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Searching for the thermodynamic limit - a DFT study of the step-wise water oxidation of the bipyramidal Cu-7 cluster
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-3832-2331
Swedish Nuclear Fuel and Waste Management Co (SKB).
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0003-2673-075X
2014 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 16, no 6, 2452-2464 p.Article in journal (Refereed) Published
Abstract [en]

Oxidative degradation of copper in aqueous environments is a major concern in areas such as catalysis, electronics and construction engineering. A particular challenge is to systematically investigate the details of this process for non-ideal copper surfaces and particles under the conditions found in most real applications. To this end, we have used hybrid density functional theory to study the oxidation of a Cu-7 cluster in water solution. Especially, the role of a large water coverage is explored. This has resulted in the conclusion that, under atmospheric H-2 pressures, the thermodynamically most favored state of degradation is achieved upon the generation of four H-2 molecules (i.e. Cu-7 + 8H(2)O -> Cu-7(OH)(8) + 4H(2)) in both condensed and gas phases. This state corresponds to an average oxidation state below Cu(I). The calculations suggest that the oxidation reaction is slow at ambient temperatures with the water dissociation as the rate-limiting step. Our findings are expected to have implication for, among other areas, the copper catalyzed water-gas shift reaction, and for the general understanding of copper corrosion in aqueous environments.

Place, publisher, year, edition, pages
2014. Vol. 16, no 6, 2452-2464 p.
Keyword [en]
Gas Shift Reaction, Small Copper Clusters, Continuum Dielectric Theory, Solvation Free-Energies, Near-Ambient Conditions, Ab-Initio, Dissociative Adsorption, Structure Sensitivity, Hyperfine-Structure, Fundamental-Aspects
National Category
Physical Sciences Chemical Sciences
URN: urn:nbn:se:kth:diva-141318DOI: 10.1039/c3cp53865fISI: 000329926700032ScopusID: 2-s2.0-84892606991OAI: diva2:696514

QC 20140214

Available from: 2014-02-14 Created: 2014-02-13 Last updated: 2014-02-14Bibliographically approved

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Halldin Stenlid, JoakimJohansson, Adam JohannesBrinck, Tore
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