Department of Chemistry , Keio University , 3-14-1 Hiyoshi , Yokohama 223-8522 , Japan.
JST-ACCEL , 3-14-1 Hiyoshi , Yokohama 223-8522 , Japan.
J Am Chem Soc. 2019 May 8;141(18):7414-7420. doi: 10.1021/jacs.9b01773. Epub 2019 Apr 23.
The main product obtained by electrochemical reduction of CO depends on the electrode material, and in many cases the Faradaic efficiency for this is determined by the electrolyte. Only a few investigations in which attempts to produce different products from the same electrode material have been done so far. In this work, we focus on boron-doped diamond (BDD) electrodes with which plentiful amounts of formic acid and small amounts of carbon monoxide have been produced. By optimizing certain parameters and conditions used in the electrochemical process with BDD electrodes, such as the electrolyte, the boron concentration of the BDD electrode, and the applied potential, we were able to control the selectivity and efficiency with which carbon monoxide is produced. On one hand, with a BDD electrode with 1% boron used for the cathode and KClO for the catholyte, the selectivity for producing carbon monoxide was high. On the other hand, with a BDD electrode with 0.1% boron used for the cathode and KCl for the catholyte, the production of formic acid was the most evident. In situ attenuated total reflectance-infrared (ATR-IR) measurements during electrolysis showed that CO intermediates were adsorbed on the BDD surface in the KClO aqueous solution. Here, switchable product selectivity was achieved when reducing CO using BDD electrodes.
电化学还原 CO 得到的主要产物取决于电极材料,在许多情况下,这种法拉第效率取决于电解质。迄今为止,只有少数试图从相同的电极材料中生产不同产物的研究。在这项工作中,我们专注于硼掺杂金刚石(BDD)电极,通过该电极可以大量生产甲酸和少量一氧化碳。通过优化电化学过程中使用 BDD 电极的某些参数和条件,例如电解质、BDD 电极的硼浓度和施加的电势,我们能够控制一氧化碳的生成选择性和效率。一方面,使用 1%硼掺杂的 BDD 电极作为阴极,并用 KClO 作为阴极电解液,生产一氧化碳的选择性很高。另一方面,使用 0.1%硼掺杂的 BDD 电极作为阴极,并用 KCl 作为阴极电解液,甲酸的生成最为明显。电解过程中的原位衰减全反射-红外(ATR-IR)测量表明,在 KClO 水溶液中,CO 中间体被吸附在 BDD 表面上。在这里,使用 BDD 电极还原 CO 时实现了可切换的产物选择性。