Supporting Information

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1 Supporting Information First-Principles-based Microkinetics Simulations of Synthesis Gas Conversion on a Stepped Rhodium Surface Ivo A.W. Filot, Robin J.P. Broos, Jeaphianne P.M. van Rijn, Gerardus J.H.A. van Heugten, Rutger A. van Santen and Emiel J.M. Hensen* Laboratory of Inorganic Materials Chemistry, Schuit Institute of Catalysis, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands e.j.m.hensen@tue.nl 1

2 Table S1: Overview of adsorption geometries of the all the surface intermediates on the Rh(211) surface. Adsorbate Site Geometry CO 1 T h Threefold C F Fourfold CH F Fourfold CH 2 B 2 Bridged CH 3 T Top site, step-edge CH 4 Gas phase Gas phase CHO B 2 Bridged CH 2 O B 2, T Bridged C, Top O CH 3 O T Top O CH 3 OH T Top O COH B 2 Bridged C CHOH B 2 Bridged C CH 2 OH B 2 Bridged C CC 1 F, T h C 1 fourfold, C 2 threefold CCH 1 F, T h C 1 fourfold, C 2 threefold CCH 2 1 F, T h C 1 fourfold, C 2 threefold CCH 3 F C 1 fourfold, methyl towards gas phase CHCH T 1 1 h, T f C 1 threefold, C 2 threefold CHCH 2 B 2 C 1 bridged CHCH 3 B 2 C 1 bridged CH 2 CH 2 T, T C 1 top, C 2 top CH 2 CH 3 B 2 C 1 bridged CH 3 CH 3 Gas phase Gas phase (eclipsed) CCO T 2 2 f, T h C 1 threefold, C 2 threefold, O on top CHCO 1 T f C 1 bridged, C 2 top CH 2 CO T 2 2 f, T h C 1 threefold, C 2 bridged, O top CCOH T 2 2 f, T h C 1 threefold, C 2 threefold CHCOH T 2 2 f, T h C 1 threefold, C 2 threefold CH 2 COH T 2 2 f, T h C 1 bridged, C 2 bridged, O top CH 3 COH 2 T f C 2 bridged, O top CCHO 2 T h C 1 threefold CHCHO 2 T h C 1 threefold CH 2 CHO T 2 2 h, T f C 1 bridged, C 2 top, O top CH 3 CHO B 2 C 2 top, O top CCHOH 1 T h C 1 threefold CHCHOH T 2 2 h, T f C 1 bridged, C 2 bridged CH 2 CHOH T 2 2 h, T f C 1 top, C 2 bridged CH 3 CHOH T 2 2 h, T f C 2 bridged CCH 2 O 2 T h C 1 threefold, O top CHCH 2 O 2 T h C 1 bridged, O top CH 2 CH 2 O T 2 2 h, T f C 1 top, C 2 top, O bridged CH 3 CH 2 O B 2 C 2 -H top, O top CCH 2 OH 2 T h C 1 bridged CHCH 2 OH T 2 2 h, T f C 1 bridged CH 2 CH 2 OH 2 T f C 2 bridged, O top CH 3 CH 2 OH Gas phase Gas phase 2

3 Table S2: Direct and hydrogen-mediated CO dissociation on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zeropoint energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 1 CO* + * C* + O* CO* + H* COH* CO* + H* CHO* COH* + * C* + OH* CHO* + * CH* + O*

4 Table S3: Methanation pathway from adsorbed carbon on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 6 C* + H * CH* + * CH* + H* CH 2 * + * CH 2 * + H* CH 3 * + * CH 3 * + H* CH 4 + 2*

5 Table S4: CH x -OH y hydrogenation reactions on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 10 CHO* + H* CHOH* + * CH 2 O* + H* CH 2 OH* + * CH 3 O* + H* CH 3 OH* + * CHO* + H* CH 2 O* + * CH 2 O* + H* CH 3 O* + * COH* + H* CHOH* + * CHOH* + H* CH 2 OH* + * CH 2 OH* + H* CH 3 OH* + *

6 Figure S1: Schematic representation of CH x +OH y coupling. The CH x moiety resides at the step-edge. OH y insertion proceeds by migrating the OH y moiety to the upper-edge, thus enabling the formation of an C O bond. 6

7 Table S5: CH x +OH y coupling reactions on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 18 CH* + OH* CHOH* + * CH 2 * + OH* CH 2 OH* + * CH 3 * + OH* CH 3 OH* + * CH 2 * + O* CH 2 O* + * CH 3 * + O* CH 3 O* + *

