ARTICLE

pubs.acs.org/EF

Effect of the Pore Length on CO2 Adsorption over Amine-Modified

Mesoporous Silicas
Aliakbar Heydari-Gorji, Yong Yang, and Abdelhamid Sayari*
Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada
bS Supporting Information
ABSTRACT: Carbon dioxide adsorption was investigated in the presence of polyethylenimine (PEI)-impregnated mesoporous
silicas with different pore lengths, namely, pore-expanded MCM-41, conventional SBA-15 with different pore diameters (7.2 and
10.5 nm), and SBA-15 with platelet morphology. The pore lengths of the silica supports were ca. 25, 1.5, and 0.2 μm, respectively.
Under comparable conditions, the adsorption performance was found to be strongly dependent upon the pore length. The materials
with the shortest channels showed the highest capacity and fastest adsorption. These findings were associated with diminished
diffusion resistance and enhanced amine accessibility inside the pores.

’ INTRODUCTION the importance of the pore size and volume.5,6 Zelenak et al.3
As the concentration of carbon dioxide (CO2) in the atmo- studied the effects of the pore size and architecture of amine-
sphere keeps increasing, serious concerns have been raised with functionalized mesoporous silicas, such as MCM-41, SBA-12,
respect to its impact on the environment. However, fossil fuels and SBA-15, on CO2 sorption. They reported that SBA-15 with
that are the main source of anthropogenic CO2 will remain the large pores has the highest CO2 uptake, while higher accessi-
leading source of energy for years to come, for both power bility of amine groups within the three-dimensional pore
generation and vehicle transportation.1 Thus, removal and structure of SBA-12 silica resulted in faster CO2 adsorption.
ultimately sequestration of CO2 is an essential step to address Ahn’s group14,16 has recently investigated the adsorptive prop-
the greenhouse gas effect. Also, the removal of CO2 from erties of polyethylenimine (PEI) impregnated on a variety of
different process gas streams is an important requirement for ordered mesoporous silicas. They demonstrated that, under
various applications. Therefore, it is critical to develop effective otherwise the same conditions, the CO2 adsorption capacity
methods for CO2 capture. Among the strategies for CO2 and also the rate of adsorption increased with an increasing
separation, adsorption is an attractive method to complement average pore diameter of the support. Interestingly, it was
or replace the current technologies, because of its low energy shown that, even though MCM-48 and SBA-16 possessed
requirement and also easy operation and maintenance.1,2 three-dimensional pore connectivity, their adsorption capaci-
Suitable adsorbents for CO2 removal should combine several ties were lower than those of one-dimensional supports with a
attributes, including high adsorption capacity, high selectivity larger pore size.14 They also reported that the PEI-impregnated
toward CO2, fast kinetics, mild conditions for desorption, and silica monolith with a very large pore size (17 and 120 nm) and
high stability.1 In recent years, intensive research activities volume (3.2 cm3/g) exhibited a very high CO2 adsorption
have been focused on the development of amine-containing capacity (323 mg/g of PEI).16 Yan et al.22 compared several
adsorbents.3 22 The amine species were supported most often PEI-impregnated SBA-15 materials and concluded that the
on mesoporous silicas via surface grafting of aminosilanes3 9 or CO2 adsorption capacity was dependent upon the total pore
physical impregnation.10 22 The structure of the silica support volume of the support, but the pore size was not the main factor
was found to play a vital role in the performance of these influencing the CO2 uptake. In addition to the pore structure,
adsorbents. Various mesoporous silicas, such as SBA-12,3 SBA- the nature of the silica surface is also important. Heydari-Gorji
15,4,14,15,23 MCM-41,11,14 MCM-48,14 pore-expanded MCM- et al.11 showed that PEI supported on hydrophobic PE-MCM-
41,5,6,8,10,11 SBA-16,14 KIT-6,14 monolith,16 HMS,17 mesocelullar 41, whose surface is covered by a layer of long-chain alkyl
silica foam,19 and mesoporous silica microspheres,20 were inves- groups, was a more efficient CO2 adsorbent than PEI supported
tigated, and the importance of the pore size and pore volume of on the corresponding calcined silica, as well as all PEI-impreg-
the supports on CO2 adsorption capacity was demonstrated. nated materials reported in the literature.
Sayari’s group5,6,8 showed the beneficial effect of using materials Hence, it is seen that a larger pore size and accordingly pore
with a pore diameter and volume larger than typical MCM-41 silica. volume resulted in enhanced accessibility of amine groups or
To do so, they used pore-expanded MCM-41 (PE-MCM-41) with higher amine loading, with increased carbon dioxide sorption
a pore size and pore volume up to 20 nm and 3.5 cm3/g.23,24 They capacity. Nonetheless, the size of the pores cannot affect the
reported that, under otherwise the same conditions, triamine-
grafted PE-MCM-41 had 50% higher CO2 uptake than its Received: May 23, 2011
MCM-41 counterpart. Moreover, TRI-PE-MCM-41 adsorbed Revised: August 3, 2011
CO2 about 30% faster than MCM-41-based material, showing Published: August 04, 2011

