Deciphering Metal–Oxide and Metal–Metal Interplay via Surface Organometallic Chemistry: A Case Study with CO₂ Hydrogenation to Methanol

Processes that rely on heterogeneous catalysts underpin the production of bulk chemicals and fuels. In spite of this, understanding of the interplay between the structure and reactivity of these complex materials remains elusive-rendering rational improvement of existing systems challenging. Herein, we describe efforts to understand complex materials capable of selective thermochemical conversion of CO2 to methanol using a surface organometallic chemistry (SOMC) approach. In particular, we focus on the remarkable, but often subtle, roles of metal-metal synergy and metal-support interfaces in determining the reactivity of many different systems for the conversion of CO2 to methanol. Specifically, we explore synthetic and analytical strategies for the systematic study of synergistic behaviors of multi-component catalytic systems in the context of CO2 hydrogenation, and we discuss how the insights obtained can inform the design of materials. We also address limitations of the approach employed and opportunities to expand upon the observations emerging from this work, before attempting to establish transposable and generalizable trends for Cu-based catalysts and beyond.