Active control of methanol carbonylation selectivity over AU/carbon anode by electrochemical potential
Active control of methanol carbonylation selectivity over AU/carbon anode by electrochemical potential
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DOI：
10.1021/jp0448752
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发表时间：
2005-05-12
影响因子：
3.3
通讯作者：
Otsuka, K
中科院分区：
文献类型：
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作者：
Funakawa, A;Yamanaka, I;Otsuka, K
研究了甲醇在Au负载碳阳极上的氧化羰基化反应，羰基化反应的主要产物为草酸二甲酯（DMO）和碳酸二甲酯（DMC）。次要氧化产物为二甲氧基甲烷（DMM）和甲酸甲酯（MF）。研究了不同反应条件对羰基化活性和选择性的影响。对DMO和DMC的选择性可由电化学电位控制。采用循环伏安法（CV）、Au3+、甲醇和CO的化学计量反应以及紫外可见光谱研究了Au/碳阳极的电催化作用。采用XRD、SEM、BE等方法对Au/碳阳极进行了羰基化前后的表征。这些实验结果有力地表明，Au氧化态的转变影响了其对DMO和DMC羰基化选择性的变化。Au-0是在低电位（+1.3 V）下通过直接电化学羰基化选择性形成DMO的活性物质。
Electrochemical oxidative carbonylation of methanol was studied over Au supported carbon anode in CO. The major carbonylation products were dimethyl oxalate (DMO) and dimethyl carbonate (DMC). The minor oxidation products were dimethoxy methane (DMM) and methyl formate (MF) from methanol and CO2. Influences of various reaction conditions were studied on carbonylation activities and selectivities. The selectivities to DMO and DMC can be controlled by the electrochemical potential. Electrocatalysis of Au/carbon anode was studied by cyclic voltammetry (CV), stoichiometric reactions among Au3+, methanol, and CO, and UV-vis spectra. The Au/carbon anode was characterized by XRD, SEM, and BE images before and after the carbonylation. These experimental facts strongly suggest that transition of oxidation states of Au affects changing of the carbonylation selectivities to DMO and DMC. Au-0 is the active species for the selective DMO formation by direct electrochemical carbonylation at low potentials (+1.3 V).