Deimel, Martin;
Prats, Hector;
Seibt, Michael;
Reuter, Karsten;
Andersen, Mie;
(2022)
Selectivity Trends and Role of Adsorbate–Adsorbate Interactions in CO Hydrogenation on Rhodium Catalysts.
ACS Catalysis
, 12
(13)
pp. 7907-7917.
10.1021/acscatal.2c02353.
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Abstract
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.
| Type: | Article |
|---|---|
| Title: | Selectivity Trends and Role of Adsorbate–Adsorbate Interactions in CO Hydrogenation on Rhodium Catalysts |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acscatal.2c02353 |
| Publisher version: | https://doi.org/10.1021/acscatal.2c02353 |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher's terms and conditions. |
| Keywords: | Adsorption, Aldehydes, Hydrocarbons, Nanoparticles, Selectivity |
| UCL classification: | UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering UCL > Provost and Vice Provost Offices > UCL BEAMS UCL |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10153272 |
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