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On the lack of beneficial role of Rh towards C-C bond cleavage_chemRxiv.pdf (1002.19 kB)
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On the Lack of Beneficial Role of Rh Towards C-C Bond Cleavage During Low Temperature Ethanol Electrooxidation on Pt-Rh Nanoalloys

preprint
submitted on 17.05.2018 and posted on 18.05.2018 by Justyna Piwowar, Adam Lewera
Numerous reports in scientific literature claim the increased activity of Rh-containing systems towards C-C bond scission in electrocatalytic oxidation of ethanol at ambient temperatures. Due to the claimed C-C bond breaking ability, Rh-containing systems are intensively investigated and widely recognized as the most promising candidates as anode materials for ethanol-feed low temperature fuel cells. This study aims at verifying the claim of beneficial role of Rh towards C-C bond scission during low temperature ethanol electrooxidation on Pt-Rh nanoparticles. We determined that the surface-normalized amounts of CO2 produced during ethanol oxidation are comparable on Pt, Rh and Pt-Rh nanoalloys, and smaller than CO2 amounts obtained on exactly the same electrode from oxidation of monolayer of adsorbed CO. The whole amount of CO2 detected during ethanol oxidation, regardless of Rh presence, or lack of thereof, seems to come exclusively from oxidation of submonolayer of COads produced during dissociative adsorption of ethanol at low electrode potential, and its subsequent oxidation at sufficiently high electrode potential. Our work suggest that Rh-containing alloys are not more active towards C-C bond scission than pure Pt, and on both metals the mechanism of oxidation of ethanol to CO2 proceeds via the submonolayer of COads, which limits the quantity of CO2 produced from ethanol at room temperature to negligible amount. The higher activity of Rh-containing materials towards C-C bond scission claimed in literature was determined to be due to overinterpretation of selectivity data.
To characterized the samples we used techniques like XPS, TEM, and cyclic voltammetry. For drove a conclusions we compere amount of CO2 detected in DEMS during ethanol oxidation reaction and so called CO stripping experiment.

Funding

This project was funded from Polish National Science Centre budget based on decision number DEC-2013/09/B/ST4/00099. The study was carried out at the Biological and Chemical Research Centre, University of Warsaw, established within the project co-financed by European Union from the European Regional Development Fund under the Operational Programme Innovative Economy, 2007 – 2013.

History

Email Address of Submitting Author

jpiwowar@chem.uw.edu.pl

Email Address(es) for Other Author(s)

alewera@chem.uw.edu.pl

Institution

University of Warsaw, Faculty of Chemistry, Biological and Chemical Research Centre

Country

Poland

ORCID For Submitting Author

0000-0002-3468-811X

Declaration of Conflict of Interest

no conflict of interest

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