Supporting Information

Influence of Indium as a promoter on the

stability and selectivity of the nanocrystalline

Cu/CeO2 catalyst for CO2 hydrogenation to

methanol

Sachin Kumar Sharma,a,b Bappi Paul,a,c Rohan Singh Pal,a,b Piyali Bhanja,d Arghya

Banerjee*,e Chanchal Samanta*,f Rajaram Bal*a,b

a Light Stock Processing Division, CSIR-Indian Institute of Petroleum, Dehradun 248005,

India. Fax: +91 135 2660202; Tel: +91 135 2525917.

b Academy of Scientific and Innovative Research (AcSIR), Ghaziabad- 201002, India
c Department of Chemistry, National Institute of Technology Nagaland, Dimapur, Nagaland

797103, India
d CSIR-Institute of Minerals and Materials Technology, Bhubaneswar 751013, India
e Department of Chemical Engineering, IIT Ropar, Ropar- 140001, India
f Bharat Petroleum Corporation Ltd., Greater Noida, Uttar Pradesh 201306, India.

**Corresponding author E-mail: raja@iip.res.in (R. Bal); banerjee.arghya@gmail.com;

arghyab@iitrpr.ac.in (A. Banerjee); chanchalsamanta@bharatpetroleum.in (C. samanta)

S1
 1. EXPERIMENTAL

1.1 Catalytic synthesis

In-Cu/CeO2 catalyst was prepared by a two-step method, where CeO2 was prepared first by

hydrothermal method, and then In-Cu was deposited over CeO2. In a typical synthesis process

for the preparation of CeO2, 12.6 g of Ce (NO3)3.6H2O is dissolved in 80 ml of water and stirred

vigorously for 30 minutes. Then 1.17 g sodium lauroyl sarcosinate dissolved in 40 ml of water

was added to the above solution and stirred for 1 h. (2 M) Na2CO3 solution (in water) was

added dropwise to precipitate the salt completely (pH ~ 9). After 2 h of stirring, 0.6 ml of

dodecanethiol was added, keeping the mole ratio of Cu: dodecanethiol is 1: 1. the whole

mixture was put into an autoclave and treated at 180 °C for 2 days. After cooling the autoclave

to room temperature, the precipitate was washed with water and dried at 100 °C for 10 h. The

dried material was calcined at 450 °C for 4 h. The obtained CeO2 powder support was then

used for catalyst preparation.

Typical preparation of 1wt% In and 5wt% supported on CeO2 is as follows: 0.91 g Copper(II)

nitrate hemi(pentahydrate) (Cu(NO3)2· 2.5H2O), 0.01 g Indium(III) nitrate hydrate [In(NO3)3 ·

xH2O], 0.7 g of cetyltrimethylammonium bromide and 2 g CeO2 were mixed well by excessive

grinding. The whole mixture was then put into a quartz vessel and initially heated at 130 °C

for 2 h by a gradual increase in temperature. Sublimation of the metal salts was observed after

reaching the temperature, and it was continued for 3 h, and finally, the mixture was heated at

550 °C for 4 h in air. The prepared catalyst is denoted as (wt%)In-(wt%) Cu/CeO2. In a similar

way, different In loaded (0.5 wt% and 2.0 wt%) catalysts were also prepared. For comparison,

a catalyst without indium (5wt%Cu/CeO2) was also prepared.

Catalysts were thoroughly characterized by XRD, N2-physisorption, ICP-AES, TPR, XPS, HR-

TEM, DRIFT-IR spectroscopy, and N2O titration techniques to determine physicochemical

S2
properties of catalysts. The details of the characterization methods are given in the supporting

information.

