Reaction cycles and poisoning in catalysis by gold clusters: A thermodynamics approach
Beret EC, Van Wijk MM, Ghiringhelli LM (2014)
Publication Type: Journal article
Publication year: 2014
Journal
Book Volume: 114
Pages Range: 57-65
Journal Issue: 1
DOI: 10.1002/qua.24503
Abstract
In heterogeneous catalysis, a catalytic process takes place at finite temperature and at finite pressure of the atmosphere of the reactant gases. By applying ab initio atomistic thermodynamics to the model case of free Au 2 and Au2- clusters in an atmosphere of O2 and CO, we derive all the thermodynamically possible reaction paths for the oxidation of CO to CO2. This analysis lets us explain how gold clusters enable oxidation reactions without breaking the spin-conservation rule. Furthermore, we identify special cluster + ligands compositions such as reaction intermediates and poisoned species. In particular, a thermodynamically driven poisoning is identified for the catalytic system containing free Au2, and the experimental (p, T) conditions that avoid its formation are suggested. This implies that for some systems a catalytic cycle can be established, on thermodynamics grounds, only in a defined range of temperatures and pressures. In addition, our predictions for Au2- provide the so far most complete interpretation of the available experimental data (Socaciu et al, J. Am. Chem. Soc. 2003). © 2013 Wiley Periodicals, Inc. Heterogeneous catalytic processes take place at the finite temperature and pressure of the atmosphere of the reactant gases. By applying ab initio atomistic thermodynamics, it is possible to derive all the thermodynamically possible reaction paths for the oxidation of CO to CO2 catalyzed by the model clusters Au2- and Au2. In the latter case, a thermodynamically driven poisoning is identified, and the experimental (p, T) conditions that avoid its formation are suggested. Copyright © 2013 Wiley Periodicals, Inc.
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APA:
Beret, E.C., Van Wijk, M.M., & Ghiringhelli, L.M. (2014). Reaction cycles and poisoning in catalysis by gold clusters: A thermodynamics approach. International Journal of Quantum Chemistry, 114(1), 57-65. https://dx.doi.org/10.1002/qua.24503
MLA:
Beret, Elizabeth C., Merel M. Van Wijk, and Luca M. Ghiringhelli. "Reaction cycles and poisoning in catalysis by gold clusters: A thermodynamics approach." International Journal of Quantum Chemistry 114.1 (2014): 57-65.
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