Supplementary Information

High-entropy intermetallics on ceria as efficient catalysts

for the oxidative dehydrogenation of propane using CO2

Feilong Xing,1 Jiamin Ma,1 Ken-ichi Shimizu,1 Shinya Furukawa*,1,2

1
Institute for Catalysis, Hokkaido University, N21, W10, Sapporo 001-0021, Japan
2
Japan Science and Technology Agency, PRESTO, Chiyodaku, Tokyo 102-0076, Japan

Corresponding authors
Shinya Furukawa
Institute for Catalysis, Hokkaido University, N21, W10, Sapporo 001-0021, Japan
E-mail: furukawa@cat.hokudai.ac.jp,
Fax: +81-11-706-9163

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Supplementary Fig. 1: HAADF-STEM-EDX analysis on HEI. a HAADF-STEM image of HEI/CeO2
(PtCoNiInGaSn/CeO2). Atomic ratios in the regions designated by dotted yellow circles 1-4 were
calculated and shown in Supplementary Fig. 3. b-g Elemental maps of (b) Pt, (c) Ni, (d) Co, (e) Ga, (f)
In, and (g) Sn on HEI/CeO2 acquired using EDX analysis.

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Supplementary Fig. 2: HAADF-STEM-EDX analysis on HEI. a HAADF-STEM image of HEI/CeO2
(PtCoNiInGaSn/CeO2). Atomic ratio in the region designated by dotted yellow circle 5 was calculated
and shown in Supplementary Fig. 3. b-g Elemental maps of (b) Pt, (c) Ni, (d) Co, (e) Ga, (f) In, and (g)
Sn on HEI/CeO2 acquired using EDX analysis.

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Supplementary Fig. 3: Elemental analysis on HEI. Atomic ratios of Pt+Co+Ni and Sn+In+Ga in the
regions 1–5 designated by dotted circles in Supplementary Fig. 1 and Supplementary Fig. 2.

Supplementary Fig. 4: H2-TPR analysis. H2-TPR profiles of unreduced Pt/CeO2, Pt–Co–In/CeO2, and
HEI/CeO2.

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Supplementary Table 1. Reduction potentials of metals cations involved in this study.1,2

Reduction E0 (V) vs. SHE

Pt2+ + 2e− → Pt(0) +1.18

Ni2+ + 2e− → Ni(0) −0.236

Co2+ + 2e− → Co(0) −0.282

Sn2+ + 2e− → Sn(0) −0.141

In3+ + 3e− →In(0) −0.338

CeO2 + e− → Ce2O3 −0.364

Ga3+ + 3e− → Ga(0) -0.549

Supplementary Fig. 5: EXAFS oscillations of HEI. a Pt LIII-, b Co K-, c Ni K-, d In K-, e Sn K-, and f
Ga K-edge EXAFS spectra of the in-situ reduced HEI/CeO2 catalysts and reference compounds.

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Supplementary Fig. 6: Fourier transforms of EXAFS of HEI. Fourier transforms of a Pt LIII-, b Co
K-, c Ni K-, d In K-, e Sn K-, and f Ga K-edge EXAFS of the in-situ reduced HEI/CeO2 catalysts and
reference compounds.

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Supplementary Fig. 7: Curve-fitting analysis for HEI. Curve-fitting for the Pt LIII-, Co K-, Ni K-, In
K-, Sn K-, and Ga K-edge k3-weighted EXAFS oscillations of HEI/CeO2. The k3-weighted EXAFS
oscillation was Fourier-transformed in the k range of 3−12 Å−1 for all edges. Curve-fitting was performed
using the back Fourier-transforms of the coordination peaks ranging between 1.3−3.7 Å, 1.0−3.0 Å,
1.0−3.0 Å, 1.2−4.0 Å, 1.0−3.0 Å, and 1.0−3.0 Å for Pt LIII-, Co K-, Ni K-, In K-, Sn K-, and Ga K-edge,
respectively.

