A novel, direct and efficient electroreduction method of benzyl bromide in ionic liquid BMIMBF 4 has been developed by potentiostatic electrolysis. Under the atmospheric pressure of CO 2 , the electrosynthesis was performed in an undivided cell with Cu-Ni cathode and Al anode. A moderate yield (39.4%) of ethyl phenylacetate 1 as the principal product was obtained, accompanied astonishingly by yield (4.6%) of benzyl ether 2. Synthetic factors such as electrode material, working potential and electric charge were found to influence the carboxylation yields. The results indicate that the porous structure Cu-Ni alloy electrode with different adsorption energies for CO 2 and benzyl bromide played an ensemble effect role in the reaction efficiency and products distribution. Moreover, the ionic liquid was successfully recycled and a plausible reaction mechanism was proposed.
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