy (EIS), Mott–Schottky, and photocurrent response. The UV–DRS spectra show an improved band gap
(1.88 eV) for the composite in comparison with pristine BiVO4 (2.39 eV). The XRD patterns reveal the presence of
monoclinic phases of BiVO4 and Co3Se4 in the composite. This is further confirmed by the microscopic studies
that show the surface coating of Co3Se4 on BiVO4. The composite photoanode shows improved photocurrent
density and low charge transfer resistance in comparison with the pristine semiconductors. Theoretical calcu­
lations reveal charge redistributions at the interface between Co3Se4 and BiVO4. Furthermore, the density of
states, Bader charge and electrostatic potential drop reveals that the synergistic effect of built-in electric field
directed from the BiVO4 surface to the Co3Se4 surface facilitates the efficient separation of charge carriers in the
Co3Se4/BiVO4 interface and thus prevents carrier recombination rate. This provides the composite with the
capacity to effectively degrade SMX with improved efficiency. At optimum conditions, the SMX degradation
efficiency reached 75% with a rate constant of 0.0115 min–1. The holes majorly facilitate the degradation of
SMX, as revealed by the scavenger study. Comparative studies indicate that photoelectrocatalytic contributions
supersede photocatalytic and electrocatalytic contributions.

1. Introduction industrial wastes, as well as wastewater effluents, which find their way
to the proximate water bodies [4,5]. The bioaccumulation, as well as
Pharmaceuticals in water bodies have been reported and considered modification of the pharmaceuticals under ambient conditions in water
as emerging contaminants due to the adverse effect they may pose on the bodies, is a great risk that can lead to an increase in drug resistance and
environment and ecosystem, even at low concentrations (10–6–10–9 g/L) reduction in efficacy over a long period [1,5]. A typical example is a
[1–3]. Pharmaceuticals find their path to the environment through sulfamethoxazole (SMX), a common antibiotic recommended as a
excreta, treated sewage sludge, leachate from landfill, medical and medication for the treatment of infection in clinics, livestock, poultry,

Abbreviations: BVO, BiVO4; CS, Co3Se4; CSB, Co3Se4/BiVO4; SMX, Sulfamethoxazole; PEC, Photoelectrocatalysis.
* Corresponding author at: Department of Chemical Sciences, Faculty of Science, University of Johannesburg, Johannesburg, South Africa.
E-mail address: [email protected] (N. Mabuba).

https://doi.org/10.1016/j.surfin.2022.102534
Received 12 September 2022; Received in revised form 19 November 2022; Accepted 27 November 2022
Available online 29 November 2022
2468-0230/© 2022 Elsevier B.V. All rights reserved.
T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