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Supplementary Table 2. Results of EXAFS curve-fitting for HEI/CeO2 and the reference foils

Sample Edge Shell So2 a CN b R (Å) c ∆Eo (eV) d σ2 (Å2) e R-factor

Pt foil Pt LⅢ Pt–Pt 0.95 12 (fix) 2.77 ± 0.00 7.9 ± 1.4 0.005 0.005
Co foil Co K Co–Co 0.80 12 (fix) 2.50 ± 0.00 -5.2 ± 0.4 0.006 0.003
Ni foil Ni K Ni-Ni 0.84 12 (fix) 2.77 ± 0.00 6.0 ± 0.6 0.006 0.003
Sn–Sn 4 (fix) 3.02 ± 0.00
Sn foil Sn K 1.04 3.4 ± 1.1 0.010 0.013
Sn–Sn 2 (fix) 3.18 ± 0.00
Ga-O 1 (fix) 1.87 ± 0.00 0.010
Ga2O3 Ga K Ga-O 1.03 3 (fix) 2.02 ± 0.00 8.0 ± 2.4 0.001 0.015
Ga-Ga 2 (fix) 3.06 ± 0.00 0.001
In–In 4 (fix) 3.16 ± 0.01
In foil In K 0.87 2.1 ± 0.7 0.016 0.003
In–In 8 (fix) 3.32 ± 0.04
Pt–Ga 0.7 ± 0.0 2.57 ± 0.02 0.008
0.009
Pt LⅢ Pt–Sn/In 0.82 2.6 ± 0.3 2.63 ± 0.01 0.8 ± 1.1 0.008
Pt–Pt 1.9 ± 0.2 2.71 ± 0.01 0.008
Co–Co 7.6 ± 0.6 2.49 ± 0.00 0.007
Co K 0.80 5.1 ± 0.7 0.002
Co-In/Sn 3.8 ± 0.6 2.68 ± 0.00 0.040
Ni-Ni 2.0 ± 0.5 2.48 ± 0.03 0.009
Ni K 0.84 -9.5 ± 2.1 0.008
Ni-Sn/In 3.7 ± 3.3 2.61 ± 0.04 0.007
HEI
Sn-O 1.4 ± 0.3 2.12 ± 0.02 0.005
/CeO2
Sn K Sn-Co/Ni 1.04 1.1 ± 0.4 2.61 ± 0.00 5.4 ± 2.9 0.005 0.003
Sn-Pt 3.4 ± 2.2 2.73 ± 0.02 0.016
Ga-O 1.8 ± 1.6 1.74 ± 0.02 0.012
Ga K 1.03 -10.0 ± 2.9 0.003
Ga-Ni/Co 3.1 ± 3.3 1.93 ± 0.03 0.007
In–O 1.6 ± 0.7 2.14 ± 0.02 0.007
In K In–Co/Ni 0.87 0.3 ± 0.3 2.63 ± 0.03 4.5 ± 4.0 0.001 0.016
In–Pt 3.3 ± 1.9 2.71 ± 0.04 0.011
a
Amplitude factor. b Coordination number. c Distance between absorber and backscatterer atoms. d
Correction term in the absorption edge. e Debye–Waller factor.

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Supplementary Table 3. Information about coke on the spent catalyst. a

catalyst coke wt% b average coke sel. (%) c coke TON d

Pt/CeO2 0.3 0.004 17.0

Pt–Co–In/CeO2 0.2 0.003 11.6

HEI/CeO2 0.1 0.001 2.9

a
The catalysts after 50 h of catalytic run were used. b Gram coke per gram catalyst ×100. c Mole of
accumulated coke / total mole of converted C3H8 × 3. See Equation (16) for details. Since the coke
selectivity was too low to change the net C3H6 selectivity, we ignored coke in the calculation of C3H6
selectivity. d See Equation (17) for details.

Supplementary Table 4. Metal dispersions of CeO2-supported Pt–based catalysts.a

Active metal (Pt and Co) dispersion (%)
Catalyst
estimated by CO chemisorption
Pt/CeO2 25.4
PtSn/CeO2 70.0
Pt–Co–In/CeO2 29.6
HEI/CeO2 30.3
PtSn/CeO2 spent 15.0
Pt–Co–In/CeO2 spent 6.9
HEI/CeO2 spent 30.2
HEI/Al2O3 34.2
HEI/SiO2 19.7
a
The loading amount of Pt was fixed at 1 wt% for all the catalysts.