r 2011 American Chemical Society 4206 dx.doi.org/10.1021/ef200765f | Energy Fuels 2011, 25, 4206–4210
Energy & Fuels ARTICLE

Table 1. Structural Properties of Materials

pore length
materials SBET (m2/g) Vp (cm3/g) Dp (nm) (μm)

PE-MCM-41 1254 2.44 11.4 25 40

SBA-15LP 580 0.95 10.5 1.5 3
SBA-15SP 746 0.8 7.2 1.5 3
SBA-15PLT 590 1.40 13.6 0.2

hydrophobic supports11 or supports with a three-dimensional

pore structure.3 Although the beneficial effect of the short
diffusion pathway on bioimmobilization25 and catalysis26 has
been reported, to the best of our knowledge, the effect of the
support pore length on the adsorption properties of amine-
impregnated materials has not been addressed. Here, we describe
the effect of the mesoporous silica pore length on the CO2
adsorption performance upon impregnation with PEI. We used
calcined pore-expanded MCM-41, conventional SBA-15 with
different pore sizes, and SBA-15 platelets with very short
channels, referred to as PE-MCM-41, SBA-15LP and SBA-
15SP, and SBA-15PLT, respectively, where LP stands for large
pore, SP stands for small pore, and PLT stands for platelet. As for
PEI-containing materials, they were designated by the name of
the support followed by (x), where x is the PEI loading in weight
percent.

’ RESULTS AND DISCUSSION

Typical scanning electron microscopy (SEM) images with
different magnifications for the support materials are shown in
Figure 1. As seen in Figure 1a, PE-MCM-41 exhibits particles
with more than 25 μm size. Figure 1b reveals that the morphol-
ogy of SBA-15LP consists of ca. 1.5 μm long rod-shaped particles
aggregated into bundles. Figure 1c shows that SBA-15PLT is
comprised of monodispersed hexagonal thin platelets, whose
average width and thickness were 750 850 and 200 nm, respec-
tively. The pore length was considered to be equal to the length
of the particles along their pore channels. Notice that some SBA-
15 samples reported in the literature27 showed some silica
nanotubes curl at the end of the particles and run along the
channel in the opposite direction, which may affect the average
pore length. Our transmission electron microscopy (TEM)
images (see Figure S2 of the Supporting Information) showed
no evidence of such behavior. Nonetheless, because the particle
sizes of the three samples (PE-MCM-41, SBA-15LP, and SBA-
15PLT) along their channels differ by at least 1 order of
magnitude (last column of Table 1), our conclusions remain
valid, even if some silica nanotubes run along the main axis twice
or thrice.
The nitrogen adsorption desorption isotherms of the mate-
rials are shown in Figure S1 of the Supporting Information.
Figure 1. SEM images of (a) PE-MCM-41, (b) SBA-15LP, and
Table 1 shows the pore size, pore length, surface area, and pore
(c) SBA-15PLT with different magnifications. volume of these materials. Additional characterization of PE-
MCM-41 and SBA-15 samples may be found elsewhere.23,24,28,29
The surface area of SBA-15LP/SP and SBA-15PLT after im-
adsorption performance when the pores of the adsorbent are pregnation with 50 and 55 wt % PEI, respectively, was almost nil,
completely filled. Moreover, despite the improvement in adsorp- although PE-MCM-41(55) exhibited a surface area of 37.4 m2/g.
tion capacity via proper selection of supports, most of the This indicates that the channels of SBA-15PLT(55), SBA-15LP-
materials used showed an optimum adsorption temperature at (50), and SBA-15SP(50) were completely filled with PEI.
about 75 °C, with little or no adsorption at room temperature. To The CO2 adsorption uptake of PEI-supported materials is the
circumvent the adverse effect of diffusion limitation at low result of a complex interplay of diffusion resistance, rate of
temperature and high PEI loading, it was recommended to use adsorption, and accessibility of adsorption sites, in addition to
4207 dx.doi.org/10.1021/ef200765f |Energy Fuels 2011, 25, 4206–4210
Energy & Fuels ARTICLE

