A systematic theoretical study on FeO x -supported single-atom catalysts: M 1 /FeO x for CO oxidation

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1 Electronic Supplementary Material A systematic theoretical study on FeO x -supported single-atom catalysts: M 1 /FeO x for CO oxidation Jinxia Liang 1,2,3, Qi Yu 2, Xiaofeng Yang 4 ( ), Tao Zhang 4, and Jun Li 3 ( ) 1 Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Synergetic Innovation Center of Scientific Big Data for Advanced Manufacturing Technology, Guizhou Education University, Guiyang , China 2 Shaanxi Key Laboratory of Catalysis, Shaanxi University of Technology, Hanzhong , China 3 Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing , China 4 State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian , China Supporting information to Figure S1 Proposed reaction pathways for the formation of the first CO 2 on the surface of the M 1 /FeO x (M = Fe, Co; Ru, Rh; Os, Ir) catalysts via E-R mechanism. The schematic structures correspond to the structures of initial reactant (R), transition state (TS) and final product (P), respectively. Address correspondence to Xiaofeng Yang, yangxf2003@dicp.ac.cn; Jun Li, junli@tsinghua.edu.cn

2 Table S1 Optimized partial bond lengths of M 1 /FeO x (M = Fe, Co; Ru, Rh; Os, Ir) with the dissociated oxygen for formation of the first CO 2. Bond lengths/å I ii dis iii dis TS1 dis iv Fe-O A Fe-O A Fe-O B Fe-O C O B -O C (Fe)C-O B Co-O A Co-O A Co-O B Co-O C O B -O C (Co)C-O B Ru-O A Ru-O A Ru-O B Ru-O C O B -O C (Ru)C-O B Rh-O A Rh-O A Rh-O B Rh-O C O B -O C (Rh)C-O B Os-O A Os-O A Os-O B Os-O C O B -O C (Os)C-O B Ir-O A Ir-O A Ir-O B Ir-O C O B -O C (Ir)C-O B

3 Table S2 Calculated adsorption energies (E ad, ev) and dissociated adsorption energies (E dis, ev) of O 2 on oxygen-defective M 1 /FeO x (M = Fe, Co, Ni, Cu; Ru, Rh, Pd, Ag; Os, Ir, Au). Fe Co Ni Cu Ru Rh Pd Ag Os Ir Au E ad E dis Table S3 Optimized partial bond lengths of M 1 /FeO x (M = Fe, Co; Ru, Rh; Os, Ir) with the dissociated oxygen for the formation of the first CO 2 via E-R mechanism. Distance Fe Co 1 Ru 1 Rh 1 Os 1 Ir 1 C-O D (R) C-O B (R) M 1 -O B (R) C-O D (TS) C-O B (TS) M 1 -O B (TS) Table S4 Optimized partial bond lengths of M 1 /FeO x (M = Ni, Cu; Pd, Ag; Pt, Au) with molecular oxygen adsorption for the formation of the first CO 2. Bond lengths/å I ii ad iii ad TS1 ad Iv Ni-O A Ni-O A Ni-O B Ni-O C O B -O C (Ni)C-O B Cu-O A Cu-O A Cu-O B Cu-O C O B -O C (Cu)C-O B Pd-O A Pd-O A Pd-O B Pd-O C O B -O C (Pd)C-O B Ag-O A Ag-O A Ag-O B Ag-O C O B -O C Nano Research

4 (Continued) Bond lengths/å I ii ad iii ad TS1 ad Iv (Ag)C-O B Pt-O A Pt-O A Pt-O B Pt-O C O B -O C (Pt)C-O B Au-O A Au-O A Au-O B Au-O C O B -O C (Au)C-O B Table S5 Optimized partial bond lengths of M 1 /FeO x (M = Fe, Co; Rh, Pd; Ir, Au) for the formation of the second CO 2 in Pathway I and II Bond lengths/å v TS2 Vi TS3 Vii Fe-O A Fe-O A Fe-O C Fe-C Co-O A Co-O A Co-O C Co-C Rh-O A Rh-O A Rh-O C Rh-C Pd-O A Pd-O A Pd-O C Pd-C Ir-O A Ir-O A Ir-O C Ir-C Au-O A Au-O A Au-O C Au-C

