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Selectivity Effects in Bimetallic Catalysis: Role of the Metal Sites in the Decomposition of Formic Acid into H 2 and CO 2 by the Coinage Metal Binuclear Complexes [dppmMM′(H)] +
Author(s) -
Zavras Athanasios,
Krstić Marjan,
Dugourd Philippe,
BonačićKoutecký Vlasta,
O'Hair Richard A. J.
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201601675
Subject(s) - bimetallic strip , chemistry , dehydrogenation , catalysis , formic acid , inorganic chemistry , hydride , dissociation (chemistry) , reactivity (psychology) , metal , copper , decarboxylation , selectivity , hydrogen , photochemistry , organic chemistry , medicine , alternative medicine , pathology
Design of new bimetallic catalysts requires an understanding of how cooperative effects of the metal sites influences reactivity. Here we show how switching one or both of the silver atoms in binuclear silver hydride cations, [dppmAg 2 (H)] + (dppm=1,1‐Bis(diphenylphosphino)‐methane), with all combinations of copper and/or gold maintains selective dehydrogenation of formic acid, enhancing reactivity by up to 2 orders of magnitude. This is a key step in the selective, catalyzed extrusion of carbon dioxide from formic acid, HO 2 CH, with important applications in hydrogen storage and in situ generation of H 2 . Decarboxylation of [dppmMM′(O 2 CH)] + through collision induced dissociation regenerates [dppmMM′(H)] + . DFT calculations provide insights into these cooperative effects. The copper homobinuclear catalyst performs best overall.