Yang Ying, McElwee-White Lisa
Department of Chemistry and Center for Catalysis, University of Florida, Gainesville, FL 32611-7200, USA.
Dalton Trans. 2004 Aug 7(15):2352-6. doi: 10.1039/B405784H. Epub 2004 Jun 18.
The electrochemical oxidation of methanol was carried out using a series of dppm-bridged Ru/Pd, Ru/Pt and Ru/Au heterobimetallic complexes as catalysts. The major oxidation products were formaldehyde dimethyl acetal (dimethoxymethane, DMM) and methyl formate (MF). The Ru/Pd and Ru/Pt bimetallic catalysts generally afforded lower product ratios of DMM/MF and higher current efficiencies than the Ru/Au catalysts. The Ru/Au bimetallics exhibited product ratios and current efficiencies similar to those obtained from the Ru mononuclear compound CpRu(PPh(3))(2)Cl. Increasing the methanol concentration afforded higher current efficiencies, while the addition of water to the samples shifted the product distribution toward the more highly oxidized product, MF.
使用一系列二亚甲基二膦(dppm)桥联的Ru/Pd、Ru/Pt和Ru/Au异双金属配合物作为催化剂进行甲醇的电化学氧化。主要氧化产物为甲醛缩二甲醇(二甲氧基甲烷,DMM)和甲酸甲酯(MF)。与Ru/Au催化剂相比,Ru/Pd和Ru/Pt双金属催化剂通常具有更低的DMM/MF产物比和更高的电流效率。Ru/Au双金属催化剂表现出的产物比和电流效率与从Ru单核化合物CpRu(PPh(3))(2)Cl获得的相似。增加甲醇浓度可提高电流效率,而向样品中加水会使产物分布向氧化程度更高的产物MF偏移。