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Supplementary Fig. 8: Net C3H6 selectivity. Net C3H6 selectivity considering CO formed from CxHy via
dry reforming obtained in CO2–ODP over monometallic Pt/CeO2, PtSn/CeO2, PtCoIn/CeO2, and
HEI/CeO2. Pt/CeO2 showed an increase in the net C3H6 selectivity, even though C3H6 selectivity in HC
was constant, indicating that dry reforming was inhibited as the reaction proceeded.

Supplementary Fig. 9: Material balances in CO2-ODP over the HEI/CeO2 catalyst. Material balance
in COx was higher than unity while that in CxHy was lower, indicating that dry reforming of propane
occurred as a side reaction. Although this trend was prominent at the initial stage of the reaction (<5 h), it
became minor with time. However, total material balance was always close to unity, which is consisnt
with the very low coke selectivity.

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Supplementary Fig. 10: Catalytic performance of monometallic Pt/CeO2, PtCo/CeO2, PtNi/CeO2,
PtIn/CeO2, PtGa/CeO2, and HEI/CeO2 in CO2–ODP. a C3H8 conversion, b CO2 conversion, c net C3H6
selectivity considering CO formed from CxHy, and d C3H6 selectivity in CxHy.

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Supplementary Fig. 11: Catalytic performance of PtCoNiSn3/CeO2 and HEI/CeO2 in CO2–ODP. a
C3H8 conversion, b CO2 conversion, c net C3H6 selectivity considering CO formed from CxHy, and d C3H6
selectivity in CxHy.

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Supplementary Fig. 12: Catalytic performance of PtCoNiSnIn/CeO2 (Pt:Co:Ni:Sn:In =
1:1:1:1.5:1.5) and HEI/CeO2 in CO2–ODP. a C3H8 conversion, b CO2 conversion, c net C3H6 selectivity
considering CO formed from CxHy, and d C3H6 selectivity in CxHy.

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Supplementary Fig. 13: Catalytic performance of HEI/Al2O3, HEI/SiO2, and HEI/CeO2 in CO2–
ODP. a C3H8 conversion, b CO2 conversion, c net C3H6 selectivity considering CO formed from CxHy,
and d C3H6 selectivity in CxHy.

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Supplementary Fig. 14: Catalytic performance of PtSn/CeO2 catalyst in the CO2-ODP before and
after regeneration procedure. a C3H8 conversion, b CO2 conversion, c C3H6 selectivity in HC, and d
net C3H6 selectivity.

Supplementary Fig. 15: Catalytic performance of HEI/CeO2 (200mg) in the CO2-ODP. a C3H8
conversion, b CO2 conversion, c net C3H6 selectivity, and d C3H6 selectivity in CxHy.
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Supplementary Fig. 16: Catalytic performance of HEI/CeO2 and reported systems for CO2-ODP. a
Mean catalyst life (τ = kd−1). b Specific activity (mLC3H6/CO2·min−1·gAM−1) for C3H6 formation and CO2
conversion. c C3H6 yield CO2 conversion, and CO2 utilization efficiency. See Supplementary Tables 5
and 6 for which selectivity/yield description (net or in hydrocarbons) was used for each entry. For entries
19 and 20 (HEI, this study), selectivity/yield in hydrocarbons are shown.

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Supplementary Table 5. Summary of the catalytic performance of HEI/CeO2 and other reported catalysts for CO2-ODP.

temp. gas feed ratio time (h) C3H8 conv. (%) C3H6 sel. (%) a kd τ
No catalyst ref.
(°C) C3H8:CO2:He initial final initial final initial final (h-1) (h)
1 Ga8Al2O15 500 2.5: 5:92.5 0.25 8 49.7 33.1 91.7 98 0.089 11.2 3