and aquaculture [5,6]. SMX and its metabolites (N–acetyl–SMX and combination with other materials (Co3Se4/TiO2 [64] Co3Se4/CoSe2 [65]
N–SMX glucoside acid) have been discovered in water bodies (25–30 and Co/Co3Se4 [66]) as suitable electrocatalytic materials for the evo­
ng/L) as well as drinking water that has been treated and certified for lution of oxygen and hydrogen in water. Co3Se4 has high conductivity
consumption [1,7–10]. This is a great concern as it revealed the limi­ and good adsorption with broad absorption in the range 200–700 nm. It
tation of the current protocols adopted in wastewater treatment. Hence, is non–toxic and inexpensive. We envisage that a combination of BiVO4
the need for an improved wastewater treatment system that can effec­ and Co3Se4 will create a S–Scheme heterojunction suitable for separa­
tively remove pharmaceuticals such as SMX from water. Studies at the tion of charge carriers with an improvement in the photoelectrocatalytic
cellular and molecular levels have indicated the toxicity of SMX to degradation of contaminants in water. The relatively lower band gap of
aquatic life and its carcinogenic tendency [7,11]. The conventional Co3Se4 with a higher conduction band is suitable to facilitate the
techniques (activated sludge, coagulation, biological and sand filtration, S–Scheme when combined with BiVO4 which is a semiconductor with a
ozonation, photolysis, adsorption, ultrasound, and osmosis) adopted for higher band gap but lower conduction band. In the S–Scheme, an in­
wastewater treatment are mostly inadequate to effectively remove ternal electric field is generated at the heterojunction of the combined
pharmaceuticals from wastewater [12–17]. semiconductors and under illumination, the electric field as well as
The removal of SMX from an aqueous solution has been conducted aligned Fermi energy levels of the combined materials will cause the
using adsorption, Fenton/Photo–Fenton, photocatalytic degradation, electrons to transit from the conduction band of an oxidation photo­
and electrochemical oxidation processes [5,18–20]. These processes catalyst (BiVO4) to the valence band of a reduction photocatalyst
have their associated limitations. Although adsorption is relatively less (Co3Se4). This will prevent the recombination of the electrons in the
expensive, it leads to the accumulation of used adsorbents (activated conduction band of Co3Se4 and the holes in the valence band of BiVO4.
carbon [21], biochar [22], carbon nanotubes [18] and graphene [23]) These charge carriers will be readily available for degradation of dis­
and most often recovery is more expensive while proper disposal of used solved contaminants such as SMX [67,68].
adsorbents is rarely considered. Unlike adsorption, the Fenton/Pho­ The creation of the S-scheme heterojunction is a new route to over­
to–Fenton processes rely on the generation of hydroxyl radicals from come the challenges associated with the conventional type II and
H2O2 which help to degrade SMX. However, the insolubility of Fe(OH)3, Z–schemes that suffer greatly from charge recombination, high redox
leaching of ions from catalysts, complexation of ions with SMX and potential, use of redox shuttles, and columbic repulsion at the hetero­
difficulty in the complete removal of the leachates limit the applications junctions, which hampered their performances [69,70]. Although the
[24]. The photocatalytic degradation and the electrochemical oxidation Z–scheme has been greatly improved via the introduction of solid redox
processes are based on the use of light energy and electrical energy, shuttles and use of multiple semiconductors to promote charge separa­
respectively, to generate radicals with capacity to degrade pollutants. tion and improve absorption of light in the visible spectrum [71–73],
While the efficiency of photocatalytic process is limited by the light there are still limitations which hinders catalytic efficiency. The several
absorption capacity of the catalysts used (TiO2 [25], Cu–TiO2 [26], benefits of S–Scheme over the conventional schemes are recently well
reduced graphene–WO3 [27] and Au–TiO2 [28]) and the effective sep­ highlighted and new heterojunctions are created based on S–Scheme
aration of the charge carriers (electrons and holes), the electrochemical with improvement in catalytic performance [74]. The catalytic perfor­
process is limited by current density, electrical conductivity and fouling mance of TiO2/Bi2O3 S–Scheme heterojunction was greatly improved by
of the electrodes (boron–doped diamond) [29,30], Ti/SnO2–Sb/­ introduction of polystyrene-sphere as support for the catalyst. The pol­
Ce–PbO2 [31], as well as the cost of electricity [32,33]. ystyrene–sphere minimizes agglomeration and improves the contact
The photocatalytic and electrochemical oxidation processes have the between the catalyst and the reactants. This helps to enhance the gen­
advantages of no sludge, limited chemical consumption and simple eration of H2O2 and the conversion of furfuryl alcohol to furoic acid
operational procedure that can be optimized to improve energy effi­ [75]. Herein, we report the photoelectrocatalytic performance of a novel
ciency and performance. Recently, photoelectrocatalysis (PEC) has S–Scheme Co3Se4/BiVO4 for the degradation of SMX in water. The
emerged, which synergistically combines the benefits of photocatalytic introduction of Co3Se4 improves the photon absorption capacity and
and electrochemical processes [34–38]. PEC has been demonstrated conductivity of the composite (Co3Se4/BiVO4) when compared to pris­
using different catalysts to show improved performance over photo­ tine BiVO4 and Co3Se4 with a corresponding increase in PEC perfor­
catalytic and electrochemical processes [35,39,40]. This has been mance. The holes account for the highest contribution to the
attributed to the applied potential which helps to limit the recombina­ degradation of SMX in this study. This study involves the design of a PEC
tion of charge carriers generated and make them available for partici­ catalyst with improved performance in the degradation of pharmaceu­
pation in the degradation of pharmaceuticals as well as the formation of tical in wastewater. The Co3Se4/BiVO4 heterojunction creates a suitable
radicals that are also essential in the degradation process [37,41]. PEC interface for enhancement in transition of charge carriers based on
requires the fabrication of photoactive materials as anode to trap light S-scheme without the limitations associated with conventional photo­
energy. The PEC performances of different Semiconductors (NiFeCoO catalysts. Furthermore, plane–wave density functional theory (DFT)
[42], WO3 [41], Pd–ZnO/N–doped carbon [43], BiVO4 [44–46], simulations are also performed to countercheck the experimental data
Cu2O/Ag3PO4 [47], Ti/TiO2 [48], CuO [49], ZnO/MoS2 [50], Mn/BiOBr and elucidate the enhanced photocatalytic performance of Co3Se4/­
[51], and ZnO [52]) have been evaluated. Among these materials, BiVO4 heterojunction. The present perspectives from our experimental
Monoclinic scheelite bismuth vanadate (BiVO4; n–type semiconductor and theoretical studies contribute to the general understanding of a
with 2.4–2.5 eV band gap capable of absorbing visible light energy) has reasonable mechanism of a direct S–Scheme photocatalytic system.
considerable advantage because it is; relatively cheap, non–toxic, ther­
mally stable, simple to prepare and has good resistance to photo­ 2. Materials and method
corrosion [53]. However, its efficiency is hampered by poor
conductivity and low adsorption as well as recombination of charge 2.1. Materials
carriers. The constraints associated with the use of BiVO4 as anodic
material are ameliorated through the creation of heterojunction by Bismuth (III) nitrate pentahydrate (Bi(NO3)3.5H2O), ammonium
combining it with other suitable materials (ZnO/BiVO4 [54], NiSe/­ vanadate (NH4VO3), cobalt (II) chloride hexahydrate (CoCl2.6H2O),
BiVO4 [55], NiO/BiVO4 [56], BiVO4/WO3 [57], Ag–BiVO4/BiOI [34], sodium selenite (Na2SeO3), ethylene glycol (EG), sulfamethoxazole
BiVO4/NiSe [58], BiVO4/TiO2 [59], WO3/W:BiVO4/BiVO4 [60] and (SMX), p–benzoquinone, Polyvinylidene fluoride (PVDF),
CeO/BiVO4 [61]) for synergic interaction leading to improvement band N–methyl–2–pyrrolidone (NMP), sodium sulfate (Na2SO4), potassium
gap. permanganate (KMnO4), potassium hexacyanoferrate (II) (K4Fe(CN)6)
Co3Se4 has been demonstrated in its pristine form [62,63] and also in and potassium hexacyanoferrate (III) (K3Fe(CN)6). All chemicals were

