Electrooxidation of Ethanol and Methanol Using the Molecular Catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2](10.)

YuPing Liu; Shu-Feng Zhao; Si-Xuan Guo; Alan M Bond; Jie Zhang; Guibo Zhu; Craig L Hill; Yurii V Geletii

doi:10.1021/jacs.5b11408

Electrooxidation of Ethanol and Methanol Using the Molecular Catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2](10.)

J Am Chem Soc. 2016 Mar 2;138(8):2617-28. doi: 10.1021/jacs.5b11408. Epub 2016 Feb 22.

Authors

YuPing Liu^{1

2}, Shu-Feng Zhao^{1

2}, Si-Xuan Guo^{1

2}, Alan M Bond^{1

2}, Jie Zhang^{1

2}, Guibo Zhu^{1

2}, Craig L Hill^{1

2}, Yurii V Geletii^{1

2}

Affiliations

¹ School of Chemistry and ARC Centre of Excellence for Electromaterials Science, Monash University , Clayton, Victoria 3800, Australia.
² Department of Chemistry, Emory University , 1515 Dickey Drive, Atlanta, Georgia 30322, United States.

PMID: 26848832
DOI: 10.1021/jacs.5b11408

Abstract

Highly efficient electrocatalytic oxidation of ethanol and methanol has been achieved using the ruthenium-containing polyoxometalate molecular catalyst, [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2](10-) ([1(γ-SiW10O36)2](10-)). Voltammetric studies with dissolved and surface-confined forms of [1(γ-SiW10O36)2](10-) suggest that the oxidized forms of 1 can act as active catalysts for alcohol oxidation in both aqueous (over a wide pH range covering acidic, neutral, and alkaline) and alcohol media. Under these conditions, the initial form of 1 also exhibits considerable reactivity, especially in neutral solution containing 1.0 M NaNO3. To identify the oxidation products, preparative scale bulk electrolysis experiments were undertaken. The products detected by NMR, gas chromatography (GC), and GC-mass spectrometry from oxidation of ethanol are 1,1-diethoxyethane and ethyl acetate formed from condensation of acetaldehyde or acetic acid with excess ethanol. Similarly, the oxidation of methanol generates formaldehyde and formic acid which then condense with methanol to form dimethoxymethane and methyl formate, respectively. These results demonstrate that electrocatalytic oxidation of ethanol and methanol occurs via two- and four-electron oxidation processes to yield aldehydes and acids. The total faradaic efficiencies of electrocatalytic oxidation of both alcohols exceed 94%. The numbers of aldehyde and acid products per catalyst were also calculated and compared with the literature reported values. The results suggest that 1 is one of the most active molecular electrocatalysts for methanol and ethanol oxidation.