Figure 2. CO2 uptake for (a) SBA-15PLT(55), (b) SBA-15LP(50),

(c) SBA-15SP(50), and (d) PE-MCM-41(55) at different temperatures Figure 3. Dynamic uptake of pure CO2 on SBA-15PLT(55), SBA-
after 180 min of exposure to pure CO2. 15LP(50), and PE-MCM-41(55) versus time at 75 °C.

temperature and CO2 partial pressure. Larger pore size/pore

volume supports accommodate larger quantities of amine, but Table 2. CO2 Adsorption Efficiency (mg/g of PEI) of Ad-
the accessibility of amine sites and the diffusion pathway are also sorbents in the Presence of Pure CO2
important factors, which affect the CO2 uptake. A comparison of adsorption temperature (°C)
the adsorptive properties of PE-MCM-41-, conventional SBA-
15-, and SBA-15PLT-based adsorbents offers an excellent adsorbent 25 50 75 100
example to illustrate the effect of the pore length.
SBA-15PLT(55) 205 302 314 257
Figure 2 shows the CO2 uptake for PE-MCM-41(55), SBA-
15LP(50), SBA-15SP(50), and SBA-15PLT(55) in the presence SBA-15LP(50) 145 228 281 256
of pure CO2 at different temperatures after 180 min of exposure. PE-MCM-41(55) 68 113 162 228
PEI-modified conventional SBA-15 (traces b and c) with differ-
ent pore diameters, i.e., 7.2 and 10.5 nm, exhibited the same CO2 thermodynamic limitation, because beyond the optimum tempera-
uptake. Therefore, the effect of the pore diameter can be ture, the diffusion resistance is no longer a limiting factor. In
neglected for materials with completely filled pores. Figure 2 contrast, in the presence of PE-MCM-41(55), the equilibrium
shows that, up to ca. 90 °C, the shorter the pore length, the higher was not achieved even at 100 °C.
the CO2 uptake. In particular, SBA-15PLT(55) outperformed Figure 3 shows the dynamic uptake of the adsorbents at 75 °C
the three other adsorbents at all temperatures. Although SBA- using dry pure CO2. These behaviors are strongly dependent upon
15PLT had a lower surface area and pore volume than PE-MCM- the length of the channels in the materials. As the channel length
41 (Table 1), SBA-15PLT(55) exhibited a much higher CO2 decreases, the CO2 uptake will be controlled by the faster
uptake than PE-MCM-41(55). For instance, at 50 °C, the CO2 adsorption kinetics, leading to significantly higher CO2 uptake.
working capacity for the SBA-15PLT-based adsorbent was 2.7 The SBA-15PLT-based adsorbent, with the shortest pore length,
and 1.45 times higher than its PE-MCM-41 and SBA-15LP showed the fastest adsorption kinetics. After the initial sharp
counterparts, respectively. It is likely that SBA-15PLT(x) adsor- increase, the CO2 uptake over SBA-15PLT(55) leveled off. In
bents, with the shortest diffusion pathway, exhibit higher amine contrast, the CO2 uptake for SBA-15LP- and PE-MCM-41-based
accessibility with diminished diffusion resistance, leading to adsorbents increased even after 180 min, albeit at a slow rate,
higher CO2 uptake. On the contrary, in materials with longer indicating that the adsorption did not reach its thermodynamic
pore channels, such as PE-MCM-41 and conventional SBA-15, equilibrium. Moreover, SBA-15PLT(55) also showed very fast
there is stronger diffusion resistance, giving rise to lower CO2 desorption kinetics (see Figure S4 of the Supporting Information).
uptake. Table 2 shows that, in terms of CO2 adsorption efficiency, i.e.,
Contrary to most literature data dealing with supported PEI, CO2 uptake per gram of PEI, SBA-15PLT(55) outperformed the
SBA-15PLT(55) adsorbed a significant amount of CO2 (11.3 wt %) two other adsorbents with longer channels, at all temperatures.
at room temperature. Other materials adsorbed more modest Because most CO2-containing process gases are dilute, the
amounts of CO2. This is because, at low temperature, the adsorption performance of the current adsorbents was investigated in
is a diffusion-controlled process. As the temperature increased, the the presence of 10% CO2 in N2. As Figure 4 shows, the tem-
adsorption capacity for all adsorbents increased and reached a perature dependence of the CO2 uptake was strongly affected
maximum CO2 uptake at ca. 65 and 75 °C for SBA-15PLT(55) by the pore length. The behavior of CO2 adsorption versus the
and conventional SBA-15(50), respectively, whereas up to 100 °C, temperature is associated with two conflicting properties,
no maximum uptake was found for PE-MCM-41(55). For shorter namely, the thermodynamic adsorption capacity and the diffu-
channel supports, SBA-15PLT and conventional SBA-15, at 100 °C, sion resistance, both of which increase at a decreasing tempera-
the adsorption capacity decreased to 80 and 90% of maximum ture and an increasing channel length. Thus, because of the
capacity, respectively. The decreasing uptake is consistent with the dominant role of diffusion limitation at low temperature
4208 dx.doi.org/10.1021/ef200765f |Energy Fuels 2011, 25, 4206–4210
Energy & Fuels ARTICLE