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T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

used as procured from Sigma–Aldrich (South Africa) and were used (geometrical area of 2 cm x 2 cm) was then left dry in an oven at 60 ◦ C
without further purification. for 2 h. The same method was employed for the fabrication of FTO/BVO
and FTO/CS electrodes, respectively.
2.2. Synthesis of cobalt selenide Co3Se4
2.7. Photoelectrochemical experiments
Solvothermal synthesis of Co3Se4 was achieved by initial dissolution
of cobalt (II) chloride hexahydrate (1 mmol, 238 mg) and sodium sele­
The photoelectrochemical study was performed using a standard
nite (1.3 mmol 230 mg) in 30 mL of EG via sonication for 30 min. The
three–electrode cell consisting of the fabricated anode, platinum wire
mixture was transferred into a Teflon–lined autoclave (50 mL), sealed
and Ag/AgCl (3.0 M KCl) as working–, counter– and reference elec­
and kept in a muffle furnance at 180 ◦ C for 24 h in a muffle furnace. The
trodes, respectively. A xenon lamp (100 W) solar simulator was used as a
obtained product after cooling to room temperature was washed several
source of light. A 10 cm distance was maintained between the vertically
times with distilled water and ethanol, and dried at 80 ◦ C for 8 h in an
positioned photoanode and the incident light. The impedance spectro­
oven.
scopic study was conducted in a 5 mM solution of [Fe(CN)6]3–/[Fe
(CN)6]4– (prepared in a 0.1 M KCl solution). Photocurrent measurements
2.3. Synthesis of BiVO4
were carried out in a 0.1 M Na2SO4 solution. The data for the Mott
Schottky were acquired by scanning at room temperature in 0.1 M
For the synthesis of BiVO4, we adopted a method reported by Soltani
Na2SO4 solution in the absence of light. The PEC degradation study of
et al. [55] with slight modification. Typically, equimolar weight of Bi
SMX was conducted in a 100 mL reactor (quartz glass) containing 10
(NO3)3.5H2O (20 mmol) and NH4VO3 (20 mmol) were dissolved in 40
mg/L of SMX in a 0.1 M Na2SO4 (supporting electrolyte). The degra­
mL of EG and hot water, respectively. The aqueous NH4VO3 solution was
dation study was also conducted in the absence of light to establish the
added gradually into the Bi(NO3)3.5H2O/EG solution under vigorous
contribution of electrochemical process using only the bias potential.
stirring for 30 min and then ultrasonic irradiation was applied at 40 ◦ C
The degradation was monitored at intervals by measuring the absor­
for 30 min. The obtained yellowish precipitate was washed several times
bance via UV–vis spectrophotometer to determine the concentration
with ethanol and distilled water. The yellow product was subsequently
decay and photodegradation pattern of SMX.
calcined in air at 400 ℃ for 1 hour.

