Publication Date

6-10-2021

Department

Ames Laboratory; Chemistry

Campus Units

Ames Laboratory, Chemistry

OSTI ID+

1808608

Report Number

IS-J 10555

DOI

10.1002/anie.202106515

Journal Title

Angewandte Chemie International Edition

Volume Number

60

Issue Number

33

First Page

18309

Last Page

18317

Abstract

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

Language

en

Publisher

Iowa State University Digital Repository, Ames IA (United States)

Available for download on Friday, June 10, 2022

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