1.2. Hydrogenation of CO2 to MeOH

The activity measurement of CO2 hydrogenation to MeOH over Cu/CeO2 and In-Cu/CeO2

catalyst was conducted in a continuous fixed-bed tubular reactor (Figure S8, supporting

information). 0.5 g of the catalyst was loaded into the reactor, and a K-type thermocouple was

inserted at the centre of the furnace. Before each reaction, the catalyst was initially treated

(heating rate 2 C/min) under a flow of 10 ml/min H2 (10% H2 in Helium) at 250 °C for 2 h

under atmospheric pressure. The reactor was allowed to cool down to 190 °C, and a gas mixture

of CO2/H2/N2 = 1: 3: 1 (flow rate: 60 ml/min) was passed over the catalyst bed in the reactor

to reach the reactor pressure of 3.0 MPa. The corresponding weight, hourly space velocity

(WHSV), was 7200 ml. gCat-1. h-1 and the flow of gaseous mixture were passed over the

catalyst bed for 18 hours at 210 °C. During this time, a steady state of the reaction was reached.

Subsequently, the products were quantitatively analyzed by using online gas chromatography

(Agilent 7890A), equipped with a two-column system connected to a thermal conductivity

detector (TCD) using porapack-Q column (for analyzing H2, N2, CO, CO2, and H2O), and HP-

Plot Q (for analyzing CH3OH and CH4). In all the experiments, CH4 concentration in the outlet

gas mixture was found to be nil. Carbon balance was estimated from the conversion of CO2

and selectivity of CH3OH, CH4, and CO using N2 as the internal standard. The material balance

and carbon balance were calculated with an accuracy of ± 3% (between 97% and 103%). The

CO2 conversion (CCO2), MeOH selectivity (PCH3OH) were analyzed using the equations given

below:
𝐹𝑒𝑒𝑑𝐶𝑂2, 𝑖𝑛 ― 𝐹𝑒𝑒𝑑𝐶𝑂2, 𝑜𝑢𝑡
𝐶𝐶𝑂2 = 𝐹𝑒𝑒𝑑𝐶𝑂2, 𝑖𝑛 × 100% …………… (3)

𝐹𝑒𝑒𝑑𝐶𝐻3𝑂𝐻, 𝑜𝑢𝑡
𝑃𝐶𝐻3𝑂𝐻 = 𝐹𝑒𝑒𝑑𝐶𝑂 ,𝑖𝑛 ― 𝐹𝑒𝑒𝑑𝐶𝑂 ,𝑜𝑢𝑡 × 100% .……………. (4)
2 2

S3
2. CATALYST CHARACTERIZATION

N2 adsorption-desorption isotherms investigated the nature of the porosity of the metal loaded

catalysts at -180°C (Micromeritics ASAP 2020 Surface Area & Porosity Analyser) using the

BET equation. Pore size distributions were determined using the Barrett-Joyner-Halenda (BJH)

model of cylindrical pore approximation. Before each measurement, the sample was degassed

under vacuum at 300 ℃ for 4h.

The powder X-ray diffraction patterns (XRD) were recorded on a Proto Advance X-ray

diffractometer fitted with a Lynx eye high-speed strip detector using Cu Kα radiation.

Temperature programmed reduction (TPR) was carried out in a Micromeritics, Auto Chem II

2920 instrument in the temperature range of 100–1000 ℃ with a heating rate of 10 ℃/min using

helium as the carrier gas. Micromeritics, Auto Chem II 2920 instrument connected with a

thermal conductivity detector (TCD) and Quadrupole mass analyzer connected online with the

Chemisorption unit was used to carry out the Metal dispersion analysis by H2-chemisorption

technique. All the In-Cu/CeO2 catalysts (~150 mg) were first reduced at 250 °C 2h with

10%H2/90%Ar to reduce the Cu species present on the surface, followed by purging with He

for 1 h and cooled down 40 °C. The catalysts were then exposed to 10%N2O/90%He for 2h to

oxidize surface Cu atoms to Cu2O, and the decomposition of N2O was monitored by TCD. The

catalysts were cooled to room temperature, and temperature-programmed reduction (TPR) was

performed with 10%H2/90%Ar flow to reduce back Cu2O to metallic Cu using the ramp rate

of 10 °C /min to 3000 °C. Cu surface area and dispersion were calculated from the amount of

H2 consumed during the TPR step by assuming that Cu crystallites are spherical in nature. 1-2

The Cu surface area (S.A.) was calculated based on the following equation:

Cu S.A. (m2/g) = [100 (Mol H2) (SF) (NA)] / [(SDCu) (WCu)]

S4
Where Mol H2 = amount of H2 consumed during the TPR step per unit mass of the catalyst

(mol H2/gcat)

SF = stoichiometric factor =2

NA = Avogadro’s number = 6.022 x 1023

SDCu = copper surface density = 1.46 x 1019 atoms / m2

WCu = Cu content of the catalyst determined from ICP-AES analysis (wt%)

Copper dispersion is defined as the ratio of the surface copper atoms to the total copper atoms

present in the catalyst. 3-5 The following equation is used to calculate the % Cu dispersion from

the same experiment.

