钴席夫碱配合物电催化还原CO_2研究  

Performance study of cobalt schiff base complexes towards electrocatalytic CO_2 reduction

作　　者：周倩倩 黎挺挺 郑岳青[1] ZHOU Qian-qian;LI Ting-ting;ZHENG Yue-qing(Research Center of Applied Solid State Chemistry, Ningbo University, Ningbo 315211, China)

机构地区：[1]宁波大学应用固体化学研究中心,浙江宁波315211

出　　处：《宁波大学学报（理工版）》2019年第3期115-120,共6页Journal of Ningbo University：Natural Science and Engineering Edition

基　　金：国家自然科学基金(21603110);宁波市自然科学基金(2016A610069);宁波大学科研项目(XYL16001);宁波大学王宽诚幸福基金

摘　　要：报道了3例含不同官能团的单核席夫碱(N,N'-双(水杨醛)-1,2-苯二胺)钴(Ⅱ)配合物在无水有机溶剂和在含10%H_2O的有机溶剂中的电催化还原CO_2性能.同时,通过研究配合物电子效应对其催化性能影响实验发现:具有吸电子基团(-F)的配合物1表现出最低的催化起始电位(Eonset=-1.55 V相对于Ag/AgCl),而具有给电子基团(-OCH3)的配合物3则具有最高的催化活性,其催化转换频率和法拉第效率分别为620 s-1和68.5%.以上结果表明,钴席夫碱配合物具有高活性和高选择性电催化还原CO_2性能,而且通过对分子催化剂电子效应的调控可以实现对其催化活性的优化.The electrocatalytic reduction of carbon dioxide to value-added chemical fuels is an important project in green and energy chemistry. In the current study, the electrocatalytic performance for CO2 reduction driven by three mononuclear Co(Ⅱ) complexes containing salophen (salophen=N,N'-bis(salicylaldheyde)-1,2-phenyldiamine) ligands with various substitutes were examined in dry organic homogeneous medium and the mixture solution containing 10% H2O (V/V), respectively. Furthermore, the electronic effects of complexes on catalytic activities were investigated. Complex 1 with electron-withdrawing groups (-F) emerged as a catalyst with the lowest catalytic onset potential (Eonset=-1.55 V vs Ag/AgCl);whereas complex 3 with electron-donating groups (-OCH3) had the highest catalytic activity and achieved turnover frequency and Faradaic efficiency of 620 s^-1 and 68.5%, respectively. The results indicated that these cobalt schiff base complexes have high activity and selectivity for the electrocatalytic reduction of CO2 to CO, and the catalytic performances of these complexes could be rationally optimized in terms of electronic effects from their ligands.

关 键 词：钴(Ⅱ)配合物 席夫碱 电催化 CO2还原 均相体系 

分 类 号：O646.5[理学—物理化学]