8 Table S6: CH x +CH y coupling reactions on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 23 C* + C* CC* + * C* + CH* CCH* + * C* + CH 3 * CCH 3 * + * CH* + CH* CHCH* + * CH* + CH 3 * CHCH 3 * CH 2 * + CH 2 * CH 2 CH 2 *

9 Figure S2: Schematic representation of CH x +CH y coupling. One of the CH x moieties resides in the step. CH y insertion proceeds by migrating the CH y moiety to the lower-edge, thus facilitating the formation of an C C bond. 9

10 Table S7: CH x +CO coupling reactions on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 29 C* + CO* CCO* CH* + CO* CHCO* CH 2 * + CO* CH 2 CO*

11 Table S8: CH x CH y hydrogenation reactions on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 32 CC* + H* CCH* + * CCH* + H* CCH 2 * + * CCH 2 * + H* CCH 3 * + * CCH* + H* CHCH* + * CCH 2 * + H* CHCH 2 * + * CCH 3 * +H* CHCH 3 * +* CHCH* + H* CHCH 2 * + * CHCH 2 * + H* CHCH 3 * + * CHCH 2 * + H* CH 2 CH 2 * + * CHCH 3 * + H* CH 2 CH 3 * + * CH 2 CH 2 * + H* CH 2 CH 3 * + * CH 2 CH 3 * + H* CH 3 CH 3 * + *

12 Table S9: CH x CH y O z hydrogenation reactions on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 44 CCO* + H* CCHO* + * CCO* + H* CCHO* + * CCO* + H* CCOH* + * CHCO* + H* CH 2 CO* + * CHCO* + H* CHCHO* + * CHCO* + H* CHCOH* + * CCHO* + H* CHCHO* + * CCHO* + H* CCH 2 O* + * CCHO* + H* CCHOH* + * CCOH* + H* CHCOH* + * CCOH* + H* CCHOH* + * CH 2 CO* + H* CH 2 *CHO* + * CH 2 CO* + H* CH 2 COH* + * CHCHO* + H* CH 2 CHO* + * CHCHO* + H* CHCH 2 O* + * CHCHO* + H* CHCHOH* + * CHCOH* +H* CH 2 COH* + * CHCOH* + H* CHCHOH* + * CCH 2 O* + H* CHCH 2 O* + * CCH 2 O* + H* CCH 2 OH* + * CCHOH* + H* CHCHOH* + * CCHOH* + H* CCH 2 OH* CH 2 CHO* + H* CH 3 CHO* + * CH 2 CHO* + H* CH 2 CH 2 O* + * CH 2 CHO* + H* CH 2 CHOH* CH 2 COH* + H* CH 3 COH* + * CH 2 COH* + H* CH 2 CHOH* + * CHCH 2 O* + H* CH 2 CH 2 O* + * CHCH 2 O* + H* CHCH 2 OH* + * CHCHOH* + H* CH 2 CHOH* + * CHCHOH* + H* CHCH 2 OH* + * CCH 2 OH* + H* CHCH 2 OH* + * CH 3 CHO* + H* CH 3 CH 2 O* + * CH 3 CHO* + H* CH 3 CHOH* + * CH 3 COH* + H* CH 3 CHOH* + * CH 2 CH 2 O* + H* CH 3 CH 2 O* + * CH 2 CH 2 O* + H* CH 2 CH 2 OH* + * CH 2 CHOH* + H* CH 3 CHOH* + * CH 2 CHOH* + H* CH 2 CH 2 OH* + * CHCH 2 OH* + H* CH 2 CH 2 OH* + * CH 3 CH 2 O* + H* CH 3 CH 2 OH* + * CH 3 CHOH* + H* CH 3 CH 2 OH* + * CH 2 CH 2 OH* + H* CH 3 CH 2 OH* + *

13 Table S10: Oxygen removal reactions on Rh(211). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-point-energy corrections. All elementary reaction steps are zero-point energy and migration corrected. (see the method section for more information) Index Elementary reaction Forward E act Backward E act 87 O* + H* OH* + * OH* + OH* H 2 O* + O* OH* + H* H 2 O* + * CO* + O* CO 2 * + *

14 Table S11: Reaction barriers for C-O bond scission extrapolated from HC-O bond scission elementary reaction step. Index Elementary reaction Forward E act Backward E act X1 CCO* + * CC* + O* X2 CHCO* + H* CCH* + O* X3 CH 2 CO* + H* CCH 2 * + O*

