School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK.
Angew Chem Int Ed Engl. 2017 Oct 9;56(42):12919-12924. doi: 10.1002/anie.201706463. Epub 2017 Sep 18.
The electrochemical reduction of CO into fuels has gained significant attention recently as source of renewable carbon-based fuels. The unique high selectivity of copper in the electrochemical reduction of CO to hydrocarbons has called much interest in discovering its mechanism. In order to provide significant information about the role of oxygen in the electrochemical reduction of CO on Cu electrodes, the conditions of the surface structure and the composition of the Cu single crystal electrodes were controlled over time. This was achieved using pulsed voltammetry, since the pulse sequence can be programmed to guarantee reproducible initial conditions for the reaction at every fraction of time and at a given frequency. In contrast to the selectivity of CO reduction using cyclic voltammetry and chronoamperometric methods, a large selection of oxygenated hydrocarbons was found under alternating voltage conditions. Product selectivity towards the formation of oxygenated hydrocarbon was associated to the coverage of oxygen species, which is surface-structure- and potential-dependent.
电化学还原 CO 为燃料作为可再生碳基燃料的来源最近受到了广泛关注。铜在电化学还原 CO 为烃类方面的独特高选择性引起了人们对其机制的极大兴趣。为了提供关于 CO 在 Cu 电极上电化学还原过程中氧作用的重要信息，通过控制铜单晶电极的表面结构和组成随时间的变化来实现。这是通过使用脉冲伏安法来完成的，因为脉冲序列可以编程以保证在给定的频率和任意时间分数下，反应具有可重复的初始条件。与使用循环伏安法和计时安培法的 CO 还原选择性相反，在交变电压条件下发现了大量含氧烃。含氧碳氢化合物的产物选择性与氧物种的覆盖率有关，而氧物种的覆盖率与表面结构和电位有关。
