Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis
Abstract Selective electrochemical water oxidation via a 2e− pathway represents a sustainable H2O2 electrosynthesis route. However, the low activity and selectivity due to competing 4e− oxygen evolution and challenges in separating in-situ-generated H2O2 for subsequent reactions. Herein, we develop...
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-62290-z |
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| author | Fan He Yingnan Liu Xianyun Peng Yaqi Chen Qiang Zheng Bin Yang Zhongjian Li Qiang Zhou Qinghua Zhang Jianguo Lu Lecheng Lei Gang Wu Yang Hou |
| author_facet | Fan He Yingnan Liu Xianyun Peng Yaqi Chen Qiang Zheng Bin Yang Zhongjian Li Qiang Zhou Qinghua Zhang Jianguo Lu Lecheng Lei Gang Wu Yang Hou |
| author_sort | Fan He |
| collection | DOAJ |
| description | Abstract Selective electrochemical water oxidation via a 2e− pathway represents a sustainable H2O2 electrosynthesis route. However, the low activity and selectivity due to competing 4e− oxygen evolution and challenges in separating in-situ-generated H2O2 for subsequent reactions. Herein, we develop an unsaturated coordinative bismuth-benzene tricarboxylic acid metal-organic framework using a hetero-linker doping strategy. The catalyst demonstrates enhanced performance in selective H2O2 synthesis, achieving a low overpotential of 0.98 V and high selectivity with a Faradaic efficiency of 79.1%. The accumulated ~6.17 wt.% H2O2 enables an efficient direct conversion of butanone ammoximation to butanone oxime, showing a high conversion rate of 80.2% and a selectivity of 81.1%. Structural characterizations reveal the unsaturated coordination in the central bismuth atoms. These unsaturated coordinative bismuth sites modulate the OH* intermediate adsorption and optimize the free energy of OH* → H2O2, as revealed by in-situ attenuated total reflection Fourier transform infrared spectroscopy and theoretical calculations. This work provides a strategy for rationalizing selective 2e− water oxidation catalysts and advances the industrially valuable reaction for value-added chemicals production. |
| format | Article |
| id | doaj-art-1ed82cc440f441f4858b00a9600a3b5c |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-1ed82cc440f441f4858b00a9600a3b5c2025-08-20T03:05:10ZengNature PortfolioNature Communications2041-17232025-07-0116111010.1038/s41467-025-62290-zCoordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesisFan He0Yingnan Liu1Xianyun Peng2Yaqi Chen3Qiang Zheng4Bin Yang5Zhongjian Li6Qiang Zhou7Qinghua Zhang8Jianguo Lu9Lecheng Lei10Gang Wu11Yang Hou12Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityCAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Centre for Nanoscience and TechnologyKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityZhejiang Jinhua New Material Co. Ltd.Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityState Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang UniversityKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityDepartment of Chemical and Biological Engineering, University at BuffaloKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang UniversityAbstract Selective electrochemical water oxidation via a 2e− pathway represents a sustainable H2O2 electrosynthesis route. However, the low activity and selectivity due to competing 4e− oxygen evolution and challenges in separating in-situ-generated H2O2 for subsequent reactions. Herein, we develop an unsaturated coordinative bismuth-benzene tricarboxylic acid metal-organic framework using a hetero-linker doping strategy. The catalyst demonstrates enhanced performance in selective H2O2 synthesis, achieving a low overpotential of 0.98 V and high selectivity with a Faradaic efficiency of 79.1%. The accumulated ~6.17 wt.% H2O2 enables an efficient direct conversion of butanone ammoximation to butanone oxime, showing a high conversion rate of 80.2% and a selectivity of 81.1%. Structural characterizations reveal the unsaturated coordination in the central bismuth atoms. These unsaturated coordinative bismuth sites modulate the OH* intermediate adsorption and optimize the free energy of OH* → H2O2, as revealed by in-situ attenuated total reflection Fourier transform infrared spectroscopy and theoretical calculations. This work provides a strategy for rationalizing selective 2e− water oxidation catalysts and advances the industrially valuable reaction for value-added chemicals production.https://doi.org/10.1038/s41467-025-62290-z |
| spellingShingle | Fan He Yingnan Liu Xianyun Peng Yaqi Chen Qiang Zheng Bin Yang Zhongjian Li Qiang Zhou Qinghua Zhang Jianguo Lu Lecheng Lei Gang Wu Yang Hou Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis Nature Communications |
| title | Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis |
| title_full | Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis |
| title_fullStr | Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis |
| title_full_unstemmed | Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis |
| title_short | Coordinatively unsaturated bismuth sites accelerate in-situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis |
| title_sort | coordinatively unsaturated bismuth sites accelerate in situ hydrogen peroxide electrochemical formation for efficient butanone oxime synthesis |
| url | https://doi.org/10.1038/s41467-025-62290-z |
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