Unravelling structure sensitivity in CO2 hydrogenation over nickel

Continuous efforts in the field of materials science have allowed us to generate smaller and smaller metal nanoparticles, creating new opportunities to understand catalytic properties that depend on the metal particle size. Structure sensitivity is the phenomenon where not all surface atoms in a supported metal catalyst have the same activity. Understanding structure sensitivity can assist in the rational design of catalysts, allowing control over mechanisms, activity and selectivity, and thus even the viability of a catalytic reaction. Here, using a unique set of well-defined silica-supported Ni nanoclusters (1–7 nm) and advanced characterization methods, we prove how structure sensitivity influences the mechanism of catalytic CO2 reduction, the nature of which has been long debated. These findings bring fundamental new understanding of CO2 hydrogenation over Ni and allow us to control both activity and selectivity, which can be a means for CO2 emission abatement through its valorization as a low- or even negative-cost feedstock on a low-cost transition-metal catalyst. Understanding structure sensitivity—how the structural morphology of a surface influences a catalytic reaction—is important for rational catalyst design. Here, the synthesis and in-depth characterization of a range of size-defined nickel clusters shows the structure sensitivity of CO2 hydrogenation, and also identifies two size-dependent reaction pathways.