15 Selectivity [-] CH3CH2OH CH3CHO CH2CH2 CH2O CH4 CO Temperature [K] Figure S3: Carbon based product selectivity (including CO 2 ) as a function of temperature in the microkinetic simulation CO hydrogenation over the Rh(211) surface. 15

16 Figure S4: Oxygen based product selectivity as a function of temperature in the microkinetic simulation CO hydrogenation over the Rh(211) surface. 16

17 Figure S5: Surface coverage as a function of temperature. Only species with a surface coverage higher than 1% are included. 17

18 Figure S6a: Apparent activation energy as function of temperature for the microkinetics simulation on Rh(211). The dashed areas indicate values typically reported in experimental studies. 1-5 Figure S6b: Reaction order as a function of temperature for the microkinetics simulation on Rh(211). The dashed areas indicate values typically reported in experimental studies

19 Table S12: Ethanol formation on Rh(111). The data has been taken from the work of Choi and Liu. 6 Index Elementary reaction Forward E act Backward E act C1 HCO* + H* CH 2 O* + * 42 0 C2 CH 2 O* + H* CH 3 O* + * C3 CH 3 O* + H* CH 3 OH* + * C4 CO* + H* HCO* + * C5 CH 3 * + O* CH 3 O* + * C6 CH 3 * + CO* CH 3 CO + * C7 CH 3 CO* + H* CH 3 CHO* + * C8 CH 3 CO* + H* CH 3 COH* + * 82 9 C9 CH 3 COH* + H* CH 3 CHOH* + * C10 CH 3 CHOH* + H* CH 3 CH 2 OH* + *

20 Table S13: Methanation on Rh(111). The reported forward and reverse energies are in relation to the most stable states found for the reactants and products and include zero-pointenergy corrections. The data has been taken from the work of Zhu et al. 7 Index Elementary reaction Forward E act Backward E act Z1 CO* + * CO* + * Z2 C* + H* CH* + * Z3 CH* + H* CH 2 * + * 62 3 Z4 CH 2 * + H* CH 3 * + * Z5 CH 3 * + H* CH 4 + 2* Z6 CO* + H* CHO* + * Z7 CO* + H* COH* + * Z8 CHO* + * CH* + O* Z9 COH* + * C* + OH* Z10 O* + H* OH* + * Z11 OH* + H* H 2 O * + * Z12 2OH* H 2 O* + O*

21 Table S14: Overview of rate constants of all relevant elementary reaction steps at T=700K. Index Elementary reaction Forward rate constant Backward rate constant 1 CO* + * C* + O* 6.16E E+05 2 CO* + H* COH* 5.23E E+08 3 CO* + H* CHO* 2.44E E+11 4 COH* + * C* + OH* 2.68E E-03 5 CHO* + * CH* + O* 3.37E E-04 6 C* + H * CH* + * 3.43E E+06 7 CH* + H* CH 2 * + * 4.39E E+09 8 CH 2 * + H* CH 3 * + * 2.03E E+09 9 CH 3 * + H* CH 4 + 2* 7.25E E CHO* + H* CHOH* + * 2.73E E CH 2 O* + H* CH 2 OH* + * 3.29E E CH 3 O* + H* CH 3 OH* + * 6.00E E CHO* + H* CH 2 O* + * 9.23E E CH 2 O* + H* CH 3 O* + * 2.42E E COH* + H* CHOH* + * 1.62E E CHOH* + H* CH 2 OH* + * 3.38E E CH 2 OH* + H* CH 3 OH* + * 6.19E E CH* + OH* CHOH* + * 5.57E E CH 2 * + OH* CH 2 OH* + * 1.16E E CH 3 * + OH* CH 3 OH* + * 3.82E E CH 2 * + O* CH 2 O* + * 6.44E E CH 3 * + O* CH 3 O* + * 5.71E E C* + C* CC* + * 2.91E E C* + CH* CCH* + * 2.89E E C* + CH 3 * CCH 3 * + * 1.24E E CH* + CH* CHCH* + * 9.84E E CH* + CH 3 * CHCH 3 * 1.61E E CH 2 * + CH 2 * CH 2 CH 2 * 2.53E E C* + CO* CCO* 1.07E E CH* + CO* CHCO* 1.37E E CH 2 * + CO* CH 2 CO* 1.36E E CC* + H* CCH* + * 5.79E E CCH* + H* CCH 2 * + * 2.00E E CCH 2 * + H* CCH 3 * + * 2.79E E CCH* + H* CHCH* + * 2.30E E CCH 2 * + H* CHCH 2 * + * 3.23E E CCH 3 * +H* CHCH 3 * +* 1.25E E CHCH* + H* CHCH 2 * + * 2.38E E CHCH 2 * + H* CHCH 3 * + * 8.45E E CHCH 2 * + H* CH 2 CH 2 * + * 8.68E E CHCH 3 * + H* CH 2 CH 3 * + * 2.92E E CH 2 CH 2 * + H* CH 2 CH 3 * + * 1.36E E CH 2 CH 3 * + H* CH 3 CH 3 * + * 1.62E E CCO* + H* CCHO* + * 1.03E E CCO* + H* CCHO* + * 1.63E E CCO* + H* CCOH* + * 3.21E E CHCO* + H* CH 2 CO* + * 3.02E E CHCO* + H* CHCHO* + * 1.05E E CHCO* + H* CHCOH* + * 8.79E E CCHO* + H* CHCHO* + * 4.02E E CCHO* + H* CCH 2 O* + * 4.65E E CCHO* + H* CCHOH* + * 3.92E E CCOH* + H* CHCOH* + * 3.97E E CCOH* + H* CCHOH* + * 8.00E E+00 21

