电泳剂
催化作用
选择性
分子
质子
电子转移
材料科学
乙烯
电化学
组合化学
化学物理
计算化学
光化学
化学
物理化学
有机化学
物理
电极
量子力学
作者
Xianlong Zhou,Jieqiong Shan,Min Zheng,Huan Li,Bao Yu Xia,Yao Zheng
标识
DOI:10.1007/s40843-023-2676-y
摘要
Cu is the only transition metal that can achieve electrochemical CO2 reduction (CRR) with the generation of hydrocarbons and oxygenates. However, it is still challenging to regulate CRR selectivity in a broad product distribution on Cu. Here, we selected a series of molecules with varying electrophilicity to modify Cu catalysts that achieve a high CRR selectivity towards either CH4 or C2H4. Theoretical analysis shows that molecular electrophilicity determines catalyst’s proton availability, which promotes or inhibits the critical proton-coupled electron transfer (PCET) process in CRR. Consequently, the molecule with low electrophilicity (e.g., 1,2-bis(4-pyridyl)ethane) can facilitate proton transfer to hydro-genate *CO intermediates to generate CH4 with a Faradaic efficiency (FE) of 58.2%, while the molecule with high electrophilicity (e.g., trans-1,2-bis(4-pyridyl)ethylene) can build stronger hydrogen bonds to stabilize *CO for further dimerization, realizing an FE of 65.9% for C2H4. The combination of theoretical computation and in situ spectroscopic characterizations reveal that using molecular electrophilicity can tune catalyst’s proton availability, thereby altering its CRR pathway of either *CO hydrogenation or *CO-*CO dimerization. This work provides new understanding of CRR selectivity by tuning the PCET process instead of materials engineering.
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