Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials.
Spectro-Electrochemical Examination of the Formation of Dimethyl Carbonate from CO and Methanol at Different Electrode Materials.
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DOI：
10.1021/jacs.7b08208
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发表时间：
2017-10-18
影响因子：
15
通讯作者：
Koper MTM
中科院分区：
文献类型：
--
作者：
Figueiredo MC;Trieu V;Eiden S;Koper MTM
在这项工作中，我们报道了在低过电位下，甲醇与CO在金属电极上进行电化学氧化羰基化合成碳酸二甲酯的基本机理研究。首次证明该反应是在金属催化剂上进行的，不需要氧化金属或添加剂。此外，还利用原位光谱电化学技术对该电合成反应进行了研究，以揭示反应中间产物，揭示反应机理。用傅里叶变换红外光谱分析了不同的电极材料(金、钯、铂和银)对反应的影响以及产物和中间体对外加电位的依赖关系。观察到，只有当电极能够分解/氧化甲醇形成(吸附的)甲氧基，并进一步与CO反应生成碳酸二甲酯时，才会形成碳酸二甲酯。此外，电极对CO的吸附不能太强，否则会因为CO的表面中毒而抑制进一步的反应。
In this work, we report a fundamental mechanistic study of the electrochemical oxidative carbonylation of methanol with CO for the synthesis of dimethyl carbonate on metallic electrodes at low overpotentials. For the first time, the reaction was shown to take place on the metallic catalysts without need of oxidized metals or additives. Moreover, in-situ spectroelectrochemical techniques were applied to this electrosynthesis reaction in order to reveal the reaction intermediates and to shed light into the reaction mechanism. Fourier transformed infrared spectroscopy was used with different electrode materials (Au, Pd, Pt, and Ag) to assess the effect of the electrode material on the reaction and the dependence of products and intermediates on the applied potentials. It was observed that the dimethyl carbonate is only formed when the electrode is able to decompose/oxidize MeOH to form (adsorbed) methoxy groups that can further react with CO to dimethyl carbonate. Furthermore, the electrode needs to adsorb CO not too strongly; otherwise, further reaction will be inhibited because of surface poisoning by CO.
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