2 Ru1Cr10Ox/SiO2 500 1:1:1 0.67 7 9 6.5 (85) (90) 0.053 18.8 4

3 Pd/CeZrAlOx 500 26:37:37 0.17 140 16 2 80 98 0.016 62.6 5

4 7%Cr/SBA-1 550 1:5:9 0.17 4 37.7 16 85 91 0.347 2.9 6

5 Cr-O/SiO2 550 1:5 0.17 0 17.2 – 94.4 – – – 7

6 Cr2O3–ZrO2 180 550 2.5:5:92.5 0.17 6 53.3 27.8 (79) (90.8) 0.186 5.4 8

7 Ga2O3–M 550 1:5:9 0.17 4 19 11 91.6 95 0.167 6.0 9

8 FeCeO2 550 1:1:2 0.10 20 17.5 14 (48) (53) 0.013 75.2 10

9 Fe3Ni/CeO2 550 1:1:2 0.10 10 4.8 3.4 30 58.2 0.036 27.5 11

10 20%ZnO-ZrO2 550 1:4:20 0.08 2 24 20 65 70 0.165 6.1 12

11 15V-15Zr@ZSM-5 550 2.5:5:92.5 1.0 6 35 39 87 90 – – 13

12 0.5%PtSnCe/SiO2 550 1:1:5 0.08 6 55 33 (89.1) (93.4) 0.154 6.5 14

13 Ga2O3V2O5/ZSM-5 550 – 0.50 6 30 35 87 90 – – 15

14 FeNi/Ceria-Vo-R 550 2.4:4.8:10 0.33 3 23 21 (42) (42) 0.054 18.6 16

15 12% In/HZSM-5 580 1:4:5 1.0 6 25.2 17.6 75 70 0.101 9.9 17

16 GaN/NaZSM-5 600 1:2:7 0.08 10 46 34 62 78 0.053 18.7 18

17 CaO/ZSM-5 600 5:5:90 0.08 – 23.1 – 39 – – – 19

18 2Cr-Ca/ZrO2 600 1:3:6 0.08 10 20.2 9.5 93.5 94.6 0.089 11.3 20

19 HEI/CeO2 200mg 600 1:1:2 8 (0.5) b 90 44 31 92 (89) 93 (91) 0.010 97.7 This
20 HEI/CeO2 100mg 600 1:1:2 8 (0.5) b
50 30 20 94 (92) 90 (89) 0.011 92.6 work
21 Pt–Co–In/CeO2 600 1:1:2 0.08 50 61 35 (82) (94) 0.022 46.3 21

22 Ga2O3/HZSM-48 600 2.5:5:92.5 1.0 10 52.6 48.2 42.2 45.6 0.020 51.1 22

23 ZnO/HZSM-5 600 2.5:5:92.5 1.0 30 68.3 41.5 46.8 62.1 0.038 26.1 23

24 Cr-MSU-28 600 1:1:08 0.17 2 44 36.8 86 90.4 0.163 6.1 24

25 5%Cr/SiO2 600 15:30:55 0.55 20 80 53 50 90.6 0.078 12.8 25

26 2%Cr2O3/SiO2 600 15:30:55 0.3 17 71 50 (66) (90) 0.055 18.3 26

27 15%Ga/ZrO2 600 2.5:5:92.5 0.17 3 38.6 6 45.4 77 0.807 1.2 27

28 Ga2O3/TiO2 600 2.5:5:92.5 0.17 3 32 2.5 (73) – 1.027 1.0 28

29 Ga2O3/Al2O3 600 2.5:5:92.5 0.17 3 26 17 (94) – 0.190 5.2 28

30 Ga2O3/ZrO2 600 2.5:5:92.5 0.17 3 30 7 (65) – 0.614 1.6 28

31 Ga2O3/SiO2 600 2.5:5:92.5 0.17 3 6.4 6 (92) – 0.024 41.2 28

32 Ga2O3/MgO 600 2.5:5:92.5 0.17 3 4.3 2.5 (29) – 0.198 5.1 28

33 10%In2O3/Al2O3 600 2.5:10:87.5 0.17 8 24 20 29 84 0.030 33.5 29

34 In-Al-20 600 2.5:10:87.5 0.17 12 35 29 (20) (78) 0.023 42.8 30

35 5.2V-MSNS 600 1:4:4 0.17 24 58 19 (84) (89) 0.074 13.4 31

36 Cr/MSS-2 600 1:4:4 0.17 4 69 33 (79) (90) 0.394 2.5 32

37 0.5 Ni-Cr/Si 600 1:1:8 0.17 12 90 19 0 90 0.308 3.2 33

38 7 Ga/SiO2-A 650 1:2 0.08 20 33 21 (78) (77) 0.031 32.3 34

a
Values with and without parenthesis indicate net C3H6 selectivity and C3H6 selectivity in hydrocarbon, respectively. The
b

data at time on stream of 8 h was used for the initial values of C3H8(6) because the induction period was observed in net
C3H6 selectivity as shown in Supplementary Fig. 8. For the initial values of CO2, time on stream of 0.5 h was employed.