2.4. Synthesis of Co3Se4/BiVO4 heterojunction 2.8. Computational methodology

The Co3Se4/BiVO4 heterojunction was prepared by adopting the In the present work, all the calculations of electronic properties and
procedure for the synthesis of Co3Se4 with the addition of 400 mg of geometric optimization were obtained from first principles based on
BiVO4 to obtain a composite with 10 mol% relative to BiVO4. Typically, DFT within the open–source Quantum Espresso package [76]. The ex­
BiVO4 (400 mg), cobalt (II) chloride hexahydrate (0.123 mmol) and the change and correlation potential were described by the generalized
corresponding amount of Na2SeO3 were dissolved in EG (30 mL) and gradient approximation (GGA) of the Perdew–Burke–Ernzerhof (PBE)
transferred to a Teflon–lined autoclave maintained at 180 ◦ C for 24 h. parametrization [77] using the norm–conserving Vanderbilt pseudopo­
Thereafter, the autoclave was allowed to cool to room temperature and tential [78]. A large vacuum space of ~25 Å was used to avoid in­
the yellowish green product was collected by centrifugation, rinsed with teractions between two adjacent layers. Additionally, we applied the
deionized water and ethanol several times, then dried at 60 ◦ C for 12 h. dispersion–corrected DFT–D3(BJ) method by Grimme [79,80] to ac­
The sample is subsequently labelled CSB while the pristine samples of count for the long–range effect of van der Waal (vdW) interactions. The
BiVO4 and Co3Se4 are labelled BVO and CS, respectively. cut off energy for electronic wave functions was set to 45 Ry, and both
the convergence criteria for force and energy were set to 0.001 Ry/Bohr
2.5. Characterization instruments and 10–8 Ry, respectively. The Monkhorst–Pack [81] k–point grids of 10
× 10 × 1 was used to sample the first Brillouin zone (BZ). To obtain more
The phases and the crystallinity of the composite were determined by accurate electronic properties, the Heyd–Scuseria–Ernzerhof (HSE06)
powdered X–ray diffraction study conducted on XRD, Ultima IV–Rigaku, hybrid functional [82] was used. Here the screening parameter of 0.2
Japan. The morphology, dimension and elemental constituents were Å–1 and mixing exchange parameter of 0.25 were adopted in all
obtained using the field emission–scanning electron microscopy calculations.
(FE–SEM, Zeiss Crossbeam 540, United Kingdom) coupled with energy
dispersive X–ray spectroscopy (EDS). The transmission electron micro­ 3. Results and discussion
scopy (TEM, JEM–2100, Japan) was used to obtain high resolution im­
ages of the composite. The optical spectra were acquired on a UV–vis 3.1. Structural and morphological study of the composite
spectrophotometer (Agilent Technologies Cary 60 UV–vis, Malaysia).
Electrochemical impedance spectroscopy (EIS) and Mott Schottky, The X–ray diffractograms of the pristine BVO, CS and CSB are shown
photocurrent response was measured using an Autolab Potentiostat in Fig. 1. The characteristic peaks associated with monoclinic scheelite
(PGSTAT204, Netherlands) workstation. BVO (JCPDS No. 04-010-5713); 18.67◦ (110, 011), 28.86◦ (121), 30.50◦
(040), 34.50◦ (200), 35.05◦ (002), 39.79◦ (211) and 42.32◦ (150) as well
2.6. Fabrication of electrodes as the peaks corresponding to monoclinic CS (JCPDS No. 04-015-1919);
34.03◦ (111), 51.22◦ (313) and 62.91◦ (711) are observed in the dif­
The electrodes were fabricated by drop–casting technique using fractograms of the respective pristine semiconductors and the compos­
fluorine–doped tin oxide (FTO) as a substrate. Firstly, FTO glass was ite. This indicates the successful incorporation of CS into BVO. The
pre–treated by sonicating in acetone for 10 min, rinsed in deionized absence of other peaks indicates phase purity of the composite.
water, and dried in the oven at 60 ◦ C. Prior to the coating of CSB com­ The SEM micrographs (Fig. 2) shows that the pristine BVO adopts
posite on the FTO glass, 100 mg of CSB powder sample was dispersed in irregular pattern of block shapes resulting from agglomeration while the
100 μL NMP, 5 mg PVDF and stirred vigorously to obtain a slurry of the pristine CS forms clusters of spherical shape. The micrograph of the
perfectly dispersed powder. The CSB slurry was subsequently drop- composite CSB reveals the CS anchoring on the surface of BVO blocks
coated carefully on the conductive surface of the FTO glass to obtain while the corresponding EDX spectrum indicates the coexistence of Bi,
an evenly distributed film of CSB on the substrate. The electrode V, Co and Se which are the constituents of the composite. The absence of

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T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

Fig. 1. The XRD patterns of CS, BVO and CSB.

Fig. 2. The SEM micrographs of (a) BVO, (b) CS, (c) CSB (d) and the corresponding EDX for CSB.

other elements indicates the purity of the composite which is in conso­ (Fig. 3b). This close interaction will provide a suitable channel for the
nant with the phase purity observed in the corresponding diffractogram. easy transition of charge carriers at the heterojunction leading to
Bi and V are most prevalent among the elements which is in accordance enhancement of charge separation.
with the bulk phase of BVO. Similarly, the TEM micrographs (Fig. 3a)
reveals the clustering of the CS with interplanar d–spacing 0.261 nm 3.2. The optical properties
corresponding to the (111) plane as revealed by the lattice fringe (inset:
Fig. 3a) [64,83]. The CS anchors on the surface of BVO in the composite The UV–vis diffuse refelectance spectroscopic (DRS) study provides

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T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

Fig. 3. The TEM micrographs of (a) CS (inset: the coresponding lattice fringe) (b) CSB.

insight to the optical properties of the composite. The DRS spectra incorporation of CS. This can be attributed to the photosensitization and
(Fig. 4a) of the pristine BVO and CS reveal absorption in UV and visible charge transfer capability of CS which can drastically reduce charge
region of the light spectrum with wavelenght edge at 523 nm for BVO carrier recommbination with a coresponding enhancement in PEC ac­
while CS absorption covers the spectrum range 236–800 nm. The tivity. This is reflected in the band gaps obtained by the extrapolation of
intrinsic absorption of BVO is preserved in the composite, which also Tauc’s plot (Fig. 4b–c) derived based on Eqaution 1, where α, h, v, A, Eg
shows improved absorption in the visible region in comparison with and n, respectively, represent; the coefficient of absorption, Plank’s
pristine BVO due to synergic interaction resulting from the constant, frequency of the incident photon, constant, the band gap, and

Fig. 4. The UV–vis DRS spectra of BVO, CS, CSB (a) and the coresponding Tauc’s plots (b–d).

