TY - JOUR
T1 - Electrooxidation of ethanol and methanol using the molecular catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10-
AU - Liu, Yuping
AU - Zhao, Shufeng
AU - Guo, SiXuan
AU - Bond, Alan
AU - Zhang, Jie
AU - Zhu, Guibo
AU - Hill, Craig L.
AU - Geletii, Yurii V
PY - 2016/3/2
Y1 - 2016/3/2
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84959451828&partnerID=8YFLogxK
U2 - 10.1021/jacs.5b11408
DO - 10.1021/jacs.5b11408
M3 - Article
AN - SCOPUS:84959451828
VL - 138
SP - 2617
EP - 2628
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 8
ER -