pubs.acs.

org/JACS Article

Wettability Engineering of Solar Methanol Synthesis

Zhe Lu,# Yangfan Xu,# Zeshu Zhang,# Junchuan Sun, Xue Ding, Wei Sun, Wenguang Tu, Yong Zhou,
Yingfang Yao,* Geoffrey A. Ozin,* Lu Wang,* and Zhigang Zou
Cite This: J. Am. Chem. Soc. 2023, 145, 26052−26060 Read Online

ACCESS Metrics & More Article Recommendations *

sı Supporting Information

ABSTRACT: Engineering the wettability of surfaces with hydrophobic

See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

organics has myriad applications in heterogeneous catalysis and the large-scale

chemical industry; however, the mechanisms behind may surpass the proverbial
Downloaded via MAE FAH LUANG UNIV on April 15, 2024 at 21:34:14 (UTC).

hydrophobic kinetic benefits. Herein, the well-studied In2O3 methanol synthesis

photocatalyst has been used as an archetype platform for a hydrophobic
treatment to enhance its performance. With this strategy, the modified samples
facilitated the tuning of a wide range of methanol production rates and
selectivity, which were optimized at 1436 μmol gcat−1 h−1 and 61%, respectively.
Based on in situ DRIFTS and temperature-programmed desorption-mass
spectrometry, the surface-decorated alkylsilane coating on In2O3 not only
kinetically enhanced the methanol synthesis by repelling the produced polar
molecules but also donated surface active H to facilitate the subsequent
hydrogenation reaction. Such a wettability design strategy seems to have
universal applicability, judged by its success with other CO2 hydrogenation catalysts, including Fe2O3, CeO2, ZrO2, and Co3O4.
Based on the discovered kinetic and mechanistic benefits, the enhanced hydrogenation ability enabled by hydrophobic alkyl groups
unleashes the potential of the surface organic chemistry modification strategy for other important catalytic hydrogenation reactions.

■ INTRODUCTION
The conversion of CO2 with green H2 into valuable methanol
has been envisioned as a promising approach to alleviate the
atmospheric CO2 concentration and curtail the reliance on
fossil fuels.1,2 Conventional methanol synthesis is energy-
intensive, necessitating high reaction temperatures (>240 °C)
and pressures (∼5 MPa).3,4 Incorporating solar energy via
photothermal catalysis has the potential to surmount this
obstacle;5−8 however, exploring the efficient photothermal
catalysts with stable performance remains challenging.
In detail, the synthesis of methanol (eq 1) in the
heterogeneous catalytic hydrogenation of CO2 with respect
to the competing reverse water gas shift (RWGS) CO pathway
(eq 2) is pressure- and temperature-dependent. The methanol
and CO pathways are respectively exothermic and endother-
mic, and by the thermodynamic principle of Le Chatelier for
these equilibrium reactions, the former is favored at low
temperatures and high pressures, while the latter is at high
temperatures with little sensitivity to pressure.1−3
CO2 + 3H 2 CH3OH + H 2O H0 = 50 kJ mol
CO2 + H 2 CO + H 2O H 0= + 39 kJ mol
Both reactions, however, are challenged by the cogeneration
of product water as it can deactivate the catalyst by
coordinating to and subsequently restructuring surface active
sites.9−12 We hypothesize that an effective means to circum-
vent both the selectivity and durability problem is to make the
catalyst surface hydrophobic by decorating it with chemically
tethered alkyl chains.9,10 By this means, it is envisioned that an
organically tailored hydrophobic catalyst surface will selectively
repel strongly polar water and methanol relative to weakly
polar CO products, thereby favoring the methanol reaction
pathway over CO.10,13 Despite the advantage in the desorption
of produced molecules, other mechanistic benefits remain to
be discovered. Thus, it would be of great scientific interest and
technological importance if the hydrophobic surface could play
other roles to facilitate the catalytic process.
Herein, the viability of the surface wettability effect was
experimentally demonstrated for a series of metal oxide
catalysts, exemplified by indium, iron, zirconium, cerium, and
cobalt oxides. Each of these is observed to positively shift the
kinetic rate and thermodynamic conversion toward methanol
or CH4 compared to CO. This advance portends a universal
paradigm for activity and selectivity management in gas-phase
1
heterogeneous CO2 photocatalysis.
(1)
Received: July 10, 2023
1
Revised: November 6, 2023
(2) Accepted: November 7, 2023
Published: November 20, 2023

