Ames Laboratory; Chemistry
Ames Laboratory, Chemistry
Angewandte Chemie International Edition
Effective control on chemoselectivity in the catalytic hydrogenation of C=O over C=C bonds is uncommon with Pd-based catalysts because of the favored adsorption of C=C bonds on Pd surface. Here we report a unique orthorhombic PdSn intermetallic phase with unprecedented chemoselectivity toward C=O hydrogenation. We observed the formation and metastability of this PdSn phase in situ. During a natural cooling process, the PdSn nanoparticles readily revert to the favored Pd3Sn2 phase. Instead, using a thermal quenching method, we prepared a pure-phase PdSn nanocatalyst. PdSn shows an >96 % selectivity toward hydrogenating C=O bonds of various α,β-unsaturated aldehydes, highest in reported Pd-based catalysts. Further study suggests that efficient quenching prevents the reversion from PdSn- to Pd3Sn2-structured surface, the key to the desired catalytic performance. Density functional theory calculations and analysis of reaction kinetics provide an explanation for the observed high selectivity.
DOE Contract Number(s)
AC02-07CH11358; SC0018284; SC0013897; AC02-06CH11357
Iowa State University Digital Repository, Ames IA (United States)
Available for download on Friday, June 10, 2022