Theoretical study of selective hydrogenolysis of methyl vinyl carbinol over Au-Ni bimetallic catalyst: Toward constructing a working hypothesis for the role of dichloroethane solvent and perimeter sites

[Display omitted] •The hydrogenation of benzylic alcohols on Au-Ni bimetal catalyst was surveyed.•DCE solvent directly reacted with the catalyst to produce HCl and the carbocation.•The presence of the exposed Au site is indispensable for producing HCl.•The Ni perimeter site promoted the hydrogenation of the carbocation. Au-Ni bimetallic nanoparticles catalyze the hydrogenolysis of the hydroxy group of benzylic alcohols by activating H2 with dichloroethane solvent. To propose a working hypothesis for their reaction mechanism, we performed theoretical calculations for the hydroxylation of methyl vinyl carbinol over the Au1Ni19 cluster. The results showed that there’re two reaction cycles, depending on the presence of HCl. Firstly, the solvent acted as a sacrificial reagent to produce the carbocation intermediate, while HCl was produced in other reaction. It was found that the presence of the exposed Au site played an important role for producing HCl and subsequent hydrogenolysis.