© 2023 American Chemical Society https://doi.org/10.1021/jacs.3c07349

26052 J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society
■ EXPERIMENTAL SECTION
Synthesis of Samples. The precipitation method was used to
synthesize In2O3. To be specific, 2 g of In(NO3)3·xH2O (99.99%) was
dissolved in 200 mL of deionized water. Then, under stirring, 100 mL
of a 0.1 M Na2CO3·10H2O (99.99%) solution was added until the pH
reached 8. The mixture was aged at 80 °C under 3 h continuous
stirring and then collected and washed by suction filtration. After
drying at 80 °C overnight, the sample was calcined at 400 °C (2 °C
min−1) for 1 h to obtain In2O3 (denoted as S0). Co3O4 was prepared
by the same method. The preparation of alkylsilane-modified In2O3
was achieved by silanization reactions (Figure S1). 100 mg portion of
prepared In2O3 was mixed with 2 mL of toluene. Subsequently, 10 μL
of triethoxyoctylsilane (TEOOS, 98%) was added. The mixture was
then refluxed at 50 °C for 3 h under stirring. After that, the products
were centrifugally separated and washed with toluene and ethanol
several times. Then, they were transferred into a vacuum oven at 120
°C and dried for 24 h. The obtained catalysts were named S2.
Similarly, the catalysts synthesized from 5, 40, and 120 μL of TEOOS
were named S1, S3, and S4, respectively. Alkylsilane-decorated ZrO2
(99.99%), CeO2 (99.9%), Fe2O3 (99.8%), and Co3O4 were
synthesized by the same process as S2. The products were named
ZrO2−Si, CeO2−Si, Fe2O3−Si, and Co3O4−Si, respectively. C1, C4,
C6, C10, and C12 with the same theoretical Si content as S2 were
prepared using a similar process, with the feedstock of methyl-
triethoxysilane (98%), buthyltriethoxysilane (94%), hexyltrimethox-
ysilane (98%), decyltriethoxysilane (98%), and dodecyltriethoxysilane
(97%), respectively.
Structural Characterizations. The Si content was determined
through an inductively coupled plasma spectrometer (ICP) using an
Agilent 5110. The water droplet contact angles were obtained with a
Sindin SDC-500 contact angle meter. The attenuated total reflectance
infrared spectroscopy (ATR-IR) tests were performed on a Thermo
Nicolet iS50 Fourier-transform infrared (FTIR) spectrometer with an
integrated ATR module. The phase compositions of the samples were
characterized by a Rigaku Smartlab diffractometer equipped with a Cu
Kα radiation source (λ = 1.54056 Å). The X-ray source was operated
at 40 kV and 200 mA. The phase identification was made by
comparison to the Joint Committee on Powder Diffraction Standards
(JCPDS). The N2 physical adsorption−desorption test can be used to
analyze the specific surface area and pore structure. The test was
confirmed on a Micromeritics ASAP 2010 instrument. The specific
surface area was analyzed by the Brunauer−Emmett−Teller (BET)
method. The pore structure was investigated by the Barrett−Joyner−
Halenda (BJH) method. The surface compositional and chemical
states of catalysts were analyzed through X-ray photoelectron
spectroscopy (XPS) using an AXIS SUPRA+ spectrometer with an
Al Kα X-ray source. The operating conditions were chosen as 15 kV
and 27 A. The carbon C 1s at 284.8 eV was used for calibration.
Electron spin resonance (ESR) spectra of the samples were also
recorded for more complete and fine structural information. It was
conducted at room temperature using a Bruker A300 EPR
spectrometer operated at the X-band frequency. The morphology of
samples was investigated through transmission electron microscopy
(TEM). The TEM images, high-resolution TEM (HRTEM) images,
and EDX mapping were obtained using a JEOL JEM-2100F
microscope at the accelerating voltage of 200 kV. The weight loss
and heat changes of samples at different temperatures were
investigated through thermogravimetry analysis (TGA) with differ-
ential scanning calorimetry (DSC) and mass spectrometry (MS). The
samples were tested in a Netzsch STA449F3-QMS403D thermogravi-
metric analyzer under N2.
Mechanism Study. H2 temperature-programmed desorption
(TPD) was conducted on a chemisorption analyzer (Micromeritics
Autochem II 2920). 100 mg portion of the as-prepared sample was
pretreated under flowing argon for 0.5 h at room temperature and
then heated to 300 °C for 0.5 h and further 400 °C for 1 h. Then, the
sample was cooled to 50 °C under flowing argon. After stabilization, a
mixture gas of 10% H2 in N2 was introduced for 1 h. Subsequently,
the gas was switched into argon for 1 h sweeping. Then, the sample
26053
pubs.acs.org/JACS Article
was heated (10 °C min−1) under argon. The effluent gas was analyzed
using a PFEIFFER OmniSTAR. Similarly, CO2-TPD and water-TPD
were tested through the same processes with the preadsorption gas of
CO2 and 3% H2O/Ar, respectively. The only difference for water-
TPD is that it was tested directly after preadsorption without a
sweeping procedure. Moreover, we conducted in situ diffuse
reflectance infrared Fourier transform (DRIFTS) to characterize the
adsorbed species on the sample surface and further monitor the
catalytic reaction process in real-time. The tests were performed on a
Thermo Nicolet iS50 FTIR spectrometer with a high-precision
mercury−cadmium−telluride (MCT) detector cooled by liquid
nitrogen. Beyond an infrared spectrometer, the experimental system
consists of a diffuse reflectance accessory (Praying Mantis, Harrick), a
high-temperature cell (HVC, Harrick, equipped with CaF2 windows),
a gas system, and a heating and temperature control device. Before the
in situ tests, the catalyst was purged under a flowing Ar atmosphere at
