Open Circuit Potential of a Au Catalyst during Selective Oxidation of Glycerol

Chen, Yaxin; Kung, Harold H.

doi:10.1021/acs.jpcc.4c06690

Open Circuit Potential of a Au Catalyst during Selective Oxidation of Glycerol

Journal Article · Thu Nov 21 00:00:00 EST 2024 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.4c06690· OSTI ID:2481096

Chen, Yaxin ^[1]; ^[2]

Northwestern University, Evanston, IL (United States); Fudan University, Shanghai (China)
Northwestern University, Evanston, IL (United States)

It has been of great interest to understand relationships between the potential of a metal catalyst and its thermochemical catalytic activity, especially in an aqueous phase environment. In the literature, there are correlations of open circuit potential with reaction rates or surface concentrations of reaction intermediates. In this study, we measured the open circuit potential (OCP) of a Au gauze during selective oxidation of glycerol to glyceric acid and hydrogen peroxide in a basic solution, as a function of hydroxide and alcoholate concentrations. It is found that applying a potential to the Au catalyst has no influence on the reaction rate. Although a rough correlation appears to exist between OCP and reaction rate, the data are better fit to an equation which assumes that the potential of the metal (i.e. the OCP) is in equilibrium with the electrochemical potential of the solution, which is defined by the thermodynamic activities of the oxidizing and reducing species. The equation: OCP = constant + Σ_ox[(RT/FZ_ox)ln[Ox]] - Σ_red[(RT/FZ_red)ln[Red]] implicitly assumes that the Au metal functions as a probing electrode. It is further found that this equation also applies to the Au-catalyzed H₂O₂ oxidation/decomposition reaction in a basic medium, and possibly to formic acid dehydrogenation. Here, we postulate that the apparent correlation between OCP and reaction rate is due to the fact that the reaction rate is proportional to the concentrations of the reaction products and/or reactants that define the electrochemical potential of the solution.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 2481096

Journal Information:: Journal of Physical Chemistry. C, Vol. 128, Issue 48; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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