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T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

a superscript with value (1, 2 or 3) depending on the optical transition ( )n/2

property of the semiconductor. In this study, “n” is taken as 1 since BVO (αhv) = A hv − − Eg (1)
is considered as a direct transition semiconductor [37]. The formation of
the heterojunction in the composite conspicuously reduces the band gap 3.3. Electrochemical and Photoelectrochemical performance
energy of BVO (2.39 eV) by 22% to 1.88 eV which can be attributed to
the incorpoartion of CS with an estimated band gap of 1.43 eV. This is The Nyquist plots (Fig. 5a), generated from the electrochemical
expected to promote the photon absorption that will drive the gen­ impedance spectroscopic study conducted at 0.25 V potential, provide
ertaion of charge carriers on the surface of the composite. The observed an insight to the charge–transfer properties of the composite in com­
band gaps of BVO and CS in this study are in agrrement with those re­ parison with the pristine BVO and CS. The composite possesses the least
ported in the literature [46,60,64]. resistance to charge–transfer (Rct = 10.30 Ω) as revealed by the diameter

Fig. 5. (a) The Nyquist plots (EIS); (b) photocurrent response; (c–e) Mott–Schottky plots of BVO, CS and CSB.

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T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

of the semicircular arc in the corresponding plot. This is more than 10 and CS, respectively.
folds lower than 109.5 Ω observed in BVO and 3 folds lower than 31.08 The photoelectrochemical efficiency of the composite is also estab­
Ω recorded for CS. It is important to note that the diameter of the lished with the Mott Schottky plots (Fig. 5c–e). The obtained intercept
semicircle is inversely related to the charge–transfer resistance [47,84]. and the slope of the plot of 1/C2 against Eapp determine the flat band
Thus, the composite demonstrates the highest charge–transfer efficiency potential (the potential at which there is no depletion layer at the
in comparison to the pristine semiconductors. This will eventually semiconductor/electrolyte interface) and the donor density (the number
cumulate to drastic reduction in recombination of the photo–generated of the dopant per volume) based on the Eq. (3).
charge carriers and enhancement in PEC activity. ( )
1 2 KT
The photocurrent density measurement also indicates the superior = . E app − E FB − (3)
C2 qεε0 ND q
capacity of the composite over the pristine semiconductors to promote
the generation and the separation of charge carriers when illuminated. Where C, q, ε, ε0, ND, Eapp, EFB, K and T represent the capacitance at
The chopped light photo response (Fig. 5b) shows that the illumination the semiconductor/electrolyte interface (F.cm–2), elementary charge
of the electrodes leads to spike in photocurrent, which can be attributed (1.6 × 10–19 C), relative dieletric constant of semiconductor (BVO: 68)
to the charging of the capacitance at the point of contact between the [35,85], permittivity of vacuum (8.85 × 10–12 F.m–1), donor density
electrode and the electrolyte. However, the migration of the charge (cm–3), applied potential (V), flat band potential (V), Boltzmann con­
carriers from the semiconductor through the substrate FTO (electrons) stant (1.38 × 10–23 F.m–1) and absolute temperature (K). The tempera­
and the electrolyte (holes) leads to decrease in photocurrent when the ture dependent term (KT q
) is negligible at room temperature and it can be
illumination is cut–off. A rapid decrease also signals charge carriers ignored. The flat band potential of the composite (0.15 V) is lower than
recombination within the semiconductor [46,55]. As the number of the pristine BVO (0.36 V) and CS (0.20 V). This indicates that the pho­
cycles (on/off) increases, a steady state condition is attained, which to–generated electrons–holes will experience greater restraint in
indicates that the rates of the generation and recombination of the recombination, which will make them available for photo­
charge carriers have reached equilibrium. At the steady state, the cur­ electrocatalytic activity. The slopes of the plots are positive as expected
rent density of the composite (0.062mAcm− 2) is observed to be higher for n–type semiconductors. The higher donor density of the composite
than 0.031 mAcm− 2 and 0.007 mAcm− 2 recorded for the pristine BVO (3.24 × 1018 cm–1) indicates increase in carrier density of the

Fig. 6. The degradation of SMX on (a) CSB, BVO and CS with coresponding kinetic plots (b) as well as the photocatalytic, electrocatalytic and PEC degradation (c)of
SMX with coresponding kinetic plots (d).