373 K for 3 h to remove possible impurity molecules. Then, the
background spectrum under an Ar atmosphere at different temper-
atures was collected to subtract the interference of H2O and CO2 on
the sample spectrum. The scanning resolution was 2 cm−1, and the
number of scans was 32 times. In the H2 adsorption experiment, the
ratio of H2 and Ar was 6:14. The ratio of CO2 and Ar was 2:18 in CO2
adsorption tests. After testing at 250 °C under CO2/Ar, H2 was
introduced into the system (H2/CO2/Ar: 6/2/12). The residual gas
after D2 adsorption was detected via a Hiden HPR-20 EGA mass
spectrometer.
Evaluation of Catalytic Performance. The catalytic perform-
ance was obtained through a batch reactor with a silica viewport at the
top (Figure S2). The reactor (25.2 mL) was loaded with 5 mg of
catalysts and purged with H2 (4.5 bar) and CO2 (1.5 bar) at room
temperature. The reaction was conducted at 200 °C for 0.5 h. A Xe
light (320−780 nm) was used for providing light irradiation from top
to bottom with a light intensity of ∼12 suns. Products were analyzed
with an online gas chromatograph (GC, Panna A91Plus) equipped
with a flame-ionized detector (FID) and a thermal conductivity
detector (TCD). The product after isotope labeling reactions were
analyzed through a Xevo G2-XS QTof mass spectrometer using the
atmospheric pressure ionization (API) mode. The selectivity and
reaction rate of product i (i = methanol or CO, etc.) were calculated
as follows
ni
ri =
(mcat × t )
Si = ri / ri×100%
i
where ni is the moles of product i, t is the reaction time, and mcat is the
catalyst sample weight.
■ RESULTS AND DISCUSSION
Structural Characterization. The hydrophobic In2O3
samples were prepared via a silanization reaction under reflux
with toluene. The original In2O3 is labeled as S0. From the ICP
results, the samples with Si contents of 0.050, 0.085, 0.103, and
0.117 wt % are labeled as S1, S2, S3, and S4, respectively.
During the thermal treatment under N2, all samples exhibited
weight loss and prominent derivative thermogravimetry
(DTG) peaks with similar DSC curves from 300 to 400 °C
(Figure S3). It implies that the decorated alkyl chains are
thermally stable until 300 °C in N2. The excellent thermal
stability can be inferred from the minor weight loss of S1−S4
from 50 to 200 °C. As shown in Figures 1A and S4A, the
increased alkylsilane content leads to an increase in contact
angle: 23.7, 57.5, 137.7, 147.6, and 156.0° from S0 to S4,
respectively. In addition, the S1 to S4 samples show a receding
water signal from 3700 to 3500 cm−1 (Figure S4B).14 It implies
the reinforced hydrophobicity on S1−S4. From powder X-ray
https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society
Figure 1. Structural and elemental characterizations of S1−S4. The contact angle (A), XRD spectra (B), and high-resolution XPS spectra (C) of In
3d over S0 and S2. (D) The scanning TEM and energy-dispersive X-ray spectroscopy mapping results of S2. (E) Schematic of the proposed surface
structure of S1−S4 (region I: highly dense surface with crystallized/ordered structure; region II: less-dense surface with disordered structure).
diffraction (XRD) results (Figure 1B), all samples exhibit a
cubic bixbyite structured phase (#PDF 06-0416),8 and SiO2-
related signals cannot be observed, indicating the decorated
alkylsilane coating is amorphous or in extremely minimal
content.
The Si signals can be found in the XPS of S1−S4, indicating
the successful modification (Figure S5). In the high-resolution
In 3d core-level spectra (Figure 1C), two peaks at 444 and 452
eV can be assigned to In 3d5/2 and 3d3/2, respectively.15,16 It
can be found that the In 3d peaks gradually move to higher
binding energy with an ∼0.1 eV shift from S0 to S4, which
could be attributed to the generation of electron-deficient In
by the added alkylsilanes.16,17 Owing to the higher electro-
negativity of the added Si and O (Si−O−In bonds),18 the
outer electrons of In could be attracted and result in lowered
electron density. Furthermore, an electric field can be
generated due to the different electronegativity and thus
enhance polarization and result in enhanced ESR signals with
smaller g values at 2.003 (from 2.004 of S0) over S1−S4
(Figure S6).19,20
All samples exhibit a similar appearance, with a particle size
of ∼10 nm (Figure S7). According to the elemental mapping
shown in Figure 1D, the Si element is uniformly distributed on
the In2O3 nanoparticles (Figure 1D).14,21 The decoration of
alkylsilanes generates mesopores with a radius of ∼2 nm,
leading to enlarged specific surface areas from 72 m2 g−1 of S0
to ∼90 m2 g−1 of S1−S4 (Figures S8C and S9).10 Based on the
aforementioned results, a representative schematic of the
decorated In2O3 surface is proposed in Figure 1E. Different
amounts of decorated alkylsilanes induce different crystal-
linities and coverage of alkyl chains.22,23 The order of
26054
pubs.acs.org/JACS Article
crystallinity of the decorated alkylsilanes is increased ranging
from S1 to S4 (Figure S4C).
Photothermal Catalytic Performance. The catalytic
performance for photothermal CO2 hydrogenation is shown
in Figure 2A. The optimum alkylsilane coating over S2 leads to
excellent photothermal catalytic activity. At 200 °C, S0, the
ordinary In2O3, exhibits the methanol rate of 189 and 709
μmol gcat−1 h−1 for both dark and light conditions with
methanol selectivity of 50 and 53%, respectively. On the
contrary, S2 exhibits a methanol rate of 242 and 1436 μmol
