Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site Catalysts
Abstract Electrochemical co‐reduction of carbon dioxide and nitrates (CO2NO3RR) holds promise for sustainable urea production. However, the sluggish kinetics of the sixteen‐electron transfer and unclear mechanistic understanding strongly impede its development. Here, combined experimental and comput...
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Wiley
2025-07-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202501882 |
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| author | Qinglan Zhao Yushen Liu Yuan Zhang Shangqian Zhu Hongming Xu Mohammad Farhadpour Fei Xiao Minghui Xing Dapeng Cao Xueping Qin Tejs Vegge Minhua Shao |
| author_facet | Qinglan Zhao Yushen Liu Yuan Zhang Shangqian Zhu Hongming Xu Mohammad Farhadpour Fei Xiao Minghui Xing Dapeng Cao Xueping Qin Tejs Vegge Minhua Shao |
| author_sort | Qinglan Zhao |
| collection | DOAJ |
| description | Abstract Electrochemical co‐reduction of carbon dioxide and nitrates (CO2NO3RR) holds promise for sustainable urea production. However, the sluggish kinetics of the sixteen‐electron transfer and unclear mechanistic understanding strongly impede its development. Here, combined experimental and computational approaches are employed to screen a series of metal phthalocyanine as model catalysts (MPcs, M = Zn, Co, Ni, Cu, and Fe) to uncover the activity‐selectivity trends in electrochemical CO2NO3RR. The theoretical simulations reveal that the thermodynamics of urea synthesis is significantly influenced by key intermediates, where the enhanced adsorption of *HOOCNO, coupled with reduced adsorptions of *N and *COOH, and moderate adsorption of *H2O, can significantly promote the urea production. ΔG*HOOCNO−ΔG*N−ΔG*COOH+ΔG*H2O as a potential descriptor is proposed for predicting the efficiency of CO2NO3RR toward urea formation. The findings provide systematic guidance for the future design of high‐efficiency catalysts for urea electrosynthesis, addressing a crucial need for sustainable nitrogen fixation. |
| format | Article |
| id | doaj-art-c026a0fd2deb4bbd8a2dedddb9c2cc1b |
| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-c026a0fd2deb4bbd8a2dedddb9c2cc1b2025-08-20T03:50:58ZengWileyAdvanced Science2198-38442025-07-011227n/an/a10.1002/advs.202501882Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site CatalystsQinglan Zhao0Yushen Liu1Yuan Zhang2Shangqian Zhu3Hongming Xu4Mohammad Farhadpour5Fei Xiao6Minghui Xing7Dapeng Cao8Xueping Qin9Tejs Vegge10Minhua Shao11Department of Chemical and Biological Engineering The Hong Kong University of Science and Technology Clear Water Bay, Kowloon Hong Kong P. R. ChinaDepartment of Chemical and Biological Engineering The Hong Kong University of Science and Technology Clear Water Bay, Kowloon Hong Kong P. R. ChinaDepartment of Chemical and Biological Engineering The Hong Kong University of Science and Technology Clear Water Bay, Kowloon Hong Kong P. R. ChinaSchool of Chemistry and Chemical Engineering Southeast University Jiangning District Nanjing Jiangsu 211189 P. R. ChinaDepartment of Chemical and Biological Engineering The Hong Kong University of Science and Technology Clear Water Bay, Kowloon Hong Kong P. R. ChinaDepartment of Chemical and Biological Engineering The Hong Kong University of Science and Technology Clear Water Bay, Kowloon Hong Kong P. R. ChinaDepartment of Chemical and Biological Engineering The Hong Kong University of Science and Technology Clear Water Bay, Kowloon Hong Kong P. R. ChinaState Key Laboratory of Organic‐Inorganic Composites Beijing University of Chemical Technology Beijing 100029 P. R. ChinaState Key Laboratory of Organic‐Inorganic Composites Beijing University of Chemical Technology Beijing 100029 P. R. ChinaDepartment of Energy Conversion and Storage Technical University of Denmark Lyngby 2800 Kgs. DenmarkDepartment of Energy Conversion and Storage Technical University of Denmark Lyngby 2800 Kgs. DenmarkDepartment of Chemical and Biological Engineering The Hong Kong University of Science and Technology Clear Water Bay, Kowloon Hong Kong P. R. ChinaAbstract Electrochemical co‐reduction of carbon dioxide and nitrates (CO2NO3RR) holds promise for sustainable urea production. However, the sluggish kinetics of the sixteen‐electron transfer and unclear mechanistic understanding strongly impede its development. Here, combined experimental and computational approaches are employed to screen a series of metal phthalocyanine as model catalysts (MPcs, M = Zn, Co, Ni, Cu, and Fe) to uncover the activity‐selectivity trends in electrochemical CO2NO3RR. The theoretical simulations reveal that the thermodynamics of urea synthesis is significantly influenced by key intermediates, where the enhanced adsorption of *HOOCNO, coupled with reduced adsorptions of *N and *COOH, and moderate adsorption of *H2O, can significantly promote the urea production. ΔG*HOOCNO−ΔG*N−ΔG*COOH+ΔG*H2O as a potential descriptor is proposed for predicting the efficiency of CO2NO3RR toward urea formation. The findings provide systematic guidance for the future design of high‐efficiency catalysts for urea electrosynthesis, addressing a crucial need for sustainable nitrogen fixation.https://doi.org/10.1002/advs.202501882activity‐selectivity trendC‐N couplingco‐reduction reactionelectrocatalysissingle‐site catalyst |
| spellingShingle | Qinglan Zhao Yushen Liu Yuan Zhang Shangqian Zhu Hongming Xu Mohammad Farhadpour Fei Xiao Minghui Xing Dapeng Cao Xueping Qin Tejs Vegge Minhua Shao Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site Catalysts Advanced Science activity‐selectivity trend C‐N coupling co‐reduction reaction electrocatalysis single‐site catalyst |
| title | Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site Catalysts |
| title_full | Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site Catalysts |
| title_fullStr | Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site Catalysts |
| title_full_unstemmed | Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site Catalysts |
| title_short | Activity‐Selectivity Trends in Electrochemical Urea Synthesis: Co‐Reduction of CO2 and Nitrates Over Single‐Site Catalysts |
| title_sort | activity selectivity trends in electrochemical urea synthesis co reduction of co2 and nitrates over single site catalysts |
| topic | activity‐selectivity trend C‐N coupling co‐reduction reaction electrocatalysis single‐site catalyst |
| url | https://doi.org/10.1002/advs.202501882 |
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