Zhang Lei, Li Xiao-Xin, Lang Zhong-Ling, Liu Yang, Liu Jiang, Yuan Lin, Lu Wan-Yue, Xia Yuan-Sheng, Dong Long-Zhang, Yuan Da-Qiang, Lan Ya-Qian
Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P. R. China.
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, P. R. China.
J Am Chem Soc. 2021 Mar 17;143(10):3808-3816. doi: 10.1021/jacs.0c11450. Epub 2021 Mar 2.
Cu(I)-based catalysts have proven to play an important role in the formation of specific hydrocarbon products from electrochemical carbon dioxide reduction reaction (CORR). However, it is difficult to understand the effect of intrinsic cuprophilic interactions inside the Cu(I) catalysts on the electrocatalytic mechanism and performance. Herein, two stable copper(I)-based coordination polymer ( and ) catalysts are synthesized and integrated into a CO flow cell electrolyzer, which exhibited very high selectivity for electrocatalytic CO-to-CH conversion due to clearly inherent intramolecular cuprophilic interactions. Substitution of hydroxyl radicals for sulfate radicals during the electrocatalytic process results in an in situ dynamic crystal structure transition from to , which further strengthens the cuprophilic interactions inside the catalyst structure. Consequently, with enhanced cuprophilic interactions shows an outstanding product (CH) selectivity of 82% at -0.9 V (vs reversible hydrogen electrode, = 391 mA cm), which represents the best crystalline catalyst for electrocatalytic CO-to-CH conversion to date. Moreover, the detailed DFT calculations also prove that the cuprophilic interactions can effectively facilitate the electroreduction of CO to CH by decreasing the Gibbs free energy change of potential determining step (*HCOOH → *OCH). Significantly, this work first explored the effect of intrinsic cuprophilic interactions of Cu(I)-based catalysts on the electrocatalytic performance of CORR and provides an important case study for designing more stable and efficient crystalline catalysts to reduce CO to high-value carbon products.
基于Cu(I)的催化剂已被证明在电化学二氧化碳还原反应（CORR）形成特定烃类产物的过程中发挥着重要作用。然而，很难理解Cu(I)催化剂内部固有的亲铜相互作用对电催化机理和性能的影响。在此，合成了两种稳定的基于铜(I)的配位聚合物（ 和 ）催化剂，并将其集成到CO流动池电解槽中，由于明显固有的分子内亲铜相互作用，该电解槽对电催化CO转化为CH表现出非常高的选择性。在电催化过程中，用羟基自由基取代硫酸根自由基会导致原位动态晶体结构从 转变为 ，这进一步增强了催化剂结构内部的亲铜相互作用。因此，具有增强亲铜相互作用的 在-0.9 V（相对于可逆氢电极， = 391 mA cm）下表现出82%的出色产物（CH）选择性，这代表了迄今为止用于电催化CO转化为CH的最佳晶体催化剂。此外，详细的DFT计算还证明，亲铜相互作用可以通过降低电位决定步骤（*HCOOH → *OCH）的吉布斯自由能变化来有效地促进CO电还原为CH。值得注意的是，这项工作首次探索了基于Cu(I)的催化剂的固有亲铜相互作用对CORR电催化性能的影响，并为设计更稳定、高效的晶体催化剂以将CO还原为高价值碳产物提供了一个重要案例研究。