gcat−1 h−1 with methanol selectivities of 60 and 61% under dark
and light, respectively. The comparison of the methanol rate,
selectivity, and turnover frequency (TOF) of S2 under light
with other photothermal catalysts under similar conditions is
shown in Tables S1 and S2. The relatively low estimated TOF
of our samples (the S2 TOF of 4.7) could be caused by the
high density of active sites compared to other materials based
on metal active sites.1,5,13 Under light conditions, the methanol
rate of S2 is twice as high as that of S0. In sharp contrast, with
the increasing amount of surface alkyl chains, S3 and S4 exhibit
lower activity, with the methanol rate of 635 and 570 μmol
gcat−1 h−1 under light, implying that the formed Si−O−In
connection may block active sites and decrease the catalytic
performance.
The stability of S0 and S2 was further studied and is shown
in Figure 2B. The methanol rate and selectivity of S2 can be
maintained at 1313 μmol gcat−1 h−1 and 55% for 20 runs,
whereas the methanol rate and selectivity of S0 keep
decreasing gradually to 334 μmol gcat−1 h−1 and 36% in the
20th test. The post-S2 sample exhibits a similar surface Si
amount (0.0402 wt %) to the fresh S2 (0.0396 wt %) via XPS,
with the In2O3 (222) facet and a lattice distance of 0.29 nm
https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society
Figure 2. Catalytic performance. (A) Production rates and methanol selectivity of S0−S4. The error bars are based on the standard deviation. (B)
Stability tests under the light of S0 and S2. (C) Mass spectrometry of the 13CO2 labeling reaction of S2. (D) The corresponding Arrhenius plot
under light conditions on S0 and S2. (E) Dependence of formation rates on the H2 partial pressure of S0 and S2. Test conditions: ∼12 suns, 6 bar,
H2/CO2: 3:1 (purge with 0.5−3 bar Ar in E), 200 °C (A−C, E).
and remains hydrophobic without aggregation (Figures S8 and
S10 and Table S3). According to the in situ DRIFTS
measurements and water-contained activity tests, S2 exhibits
a stable Si−O−Si signal (1157 cm−1)24 under 0.24% H2O,
which is much higher than the water content of ∼0.09% under
reaction circumstance, as shown in Figures S11 and S12.
Water-TPD with MS was further conducted to confirm the
stability with water steam (Figure S13). Methane (m/z = 16)
cannot be detected from S2 before 420 °C, indicating that the
alkyl chain retains its chemical stability until 420 °C with
water. The minor physically desorbed water from 50 to 200 °C
on S2 suggests a robust ability to promote water draining.
Thus, the aggregation-induced deactivation from water can be
ameliorated, improving reaction stability.25 The 13CO2-labeling
results indicate that all products from S2 are generated by the
reaction gas (Figure 2C).
The activation energy of S0 and S2 was estimated under
illumination and is shown in Figure 2D. The S2 sample
exhibits a much higher activation energy for CO (90.9 kJ
mol−1) than that of methanol (55.7 kJ mol−1), whereas the
activation energy of methanol and CO of S0 are 67.3 kJ mol−1
and 87.1 kJ mol−1, respectively. Without illumination, the
methanol activation energy of S2 is 80.4 kJ mol−1, which is
lower than that of S0 by ∼6 kJ mol−1 (Figure S14A,B). The
assessment of local temperature was conducted by employing
parallel Arrhenius plots of CO under both dark and light
conditions, the light-induced local temperature of S0 and S2 at
200 °C was estimated to be approximately 229 and 241 °C,
respectively (Figure S14A).8 The generation of heat arises
from the nonradiative relaxation of light-induced charge
carriers on In2O3.26,27 The presence of alkylsilanes establishes
26055
pubs.acs.org/JACS Article
a thermal insulating layer, effectively curbing thermal
conduction and augmenting the local temperature of S2 by
approximately 12 °C.28,29 Nonetheless, even when compared
to the S0 sample tested in the dark at 242 °C, the S2 sample
tested at 200 °C under light still exhibits a significantly higher
methanol production rate, with an increase of ∼464 μmol
gcat−1 h−1 (Figure S14C). Judging by these results, the
decorated alkylsilanes may yield distinctive mechanistic
advantages in the CO2 hydrogenation.
Furthermore, the light also plays a vital role in selectively
lowering the methanol activation energy by 19.0 and 24.7 kJ
mol−1 on S0 and S2, respectively. Compared to the
performance tested without light under the same local
temperature, the methanol rate is enhanced (from 675.3 to
709.0 μmol gcat−1 h−1), and the selectivity increases (from 50.8
to 52.7%) when light is irradiated onto S0, suggesting the
involvement of a photochemical pathway in methanol
production (Figure S14D).15 S2 exhibits a more substantial
photochemical effect, with a methanol rate enhancement of
403.6 μmol gcat−1 h−1 and an increased methanol selectivity
from 50.3 to 60.5% (Figure S14D). As the light intensities
increase by 5 suns, a remarkable enhancement in methanol rate
is observed on S2, from 797 to 1763 μmol gcat−1 h−1 (Figure
S14E). This enhancement surpasses that of CO (from 352 to
1039 μmol of gcat−1 h−1). One can deduce that the light may
facilitate intermediate stabilization30,31 and active hydrogen
transfer,32,33 further promoting CO2 hydrogenation to
methanol. To further confirm the mechanistic benefits of
alkylsilanes, the dependence of the H2 partial pressure on the
methanol rate was investigated. As shown in Figure 2E, the S2
sample shows a much lower order of H2 at 0.23 for methanol
https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society pubs.acs.org/JACS Article