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Supplementary Table 6. Summary of the catalytic performance of HEI/CeO2 and other reported catalysts for CO2-ODP. a
active CO2 conv. (%) catalyst total CO2 F(C3H6) / WAM b F(CO2) / WAM
No catalyst species C3H8 amount flow rate util. eff.
(wt%) conc. (%) initial final (g) (mL/min) (%) initial final initial final
1 Ga8Al2O15 80 2.5 – – 0.20 10 – 0.7 0.5 – –
2 Ru1Cr10Ox/SiO2 1 33.3 12 9 0.15 30 9 (510) (390) 800 600
3 Pd/CeZrAlOx 5 26.0 – – 0.20 15 – 49.9 7.6 – –
4 7%Cr/SBA-1 7 6.7 6.7 – 0.20 30 2 45.8 20.8 47.9 –
5 Cr-O/SiO2 3.4 16.7 – – 0.50 30 – 47.8 0.0 – –
6 Cr2O3–ZrO2 180 10 2.5 – – 0.20 20 – (10.5) (6.3) – –
7 Ga2O3–M 100 6.7 2.4 – 0.20 30 1 1.7 1.0 1.2 –
8 FeCeO2 10 25.0 – – 0.20 30 – (31.5) (27.8) – –
9 Fe3Ni/CeO2 1.7 25.0 12 5.7 0.10 20 3 42.4 58.2 353 168
10 20%ZnO-ZrO2 20 4.0 5 4 0.50 50 2 3.1 2.8 4.0 3.2
11 15V-15Zr@ZSM-5 15 2.5 44 49 0.20 60 36 15.2 17.6 44.0 49.0
12 0.5%PtSnCe/SiO2 0.5 14.3 25 20 0.25 50 17 (2800) (1761) 1429 1143
13 Ga2O3V2O5/ZSM-5 4 – 45 47 0.20 15 33 – – – –
14 FeNi/Ceria-Vo-R 1.43 14.0 – – 1.00 17.2 – (16.2) (14.8) – –
15 12% In/HZSM-5 12 10.0 0.6 3 – 20 – – – – –
16 GaN/NaZSM-5 5 10.0 – – 0.20 30 – 85.6 79.6 – –
17 CaO/ZSM-5 50 5.0 75.7 – – 100 16 – – – –
18 2Cr-Ca/ZrO2 2 10.0 4.1 0.7 0.30 25 1 78.7 37.4 51.3 8.8
1012 720
19 HEI/CeO2 200mg 1 25.0 88 42 0.20 20 61 2200 1050
(979) (705)
1414 900
20 HEI/CeO2 100mg 1 25.0 53 24 0.10 20 37 2650 1200
(1380) (890)
21 Pt–Co–In/CeO2 3 25.0 83 45 0.10 20 70 (837) (548) 1385 750
22 Ga2O3/HZSM-48 5 2.5 – – 0.20 20 – 11.1 11.0 – –
23 ZnO/HZSM-5 5 2.5 – – 0.20 20 – 16.0 12.9 – –
24 Cr-MSU-28 2.8 10.0 – – 0.20 30 – 203 178 – –
25 5%Cr/SiO2 2 15.0 – – – – – 0.9 1.1 – –
26 2%Cr2O3/SiO2 2 15.0 19 – – – 11 (1.1) (1.0) 0.9 –
27 15%Ga/ZrO2 15 2.5 0 – 0.20 20 0 2.9 0.8 – –
28 Ga2O3/TiO2 5 2.5 30 – 0.20 20 26 (11.7) – 30.0 –
29 Ga2O3/Al2O3 5 2.5 5.2 – 0.20 20 2 (12.2) – 5.2 –
30 Ga2O3/ZrO2 5 2.5 29 – 0.20 20 23 (9.8) – 29.0 –
31 Ga2O3/SiO2 5 2.5 3.1 – 0.20 20 2 (2.9) – 3.1 –
32 Ga2O3/MgO 5 2.5 4.2 – 0.20 20 2 (0.6) – 4.2 –
33 10%In2O3/Al2O3 10 2.5 12 10 0.20 10 9 0.9 2.1 6.0 5.0
34 In-Al-20 20 2.5 10 8 0.20 10 8 (0.4) (1.4) 2.5 2.0
35 5.2V-MSNS 5.2 11.1 10 – 0.20 15 3 (78.1) (27.1) 64.1 –
36 Cr/MSS-2 7 11.1 15 5 0.20 18 6 (77.9) (42.4) 85.7 28.6
37 0.5 Ni-Cr/Si 0.5 10.0 55 15 0.20 30 – 0.0 513 1650 450
38 7 Ga/SiO2-A 7 33.3 – – 1.00 30 – (36.8) (23.1) – –
a
The time on stream for the initial and final values are the same with those in Supplementary Table 5. The initial time was
used for calculating CO2 utilization efficiency. b Values with and without parenthesis indicate those based on net C3H6 yield
and C3H6 yield in hydrocarbon, respectively.