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T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

heterojunction in comparison with pristine BVO (9.8 × 1016 cm–1) and EDTA, respectively. This reveals that the holes contribute majorly to PEC
CS (1.73 × 1017 cm–1) [84,85]. This corresponds to improvement in activity while the hydroxyl radicals and electrons play minor roles.
photoelectrocatalytic activity and it correlates with the observed
photocurrent density.
3.5. Theoretical studies
3.4. Photoelectrochemical degradation of sulfamethoxazole
To simulate the CSB heterojunction, CS layer (see Fig. 8a) is stacked
The performance of the photoanode in the degradation of SMX is on top of a BVO layer (see Fig. 8b). The CSB heterojunction is thoroughly
investigated at pH 6.2 with a bias potential of 1.5 V under the influence optimized under the convergence criterion of energy and force. Fig. 8c
of simulated sunlight. The reduction in the absorbance at 265 nm signals depicts the top and side views of the CSB heterojunction. The fact that
the onset of the mineralization of SMX. The pristine BVO and CS pho­ the CS and BVO layers preserve their original structure following opti­
toanodes achieve approximately 50% (0.0063 min–1) and 18% (0.0019 mization suggests that vdW force, rather than a chemical covalent bond,
min–1) degradation of SMX after 120 min (Fig. 6a, b) while a significant is responsible for the contact. The interlayer distance, which is recom­
75% (0.0115 min–1) degradation is recorded using the CSB photoanode mended to be in the range of 3–4 Å, is one of the criteria for qualifying a
over the same duration. This clearly underscores the importance of the material to form a vdW heterojunction [86]. According to calculations,
heterojunction in promoting PEC as the recombination of the charge the equilibrium separation between the CS and BVO layers is 3.275 Å,
carriers is rapidly reduced. The performance of the CSB photoanode is which is acceptable vdW interlayer spacing.
drastically reduced to 15% (0.0021 min–1) and 45% (0.0052 min–1) Before exploring the electronic properties of CSB heterojunction, its
under electrocatalytic and photocatalytic conditions, respectively stability is first investigated. To evaluate the thermodynamic stability of
(Fig. 6c, d). Thus, the improved efficiency of SMX abatement recorded the CSB heterojunction, the interface adhesion energy (Eads), which
under PEC is a combination of the influence of the applied potential and describes the combining possibility of two individual materials is ob­
the light energy, albeit the contribution from photocatalytic process is tained according to the following equation:
higher. This is an indication that the illumination of photoanode gen­ Eb = (ECSB − ECS − EBVO )/A, (4)
erates charge carriers, which migrate to the surface of the electrode. The
generated holes oxidize the SMX and interact with water molecules to where ECSB, ECS and EBVO represent the total energies of the relaxed CSB
produce highly oxidizing hydroxyl radicals that also contribute to the heterojunction, the pristine CS and BVO with the same lattice constant
degradation of SMX. This process is restricted by the recombination of as the heterojunction, respectively. A is the contact area. The interface
the charge carriers, hence the reduction in degradation efficiency. adhesion energy between the CS and BVO is calculated to be –17.586
However, with the bias potential, the separation of the charge carriers is meV/Å2, which implies that CSB heterojunction is formed by typical
promoted as the elections migrate via the circuit to the cathode and weak vdW forces (–13 to –21 meV/Å2) [87]. The negative Eads indicate
reduce the recombination rate. The variation in the apparent first order that the CSB heterojunction is energetically stable and can be syn­
rate constant generated (CSB > BVO > CS) also indicates the improved thesised. The calculated Eads which are smaller than that of SeIn2Te/C2N
efficiency of the CSB heterojunction photoanode. (–11.84 meV/Å2) [88], ZrS2/BiOCl (–13.06 meV/Å2) [89], PtSe2/GaN
It is imperative to establish the influence of the bias potential on the (–6.41 meV/Å2) [90], Zr2CO2/MoS2 (–10.42 meV/Å2) [91], GaN/BAs
PEC degradation process as the potential can promote the rate of sepa­ (–8.56 meV/Å2) [92] and GeI2/C2N (–14.94 meV/Å2) [93] vdW heter­
ration of charge carriers. Fig. 7a shows the influence of different applied ojunction means that CSB heterojunction is stable and can be syn­
potentials on the PEC activity. An increase in the degradation efficiency thesised as achieved in this study. Furthermore, thermal stability is very
is noted with gradual increase in potential. However, the rate is rapidly important for material applications. To further assess the thermal sta­
increased from 1.0 to 1.5 V. Further increase is noted at 1.8 V but at bility of the CSB heterojunction, an ab initio molecular dynamics (AIMD)
negligible rate which can be attributed to effect of oxygen generation at simulation at 300 K is carried out. No considerable structure change or
higher potential. This can lead to reduction in number of available hy­ bond breaking in the snapshots (Fig. 9a) is observed after being annealed
droxyl radicals that can enhance the PEC activity. Hence, 1.5 V is at 300 K for 100 ps, indicating that the heterojunction remains thermally
maintained in this study. Fig. 7b shows that the composite photoanode is stable. It can be observed that the total energy and temperature fluc­
relatively stable and reusable after five cycles with minimal reduction in tuation of CSB heterojunction is small during the AIMD process (Fig. 9b).
PEC efficiency. The contributory roles of electrons, holes and hydroxyl Besides, the dynamic stability of CSB heterojunction was confirmed
radicals in the mechanism adopted by the photoanode are investigated further by computing the phonon dispersion spectrum, as shown in
using the introduction of tert–butyl alcohol (t–BuOH), p–benzoquinone Fig. 9c. The absence of imaginary frequency along the entire BZ
(p–BZQ) and ethylene diamine tetraacetate (EDTA), which help to verify (Γ–M–K–Γ) shows that CSB heterojunction is dynamically stable.
the independent role of the hydroxyl radicals, electrons and holes in the To gain a thorough understanding of the electronic structure of the
abatement of SMX. Fig 7c shows a reduction in the degradation effi­ as–prepared CSB heterojunction, theoretical calculations utilizing DFT
ciency to 60, 58 and 15% with the introduction of t–BuOH, p–BZQ and are carried out. Fig. 10a and b shows that the estimated band gaps for

