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The promoting effect of adsorbed carbon monoxide on the oxidation of alcohols on a gold catalyst

Nature Chemistry volume 4, pages 177–182 (2012)Cite this article

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Abstract

In heterogeneous catalysis and electrocatalysis, adsorbed carbon monoxide typically acts as a poison or poisoning intermediate in the oxidation of alcohols. However, gold as an (electro)catalyst often exhibits unexpected properties. Here we show that carbon monoxide irreversibly adsorbed on a Au(111) surface in aqueous alkaline media can act as a promoter for the electrocatalytic oxidation of certain alcohols, in particular methanol. In comparison with bare Au(111), the onset potential for methanol oxidation is significantly lower in the presence of adsorbed CO, and formation of the main methanol oxidation products—formaldehyde and formic acid—is enhanced. By studying the effect of adsorbed CO on the oxidation of other alcohols on gold, we conclude that the presence of adsorbed CO promotes beta-hydrogen elimination, that is, C–H bond breaking. Apart from its importance to gold catalysis, this is an unanticipated example of promotion effects by co-adsorbed small molecules in electrocatalysis.

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Figure 1: Voltammetry of the Au(111) electrode in the absence (black) and presence (red) of CO.
Figure 2: Product identification by HPLC during methanol oxidation on Au(111) and Au(111)–CO.
Figure 3: FTIR spectroscopic characterization of the isotopically labelled methanol on a Au(111)–CO electrode.
Figure 4: Oxidation of 2,2-difluoroethanol on Au(111) and Au(111)–CO electrodes.
Figure 5: Illustration of the mechanism of alcohol oxidation on Au(111) as catalysed by COads.

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Acknowledgements

P.R. and M.T.M.K. acknowledge financial support from the Netherlands Organization for Scientific Research (NWO) through VENI and VICI grants, respectively, and the European Commission (through FP7 Initial Training Network ‘ELCAT’, grant agreement no. 214936-2). The research of Y.K. is performed within the framework of the CatchBio programme. The authors gratefully acknowledge support from the Smart Mix Program of The Netherlands Ministry of Economic Affairs and The Netherlands Ministry of Education, Culture and Science. The purchase of the HPLC and fraction collection system was made possible through an ‘NWO-Middelgroot’ equipment grant awarded to M.T.M.K. by NWO.

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  1. Leiden Institute of Chemistry, Leiden University, PO Box 9502, RA, Leiden, 2300, The Netherlands

    Paramaconi Rodriguez, Youngkook Kwon & Marc T. M. Koper

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  1. Paramaconi Rodriguez
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Contributions

P.R. and M.T.M.K. conceived and designed the experiments. P.R. performed the electrochemistry and FTIR experiments. P.R. and Y.K. performed the HPLC experiments. All authors contributed to the data analysis. P.R. and M.T.M.K. co-wrote the paper.

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Correspondence to Marc T. M. Koper.

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The authors declare no competing financial interests.

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Rodriguez, P., Kwon, Y. & Koper, M. The promoting effect of adsorbed carbon monoxide on the oxidation of alcohols on a gold catalyst. Nature Chem 4, 177–182 (2012). https://doi.org/10.1038/nchem.1221

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