Non-Photochemical Origin of Selectivity Difference between Light and Dark Catalytic Conditions

The interest in introducing light into heterogeneous catalysis is driven not only by the urgent need of replacing fossil energy but also by the promise of controlling product selectivity by light. The product selectivity differences observed in recent studies between light and dark reactions are often attributed to photochemical effects. Here, we report the discovery of a non-photochemical origin of selectivity difference, at essentially the same CO₂ conversion rate, between photothermal and thermal CO₂ hydrogenation reactions over a Ru/TiO_2- catalyst. While the presence of the photochemical effect from ultraviolet light is confirmed, it merely enhances the catalytic activity. Systematic investigation reveals that the gradual formation of an adsorbate-mediated strong metal-support interaction under catalytic conditions is responsible for the variation in the catalytic selectivity. We demonstrate that differences in product selectivity under light/dark reactions do not necessarily originate from photochemical effects. Our study refines the basis for determining photochemical effects and highlights the importance of excluding non-photochemical effects in mechanistic studies of light-controlled product selectivity.