化学
铜
密度泛函理论
电解
法拉第效率
催化作用
离解(化学)
电合成
选择性
联轴节(管道)
吸附
电化学
质子化
反应中间体
无机化学
反应机理
偶联反应
电催化剂
溢出效应
氢溢流
电解水
光化学
电极
计算化学
纳米技术
本体电解
多相催化
半反应
化学工程
组合化学
作者
Shicheng Zhu,Jiaqi Xu,M. Wu,Ruoou Yang,Junyuan Duan,Siyu Yang,Youwen Liu,Jing Gao,Yuanjie Pang,Huiqiao Li,Bao Yu Xia,M. Grätzel,Tianyou Zhai
摘要
The electroreduction of CO2 into high-energy-density n-propanol represent a promising approach for storing intermittent renewable electricity. However, the electrosynthesis of n-propanol encounters substantial challenges owing to the high energy barrier C–C coupling steps and the competition from C2 products, resulting in exceedingly low selectivity. Herein, we introduce a novel preprotonation reaction pathway in a mixed-coordination copper catalyst to overcome these limitations. Specifically, high-coordination copper sites (HCN-Cu) predominantly generate CO, creating a CO-rich environment for low-coordination copper sites (LCN-Cu) via a spillover effect. The LCN-Cu sites, characterized by their reduced *CO adsorption energy and enhanced water dissociation capability, facilitate the preprotonation of C1 and C2 intermediates. Consequently, protonation of *CO to form *COH occurs prior to its dimerization with another *CO molecule, thereby circumventing the traditionally high-energy barrier *CO–*CO coupling process. Density Functional Theory calculations further confirm that the rate-determining step in this pathway shifts from traditional C–C coupling to *COH formation, reducing the reaction energy barrier from 1.63 to 0.98 eV. The lower C–C coupling energy barrier will generate more *C2 intermediates and continuously couple into C3, further mitigating competition with C2 products. Following this preprotonation pathway, the mixed-coordination copper achieves record-high n-propanol Faradaic selectivity of 17.6%.
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