Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation
Abstract Understanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well‐defined FeN4 and MoN4 coordi...
| Main Authors: | , , , , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2021-10-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202102915 |
| _version_ | 1819021135670411264 |
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| author | Yajin Wang Wenzheng Cheng Pengfei Yuan Gege Yang Shichun Mu Jialin Liang Huicong Xia Kai Guo Mengli Liu Shuyan Zhao Gan Qu Bang‐An Lu Yongfeng Hu Jinsong Hu Jia‐Nan Zhang |
| author_facet | Yajin Wang Wenzheng Cheng Pengfei Yuan Gege Yang Shichun Mu Jialin Liang Huicong Xia Kai Guo Mengli Liu Shuyan Zhao Gan Qu Bang‐An Lu Yongfeng Hu Jinsong Hu Jia‐Nan Zhang |
| author_sort | Yajin Wang |
| collection | DOAJ |
| description | Abstract Understanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well‐defined FeN4 and MoN4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN4 on NRR behavior. The neighboring MoN4 can regulate the spin state of Fe center in FeN4 from high‐spin (dxy2dyz1dxz1dz21dx2−y21) to medium‐spin (dxy2dyz2dxz1dz21), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN4 instead of MoN4, and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N2. As a result, FeMoPPc with medium‐spin FeN4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH3 yields for NRR than FePPc with high‐spin FeN4 and MoPPc with MoN4, respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers. |
| first_indexed | 2024-12-21T04:02:18Z |
| format | Article |
| id | doaj.art-186ccb73688f45c1bcda05b03f0ab93c |
| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-12-21T04:02:18Z |
| publishDate | 2021-10-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj.art-186ccb73688f45c1bcda05b03f0ab93c2022-12-21T19:16:40ZengWileyAdvanced Science2198-38442021-10-01820n/an/a10.1002/advs.202102915Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin RegulationYajin Wang0Wenzheng Cheng1Pengfei Yuan2Gege Yang3Shichun Mu4Jialin Liang5Huicong Xia6Kai Guo7Mengli Liu8Shuyan Zhao9Gan Qu10Bang‐An Lu11Yongfeng Hu12Jinsong Hu13Jia‐Nan Zhang14College of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaInternational Joint Research Laboratory for Quantum Functional Materials of Henan Province and School of Physics and Microelectronics Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaState Key Laboratory of Advanced Technology for Materials Synthesis and Processing Wuhan University of Technology Wuhan 430070 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaCanadian Light Source 44 Innovation Boulevard Saskatoon Saskatoon SK S7N 2V3 CanadaBeijing National Laboratory for Molecular Sciences (BNLMS) CAS Key Laboratory of Molecular Nanostructure and Nanotechnology Institute of Chemistry Chinese Academy of Sciences Beijing 100190 ChinaCollege of Materials Science and Engineering Zhengzhou University Zhengzhou 450001 P. R. ChinaAbstract Understanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well‐defined FeN4 and MoN4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN4 on NRR behavior. The neighboring MoN4 can regulate the spin state of Fe center in FeN4 from high‐spin (dxy2dyz1dxz1dz21dx2−y21) to medium‐spin (dxy2dyz2dxz1dz21), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN4 instead of MoN4, and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N2. As a result, FeMoPPc with medium‐spin FeN4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH3 yields for NRR than FePPc with high‐spin FeN4 and MoPPc with MoN4, respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers.https://doi.org/10.1002/advs.202102915charge accumulationelectron spin statenitrogen reduction reactionsingle atom catalysts |
| spellingShingle | Yajin Wang Wenzheng Cheng Pengfei Yuan Gege Yang Shichun Mu Jialin Liang Huicong Xia Kai Guo Mengli Liu Shuyan Zhao Gan Qu Bang‐An Lu Yongfeng Hu Jinsong Hu Jia‐Nan Zhang Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation Advanced Science charge accumulation electron spin state nitrogen reduction reaction single atom catalysts |
| title | Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation |
| title_full | Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation |
| title_fullStr | Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation |
| title_full_unstemmed | Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation |
| title_short | Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation |
| title_sort | boosting nitrogen reduction to ammonia on fen4 sites by atomic spin regulation |
| topic | charge accumulation electron spin state nitrogen reduction reaction single atom catalysts |
| url | https://doi.org/10.1002/advs.202102915 |
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