Dynamic and Intermediate-Specific Local Coverage Controls the Syngas Conversion on Rh(111) Surfaces: An <i>Operando</i> 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.