Figure 3. Functions of alkyl chains. In situ DRIFTS spectra in the hydride region (A) and hydroxyl region (B) at 300 °C under Ar over S2. (C)
TGA and MS result over S0 and S2. The TPD-MS results of the absorption gas of CO2 (D) and H2 (E) over S2 and S0. (F) In situ DRIFTS spectra
in the hydroxyl region at 75 °C under H2 (Ar/H2: 14/6) over S2 [α: CH3; β: CH2; δ: In−H−; γ: InH2−; κ: In−OH+; the arrow direction in (A−F)
means the longer test time]. (G) The catalytic performance of Fe2O3, CeO2, ZrO2, and Co3O4 and their samples after alkylsilane modification
(labeled with “Si-”). Test conditions: ∼12 suns, 6 bar, H2/CO2: 3:1, 200 °C.

formation, whereas the H2 order of S0 for methanol formation
is ∼0.61. This can be further confirmed by the result of
decreased CO2 order for CO formation over S2 (Figure S15)
and indicates an enriched surface H concentration on S2.
Mechanistic Study. Kinetically speaking, the hydrophobic
coating can efficiently remove the polar molecules, such as the
produced water, methanol, and CO molecules, right shift the
reaction equilibrium, and result in better overall catalytic
performance. However, such repulsion should theoretically
benefit methanol formation, a product with a more vital
polarity than CO. Thus, the methanol selectivity should be
improved with increased hydrophobicity. However, as shown
in Figure 2A, ranging from S1 to S4, a volcano-shaped
methanol selectivity plot could be observed, implying that an
external mechanistic role could be provided by the hydro-
phobic coating.
To study the mechanistic role of the alkyl chains, detailed in
situ DRIFTS experiments were performed over S0 and S2.
Interestingly, the indium hydride-related species can be
observed at 1426 and 1640 cm−1 (In−H−), 1574 cm−1
(InH2−), as well as 3554 and 3650 cm−1 (In−OH+) under
an Ar atmosphere (Figure 3A and B).34−36 On the other hand,
the negative signals of methyl at 2968 cm−1 and methylene at
2924 and 2854 cm−1, indicate a decrement in the amount
(Figure 3B).23 The introduction of CO2 can form bicarbonates
(1635 cm−1),4 also showing the presence of active H on the
26056
surface of S2 (Figure S16). Thus, one can deduce that the alkyl
chains over the catalyst are the potential H source by
dehydrogenation with the nearby indium site.34,37 In sharp
contrast, S0 exhibits none of the above phenomena (Figures
S16 and S17). To further confirm this idea, TGA-MS was used
to verify whether the H2 could be released with thermal
treatment. As can be seen from Figure 3C, only the decorated
S2 (thermally stable up to 350 °C) could generate H2 (m/z =
2) with a peak at 300 °C, indicating that the H atoms from
alkyl chains could also participate in the reaction as the active
H. The corresponding CO2-TPD-MS of S2 indicates that the
CO could be produced by consuming the H atom from alkyl
chains, and no CO could be observed from S0 (Figure 3D). It
agrees well with the previous deduction.
Only regenerable species could be considered as a valuable
contribution to the catalytic process. The corresponding H2-
TPD-MS of S2 indicates a superior ability to activate H2 than
S0 (Figure 3E). In the meantime, H2 could also be generated
during the TPD process for S2, and only water could be
produced from S0. Another in situ DRIFTS measurement was
conducted in the H2 atmosphere to verify whether methyl and
methylene could be regenerated. As can be seen from Figure
3F, the rise of peaks from 2970 to 2860 cm−1 represents the
regeneration of methyl and methylene groups, and the
presence of a hydride signal at 1574 cm−1 agrees well with
the one formed under the Ar atmosphere (Figures 3F and
https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society
Figure 4. Mechanism study. (A) The catalytic performance is regulated by regulating the length of carbon chains. (B) In situ DRIFTS spectra in the
C−O stretch region at 250 °C under the reaction gas (CO2/H2/Ar: 2/6/12) over S2. (C) The schematic of the proposed reaction mechanism over
S2 (σ: CO; τ: HOCO*; ω: CH3O*; the arrow direction means the longer test time).
S18). To further confirm this regeneration property, D2 was
used as the control experiment, and the formation of CH2D
and CHD2 at 2933 cm−1, the electron ionization (EI) mass
spectra of H, and the formation of CHxD3‑xOD with D2 and
CO2 can be observed (Figures S19−S21). The H-D exchange
proves the participation of carbon chains in H2 activation. This
function of alkyl chains is also effective in Fe2O3, CeO2, ZrO2,
and Co3O4. As shown in Figure 3G, the production of
methanol, CH4, and C2H6 is enhanced after alkylsilane
decoration. It further confirms that the alkyl chains could
donate external H to the reaction environment and shift the
reaction from RWGS to deep hydrogenated products, such as
methanol, CH4, and C2H6 (Figures S22−S25).38
As shown in Figure 4A, the number of H atoms depends on
the length of the alkyl chains, and various chain lengths result
in different catalytic performances. While there is no significant
change in the CO rate (∼960 μmol gcat−1 h−1) from C1 to C8,
the methanol rate increases monotonically from 792 to 1436
μmol gcat−1 h−1 with an increased selectivity from 45 to 61%.
The stable CO rate and improved methanol rate could be
caused by H donation from the alkyl chains. The poor catalytic
performance from short-chain samples is mainly due to the
coverage of alkylsilane and the absence of H donation (Figure
S26). While the chain length is increased from C8 to C12, the
hydrophobicity keeps increasing (Figure S27) and favors the
