Supporting Information

First-Principles-Based Microkinetic Simulations of CO2 Hydrogenation to

Methanol over Intermetallic GaPd2: Method Development to Include Complex
Interactions between Surface Adsorbates

Panpan Wu, Jeremie Zaffran, Dongyang Xu and Bo Yang*

School of Physical Science and Technology, ShanghaiTech University, 393 Middle

Huaxia Road, Shanghai 201210, China

*Email address: yangbo1@shanghaitech.edu.cn

S1
Table S1. Shomate parameters used in the microkinetic modeling.
298- 298- 100- 500- 298- 298-
Temperature(K)
1000 1200 500 1700 1500 1300
species H2 CO2 H2O H2O CH3OH CO
A 33.07 25.00 36.30 30.09 -1.08 25.57
B -11.36 55.19 -24.11 6.83 153.25 6.10
C 11.43 -33.69 63.64 6.79 -79.53 4.05
D -2.77 7.95 -38.95 -2.53 16.47 -2.67
E -0.16 -0.14 -0.01 0.08 0.52 0.13
F -9.98 -403.61 -10.24 -250.88 -4.90 -118.01
G 172.71 228.24 237.39 223.40 199.19 227.37
H 0.00 -393.52 0.00 -241.83 0.00 -110.53

S2
Table S2. Activation energies (Ea) and reaction energies (ΔE) (in eV) of the elementary
reactions of methanol synthesis over clean and one CO pre-adsorbed GaPd2(010)
surfaces.

Clean surface 1CO

No. elementary reaction
Ea ΔE Ea ΔE

1. CO2(g) + H* → HCOO* 0.32 -0.76 0.35 -0.84

2. HCOO* + H* → HCOOH* + * 0.97 0.28 1.03 0.29

3. HCOOH* + H* → H2COOH* + * 1.11 0.26 1.09 0.26

4. H2COOH* + * → CH2O* + OH* 0.27 0.27 0.25 0.25

5. CH2O* + H* → CH3O* + * 0.38 -0.69 0.34 -0.82

6. CH3O* + H* → CH3OH(g) + 2* 0.90 0.24 0.86 0.37

7. H* + OH* → H2O(g) + 2* 0.98 0.13 0.99 0.21

8. CO2(g) + 2* → CO* + O* 0.74 -0.14 0.77 -0.19

9. O* + H* → OH* + * 1.02 -0.55 1.03 -0.56

S3
S4
Figure S1. The structures of adsorption and transition states included in elementary
steps listed in Table 1. In this figure and those hereafter, the Pd, Ga, C, O and H atoms
are represented in blue, brown, gray, red and white, respectively.

S5
Figure S2. Potential energy profiles of the preferred reaction pathway for CO(a) and
CH3OH(b) formation on GaPd2(010) surface with different coverages of surface species
used in DFT calculations. The corresponding activation and reaction energies are listed
in Table 2. The potential energy profiles on clean surface are illustrated in dash line for
comparison.

S6
S7
Figure S3. (a-b) The structures of adsorption and transition states included in CH3OH
and CO formation on GaPd2(010) surface with different coverages of surface species

S8
used in DFT calculations. The corresponding activation and reaction energies are listed
in Table 2.

Figure S4. The turn-over frequencies of (a) CO and (b) CH3OH formation in competing
reactions on GaPd2(010) surface with different coverages of surface species used in
DFT calculations, at the reactant pressure of 1 bar, respectively. Those on clean surface
is illustrated in dash line for comparison.

S9