%DCu = [104 (Mol H2) (SF) (At. Wt.Cu)] / WCu)

Where At. Wt.Cu = Atomic weight of Cu = 63.54

The mean Cu particle size is defining, by the following equation when the particles are

hemispherical in shape.6

6𝑀
𝑑𝑝 = -1
𝐷⍴𝜎𝑁0Where M is the molecular weight of Cu (63.546 g mol ), D is the Cu fractional

dispersion obtained as explained above, ρ is the Cu metal density (8.94 g cm-3), σ is the area

occupied by a surface Cu atom (6.85 A2 per atom), and N0 is the Avogadro constant.

Additional TPR experiments were also conducted separately to examine the catalyst

reducibility and also to check the metal-support interaction. Initially, ~100 mg of the catalyst

was heated in He at 350 °C for 30 min, followed by cooling at room temperature. The catalyst

temperature was then raised with 10% H2/Ar using a ramp rate 10°C/min to 500 °C. The

effluent from the reactor was passed through a trap immersed in an isopropyl alcohol/liquid

nitrogen bath to remove moisture formed during reduction. H2 consumption was detected using

a thermal conductivity detector (TCD).

S5
Transmission electron microscopy (TEM) images were recorded on a JEM 2100 (JEOL,

Japan) microscope, and samples were prepared by mounting an ethanol dispersed sample on

a Lacey carbon formvar Cu grid. Scanning Transmission electron microscopy (TEM)

images were recorded on a FEI, Tecnai G2-F30 S-TWI instrument.

X-ray photoelectron spectra (XPS) analysis was performed to find the oxidation state of the

prepared catalyst. X-ray photoelectron spectra (XPS) were recorded on a Thermo Scientific

K-Alpha X-Ray photoelectron spectrometer, and binding energies (±0.1 eV) were

determined with respect to the position of the C 1s peak at 284.6 eV.

In situ DRIFTS measurements were performed by using a high-temperature environmental

reaction chamber supported in a Praying Mantis (Harrick) DRIFTS optical system with ZnSe

windows. All of the in situ DRIFT experiments were carried out at 500 °C, using about 50

mg catalysts. Prior to each test, the sample was reduced in a hydrogen balanced helium

mixture (10 vol. % H2 balanced He mixture with a flow rate of 20 ml min-1 for 2 h at 250

°C and purged with He (20 ml min-1) for an additional 0.5 h at 250 °C. Subsequently, and

the catalyst was cooled down to 200 °C (i.e., reaction temperature). Then a flow of H2 (15

ml min-1), CO2 (5 ml min-1), or the reaction mixture (H2/N2/CO2 = 3: 1: 1, F = 20 ml min-

1) was introduced into the DRIFTS cell at 200 °C. The spectra of the adsorbed species were

obtained after the reduction step. The in-situ DRIFT spectra shown in this work were

expressed in units of absorbance (a.u.) unit, in which only bands attributed to adsorbed

species were shown.

2.1. Computational Methods

Spin polarised density functional theory calculations were performed using the Vienna ab-initio

simulation package (VASP) as developed at the Fakultat fur Physik of Universitat Wien.7-8 To

account for the weak long-range van der Waals interactions in adsorption, the vdw-DF

functional,9-10 in the generalized gradient approximation (GGA), was employed in all our

S6
calculations, with a plane wave basis set having a cutoff kinetic energy of 450 eV. The vdW-