kinetically fast RWGS reaction rather than methanol8,38 and
ends up with improved overall catalytic performance and
enhanced CO selectivity.
To further study the reaction mechanism of S2, the in situ
DRIFTS spectra under the reaction gas (CO2/H2 = 1:3) at 250
°C were recorded and shown in Figure 4B. The signals of CO
(2222 cm−1),15 HOCO* (1520, 1385, and 1253 cm−1),39,40
26057
pubs.acs.org/JACS Article
and CH3O* (1115 cm−1)40 can be observed. According to
previous studies, HOCO* could be the intermediate source for
further hydrogenation and CO formation.8,41,42 The proposed
reaction mechanism can be concluded as shown in Figure 4C,
and the CO2 hydrogenation to methanol could be conducted
through the CO-RWGS process.8,40−42 The absorbed CO2 can
be converted into HOCO* (iv), which can be directly
hydrogenated to HCO* (v) with sufficient H species. The
HOCO* species can also be hydrogenated and decomposed to
CO and water (dashed box in Figure 4C). The fewer H species
over S0 may result in a higher possibility of CO formation.
Due to the more vital ability to repel water (Figures S4, S12,
and S13), generated water from HOCO* hydrogenation on S2
can be removed simultaneously. The introduction of light
further promotes these processes on S2 by capitalizing on the
synergistic interplay of three factors. (1) The energy barrier for
methanol production in excited states is reduced, employing a
mechanism akin to that of S0.15 (2) Light promotes the
transfer of active hydrogen species.32,33 (3) Light-induced
localized electrons on oxygen vacancies can be transferred to
the antibonding orbitals of CO2 molecules, activating and
stabilizing intermediates,30,31,43 ultimately facilitating further
hydrogenation on S2. Therefore, the S2 sample can effectively
convert the CO2 into methanol.
■ CONCLUSIONS
In conclusion, the decorated alkylsilane coatings could not
only kinetically enhance the reaction by repelling the produced
polar molecules but also donate surface active H to facilitate
the subsequent hydrogenation reaction. Such a wettability
engineering strategy can also be applied to other hydro-
genation catalysts, including Fe2O3, CeO2, ZrO2, and Co3O4.
https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society
The enhanced hydrogenation ability from the corresponding
alkyl chains unleashes the potential of surface organic
decoration strategy for other important hydrogenation catalysis
reactions.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.3c07349.
Catalyst performance data; TGA-DSC, contact angle,
ATR-IR, XPS, ESR, TEM, N2 adsorption−desorption,
XRD, water-TPD-MS, MS, and in situ DRIFTS
characterization data; schematic of the proposed
salinization process; diagram of the reactor; comparison
of reported photothermal catalytic performance; com-
parison of reported TOF for methanol synthesis; surface
Si ratio from XPS; CO2 chemisorption quantity;
calculation of water content and TOF; and references
(PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Yingfang Yao − School of Science and Engineering, The
Chinese University of Hong Kong, Shenzhen, Shenzhen
518172, P. R. China; National Laboratory of Solid State
Microstructures, Collaborative Innovation Center of
Advanced Microstructures, School of Physics, Nanjing
University, Nanjing 210093, P. R. China; orcid.org/
0000-0003-4823-0094; Email: yaoyingfang@nju.edu.cn
Geoffrey A. Ozin − Solar Fuels Group, Department of
Chemistry, University of Toronto, Toronto, Ontario M5S
3H6, Canada; orcid.org/0000-0002-6315-0925;
Email: g.ozin@utoronto.ca
Lu Wang − School of Science and Engineering, The Chinese
University of Hong Kong, Shenzhen, Shenzhen 518172, P. R.
China; orcid.org/0000-0002-4165-4022;
Email: lwang@cuhk.edu.cn
Authors
Zhe Lu − School of Science and Engineering, The Chinese
University of Hong Kong, Shenzhen, Shenzhen 518172, P. R.
China; orcid.org/0000-0002-9254-7518
Yangfan Xu − Solar Fuels Group, Department of Chemistry,
University of Toronto, Toronto, Ontario M5S 3H6, Canada;
orcid.org/0000-0002-4479-6157
Zeshu Zhang − Ganjiang Innovation Academy, Chinese
Academy of Sciences, Ganzhou 341000, P. R. China
Junchuan Sun − School of Science and Engineering, The
Chinese University of Hong Kong, Shenzhen, Shenzhen
518172, P. R. China; orcid.org/0009-0009-7663-1259
Xue Ding − School of Science and Engineering, The Chinese
University of Hong Kong, Shenzhen, Shenzhen 518172, P. R.
China
Wei Sun − State Key Laboratory of Silicon Materials, School of
Materials Science and Engineering, Zhejiang University,
Hangzhou 310027, P. R. China
Wenguang Tu − School of Science and Engineering, The
Chinese University of Hong Kong, Shenzhen, Shenzhen
518172, P. R. China; orcid.org/0000-0001-8206-6166
Yong Zhou − School of Science and Engineering, The Chinese
University of Hong Kong, Shenzhen, Shenzhen 518172, P. R.
China; National Laboratory of Solid State Microstructures,
26058
pubs.acs.org/JACS Article
Collaborative Innovation Center of Advanced
Microstructures, School of Physics, Nanjing University,
Nanjing 210093, P. R. China; orcid.org/0000-0002-
9480-2586
Zhigang Zou − School of Science and Engineering, The
Chinese University of Hong Kong, Shenzhen, Shenzhen
518172, P. R. China; National Laboratory of Solid State
Microstructures, Collaborative Innovation Center of
Advanced Microstructures, School of Physics, Nanjing
University, Nanjing 210093, P. R. China; orcid.org/
0000-0003-2092-8335
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.3c07349
Author Contributions