Fig. 7. The PEC degradation of SMX by CSB at different applied potentials (a); different cycles (b) and under the influence of different scavengers (c).

8
T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

Fig. 8. The schematic geometrical structure of top (above) and side (below) views of (a) BVO, (b) CS and the CSB heterojunction. Bi, V, O, Co and Se atoms are
marked in magenta, silver, red, blue and green, respectively (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.).

Fig. 9. (a) Side view of the snapshots of the equilibrium structure of CSB heterojunction at 300 K for 100 ps. (b) Variations of total energy and temperature during
AIMD simulation at 300 K lasting for 100 ps. Bi, V, O, Co and Se atoms are marked in magenta, gray, red, blue and green balls, respectively. (c) Phonon dispersion
spectra of the CSB heterojunction (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.).

BVO and CS are 2.43 and 1.55 eV, respectively. These values are in close from Bi 6s states, while the CBM mainly stems from V 3d states with
agreement with the experimental band gaps (2.39 eV for BVO and 1.43 some contribution from Bi 6p and O 2p states. The VBM of CS is pri­
eV for CS). The projected density of states (PDOS) was calculated to marily attributed to Se 4p states with a small contribution from Co 3d
ascertain the characteristics of electrons that each atom contributes to states, as shown in Fig. 10a, while the CBM is primarily derived from Co
the monoclinic structures of CS and BVO. From the PDOS results of BVO, 4s states with a small contribution from Se 4p states, indicating strong
the VBM mainly originates from the O 2p states with some contribution hybridization between them. Fig. 10c shows the PDOS of CSB

9
T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

Fig. 10. Total and projected density of states of the (a) BVO, (b) CS and (c) CSB heterojunction. The Fermi level is set to zero as a vertical dashed line.

heterojunction. The CBM is mainly dominated by Se 4p and Co 4s, while positive on the two layers, a large potential drop (ΔV) will be induced
O 2p has a dominating contribution to the VBM. Thus, the VBM mainly across the CSB heterojunction interface. The electrostatic potential is
stem from the BVO, while the CBM is primarily attributed to the CS, plotted in Fig. 11b, and the ΔV value is 6.51 eV. The greater potential
which is consistent with the S–Scheme schematic diagram. The obtained drop has the capacity to generate a built–in electric field at the hetero­
band gap of CSB heterojunction is 1.81 eV. structure interface, which could reduce the rate of photoinduced carrier
The charge density difference is computed by subtracting the CS and recombination and boost photocatalytic activity. The Bader charge
BVO charge densities from the CSB heterojunction to comprehend the analysis is used to quantitatively examine the interlayer charge transfer,
charge transfer mechanism during heterojunction formation. Here, the and it shows that about 0.015 electrons transfer from the BVO to CS
red and blue regions denote charge accumulation and depletion, layers, which is consistent with charge density difference analysis.
respectively. Fig. 11a depicts the charge density difference of the CSB The work function is a critical physical parameter used as an intrinsic
heterojunction, showing that the interface region experiences the ma­ reference for studying band alignment and charge transfer of semi­
jority of the charge redistribution while the CS and BVO farther away conductor heterostructure [94]. The work function is defined as the
from the interface region exhibit almost no charge density. energy difference between vacuum energy and Fermi energy level [95].
This is because of the weak vdW forces between the two semi­ The calculated work functions are 7.13, 6.81 and 5.01 eV for CS, BVO
conductors. Electrons transferred from the BVO to the CS across the and CSB heterojunction, respectively, as shown in Fig. 11c–e. Charge
interface, as shown by the charge density redistribution, further redistribution will occur at the interfaces as a result of the difference in
demonstrate that the system belongs to a typical S–Scheme hetero­ the electrostatic potentials between CS and BVO. Since CS has a higher
junction as opposed to typical type II heterojunction. The charge transfer work function than BVO, when two semiconductors are in contact, the
provides a considerable interfacial built–in electric field, which can electrons from BVO flow to CS until their Fermi levels are equal. It is
facilitate the separation of charge carriers. The planar charge density consistent with the above analysis based on PDOS and charge density
difference along the z direction has also been estimated to better difference. CS and BVO surfaces become charged because of the electron
comprehend the charge transfer mechanisms that take place during the transfer, and a built–in electric field is formed at their interface and the
heterojunction formation. Charge accumulation is shown by positive electric field direction is from the BVO surface to the CS surface.
values, and charge depletion is indicated by negative values. The pla­
nar–averaged charge density difference demonstrates that electrons
transfer from BVO (Δρ < 0) to CS surface (Δρ > 0), showing that holes 3.6. The proposed mechanism of degradation of SMX
accumulate in BVO. It proves that CS can act as an electron sink to accept
an electron. Because of the accumulation of net negative charges and The combination of BVO and CS creates S–Scheme heterojunction
with aligned Fermi levels of BVO and CS in the composite [64,67]. The

