催化作用
纳米材料基催化剂
选择性
X射线吸收光谱法
铜
电化学
材料科学
X射线光电子能谱
无机化学
化学
化学工程
吸收光谱法
组合化学
物理化学
有机化学
物理
量子力学
工程类
电极
作者
Peng Wang,Tan Li,Qiqi Wu,Ruian Du,Qinghua Zhang,Wei‐Hsiang Huang,Chi-Liang Chen,Yan Fan,Haonan Chen,Yanyan Jia,Sheng Dai,Yongcai Qiu,Keyou Yan,Yuanyuan Meng,Geoffrey I. N. Waterhouse,Lin Gu,Yun Zhao,Weiwei Zhao,Guangxu Chen
出处
期刊:ACS Nano
[American Chemical Society]
日期:2022-10-12
卷期号:16 (10): 17021-17032
被引量:11
标识
DOI:10.1021/acsnano.2c07138
摘要
In certain metalloenzymes, multimetal centers with appropriate primary/secondary coordination environments allow carbon-carbon coupling reactions to occur efficiently and with high selectivity. This same function is seldom realized in molecular electrocatalysts. Herein we synthesized rod-shaped nanocatalysts with multiple copper centers through the molecular assembly of a triphenylphosphine copper complex (CuPPh). The assembled molecular CuPPh catalyst demonstrated excellent electrochemical CO2 fixation performance in aqueous solution, yielding high-value C2+ hydrocarbons (ethene) and oxygenates (ethanol) as the main products. Using density functional theory (DFT) calculations, in situ X-ray absorption spectroscopy (XAS) and quasi-in situ X-ray photoelectron spectroscopy (XPS), and reaction intermediate capture, we established that the excellent catalytic performance originated from the large number of double copper centers in the rod-shaped assemblies. Cu-Cu distances in the absence of CO2 were as long as 7.9 Å, decreasing substantially after binding CO2 molecules indicating dynamic and cooperative function. The double copper centers were shown to promote carbon-carbon coupling via a CO2 transfer-coupling mechanism involving an oxalate (OOC-COO) intermediate, allowing the efficient production of C2+ products. The assembled CuPPh nanorods showed high activity, excellent stability, and a high Faradaic efficiency (FE) to C2+ products (65.4%), with performance comparable to state-of-the-art copper oxide-based catalysts. To our knowledge, our findings demonstrate that harnessing metalloenzyme-like properties in molecularly assembled catalysts can greatly improve the selectivity of CO2RR, promoting the rational design of improved CO2 reduction catalysts.
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