Selective Hydrogenation of α,β‐Unsaturated aldehydes to Unsaturated alcohols: From Metal Nanoparticles to Nanoclusters and Single‐Atom Catalysts

Abstract

The selective hydrogenation of α,β‐unsaturated aldehydes is a pivotal process for synthesizing fine chemicals, fragrances, and pharmaceuticals. However, achieving high chemoselectivity to unsaturated alcohols remains a significant challenge due to the thermodynamic and kinetic preference for CC bond hydrogenation over CO bond reduction. To address this, various strategies for modulating the electronic and geometric structures of the supported metal catalysts have been developed. Recent advances demonstrate that downsizing the size of metal nanoparticles (NPs) to nanoclusters (NCs) or even single atoms (SAs) could effectively tune the substrate mode and reaction pathways, thereby enhancing activity, selectivity, and stability. In this review, we summarize recent progress in the selective hydrogenation of α,β‐unsaturated aldehydes into unsaturated alcohols over supported NPs, NCs, and SAs, with emphasis on the influence of the electronic and geometric structures of active sites on catalytic performance. Finally, we discuss current challenges and provide prospective on the rational design of efficient heterogeneous catalysts for this transformation.