Dynamic and Intermediate-Specific Local Coverage Controls the Syngas Conversion on Rh(111) Surfaces: An Operando Theoretical Analysis

Heterogeneous catalysts often work under high pressure with high surface coverage, which can markedly affect their catalytic performances. Herein, we propose a protocol for an operando theoretical analysis to explore, accurately and efficiently, the on-site dynamics of the adlayer using syngas conversion on Rh(111) surfaces as an example. While it is often emphasized that coadsorbates influence the intermediate reactivity greatly, our work demonstrates here that the intermediate can induce a local environment that is optimal to itself so as to optimize the reaction paths. The commonly used mean-field models fail to account for this dynamic and intermediate-specific local coverage change and thus fail to reproduce the experimental observations on the pressure-dependent selectivity changes. The present study provides new insights into how local surface coverage tunes the catalysis, highlighting the importance of the operando theoretical analysis in understanding the catalytic phenomena and providing a powerful tool for rational design of catalysts.

Automated summary

This study introduces a new protocol for an operando theoretical analysis, demonstrating the significance of local surface coverage in tuning catalysis through investigations on the conversion of Syngas on Rh(111) surfaces.