#
Z.L., Y.X., and Z.Z. contributed equally to this paper.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
All authors appreciate the support of the National Key R&D
Program of China (grants no. 2021YFF0502000), the National
Natural Science Foundation of China (grants no. 52102311
and 22208270), UofT-ZJU Joint seed Fund, the Program for
Guangdong Introducing Innovative and Entrepreneurial
Teams (grants no. 2019ZT08L101), the Special Fund for
the Sci-tech Innovation Strategy of Guangdong Province
(grants no. 210629095860472), the Shenzhen Natural Science
Foundation (grants no. GXWD20201231105722002-
20200824163747001), the Shenzhen Key Laboratory of Eco-
materials and Renewable Energy (grants no.
ZDSYS20200922160400001), NSF of Jiangsu Province (grants
no. BK20220006), support of Shenzhen Natural Science
Foundation 2022, and support of Provincial Talent Plan and
the University Development Fund (grants no. UDF01001721).
■ REFERENCES
(1) Gao, W.; Liang, S.; Wang, R.; Jiang, Q.; Zhang, Y.; Zheng, Q.;
Xie, B.; Toe, C. Y.; Zhu, X.; Wang, J.; et al. Industrial carbon dioxide
capture and utilization: state of the art and future challenges. Chem.
Soc. Rev. 2020, 49, 8584−8686.
(2) Tountas, A. A.; Peng, X.; Tavasoli, A. V.; Duchesne, P. N.;
Dingle, T. L.; Dong, Y.; Hurtado, L.; Mohan, A.; Sun, W.; Ulmer, U.;
et al. Towards solar methanol: past, present, and future. Adv. Sci.
2019, 6, 1801903.
(3) Porosoff, M. D.; Yan, B.; Chen, J. G. Catalytic reduction of CO2
by H2 for synthesis of CO, methanol and hydrocarbons: challenges
and opportunities. Energy Environ. Sci. 2016, 9, 62−73.
(4) Xie, B.; Wong, R. J.; Tan, T. H.; Higham, M.; Gibson, E. K.;
Decarolis, D.; Callison, J.; Aguey-Zinsou, K.-F.; Bowker, M.; Catlow,
C. R. A.; et al. Synergistic ultraviolet and visible light photo-activation
enables intensified low-temperature methanol synthesis over copper/
zinc oxide/alumina. Nat. Commun. 2020, 11, 1615.
(5) Zhao, J.; Liu, J.; Li, Z.; Wang, K.; Shi, R.; Wang, P.; Wang, Q.;
Waterhouse, G. I. N.; Wen, X.; Zhang, T. Ruthenium-cobalt single
atom alloy for CO photo-hydrogenation to liquid fuels at ambient
pressures. Nat. Commun. 2023, 14, 1909.
(6) Zhao, J.; Zhang, T. Storage and release of active sites for solar
methanol at ambient pressure. Chem Catal. 2023, 3, 100535.
(7) Xu, Y.-F.; Tountas, A. A.; Song, R.; Ye, J.; Wei, J.-H.; Ji, S.; Zhao,
L.; Zhou, W.; Chen, J.-H.; Zhao, G.; et al. Equilibrium photo-
thermodynamics enables a sustainable methanol synthesis. Joule 2023,
7, 738−752.
(8) Zhang, Z.; Mao, C.; Meira, D. M.; Duchesne, P. N.; Tountas, A.
A.; Li, Z.; Qiu, C.; Tang, S.; Song, R.; Ding, X.; et al. New black
https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society
indium oxide�tandem photothermal CO2-H2 methanol selective
catalyst. Nat. Commun. 2022, 13, 1512−1518.
(9) Tan, M.; Tian, S.; Zhang, T.; Wang, K.; Xiao, L.; Liang, J.; Ma,
Q.; Yang, G.; Tsubaki, N.; Tan, Y. Probing hydrophobization of a Cu/
ZnO catalyst for suppression of water-gas shift reaction in syngas
conversion. ACS Catal. 2021, 11, 4633−4643.
(10) Xu, Y.; Li, X.; Gao, J.; Wang, J.; Ma, G.; Wen, X.; Yang, Y.; Li,
Y.; Ding, M. A hydrophobic FeMn@Si catalyst increases olefins from
syngas by suppressing C1 by-products. Science 2021, 371, 610−613.
(11) Fang, W.; Wang, C.; Liu, Z.; Wang, L.; Liu, L.; Li, H.; Xu, S.;
Zheng, A.; Qin, X.; Liu, L.; et al. Physical mixing of a catalyst and a
hydrophobic polymer promotes CO hydrogenation through dehy-
dration. Science 2022, 377, 406−410.
(12) Zhao, J.; Li, Z.; Wang, P.; Miao, P.; Shi, R.; Waterhouse, G. I.;
Zhang, T. Hydrophobic modification for CO photo-hydrogenation to
olefins with low CO2 selectivity. Nano Energy 2023, 110, 108350.
(13) Wang, H.; Liu, G.; Chen, C.; Tu, W.; Lu, Y.; Wu, S.; O’Hare,
D.; Xu, R. Single-Ni sites embedded in multilayer nitrogen-doped
graphene derived from amino-functionalized MOF for highly selective
CO2 electroreduction. ACS Sustain. Chem. Eng. 2021, 9, 3792−3801.
(14) Cargnello, M.; Jaén, J. J. D.; Garrido, J. C. H.; Bakhmutsky, K.;
Montini, T.; Gámez, J. J. C.; Gorte, R. J.; Fornasiero, P. Exceptional
activity for methane combustion over modular Pd@CeO2 subunits on
functionalized Al2O3. Science 2012, 337, 713−717.
(15) Yan, T.; Wang, L.; Liang, Y.; Makaremi, M.; Wood, T. E.; Dai,
Y.; Huang, B.; Ali, F. M.; Dong, Y.; Ozin, G. A. Polymorph selection
towards photocatalytic gaseous CO2 hydrogenation. Nat. Commun.
2019, 10, 2521.
(16) Yang, C.; Pei, C.; Luo, R.; Liu, S.; Wang, Y.; Wang, Z.; Zhao,
Z.; Gong, J. Strong electronic oxide support interaction over In2O3/
ZrO2 for highly selective CO2 hydrogenation to methanol. J. Am.
Chem. Soc. 2020, 142, 19523−19531.
(17) Yang, Y.; Chai, Z.; Qin, X.; Zhang, Z.; Muhetaer, A.; Wang, C.;
Huang, H.; Yang, C.; Ma, D.; Li, Q.; et al. Light-induced redox
looping of a rhodium/CexWO3 photocatalyst for highly active and
robust dry reforming of methane. Angew. Chem., Int. Ed. 2022, 61,
No. e202200567.
(18) Lv, K.; Teng, C.; Shi, M.; Yuan, Y.; Zhu, Y.; Wang, J.; Kong, Z.;
Lu, X.; Zhu, Y. Hydrophobic and electronic properties of the E-MoS2
nanosheets induced by FAS for the CO2 electroreduction to syngas
with a wide range of CO/H2 ratios. Adv. Funct. Mater. 2018, 28,
1802339.
(19) Xing, M.; Zhang, J.; Chen, F.; Tian, B. An economic method to
prepare vacuum activated photocatalysts with high photo-activities
and photosensitivities. Chem. Commun. 2011, 47, 4947−4949.
(20) Wei, W.; Wei, Z.; Li, R.; Li, Z.; Shi, R.; Ouyang, S.; Qi, Y.;
Philips, D. L.; Yuan, H. Subsurface oxygen defects electronically