22 55 CH 2 CO* + H* CH 2 *CHO* + * 1.97E E CH 2 CO* + H* CH 2 COH* + * 4.75E E CHCHO* + H* CH 2 CHO* + * 6.40E E CHCHO* + H* CHCH 2 O* + * 9.67E E CHCHO* + H* CHCHOH* + * 4.39E E CHCOH* +H* CH 2 COH* + * 8.84E E CHCOH* + H* CHCHOH* + * 1.00E E CCH 2 O* + H* CHCH 2 O* + * 5.51E E CCH 2 O* + H* CCH 2 OH* + * 3.91E E CCHOH* + H* CHCHOH* + * 1.88E E CCHOH* + H* CCH 2 OH* 5.37E E CH 2 CHO* + H* CH 3 CHO* + * 7.78E E CH 2 CHO* + H* CH 2 CH 2 O* + * 1.06E E CH 2 CHO* + H* CH 2 CHOH* 1.07E E CH 2 COH* + H* CH 3 COH* + * 2.77E E CH 2 COH* + H* CH 2 CHOH* + * 6.81E E CHCH 2 O* + H* CH 2 CH 2 O* + * 3.18E E CHCH 2 O* + H* CHCH 2 OH* + * 5.32E E CHCHOH* + H* CH 2 CHOH* + * 1.38E E CHCHOH* + H* CHCH 2 OH* + * 3.86E E CCH 2 OH* + H* CHCH 2 OH* + * 1.81E E CH 3 CHO* + H* CH 3 CH 2 O* + * 4.18E E CH 3 CHO* + H* CH 3 CHOH* + * 1.73E E CH 3 COH* + H* CH 3 CHOH* + * 1.26E E CH 2 CH 2 O* + H* CH 3 CH 2 O* + * 2.97E E CH 2 CH 2 O* + H* CH 2 CH 2 OH* + * 1.58E E CH 2 CHOH* + H* CH 3 CHOH* + * 1.58E E CH 2 CHOH* + H* CH 2 CH 2 OH* + * 3.97E E CHCH 2 OH* + H* CH 2 CH 2 OH* + * 6.91E E CH 3 CH 2 O* + H* CH 3 CH 2 OH* + * 4.02E E CH 3 CHOH* + H* CH 3 CH 2 OH* + * 7.09E E CH 2 CH 2 OH* + H* CH 3 CH 2 OH* + * 1.90E E O* + H* OH* + * 3.66E E OH* + OH* H 2 O* + O* 2.77E E OH* + H* H 2 O* + * 2.53E E+06 22

