Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) has attracted increasing attention, because this method provides a new route for CO2 recycling utilization. As CO2 is chemically inert, this reaction requires a high over‐potential. Therefore, it is highly desirable to https://www.baidu.com/link?url=7sgOGZK4RdeP0YlNnWY50FDJ-B6Gu8Iuq8iTl2YcoqyXLYhk-sgGOP9a4kAInk5_Lilex2h9rYXC7iIGJ5gTPCNMlcGx4_GKhidbnPgmlJe&wd=&eqid=bd238ea30000d31a000000045a445227 an electrocatalyst to accelerate this reaction. In the present work, we have investigated numerous imidazolium ionic liquids (ILs) with the aim of looking for a low‐cost homogeneous catalyst with high efficiency. By comparison, 1‐butyl‐3‐methylimidazolium chloride ([Bmim][Cl]) has been selected as the most cost‐effective. To further reduce the cost of [Bmim][Cl], we added [Bmim][Cl] into propylene carbonate(PC)/tetrabutylammonium perchlorate (Bu4NClO4), and used it as the electrocatalyst. Our experimental results show that [Bmim][Cl] has a high catalytic effect for CO2 reduction. The catalytic mechanism of [Bmim][Cl] has been discussed based on electrochemical impedance spectroscopy. It is explained as follows: CO2 was first reduced to the high‐energy CO2.− radical through a one‐electron transfer. The generated CO2.− radical further reacts with [Bmim]+, resulting in the formation of a complex [CO2−Bmim]. Thus, the activation energy of CO2 reduction has been reduced.

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