Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction
Abstract Regulating the adsorption of an intermediate on an electrocatalyst by manipulating the electron spin state of the transition metal is of great significance for promoting the activation of inert nitrogen molecules (N2) during the electrocatalytic nitrogen reduction reaction (eNRR). However,...
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| Format: | Article |
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Wiley
2024-10-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202407301 |
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| author | Shuai Zhang Weihua Zhao Jiameng Liu Zheng Tao Yinpeng Zhang Shuangrun Zhao Zhihong Zhang Miao Du |
| author_facet | Shuai Zhang Weihua Zhao Jiameng Liu Zheng Tao Yinpeng Zhang Shuangrun Zhao Zhihong Zhang Miao Du |
| author_sort | Shuai Zhang |
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| description | Abstract Regulating the adsorption of an intermediate on an electrocatalyst by manipulating the electron spin state of the transition metal is of great significance for promoting the activation of inert nitrogen molecules (N2) during the electrocatalytic nitrogen reduction reaction (eNRR). However, achieving this remains challenging. Herein, a novel 2D/2D Mott–Schottky heterojunction, Co9S8/Nb2CTx‐P, is developed as an eNRR catalyst. This is achieved through the in situ growth of cobalt sulfide (Co9S8) nanosheets over a Nb2CTx MXene using a solution plasma modification method. Transformation of the Co spin state from low (t2g6eg1) to high (t2g5eg2) is achieved by adjusting the interface electronic structure and sulfur vacancy of Co9S8/Nb2CTx‐P. The adsorption ability of N2 is optimized through high spin Co(II) with more unpaired electrons, significantly accelerating the *N2→*NNH kinetic process. The Co9S8/Nb2CTx‐P exhibits a high NH3 yield of 62.62 µg h−1 mgcat.−1 and a Faradaic efficiency (FE) of 30.33% at −0.40 V versus the reversible hydrogen electrode (RHE) in 0.1 m HCl. Additionally, it achieves an NH3 yield of 41.47 µg h−1 mgcat.−1 and FE of 23.19% at −0.60 V versus RHE in 0.1 m Na2SO4. This work demonstrates a promising strategy for constructing heterojunction electrocatalysts for efficient eNRR. |
| format | Article |
| id | doaj-art-5bbff1e2c19c4eeeb0383e55853d9496 |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2024-10-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-5bbff1e2c19c4eeeb0383e55853d94962025-08-20T02:11:59ZengWileyAdvanced Science2198-38442024-10-011140n/an/a10.1002/advs.202407301Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction ReactionShuai Zhang0Weihua Zhao1Jiameng Liu2Zheng Tao3Yinpeng Zhang4Shuangrun Zhao5Zhihong Zhang6Miao Du7College of Material and Chemical Engineering Institute of New Energy Science and Technology School of Future Hydrogen Energy Technology Zhengzhou University of Light Industry Zhengzhou 450001 P. R. ChinaCollege of Material and Chemical Engineering Institute of New Energy Science and Technology School of Future Hydrogen Energy Technology Zhengzhou University of Light Industry Zhengzhou 450001 P. R. ChinaSchool of Medical Engineering Xinxiang Medical University Xinxiang 453003 P. R. ChinaCollege of Material and Chemical Engineering Institute of New Energy Science and Technology School of Future Hydrogen Energy Technology Zhengzhou University of Light Industry Zhengzhou 450001 P. R. ChinaCollege of Material and Chemical Engineering Institute of New Energy Science and Technology School of Future Hydrogen Energy Technology Zhengzhou University of Light Industry Zhengzhou 450001 P. R. ChinaCollege of Material and Chemical Engineering Institute of New Energy Science and Technology School of Future Hydrogen Energy Technology Zhengzhou University of Light Industry Zhengzhou 450001 P. R. ChinaCollege of Material and Chemical Engineering Institute of New Energy Science and Technology School of Future Hydrogen Energy Technology Zhengzhou University of Light Industry Zhengzhou 450001 P. R. ChinaCollege of Material and Chemical Engineering Institute of New Energy Science and Technology School of Future Hydrogen Energy Technology Zhengzhou University of Light Industry Zhengzhou 450001 P. R. ChinaAbstract Regulating the adsorption of an intermediate on an electrocatalyst by manipulating the electron spin state of the transition metal is of great significance for promoting the activation of inert nitrogen molecules (N2) during the electrocatalytic nitrogen reduction reaction (eNRR). However, achieving this remains challenging. Herein, a novel 2D/2D Mott–Schottky heterojunction, Co9S8/Nb2CTx‐P, is developed as an eNRR catalyst. This is achieved through the in situ growth of cobalt sulfide (Co9S8) nanosheets over a Nb2CTx MXene using a solution plasma modification method. Transformation of the Co spin state from low (t2g6eg1) to high (t2g5eg2) is achieved by adjusting the interface electronic structure and sulfur vacancy of Co9S8/Nb2CTx‐P. The adsorption ability of N2 is optimized through high spin Co(II) with more unpaired electrons, significantly accelerating the *N2→*NNH kinetic process. The Co9S8/Nb2CTx‐P exhibits a high NH3 yield of 62.62 µg h−1 mgcat.−1 and a Faradaic efficiency (FE) of 30.33% at −0.40 V versus the reversible hydrogen electrode (RHE) in 0.1 m HCl. Additionally, it achieves an NH3 yield of 41.47 µg h−1 mgcat.−1 and FE of 23.19% at −0.60 V versus RHE in 0.1 m Na2SO4. This work demonstrates a promising strategy for constructing heterojunction electrocatalysts for efficient eNRR.https://doi.org/10.1002/advs.202407301ammonia synthesiscobalt sulfideNb2CTx MXenenitrogen reduction reactionspin manipulation |
| spellingShingle | Shuai Zhang Weihua Zhao Jiameng Liu Zheng Tao Yinpeng Zhang Shuangrun Zhao Zhihong Zhang Miao Du Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction Advanced Science ammonia synthesis cobalt sulfide Nb2CTx MXene nitrogen reduction reaction spin manipulation |
| title | Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction |
| title_full | Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction |
| title_fullStr | Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction |
| title_full_unstemmed | Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction |
| title_short | Spin Manipulation of Co sites in Co9S8/Nb2CTx Mott–Schottky Heterojunction for Boosting the Electrocatalytic Nitrogen Reduction Reaction |
| title_sort | spin manipulation of co sites in co9s8 nb2ctx mott schottky heterojunction for boosting the electrocatalytic nitrogen reduction reaction |
| topic | ammonia synthesis cobalt sulfide Nb2CTx MXene nitrogen reduction reaction spin manipulation |
| url | https://doi.org/10.1002/advs.202407301 |
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