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Reversing Size‐Dependent Trends in the Oxidation of Copper Clusters through Support Effects
Author(s) -
Mammen Nisha,
Spanu Leonardo,
Tyo Eric C.,
Yang Bing,
Halder Avik,
Seifert Sönke,
Pellin Michael J.,
Vajda Stefan,
Narasimhan Shobhana
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201701355
Subject(s) - chemistry , stoichiometry , copper , cluster (spacecraft) , catalysis , oxidation state , nanoparticle , xanes , yield (engineering) , inorganic chemistry , chemical engineering , spectroscopy , metallurgy , organic chemistry , physics , materials science , quantum mechanics , computer science , engineering , programming language
Having the ability to tune the oxidation state of Cu nanoparticles is essential for their utility as catalysts. The degree of oxidation that maximizes product yield and selectivity is known to vary, depending on the particular reaction. Using first principles calculations and XANES measurements, we show that for subnanometer sizes in the gas phase, smaller Cu clusters are more resistant to oxidation. However, this trend is reversed upon deposition on an alumina support. We are able to explain this result in terms of strong cluster‐support interactions, which differ significantly for the oxidized and elemental clusters. The stable cluster phases also feature novel oxygen stoichiometries. Our results suggest that one can tune the degree of oxidation of Cu catalysts by optimizing not just their size, but also the support they are deposited on.