First-Principles Kinetic Monte Carlo Simulations for Single-Cluster Catalysis: Study of CO₂ and CH₄ Conversion on Pt/HfC

Abstract

The deposition of small transition metal (TM) clusters on transition metal carbides (TMC) gives rise to bifunctional catalysts with multiple active sites. This family of single-cluster catalysts (SCCs) offers exciting opportunities for enabling a wider range of chemical reactions owing to their strong metal-support interactions, which drastically modify the catalytic properties of the supported metal atoms. In this work, we use first-principles Kinetic Monte Carlo (KMC) simulations to investigate the conversion of CO₂ and CH₄ on Pt/HfC, which was identified as the most promising TM/TMC combination in a previous DFT-based high-throughput screening study. We analyze the interplay between the Pt clusters and the HfC support, evaluating the catalytic activity, selectivity, and adlayer composition across a broad range of operating conditions (p A , p B , and T) and Pt loadings. This study evaluates five different industrial processes, including the dry reforming (DRM), steam reforming (SRM), and partial oxidation (POM) of methane, as well as the water-gas shift (WGS) reaction and its reverse (RWGS). Our results demonstrate that the deposition of Pt clusters on HfC systematically enhances the catalytic performance, even at a Pt loading as low as ∼0.02 ML. This work illustrates the extensive catalytic benefits of SCCs and highlights the importance of considering diffusion steps and lateral interactions in kinetic modeling.