DF functional has been shown to predict CO2 and CO binding on the Cu surface reasonably

well.11 The Brillouin zone was sampled with a 3 x 3 x 1 Monkhorst Pack grid, and a tetrahedron

method of smearing having width of 0.2 eV was employed. Geometry optimization was done

using a conjugate gradient algorithm with a force convergence criterion of 0.05 eV/ Å. The Cu

surface was modelled as a 3 layer, p(5x5) unit cell of Cu(111), with the bottom layer fixed for

all the calculations. An optimised lattice constant of 3.708 Ǻ was used for the calculations,

which is in reasonable agreement with the experimental value of 3.60 Ǻ.12 The Cu-In systems

were modelled in two ways -a) 4 atom In cluster on top of a 3 layer p(5x5) unit cell of Cu(111)

and b) replacing one of the surface Cu atoms of a Cu(111) slab with In. An interslab spacing

of 15 Å was used to minimise the interslab interactions. The climbing image Nudged Elastic

Band method 7 was employed for the estimation of the transition states. 4-6 images were used

in the NEB, and the forces minimized to 0.05 eV/ Å. The NEB image closest to the transition

state was further optimized using the quasi-Newton algorithm, and vibrational frequency

analysis was done with a displacement criterion of 0.01 Å to confirm the transition state. The

binding energies of CO2, CO, and CH3OH were calculated as the electronic energy difference

between the gas phase and the adsorbed species, while the stability of other intermediates

(CHxOy) were calculated with respect to a gas phase reservoir of CO/CO2 and H2 (Equation 1-

2).

CO2 (g) + ½ H2 (g) + *  COOH* ………. (1)

CO (g) + x/2 H2 (g) + *  CHxO* ………. (2)

S7
3. RESULTS & DISCUSSIONS

3.1. TEM Analysis.

Figure S1. (a) EDX pattern, (b) TEM image, (c) SEAD pattern, and (d-h) Element mapping

(STEM) of 0.92In-4.6Cu/CeO2 catalyst.

Figure S2. HR-TEM images of spent 0.92In-4.6Cu/CeO2 catalyst after 100 h time of stream.

Reaction condition: Temperature (210 ºC), Pressure (30 bar), WHSV (7200 ml. gCat-1. h-1) and

Feed ratio (CO2: H2: N2 = 1:3:1).

S8
3.2. XPS Analysis.

Figure S3. XPS patterns (A) Cu-species and (B) Indium-species. (R: reduced; S: spent)

3.3 Catalyst activity for CO2 hydrogenation to MeOH

Figure S4. (A) CO2 conversion, (B) MeOH selectivity, (C) CO selectivity, and (D) MeOH

production rate from CO2 hydrogenation over In2O3, In2O3/CeO2 and Cu/In2O3 catalysts.

Reaction condition: Temperature = 210-290 ºC, Pressure = 30 bar, WHSV = 7200 ml. gCat-1.

h-1 and Feed ratio = CO2: H2: N2 = 1:3:1.

S9
Figure S5. MeOH formation rate vs. copper surface area for 4.8Cu/CeO2, 0.46In-4.7Cu/CeO2,

0.92In-4.6Cu/CeO2, and 1.7In-4.7Cu/CeO2 catalysts. (Methanol rate against Cu surface area is

plotted after subtracting the blank activity of In2O3)

3.4. Effect of Time on Stream on the activity of the catalyst

Figure S6. Time on stream (TOS) study over the 0.92In-4.6Cu/CeO2 catalyst. Reaction

condition: Temperature (290 ºC), Pressure (30 bar), WHSV (7200 ml. gCat-1. h-1) and Feed

ratio (CO2: H2: N2 = 1:3:1).

S10
Table S1. Parameters for 0.92In-4.6Cu/CeO2 catalyst.

Temp© m n

200 1.298 0.11

225 1.21 0.13

250 1.205 0.15

275 1.169 0.16

300 1.15 0.19

Table S2. Activation energy of 4.8Cu/CeO2, 0.46In-4.7Cu/CeO2, 0.92In-4.6Cu/CeO2, and

1.7In-4.7Cu/CeO2 catalysts.

