Constructing Metal(II)-Sulfate Site Catalysts toward Low Overpotential Carbon Dioxide Electroreduction to Fuel Chemicals

被引:3
作者
Yuan, Chen-Yue [1 ]
Feng, Li [2 ]
Qin, Xuetao [4 ]
Liu, Jin-Xun [2 ,3 ]
Li, Xin [1 ]
Sun, Xiao-Chen [1 ]
Chang, Xiao-Xia [4 ]
Xu, Bing-Jun [4 ]
Li, Wei-Xue [2 ,3 ]
Ma, Ding [4 ]
Dong, Hao [1 ]
Zhang, Ya-Wen [1 ]
机构
[1] Peking Univ, Coll Chem & Mol Engn, State Key Lab Rare Earth Mat Chem & Applicat, Beijing Natl Lab Mol Sci,PKU HKU Joint Lab Rare Ea, 5 Yiheyuan Rd Haidian Dist, Beijing 100871, Peoples R China
[2] Univ Sci & Technol China, Key Lab Precis & Intelligent Chem, Hefei 230026, Anhui, Peoples R China
[3] Univ Sci & Technol China, Hefei Natl Lab, Hefei 230088, Anhui, Peoples R China
[4] Peking Univ, Beijing Natl Lab Mol Sci, Coll Chem & Mol Engn, 5 Yiheyuan Rd Haidian Dist, Beijing 100871, Peoples R China
基金
中国国家自然科学基金;
关键词
Anions; Carbon Dioxide Electroreduction; Low Overpotential; Transition Metal; METAL-ORGANIC FRAMEWORKS; FINDING SADDLE-POINTS; ELECTROCHEMICAL REDUCTION; CO2; ELECTROREDUCTION; FORMIC-ACID; LIQUID FUEL; MORPHOLOGY; MONOXIDE; ELECTRODE; DYNAMICS;
D O I
10.1002/anie.202405255
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Precise regulation of the active site structure is an important means to enhance the activity and selectivity of catalysts in CO2 electroreduction. Here, we creatively introduce anionic groups, which can not only stabilize metal sites with strong coordination ability but also have rich interactions with protons at active sites to modify the electronic structure and proton transfer process of catalysts. This strategy helps to convert CO2 into fuel chemicals at low overpotentials. As a typical example, a composite catalyst, CuO/Cu-NSO4/CN, with highly dispersed Cu(II)-SO4 sites has been reported, in which CO2 electroreduction to formate occurs at a low overpotential with a high Faradaic efficiency (-0.5 V vs. RHE, FEformate=87.4 %). Pure HCOOH is produced with an energy conversion efficiency of 44.3 % at a cell voltage of 2.8 V. Theoretical modeling demonstrates that sulfate promotes CO2 transformation into a carboxyl intermediate followed by HCOOH generation, whose mechanism is significantly different from that of the traditional process via a formate intermediate for HCOOH production. A CuO/Cu-NSO4/CN composite containing highly dispersed Cu(II)-SO4 sites, where CO2 electroreduction to formate occurs at a low overpotential with high selectivity (-0.5 V vs. RHE, FEformate=87.4 %) via a carboxyl intermediate, was prepared. With the enlightenment of this new pathway, more metals might show their potential to convert CO2 under appropriate modulation. image
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页数:9
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