PEI impregnation. It also showed considerable CO2 uptake at

high PEI loading and low temperature because of diminished
diffusion.

’ EXPERIMENTAL SECTION
Materials and Methods. All chemicals were obtained from Sigma-
Aldrich and used as supplied. The detailed preparation of PE-MCM-41,
SBA-15LP/SP, and SBA-15PLT may be found elsewhere.23,28,29 Briefly,
MCM-41-type silica was synthesized at 80 °C using cetyltrimethylam-
monium bromide as the structure-directing agent and a 25% solution of
tetramethylammonium hydroxide in water for pH adjustment. Pore
expansion was carried out through hydrothermal treatment of as-
synthesized MCM-41 using dimethyldecylamine as the swelling agent
at 120 °C for 72 h.
Conventional SBA-15 samples were prepared as follows:28 Pluronic
P123 (4.0 g) was dissolved in 30 g of water and 120 g of 2 M HCl
solution with stirring at 40 °C. Then, 8.5 g of Tetraethyl orthosilicate
Figure 4. CO2 uptake for (a) SBA-15PLT(55), (b) SBA-15LP(50), (TEOS) was added to that solution with stirring at 40 °C for 20 h. The
and (c) PE-MCM-41(55) using pure CO2 and (d) SBA-15PLT(55), mixture was aged at 100 or 80 °C overnight without stirring to give rise
(e) SBA-15LP(50), and (f) PE-MCM-41(55) using 10% CO2 in N2 at to SBA-15LP and SBA-15SP, respectively. As for the synthesis of SBA-
different temperatures after 180 min of exposure. 15PLT,29 2.4 g of Pluronic P123 was dissolved in 84 mL of HCl solution
(1.07 M) and stirred at room temperature until the solution became
(25 °C), the adsorption capacity is no longer sensitive to the clear. Then, 13.9 g of decane was added to the solution with stirring at
CO2 partial pressure. As shown in Figure 4, at 25 °C, the room temperature for 1 h. Finally, 0.027 g of NH4F was added under
adsorbents exhibit similar uptakes in the presence of 10% CO2/ stirring, followed by 5.1 g of TEOS. The above mixture was stirred at
N2 or 100% CO2, regardless of the pore length. With an 40 °C for 20 h and then transferred to an autoclave for further reaction at
increasing temperature, all adsorbents exhibited higher CO2 100 °C for 48 h. The as-synthesized PE-MCM-41, SBA-15LP, SBA-
uptake because the effect of the decreasing resistance was more 15SP, and SBA-15PLT were calcined at 550 °C to remove the templates.
important than the effect of the decreasing equilibrium capacity. As for the preparation of CO2 adsorbents, the required amount of PEI
Beyond 50 °C for 10% CO2/N2, the capacity of SBA-15PLT- (Aldrich; average Mn ∼ 423) was dissolved in methanol before adding
(55) and SBA-15LP(50) decreased in-line with the thermo- the mesoporous silica support. The resultant slurry was continuously
dynamic behavior. Interestingly, at 75 °C, the CO2 uptake for stirred at room temperature until the solvent is evaporated, and then the
SBA-15PLT(55) in the presence of 10% CO2/N2 was con- sample was dried at 60 °C under reduced pressure (700 mmHg). The
siderably lower than that of pure CO2 (traces a and d). This adsorbents were denoted as PE-MCM-41(x), SBA-15LP(x), SBA-15SP-
capacity reduction was attributed to diminished adsorption and (x), and SBA-15PLT(x), where x represents the weight percent of PEI in
