Insights into the Interfacial Effects in Heterogeneous Metal Nanocatalysts toward Selective Hydrogenation

摘要

Heterogeneous metal catalysts are distinguished by their structure inhomogeneity and complexity. The chameleonic nature of heterogeneous metal catalysts have prevented us from deeply understanding their catalytic mechanisms at the molecular level and thus developing industrial catalysts with perfect catalytic selectivity toward desired products. This Perspective aims to summarize recent research advances in deciphering complicated interfacial effects in heterogeneous hydrogenation metal nanocatalysts toward the design of practical heterogeneous catalysts with clear catalytic mechanism and thus nearly perfect selectivity. The molecular insights on how the three key components (i.e., catalytic metal, support, and ligand modifier) of a heterogeneous metal nanocatalyst induce effective interfaces determining the hydrogenation activity and selectivity are provided. The interfaces influence not only the H_2 activation pathway but also the interaction of substrates to be hydrogenated with catalytic metal surface and thus the hydrogen transfer process. As for alloy nanocatalysts, together with the electronic and geometric ensemble effects, spillover hydrogenation occurring on catalytically "inert" metal by utilizing hydrogen atom spillover from active metal is highlighted. The metal-support interface effects are then discussed with emphasis on the molecular involvement of ligands located at the metal-support interface as well as cationic species from the support in hydrogenation. The mechanisms of how organic modifiers, with the ability to induce both 3D steric and electronic effects, on metal nanocatalysts manipulate the hydrogenation pathways are demonstrated. A brief summary is finally provided together with a perspective on the development of enzyme-like heterogeneous hydrogenation metal catalysts.