23 Table S15: Overview of rate constants of all relevant elementary reaction steps at T=1000K. Index Elementary reaction Forward rate constant Backward rate constant 1 CO* + * C* + O* 4.60E E+07 2 CO* + H* COH* 2.10E E+09 3 CO* + H* CHO* 1.19E E+12 4 COH* + * C* + OH* 1.72E E+01 5 CHO* + * CH* + O* 2.39E E+00 6 C* + H * CH* + * 2.12E E+08 7 CH* + H* CH 2 * + * 2.44E E+10 8 CH 2 * + H* CH 3 * + * 1.11E E+10 9 CH 3 * + H* CH 4 + 2* 9.54E E CHO* + H* CHOH* + * 9.91E E CH 2 O* + H* CH 2 OH* + * 1.06E E CH 3 O* + H* CH 3 OH* + * 1.32E E CHO* + H* CH 2 O* + * 3.23E E CH 2 O* + H* CH 3 O* + * 4.49E E COH* + H* CHOH* + * 4.46E E CHOH* + H* CH 2 OH* + * 8.70E E CH 2 OH* + H* CH 3 OH* + * 7.73E E CH* + OH* CHOH* + * 3.56E E CH 2 * + OH* CH 2 OH* + * 5.08E E CH 3 * + OH* CH 3 OH* + * 2.85E E CH 2 * + O* CH 2 O* + * 8.62E E CH 3 * + O* CH 3 O* + * 1.84E E C* + C* CC* + * 2.45E E C* + CH* CCH* + * 5.84E E C* + CH 3 * CCH 3 * + * 5.72E E CH* + CH* CHCH* + * 3.06E E CH* + CH 3 * CHCH 3 * 1.14E E CH 2 * + CH 2 * CH 2 CH 2 * 1.21E E C* + CO* CCO* 1.18E E CH* + CO* CHCO* 1.55E E CH 2 * + CO* CH 2 CO* 2.79E E CC* + H* CCH* + * 1.37E E CCH* + H* CCH 2 * + * 9.55E E CCH 2 * + H* CCH 3 * + * 1.72E E CCH* + H* CHCH* + * 8.78E E CCH 2 * + H* CHCH 2 * + * 9.87E E CCH 3 * +H* CHCH 3 * +* 2.40E E CHCH* + H* CHCH 2 * + * 4.35E E CHCH 2 * + H* CHCH 3 * + * 8.31E E CHCH 2 * + H* CH 2 CH 2 * + * 2.61E E CHCH 3 * + H* CH 2 CH 3 * + * 1.13E E CH 2 CH 2 * + H* CH 2 CH 3 * + * 2.71E E CH 2 CH 3 * + H* CH 3 CH 3 * + * 1.77E E CCO* + H* CCHO* + * 1.45E E CCO* + H* CCHO* + * 5.51E E CCO* + H* CCOH* + * 1.61E E CHCO* + H* CH 2 CO* + * 4.72E E CHCO* + H* CHCHO* + * 3.05E E CHCO* + H* CHCOH* + * 1.35E E CCHO* + H* CHCHO* + * 1.53E E CCHO* + H* CCH 2 O* + * 8.48E E CCHO* + H* CCHOH* + * 7.52E E CCOH* + H* CHCOH* + * 2.45E E CCOH* + H* CCHOH* + * 1.76E E+01 23

24 55 CH 2 CO* + H* CH 2 *CHO* + * 1.55E E CH 2 CO* + H* CH 2 COH* + * 2.19E E CHCHO* + H* CH 2 CHO* + * 6.29E E CHCHO* + H* CHCH 2 O* + * 3.69E E CHCHO* + H* CHCHOH* + * 1.25E E CHCOH* +H* CH 2 COH* + * 3.49E E CHCOH* + H* CHCHOH* + * 7.99E E CCH 2 O* + H* CHCH 2 O* + * 3.58E E CCH 2 O* + H* CCH 2 OH* + * 4.72E E CCHOH* + H* CHCHOH* + * 3.79E E CCHOH* + H* CCH 2 OH* 8.38E E CH 2 CHO* + H* CH 3 CHO* + * 8.92E E CH 2 CHO* + H* CH 2 CH 2 O* + * 1.28E E CH 2 CHO* + H* CH 2 CHOH* 1.29E E CH 2 COH* + H* CH 3 COH* + * 1.39E E CH 2 COH* + H* CH 2 CHOH* + * 2.15E E CHCH 2 O* + H* CH 2 CH 2 O* + * 6.01E E CHCH 2 O* + H* CHCH 2 OH* + * 3.83E E CHCHOH* + H* CH 2 CHOH* + * 7.32E E CHCHOH* + H* CHCH 2 OH* + * 3.09E E CCH 2 OH* + H* CHCH 2 OH* + * 3.84E E CH 3 CHO* + H* CH 3 CH 2 O* + * 1.41E E CH 3 CHO* + H* CH 3 CHOH* + * 1.79E E CH 3 COH* + H* CH 3 CHOH* + * 1.44E E CH 2 CH 2 O* + H* CH 3 CH 2 O* + * 2.00E E CH 2 CH 2 O* + H* CH 2 CH 2 OH* + * 3.08E E CH 2 CHOH* + H* CH 3 CHOH* + * 3.08E E CH 2 CHOH* + H* CH 2 CH 2 OH* + * 1.02E E CHCH 2 OH* + H* CH 2 CH 2 OH* + * 1.75E E CH 3 CH 2 O* + H* CH 3 CH 2 OH* + * 6.61E E CH 3 CHOH* + H* CH 3 CH 2 OH* + * 3.82E E CH 2 CH 2 OH* + H* CH 3 CH 2 OH* + * 9.07E E O* + H* OH* + * 1.14E E OH* + OH* H 2 O* + O* 9.70E E OH* + H* H 2 O* + * 6.63E E+07 24