5 Table S6 Optimized partial bond lengths of M 1 /FeO x (M = Ni, Cu; Ru, Ag; Os, Pt) for the formation of the second CO 2 in Pathway III Bond lengths/å v TS2 Vii Ni-O A Ni-O A Ni-O C Ni-C Cu-O A Cu-O A Cu-O C Cu-C Ru-O A Ru-O A Ru-O C Ru-C Ag-O A Ag-O A Ag-O C Ag-C Os-O A Os-O A Os-O C Os-C Pt-O A Pt-O A Pt-O C Pt-C Table S7 Calculated bond lengths of M 1 -O and Bader charges for M 1 single atoms in M 1 /FeO x (M = Fe, Co, Ni, Cu) with (i) and without oxygen vacancy (iv). Species M 1 -O bond length (Å) Valence electron (M) Bader charge of M (e) Fe 1 /FeO x -i 1.823, Fe 1 /FeO x -iv 1.805, 1.805, Fe-OH Fe-(OH) , Fe-(OH) , 1.816, Fe-(OH) , 1.800, 1.798, Co 1 /FeO x -i 1.739, Co 1 /FeO x -iv 1.771, 1.770, Co-OH Co-(OH) , Co-(OH) ,1.783, Co-(OH) , 1.788, 1.773, Ni 1 /FeO x -i 1.762, 1, Nano Research

6 (Continued) Species M 1 -O bond length (Å) Valence electron (M) Bader charge of M (e) Ni 1 /FeO x -iv 1.787, 1.787, Ni-OH Ni-(OH) , Ni-(OH) , 1.746, Ni-(OH) , 1.789, 1.783, Cu 1 /FeO x -i 1.816, Cu 1 /FeO x -iv 1.842, 1.842, Cu-OH Cu-(OH) , Cu-(OH) , 1.799, Cu-(OH) , 1.815, 1.818, * With core electrons represented by ECPs, the Fe(d 7 s 1 ), Co(d 8 s 1 ), Ni(d 8 s 2 ) and Cu(d 10 p 1 ) valance electrons configurations are used in the calculations. The M(OH) x (x = 1-4) molecules keep in a 20 Å 20 Å 20 Å cubic box. Table S8 Calculated bond lengths of M 1 -O, Bader charges for M 1 single atoms in M 1 /FeO x (M = Ru, Rh, Pd, Ag) with (i) and without oxygen vacancy (iv). Species M-O bond length (Å) Valence electron (M) Bader charge of M (e) Ru 1 /FeO x -i 1.870, Ru 1 /FeO x -iv 1.850, 1.850, Ru-OH Ru-(OH) , Ru-(OH) , 1.880, Ru-(OH) , 1.931, 1.931, Rh 1 /FeO x -i 1.908, Rh 1 /FeO x -iv 1.883, 1.883, Rh-OH Rh-(OH) , Rh-(OH) , 1.857, Rh-(OH) , 1.913, 1.913, Pd 1 /FeO x -i 2.049, Pd 1 /FeO x -iv 2.007, 2.008, Pd-OH Pd-(OH) , Pd-(OH) , 1.917, Pd-(OH) , 1.935, 1.941, Ag 1 /FeO x -i 2.299, Ag 1 /FeO x -iv 2.202, 2.202, Ag-OH Ag-(OH) , Ag-(OH) , 2.020, Ag-(OH) , 1.988, 1.988, * With core electrons represented by ECPs, the Ru(d 7 s 1 ), Rh(d 8 s 1 ), Pd(d 9 s 1 ) and Ag(d 10 s 1 ) valance electrons configurations are used in the calculations. The M(OH) x (x = 1-4) molecules keep in a 20 Å 20 Å 20 Å cubic box.

7 Table S9 Calculated bond lengths of M 1 -O, Bader charges for M 1 single atoms in M 1 /FeO x (M = Os, Ir, Pt, Au) with (i) and without oxygen vacancy (iv). Species M-O bond length (Å) Valence electron (M) Bader charge of M ( e ) Os 1 /FeO x -i 1.790, Os 1 /FeO x -iv 1.807, 1.797, Os-OH Os-(OH) , Os-(OH) , 1.858, Os-(OH) , 1.894, 1.902, Ir 1 /FeO x -i 1.851, Ir 1 /FeO x -iv 1.857, 1.857, Ir-OH Ir-(OH) , Ir-(OH) , 1.856, Ir-(OH) , 1.917, 1.910, Pt 1 /FeO x -i 1.930, Pt 1 /FeO x -iv 1.918, 1.919, Pt-OH Pt-(OH) , Pt-(OH) , 1.919, Pt-(OH) , 1.936, 1.944, Au 1 /FeO x -i 2.041, Au 1 /FeO x -iv 2.039, 2.040, Au-OH Au-(OH) , Au-(OH) , 2.023, * With core electrons represented by ECPs, the Os(d 6 s 2 ), Ir(d 8 s 1 ), Pt(d 9 s 1 ) and Au(d 10 s 1 ) valance electrons configurations are used in the calculations. The M(OH) x (x = 1-4) molecules keep in a 20 Å 20 Å 20 Å cubic box. Nano Research

Design of Efficient Catalysts with Double Transition Metal. Atoms on C 2 N Layer

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