Selectivity Trends and Role of Adsorbate-Adsorbate Interactions in CO Hydrogenation on Rhodium Catalysts

TY - JOUR

T1 - Selectivity Trends and Role of Adsorbate-Adsorbate Interactions in CO Hydrogenation on Rhodium Catalysts

AU - Deimel, Martin

AU - Prats, Hector

AU - Seibt, Michael

AU - Reuter, Karsten

AU - Andersen, Mie

N1 - Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/7

Y1 - 2022/7

N2 - Predictive-quality computational modeling of heterogeneously catalyzed reactions has emerged as an important tool for the analysis and assessment of activity and activity trends. In contrast, more subtle selectivities and selectivity trends still pose a significant challenge to prevalent microkinetic modeling approaches that typically employ a mean-field approximation (MFA). Here, we focus on CO hydrogenation on Rh catalysts with the possible products methane, acetaldehyde, ethanol, and water. This reaction has already been subjected to a number of experimental and theoretical studies with conflicting views on the factors controlling activity and selectivity toward the more valuable higher oxygenates. Using accelerated first-principles kinetic Monte Carlo simulations and explicitly and systematically accounting for adsorbate-adsorbate interactions through a cluster expansion approach, we model the reaction on the low-index Rh(111) and stepped Rh(211) surfaces. We find that the Rh(111) facet is selective toward methane, while the Rh(211) facet exhibits a similar selectivity toward methane and acetaldehyde. This is consistent with the experimental selectivity observed for larger, predominantly (111)-exposing Rh nanoparticles and resolves the discrepancy with earlier first-principles MFA microkinetic work that found the Rh(111) facet to be selective toward acetaldehyde. While the latter work tried to approximately account for lateral interactions through coverage-dependent rate expressions, our analysis demonstrates that this fails to sufficiently capture concomitant correlations among the adsorbed reaction intermediates that crucially determine the overall selectivity.

AB - Predictive-quality computational modeling of heterogeneously catalyzed reactions has emerged as an important tool for the analysis and assessment of activity and activity trends. In contrast, more subtle selectivities and selectivity trends still pose a significant challenge to prevalent microkinetic modeling approaches that typically employ a mean-field approximation (MFA). Here, we focus on CO hydrogenation on Rh catalysts with the possible products methane, acetaldehyde, ethanol, and water. This reaction has already been subjected to a number of experimental and theoretical studies with conflicting views on the factors controlling activity and selectivity toward the more valuable higher oxygenates. Using accelerated first-principles kinetic Monte Carlo simulations and explicitly and systematically accounting for adsorbate-adsorbate interactions through a cluster expansion approach, we model the reaction on the low-index Rh(111) and stepped Rh(211) surfaces. We find that the Rh(111) facet is selective toward methane, while the Rh(211) facet exhibits a similar selectivity toward methane and acetaldehyde. This is consistent with the experimental selectivity observed for larger, predominantly (111)-exposing Rh nanoparticles and resolves the discrepancy with earlier first-principles MFA microkinetic work that found the Rh(111) facet to be selective toward acetaldehyde. While the latter work tried to approximately account for lateral interactions through coverage-dependent rate expressions, our analysis demonstrates that this fails to sufficiently capture concomitant correlations among the adsorbed reaction intermediates that crucially determine the overall selectivity.

KW - CO hydrogenation

KW - density functional theory

KW - heterogeneous catalysis

KW - kinetic Monte Carlo

KW - microkinetic modeling

UR - https://www.scopus.com/pages/publications/85134889048

U2 - 10.1021/acscatal.2c02353

DO - 10.1021/acscatal.2c02353

M3 - Journal article

AN - SCOPUS:85134889048

SN - 2155-5435

VL - 12

SP - 7907

EP - 7917

JO - ACS Catalysis

JF - ACS Catalysis

IS - 13

ER -