25 Figure S7a: Rates of formation of C 1 and C 2 products and consumption of H 2 and CO in the microkinetics simulation of CO hydrogenation on Rh(111) using the data of Choi and Liu 6. Figure S7b: Rates of formation of C 1 and C 2 products and consumption of H 2 and CO in the microkinetics simulation of CO hydrogenation using kinetic parameters for methanation for the Rh(111) 7 (Table S13) and, for all other elementary reaction steps, the dataset obtained in the present work for the Rh(211) surface. 25

26 Figure S7c: Rates of formation of C 1 and C 2 products and consumption of H 2 and CO in the microkinetics simulation of CO hydrogenation on Rh(111) using the data of Choi and Liu 6 and (efficient) CO dissociation on Rh(211) reported by Filot et. al

27 Derivation of Degree of Selectivity Control Given that the degree of rate control is defined as: χ c,i = ( r c k i rc ) k i kj i,,ki = ( ln(r m) ln(k i ) ) k j i,,k i then we can define a degree of selectivity control as ε c,i = ( η c k i ) k i kj i,,ki Where η c is the selectivity of component c. By using the natural logarithm in the derivative, we get the following expression ε c,i = η c ( ln(η c ) ln(k i ) ) k j i,,k i Which can be rewritten as (note that the stoichiometric correction factor cancels out, because it does not depend on k i ) ln ( r c rr ) ε c,i = η c ln(k i ) ( ) kj i,,k i And by using the property ln(a/b) = ln(a) ln (b), we get ε c,i = η c (( ln(r c) ln(k i ) ) k j i,,k i ( ln(r R ) ln(k i ) ) k j i,,k i ) which can be rewritten as ε c,i = η c (χ c,i χ R,i ) 27

28 Figure S8: : Degree of rate control analysis with CO as the key component as a function of temperature. Only elementary reaction steps with an absolute degree of rate control value larger than 0.01 have been included. 28

29 Figure S9: Degree of selectivity control correlations between ethanol and other competing products. Elementary reaction steps are color-coded according to their influence on the product selectivities. A red elementary reaction step points to an opposite effect between the two products, green indicates that the products have a common rate-controlling reaction, and blue indicates that the two products have a common rate-inhibiting step. 29

30 Figure S10: (left) Reaction pathways for CO hydrogenation to C 2 products on Rh(211) (p = 20 atm, T = 1000 K, H 2 /CO ratio = 2); (right) Overview of the reaction network based on molar rates for the formation of methane from CO and H 2. The arrows indicate the existence of internal reaction loops that do not contribute to the overall CO consumption rate. 30

31 Table S11: Geometries of the initial, transition and final states of all elementary reaction steps for CO hydrogenation over a Rh(211) surface. The indices in the first column refer to the elementary reaction steps as found in Tables S

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46 90 46

47 References 1. Underwood, R. P.; Bell, A. T., Applied Catalysis, 1986, 21 (1), Sexton, B. A.; Somorjai, G. A., J. Catal., 1977, 46 (2), Gronchi, P.; Marengo, S.; Mazzocchia, C.; Tempesti, E.; Del Rosso, R., React. Kinet. Catal. Lett., 1997, 60 (1), Mazzocchia, C.; Tempesti, E.; Gronchi, P.; Giuffrè, L.; Zanderighi, L., J. Catal., 1988, 111 (2), Levin, M. E.; Salmeron, M.; Bell, A. T.; Somorjai, G. A., J. Catal., 1987, 106 (2), Choi, Y.; Liu, P., J. Am. Chem. Soc., 2009, 131 (36), Zhu, T. W.; van Grootel, P. W.; Filot, I. A. W.; Sun, S. G.; van Santen, R. A.; Hensen, E. J. M., J. Catal., 2013, 297, Filot, I. A. W.; Shetty, S. G.; Hensen, E. J. M.; van Santen, R. A., J. Phys. Chem. C, 2011, 115 (29),