Catalyst Activation Energy (KJ/mole)

4.8Cu/CeO2 79.9
0.46In-4.7Cu/CeO2 77.7
0.92In-4.6Cu/CeO2 69.1
1.7In-4.7Cu/CeO2 76.1

Table S3. TOF (s−1) values at different temperatures for 4.8Cu/CeO2, 0.46In-4.7Cu/CeO2,

0.92In-4.6Cu/CeO2, and 1.7In-4.7Cu/CeO2 catalysts.

TOFa (s-1) at different temperature

Samples
190 °C 210 °C 230 °C 250 °C 270 °C 290 °C
4.8Cu/CeO2 0.025 0.035 0.034 0.033 0.031 0.031
0.46In-4.7Cu/CeO2 0.043 0.052 0.049 0.047 0.046 0.045
0.92In-4.6Cu/CeO2 0.078 0.118 0.115 0.114 0.112 0.111
1.7In-4.7Cu/CeO2 0.054 0.061 0.060 0.058 0.054 0.053

a TOF (moles of CO2 consumed/moles of Cu present in the catalyst/sec)

Reaction condition: Temperature = 210-290 ºC, Pressure = 30 bar, WHSV = 7200 ml. gCat-1.

h-1 and Feed ratio = CO2: H2: N2 = 1:3:1.

S11
 3.5. DFT Studies.

Figure S7. Adsorbate configurations and binding energies for various intermediates on the

InCu (a-d) and In/Cu(111) (e-h) surfaces. Cu atoms are in orange, In in brown, C in grey, O in

red, and H in white.

Table S4. The comparison Cu/MgO/ZnO and other metal/oxides catalysts reaction conditions

with the selectivity of MeOH from the CO2 hydrogenation.

Catalyst H2:CO2 Pressure Temperature Conversion Selectivity (%)

References
ratio (MPa) (C) (%) CH3OH CO CH4
Cu/ZnO/Al2O3 3:1 2 200 5.19 / / / 13

Pd/ZnO/Al2O3 3:1 3 220 9.3 45 14

Cu/MgO/Al2O3 2.8:1 2 200 3.6 31 69 / 15

Cu/ZrO2 3:1 0.1 220 0.53 19.8 80.2 / 16

Cu/TiO2 3:1 0.1 220 0.54 13.8 83.6 / 16

Cu/MgO/Al2O3 3:1 2 250 0.58 17.2 / / 17

Cu/ZnO/ZrO2 3:1 3 240 19.3 48.6 / / 18

Cu/CeO2/Al2O3 5:1 3 230 N/A 71.94 27.9 / 19

Pd/rod Ga2O3 3:1 5 250 11 / 41.3 / 20

Pd/plate Ga2O3 3:1 5 250 17.3 / 51.6 / 20

Pd/ZnO 3:1 2 250 10.5 60 30 21

In2O3 3:1 4 270 1.1 54.9 / / 22

In2O3 3:1 4 330 7.1 39.7 / / 22

Pd/ZnO 3:1 2 250 5.0 70 23

Pd/ZnO 3:1 2 250 6.2 47 24

Pd/ZnO 3:1 4.5 270 14.9 56 24

Pd/Al2O3 / 5 250 3.4 29.9 / / 15

Pd/Zn/Al / 3 250 0.6 60 / / 25

Pd/ZnO 3:1 5 250 13.8 37.5 62,2 0.1 15

Cu/ZnO/Al2O3 3:1 3 230 18.7 43 / / 18

Pd/CeO2 3:1 3 200 2.1 92.9 6.3 0.8 15

Cu/ZnAl2O4 3:1 2 200 2.5 100 / / 19

S12
Cu/ZnO/Al2O3 3:1 2 250 13.4 / / / 13

Au/ZrO2 3:1 0.5 220 5.3 5 26

Cu/ZnO-rod 3:1 3 240 8 61.8 / / 27

Au/ZnO 3:1 0.5 240 0.4 50.6 26

In-Cu/CeO2 3:1 3 200 7.6 95 4.3 - This Work

In-Cu/CeO2 3:1 3 300 15.1 52.1 47.2 0.9 This Work

Figure S8. Reactor diagram of continuous fixed bed reactor set-up for CO2 hydrogenation to

MeOH production.