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Supplementary Fig. 17: H2-TPR and He-TPSR. H2-TPR profiles of unreduced HEI/CeO2 and Pt–Co–
In/CeO2 (magnification of Supplementary Fig. 4) and He-TPSR on the coked Pt–Co–In/CeO2 and
HEI/CeO2 (magnification of Fig. 3c). The reduction of CeO2 was promoted by the multi-metallization as
well as the reduction of the alloy phase shown in Supplementary Fig. 4 (a new reduction peak assignable
to the reduction of CeO2 appeared around at 400~550°C). The starting temperature of CO evolution in
the He-TPSR on HEI/CeO2 roughly agreed with this region. A similar trend was also observed for Pt–
Co–In/CeO2 (both started from 600°C). Thus, the coke combustion ability of the lattice oxygen of CeO2
seems to follow the reducibility of CeO2.

Supplementary Fig. 18: Changes in C3H8 conversion in the DDP–regeneration cycles over
HEI/Al2O3. Reaction conditions: DDP; C3H8:He = 5:10 mLmin−1 (2 h), regeneration; CO2:He = 10:10
mLmin−1 (1 h), then H2:He = 5:10 mLmin−1 (0.5 h) at 600°C.

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Supplementary Table 7. Structural information of HEI optimized by DFT.
lattice parameters / Å cell angles / degree
a 10.6585 b 13.9152 c 8.0341 α = β = γ = 90
fractional coordinates
element No. a b c element No. a b c
Pt 1 0.4989 0.253349 0.000127 In 1 0.132369 0.418577 -0.006663
Pt 2 1.000477 0.249699 -0.001157 In 2 0.36528 0.08387 0.000168
Pt 3 1.002695 0.499398 0.253125 In 3 0.631272 0.169734 0.256446
Pt 4 1.001279 0.250256 0.499994 In 4 0.621183 0.41374 0.491502
Pt 5 0.74544 0.50098 0.750795 In 5 0.629955 0.169242 0.744043
Pt 6 0.49888 1.002084 0.253777 In 6 0.86185 0.084153 0.000376
Pt 7 0.498532 1.001659 0.746333 In 7 0.861619 0.333782 0.25085
Pt 8 0.250743 0.745421 0.499885 In 8 0.864185 0.084005 0.499741
Pt 9 1.000779 1.001602 0.246267 In 9 0.131015 0.917392 0.500279
Pt 10 1.000476 1.001863 0.753671 In 10 0.120321 0.662932 0.756175
Pt 11 0.7492 0.745824 0.000406 In 11 0.375859 0.831994 0.242164
Pt 12 0.748351 0.745198 0.499531 In 12 0.374635 0.831214 0.758154
Co 1 0.251136 0.25239 0.000323 In 13 0.625435 0.916319 -0.000185
Co 2 0.254296 0.251967 0.499585 In 14 0.629601 0.916115 0.500172
Co 3 1.001574 0.498301 0.745568 In 15 0.878691 0.83321 0.250131
Co 4 0.746549 0.505096 0.247824 In 16 0.878862 0.832705 0.750004
Co 5 0.747527 0.252256 0.504361 Sn 1 0.136645 0.168034 0.249815
Co 6 0.496455 0.743425 0.001942 Sn 2 0.133174 0.41767 0.5072
Co 7 0.249256 1.001212 0.250091 Sn 3 0.138995 0.16718 0.749708
Co 8 0.249884 1.000828 0.749765 Sn 4 0.368666 0.334153 0.255663
Ni 1 0.495723 0.499376 0.247625 Sn 5 0.365006 0.086589 0.499847
Ni 2 0.49708 0.250441 0.49985 Sn 6 0.370782 0.333711 0.743915
Ni 3 0.493691 0.498495 0.753772 Sn 7 0.625469 0.419795 0.010118
Ni 4 0.254886 0.501631 0.251652 Sn 8 0.870837 0.332846 0.748453
Ni 5 0.252996 0.501038 0.748815 Sn 9 0.136246 0.913398 -0.000215
Ni 6 0.747909 0.252918 -0.003828 Sn 10 0.126128 0.668767 0.242931
Ni 7 0.498359 0.745527 0.497899 Sn 11 0.372679 0.583871 0.000053
Ni 8 0.249845 0.746757 0.000898 Sn 12 0.379299 0.577801 0.500735
Ni 9 1.004776 0.750115 0.001698 Sn 13 0.615324 0.661817 0.248051
Ni 10 1.001298 0.746294 0.497492 Sn 14 0.609215 0.666945 0.751557
Ni 11 0.748825 0.999573 0.249371 Sn 15 0.882207 0.58152 -0.002066
Ni 12 0.748987 0.999642 0.75073 Sn 16 0.878052 0.581137 0.502133

