Bond-oriented selective hydrogenation of unsaturated aldehyde by the tailoring of electronic metal-support interaction

The charge transfer between metal sites and support, widely known as electronic metal-support interaction (EMSI), is an impacting factor for the tailoring of the electronic structure of the hosted metal sites. Herein, the bond-oriented selective hydrogenation of α-methylacrolein has been observed over the Ag/SiO 2 and doped counterparts of Ag/SiZrO x , wherein the catalytic selectivity primarily relies on the electronic state of metal Ag sites. In the absence of electronic perturbation, the metal Ag 0 sites supported on the relatively inert SiO 2 exhibit the specific π-bonding configuration of chemisorbed intermediate, accounting for the C O bond-oriented hydrogenation for the methallyl alcohol. As a comparison, the distinct EMSI are observed over the doped Ag/SiZrO x and stimulates the state of electron-positive Ag δ+ sties. As a consequence, the specific δ-bonding configuration with the enhanced chemisorption strength is probed over the Ag δ+ sites, which contributes to the conjugated C C bond-oriented hydrogenation for isobutylaldehyde. These findings lay new fundamental basis on the selective hydrogenation of different unsaturated bonds of the multiple unsaturated molecules, and enrich the tool-box for the rational design of the heterogeneous catalysts for the bond-oriented selective hydrogenation of α,β-unsaturated aldehydes. • EMSI is employed as a facile strategy to tune the electronic state of the metal Ag sites. • The metal Ag sites with altered electronic structure are studied in detail to reveal the selectivity control. • The electronic structure of metal Ag sites exerts a profound influence on the chemisorption configuration and strength of reacting molecule. • The bond-oriented recognition is established to deepen the understanding for the rational design of Ag-based catalysts.