REFERENCES:

(1) Chary, K. V.; Sagar, G. V.; Srikanth, C. S.; Rao, V. V. Characterization and Catalytic

Functionalities of Copper Oxide Catalysts Supported on Zirconia. J. Phys. Chem. B 2007, 111

(3), 543-550.

(2) Balaraju, M.; Rekha, V.; Prasad, P. S.; Prasad, R.; Lingaiah, N. Selective Hydrogenolysis

of Glycerol to 1, 2 Propanediol over Cu-ZnO Catalysts. Catal. Lett. 2008, 126 (1-2), 119-124.

(3) Bartholomew, C. H.; Farrauto, R. J. Fundamentals of Industrial Catalytic Processes, John

Wiley & Sons: 2011.

S13
(4) Lasso-Alcalá, O.; Nunes, J. L.; Lasso, C.; Posada, J.; Robertson, R.; Piorski, N. M.; Tassell,

J. V.; Giarrizzo, T.; Gondolo, G. Invasion of the Indo-Pacific Blenny Omobranchus Punctatus

(Perciformes: Blenniidae) on the Atlantic Coast of Central and South America. Neotrop.

Ichthyol. 2011, 9 (3), 571-578.

(5) Natesakhawat, S.; Lekse, J. W.; Baltrus, J. P.; Ohodnicki Jr, P. R.; Howard, B. H.; Deng,

X.; Matranga, C. Active Sites and Structure-Activity Relationships of Copper-Based Catalysts

for Carbon Dioxide Hydrogenation to MeOH. ACS Catal. 2012, 2 (8), 1667-1676.

(6) Karelovic, A.; Ruiz, P. The Role of Copper Particle Size in Low Pressure MeOH Synthesis

via CO2 Hydrogenation over Cu/ZnO Catalysts. Catal. Sci. Technol. 2015, 5 (2), 869-881.

(7) Kresse, G.; Furthmüller, J. Efficient Iterative Schemes for Ab Initio Total-Energy

Calculations Using a Plane-Wave Basis Set. Phys. Rev. B 1996, 54 (16), 11169.

(8) Kresse, G.; Furthmüller, J. Efficiency of Ab-Initio Total Energy Calculations for Metals

and Semiconductors Using a Plane-Wave Basis Set. Computat. Mater. Sci. 1996, 6 (1), 15-50.

(9) Dion, M.; Rydberg, H.; Schröder, E.; Langreth, D.; Lundqvist, B. Erratum: Van Der Waals

Density Functional for General Geometries [Phys. Rev. Lett. 92, 246401 (2004)]. Phys. Rev.

Lett. 2005, 95 (10), 109902.

(10) Klimeš, J.; Bowler, D. R.; Michaelides, A. Van Der Waals Density Functionals Applied

to Solids. Phys. Rev. B 2011, 83 (19), 195131.

(11) Mohan, O.; Trinh, Q. T.; Banerjee, A.; Mushrif, S. H. Predicting CO2 Adsorption and

Reactivity on Transition Metal Surfaces Using Popular Density Functional Theory Methods.

Mol. Simul. 2019, 45 (14-15), 1163-1172.

(12) Li, Y.; Shen, J.; Chen, Y. Atomistic Simulation for Disordered TbCu7-Type Compounds

SmCo7 and Sm (Co, T)7 (T= Ti, Ga, Si, Cu, Hf, Zr). Solid State Sci. 2010, 12 (1), 33-38.

(13) Dasireddy, V. D.; Likozar, B. The role of copper oxidation state in Cu/ZnO/Al2O3 catalysts

in CO2 Hydrogenation and MeOH Productivity. Renew. Energy 2019, 140, 452-460.

S14
(14) Xu, J.; Su, X.; Liu, X.; Pan, X.; Pei, G.; Huang, Y.; Wang, X.; Zhang, T.; Geng, H. MeOH

Synthesis from CO2 and H2 over Pd/ZnO/Al2O3: Catalyst Structure Dependence of MeOH

Selectivity. Appl. Catal. A 2016, 514, 51-59.