interacting with active sites on In2O3 for enhanced photo-
thermocatalytic CO2 reduction. Nat. Commun. 2022, 13, 3199.
(21) Jin, Z.; Wang, L.; Zuidema, E.; Mondal, K.; Zhang, M.; Zhang,
J.; Wang, C.; Meng, X.; Yang, H.; Mesters, C.; et al. Hydrophobic
zeolite modification for in situ peroxide formation in methane
oxidation to methanol. Science 2020, 367, 193−197.
(22) Chen, L.; Huang, S.; Ras, R. H. A.; Tian, X. Omniphobic liquid-
like surfaces. Nat. Rev. Chem 2023, 7, 123−137.
(23) Marshall, S. T.; O’Brien, M.; Oetter, B.; Corpuz, A.; Richards,
R. M.; Schwartz, D. K.; Medlin, J. W. Controlled selectivity for
palladium catalysts using self-assembled monolayers. Nat. Mater.
2010, 9, 853−858.
(24) Swedlund, P. J.; Miskelly, G. M.; McQuillan, A. J. Silicic acid
adsorption and oligomerization at the ferrihydrite-water interface:
interpretation of ATR-IR spectra based on a model surface structure.
Langmuir 2010, 26, 3394−3401.
(25) Jiang, X.; Nie, X.; Gong, Y.; Moran, C. M.; Wang, J.; Zhu, J.;
Chang, H.; Guo, X.; Walton, K. S.; Song, C. A combined experimental
and DFT study of H2O effect on In2O3/ZrO2 catalyst for CO2
hydrogenation to methanol. J. Catal. 2020, 383, 283−296.
26059
pubs.acs.org/JACS Article
(26) Mateo, D.; Albero, J.; García, H. Titanium-perovskite-
supported RuO2 nanoparticles for photocatalytic CO2 methanation.
Joule 2019, 3, 1949−1962.
(27) Sun, J.; Sun, W.; Wang, L.; Ozin, G. A. Uniting heat and light in
heterogeneous CO2 photocatalysis: optochemical materials and
reactor engineering. Acc. Mater. Res. 2022, 3, 1260−1271.
(28) Cai, M.; Wu, Z.; Li, Z.; Wang, L.; Sun, W.; Tountas, A. A.; Li,
C.; Wang, S.; Feng, K.; Xu, A.-B.; et al. Greenhouse-inspired supra-
photothermal CO2 catalysis. Nat. Energy 2021, 6, 807−814.
(29) Han, X.; Besteiro, L. V.; Koh, C. S. L.; Lee, H. K.; Phang, I. Y.;
Phan-Quang, G. C.; Ng, J. Y.; Sim, H. Y. F.; Lay, C. L.; Govorov, A.;
et al. Intensifying heat using MOF-isolated graphene for solar-driven
seawater desalination at 98% solar-to-thermal efficiency. Adv. Funct.
Mater. 2021, 31, 2008904.
(30) Qi, Y.; Song, L.; Ouyang, S.; Liang, X.; Ning, S.; Zhang, Q.; Ye,
J. Photoinduced defect engineering: enhanced photothermal catalytic
performance of 2D black In2O3‑x nanosheets with bifunctional oxygen
vacancies. Adv. Mater. 2020, 32, 1903915.
(31) Shao, T.; Wang, X.; Dong, H.; Liu, S.; Duan, D.; Li, Y.; Song,
P.; Jiang, H.; Hou, Z.; Gao, C.; et al. A stacked plasmonic
metamaterial with strong localized electric field enables highly
efficient broadband light-driven CO2 hydrogenation. Adv. Mater.
2022, 34, 2202367.
(32) Fang, X.; Zhang, N.; Chen, S.-C.; Luo, T. Scalable total
synthesis of (−)-triptonide: serendipitous discovery of a visible-light-
promoted olefin coupling initiated by metal-catalyzed hydrogen atom
transfer (MHAT). J. Am. Chem. Soc. 2022, 144, 2292−2300.
(33) Zhang, Z.; Tian, H.; Sun, J.; Meira, D. M.; Zhang, M.; Ding, X.;
Ji, D.; Qiu, C.; Lu, Z.; Sun, L.; et al. Light-enabled coupling of tandem
ethane dehydrogenation and CO2 hydrogenation. Chem Catal. 2023,
3, 100644.
(34) Wang, C.; Han, Y.; Tian, M.; Li, L.; Lin, J.; Wang, X.; Zhang, T.
Main-group catalysts with atomically dispersed In sites for highly
efficient oxidative dehydrogenation. J. Am. Chem. Soc. 2022, 144,
16855−16865.
(35) Wang, L.; Yan, T.; Song, R.; Sun, W.; Dong, Y.; Guo, J.; Zhang,
Z.; Wang, X.; Ozin, G. A. Room-temperature activation of H2 by a
surface frustrated Lewis pair. Angew. Chem., Int. Ed. 2019, 58, 9501−
9505.
(36) Andrews, L.; Wang, X. Infrared spectra of indium hydrides in
solid hydrogen and of solid Indane. Angew. Chem., Int. Ed. 2004, 43,
1706.
(37) Maeno, Z.; Yasumura, S.; Wu, X.; Huang, M.; Liu, C.; Toyao,
T.; Shimizu, K.-I. Isolated indium hydrides in CHA zeolites:
speciation and catalysis for nonoxidative dehydrogenation of ethane.
J. Am. Chem. Soc. 2020, 142, 4820−4832.
(38) Tan, T. H.; Xie, B.; Ng, Y. H.; Abdullah, S. F. B.; Tang, H. Y.
M.; Bedford, N.; Taylor, R. A.; Aguey-Zinsou, K.-F.; Amal, R.; Scott, J.
Unlocking the potential of the formate pathway in the photo-assisted
Sabatier reaction. Nat. Catal. 2020, 3, 1034−1043.
(39) Graciani, J.; Mudiyanselage, K.; Xu, F.; Baber, A. E.; Evans, J.;
Senanayake, S. D.; Stacchiola, D. J.; Liu, P.; Hrbek, J.; Sanz, J. F.; et al.
Highly active copper-ceria and copper-ceria-titania catalysts for
methanol synthesis from CO2. Science 2014, 345, 546−550.
(40) Kattel, S.; Yan, B.; Yang, Y.; Chen, J. G.; Liu, P. Optimizing
binding energies of key intermediates for CO2 hydrogenation to
methanol over oxide-supported copper. J. Am. Chem. Soc. 2016, 138,
12440−12450.
(41) Shen, C.; Sun, K.; Zhang, Z.; Rui, N.; Jia, X.; Mei, D.; Liu, C.
Highly active Ir/In2O3 catalysts for selective hydrogenation of CO2 to
methanol: experimental and theoretical studies. ACS Catal. 2021, 11,
4036−4046.
(42) Deng, B.; Song, H.; Wang, Q.; Hong, J.; Song, S.; Zhang, Y.;
Peng, K.; Zhang, H.; Kako, T.; Ye, J. Highly efficient and stable
photothermal catalytic CO2 hydrogenation to methanol over Ru/
In2O3 under atmospheric pressure. Appl. Catal., B 2023, 327, 122471.
(43) Wang, L.; Dong, Y.; Yan, T.; Hu, Z.; Ali, F. M.; Meira, D. M.;
Duchesne, P. N.; Loh, J. Y. Y.; Qiu, C.; Storey, E. E.; et al. Black
https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060
Journal of the American Chemical Society pubs.acs.org/JACS Article

indium oxide a photothermal CO2 hydrogenation catalyst. Nat.

Commun. 2020, 11, 2432.

26060 https://doi.org/10.1021/jacs.3c07349
J. Am. Chem. Soc. 2023, 145, 26052−26060