10
T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

Fig. 11. (a) The side view of the charge density difference (isosurface value is 0.00025 Ry Bohr–3) for CSB heterojunction. Bi, V, O, Co and Se atoms are marked in
magenta, gray, red, blue and green, respectively. (c) Planar–averaged charge density difference for CSB heterojunction. Calculated electrostatic potentials for (d) CSB
heterojunction, (e) BVO and (f) CS (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.).

low band gap of CS with its higher conduction band makes it suitable for illustrated in Fig. 12 and the corresponding reaction mechanisms are
transition of electrons to the BVO with a higher band gap but a lower presented in the Eqs. (7)–(12).
conduction band. This results in internal electric field pointing from CS
hv + CS/BVO→CS/BVO (h+ + e− − ) (7)
to BVO. The associated band edge potential of the conduction and
valence bands are obtained theoretically using the Eqs. (4) and (5) [37,
h+ + H2 O →OH + H + (8)
96].
EVB = X − − Ee + 0.5Eg (5) e− − + O2 →O−2 − (9)

ECB = EVB − − Eg (6) h+ + SMX→CO2 + H2 O (10)

where EVB and ECB represent the valence band and conduction band, e− − + SMX→CO2 + H2 O (11)
respectively. Eg and X represent the band gap and the Mulliken elec­
tronegativity (BVO (6.04 eV) and CS (5.13 eV)) of the corresponding
•
O−2 − +SMX→CO2 + H2 O (12)
semiconductor obtained from the geometric mean of the absolute elec­
tronegativity of the constituent atoms [84,96]. Ee is the energy of free 4. Conclusion
electrons on the hydrogen scale with an approximate value of 4.5 eV.
The calculated EVB and ECB of BVO are 0.31 and 2.70 eV, respectively, A CSB S–Scheme-based heterojunction photoanode is successfully
while those of CS are –0.13 and 1.30 eV, respectively. On illumination, synthesized via hydrothermal process as an efficient photoanode for the
the internal electric field and the aligned Fermi levels aid the accelera­ PEC degradation of SMX. The CS/BVO composite exhibits greater PEC
tion of photo–generated electrons from conduction band of BVO efficiency than the pristine semiconductors. The improved performance
combining with the holes in the valence band of CS while keeping the correlated with high photocurrent density and low charge–transfer
electrons in the conducting band of CS and the holes in the valence band resistance demonstrated by CS/BVO. According to the work functions
of BVO separated and readily available for the degradation of SMX. The and the charge density difference, CS and BVO are in contact and formed
above analysis is confirmed by theoretical calculation based on density a heterojunction with positively and negatively charged surfaces,
of states, Bader charge, and charge density difference results. The con­ respectively. The interaction formed a built–in electric field, which was
sistency of the theoretical values with experimentally established data directed from the BVO surface to the CS surface. This strongly prohibits
shows that the S–Scheme is adopted as the conduction band of CS is the recombination of the hole and electrons in the photoanode making
populated by 4s (Co) with higher energy level while the conduction them available for the degradation of SMX. The PEC performance of CS/
band of BVO is dominated by 3d (V) with lower energy. The vdW BVO with a pseudo first order constant 0.0115 min–1 is majorly facili­
interaction indicates no changes in chemical constituents as chemical tated by the holes as revealed by the scavenger study. We demonstrate
bond does not exist at the heterojunction rather an electric field persists that the PEC of BVO can be greatly improved by introduction of CS to
leading to transition of electron across the heterojunction interface. This create a S–Scheme heterojunction for the remediation of water
is quite consistent with the S–Scheme. The semiconductors are contaminated with SMX.
compatible and stable as revealed by the favorable interface adhesion
energy and the AIMD, respectively. The proposed S–Scheme is

11
T.L. Yusuf et al. Surfaces and Interfaces 36 (2023) 102534

Fig. 12. Illustration of S–Scheme heterojunction charge transfer mechanism for degradation of SMX.

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