(15) Dasireddy, V. D.; Neja, S. Š.; Blaž, L. Correlation Between Synthesis pH, Structure and

Cu/MgO/Al2O3 Heterogeneous Catalyst Activity and Selectivity in CO2 Hydrogenation to

MeOH. J. CO2 Util. 2018, 28, 189-199.

(16) Kattel, S.; Yan, B.; Yang, Y.; Chen, J. G.; Liu, P. Optimizing Binding Energies of key

Intermediates for CO2 Hydrogenation to MeOH over Oxide-Supported Copper. J. Am. Chem.

Soc. 2016, 138 (38), 12440-12450.

(17) Dasireddy, V. D.; Štefančič, N. S.; Huš, M.; Likozar, B. Effect of Alkaline Earth Metal

Oxide (MO) Cu/MO/Al2O3 Catalysts on MeOH Synthesis Activity and Selectivity via CO2

Reduction. Fuel 2018, 233, 103-112.

(18) Li, C.; Yuan, X.; Fujimoto, K. Development of Highly Stable Catalyst for MeOH

Synthesis from Carbon Dioxide. Appl. Catal. A 2014, 469, 306-311.

(19) Huš, M.; Dasireddy, V. D.; Štefančič, N. S.; Likozar, B. Mechanism, Kinetics and

Thermodynamics of Carbon Dioxide Hydrogenation to MeOH on Cu/ZnAl2O4 Spinel-Type

Heterogeneous Catalysts. Appl. Catal. B: Environ. 2017, 207, 267-278.

(20) Zhou, X.; Qu, J.; Xu, F.; Hu, J.; Foord, J. S.; Zeng, Z.; Hong, X.; Tsang, S. C. E. Shape

Selective Plate-Form Ga2O3 with Strong Metal-Support Interaction to Overlying Pd for

Hydrogenation of CO2 to CH3OH. Chem. Commun. 2013, 49 (17), 1747-1749.

(21) Bahruji, H.; Bowker, M.; Hutchings, G.; Dimitratos, N.; Wells, P.; Gibson, E.; Jones, W.;

Brookes, C.; Morgan, D.; Lalev, G. Pd/ZnO Catalysts for Direct CO2 Hydrogenation to MeOH.

J. Catal. 2016, 343, 133-146.

(22) Sun, K.; Fan, Z.; Ye, J.; Yan, J.; Ge, Q.; Li, Y.; He, W.; Yang, W.; Liu, C.-j. Hydrogenation

of CO2 to MeOH over In2O3 Catalyst. J. CO2 Util. 2015, 12, 1-6.

S15
(23) Liao, F.; Wu, X.-P.; Zheng, J.; Li, M. M.-J.; Kroner, A.; Zeng, Z.; Hong, X.; Yuan, Y.;

Gong, X.-Q.; Tsang, S. C. E. A Promising Low Pressure MeOH Synthesis Route from CO2

Hydrogenation over Pd@Zn Core-Shell Catalysts. Green Chem. 2017, 19 (1), 270-280.

(24) Yin, Y.; Hu, B.; Li, X.; Zhou, X.; Hong, X.; Liu, G. Pd@ Zeolitic Imidazolate Framework-

8 Derived PdZn Alloy Catalysts for Efficient Hydrogenation of CO2 to MeOH. Appl. Catal. B:

Environ. 2018, 234, 143-152.

(25) Ota, A.; Kunkes, E. L.; Kasatkin, I.; Groppo, E.; Ferri, D.; Poceiro, B.; Yerga, R. M. N.;

Behrens, M. Comparative Study of Hydrotalcite-Derived Supported Pd2Ga and PdZn

Intermetallic Nanoparticles as MeOH Synthesis and MeOH Steam Reforming Catalysts. J.

Catal. 2012, 293, 27-38.

(26) Hartadi, Y.; Widmann, D.; Behm, R. J. CO2 Hydrogenation to MeOH on Supported Au

Catalysts under Moderate Reaction Conditions: Support and Particle Size Effects.

ChemSusChem 2015, 8 (3), 456-465.

(27) Lei, H.; Nie, R.; Wu, G.; Hou, Z. Hydrogenation of CO2 to CH3OH over Cu/ZnO Catalysts

with Different ZnO Morphology. Fuel 2015, 154, 161-166.

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