promoted desorption of CO2 at high temperature and low CO2 the adsorbent. Because of the low pore volume of SBA-15LP/SP, they
partial pressure. It is important to notice that the optimum were impregnated with only 50 wt % PEI.
adsorption temperature of SBA-15PLT(55) at 10% CO2/N2 SEM and TEM images were collected on JSM-7500F FESEM (JEOL)
and JEM-2100F FETEM instruments, respectively. Samples were dis-
occurred at 50 °C with 136 mg/g of CO2 uptake. To the best of
persed in ethanol using an ultrasonic bath, and a drop of the slurry was
our knowledge, this is the highest CO2 uptake ever reported for
deposited on a carbon-coated copper grid and then dried in air.
PEI-impregnated materials using 10% CO2 at 50 °C.
Adsorption Measurements. Adsorption tests were carried out
As seen in Figure 4, the evolution of CO2 uptake for PE-MCM- using a thermogravimetric analyzer connected to a gas delivery manifold.
41(55) in the presence of 10% CO2/N2 (trace f) and pure CO2 High-purity CO2 and 10% CO2 in N2 at 1 atm was used for the adsorption
(trace c) exhibits similar temperature-dependent behaviors, even runs, and ultra-high-purity (UHP) N2 was used as a regenerating purge gas
though the uptake was slightly smaller at lower CO2 partial for CO2 desorption. A sample was pretreated in flowing N2 at 100 °C,
pressures. In fact, in this case, because of the excessive length of then cooled to the desired adsorption temperature, and exposed to
the diffusion pathway, the CO2 uptake was limited by amine flowing pure CO2 or 10% CO2/N2 (90 mL/min) for 180 min. The
accessibility rather than CO2 availability, over the whole range of CO2 adsorption capacity of the adsorbent in milligrams of CO2 per gram
the temperature. Thus, the CO2 uptake was independent from the of adsorbent was calculated from the weight gain of the sample in the
gas-phase composition for the adsorbent with the longest chan- adsorption process.
nels. Figure 4 also shows that the material with intermediate pore
channels, i.e., SBA-15LP(50), exhibits intermediate behavior. ’ ASSOCIATED CONTENT

’ CONCLUSION bS Supporting Information. Material characterizations, N2

adsorption desorption isotherms, TEM images of the silicas,
In addition to the pore size and volume of the support, the and dynamic CO2 adsorption and desorption. This material is
length of the pore channels plays a significant role in the available free of charge via the Internet at http://pubs.acs.org.
performance of supported PEI for CO2 adsorption. Adsorbents
with a shorter pore length outperformed materials with longer ’ AUTHOR INFORMATION
channels in terms of CO2 uptake and adsorption and desorption
kinetics. As an illustrative example, it was found that SBA-15PLT Corresponding Author
silica with very short pore channels is a much better support for *E-mail: [email protected].
4209 dx.doi.org/10.1021/ef200765f |Energy Fuels 2011, 25, 4206–4210
Energy & Fuels ARTICLE

’ ACKNOWLEDGMENT
The financial support of the Natural Science and Engineering
Council of Canada (NSERC) is acknowledged. Abdelhamid
Sayari thanks the Federal Government for the Canada Research
Chair in Nanostructured Materials for Catalysis and Separation
(2001 2015).

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