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Supplementary Fig. 19: Structural details for DFT calculations. a The optimized structure of the
(2×2×2) supercell of PtSn and the corresponding HEI model. The first (A) and third (B) top layers of the
(004) plane were selected as representative surfaces for catalysis. b Atomic arrangement of the HEI(004):
A and B surfaces.

Supplementary Fig. 20: Adsorption sites and conformations of C3H6 on the HEI(004) surfaces
considered in this study. Dotted lines indicate the conformations of C3H6.
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Supplementary Fig. 21: DFT-optimized structures of C3Hx on HEI. Structures of initial (IS), transition
(TS), and final states (FS) in the C–H activation of C3H6 on the B3 site of HEI(004).

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Supplementary Fig. 22: DFT-optimized structures of C3Hx on PtSn. Structures of initial (IS),
transition (TS), and final states (FS) in the C–H activation of C3H6 on PtSn(110).

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Supplementary Fig. 23: DFT-optimized structures of C3Hx on Pt–Co–In. Structures of initial (IS),
transition (TS), and final states (FS) in the C–H activation of C3H6 on Pt2In3(012)–Co.

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Supplementary Fig. 24: Comparison of DFT-calculated energies. EA of 3rd C–H activation, ΔE, and
Ead of C3H6 on the surface of PtSn, PtCoIn, and HEI with eight different adsorption sites and
conformations. Average of A1 to B4 is shown as “HEI ave.”

Supplementary Fig. 25: Adsorption sites and conformations of CO2, CO, and O on the HEI(004)
surfaces. Dotted triangles indicate the region where the adsorbates are involved.

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Supplementary Fig. 26: DFT-optimized structures of COx on HEI. Structures of initial (IS), transition
(TS), and final states (FS) in CO2 activation on the B3 site of HEI(004).

Supplementary Fig. 27: DFT-optimized structures of CO2 on PtSn. Structures of initial (IS), transition
(TS), and final states (FS) in CO2 activation on PtSn(110).

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Supplementary Fig. 28: DFT-optimized structures of CO2 on Pt–Co–In. Structures of initial (IS),
transition (TS), and final states (FS) in CO2 activation on the Co site of Pt2In3(012)–Co.

Supplementary Fig. 29: Comparison of CO2 activation energy. EA of CO2 activation on the surface
of PtSn, PtCoIn, and HEI with eight different adsorption sites and conformations. Average of A1 to B4
is shown as red dotted lines.

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Supplementary Fig. 30: An example of the GC chart. A GC chart obtained from the outlet gas in

CO2-ODP over HEI/CeO2.

Supplementary Fig. 31: DFT calculation for CO adsorption. Ead (eV) of CO on some atop sites of
HEI(004):B. Yellow dotted circles indicate the adsorption sites of CO. Upper insets show the optimized
structure of CO on Co and Pt atop sites. Sn and In showed very small negative values corresponding to
only physisorption. The largely negative values for Pt, Ni, and Co indicate that they are active for CO
pulse chemisorption and should be included in the estimation of metal dispersion and TOF.

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