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Selective C−H Bond Cleavage in Methane by Small Gold Clusters
Author(s) -
Lang Sandra M.,
Bernhardt Thorsten M.,
Chernyy Valeriy,
Bakker Joost M.,
Barnett Robert N.,
Landman Uzi
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201706009
Subject(s) - methane , chemistry , catalysis , cleave , hydrocarbon , dissociation (chemistry) , selectivity , natural gas , bond cleavage , cluster (spacecraft) , photochemistry , combinatorial chemistry , nanotechnology , organic chemistry , materials science , enzyme , computer science , programming language
Methane represents the major constituent of natural gas. It is primarily used only as a source of energy by means of combustion, but could also serve as an abundant hydrocarbon feedstock for high quality chemicals. One of the major challenges in catalysis research nowadays is therefore the development of materials that selectively cleave one of the four C−H bonds of methane and thus make it amenable for further chemical conversion into valuable compounds. By employing infrared spectroscopy and first‐principles calculations it is uncovered herein that the interaction of methane with small gold cluster cations leads to selective C−H bond dissociation and the formation of hydrido methyl complexes, H‐Au x + ‐CH 3 . The distinctive selectivity offered by these gold clusters originates from a fine interplay between the closed‐shell nature of the d states and relativistic effects in gold. Such fine balance in fundamental interactions could prove to be a tunable feature in the rational design of a catalyst.