Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen Batteries
ABSTRACT Understanding and regulating the electronic states of single‐atom sites near the Fermi energy level are essential for developing effective electrocatalysts for lithium–oxygen batteries (LOBs). In this study, we introduce an axial oxygen ligand at the metal center of cobalt porphyrin (CoPP)...
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| Format: | Article |
| Language: | English |
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Wiley
2025-06-01
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| Series: | SusMat |
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| Online Access: | https://doi.org/10.1002/sus2.70007 |
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| author | Pengfei Liu Chuan Wang Chenrui Zeng Shuhan Wang Xudong Yu Haoruo Xiao Yan Huang Yang Zhang Ying Zeng Chaozhu Shu Zhenxing Liang |
| author_facet | Pengfei Liu Chuan Wang Chenrui Zeng Shuhan Wang Xudong Yu Haoruo Xiao Yan Huang Yang Zhang Ying Zeng Chaozhu Shu Zhenxing Liang |
| author_sort | Pengfei Liu |
| collection | DOAJ |
| description | ABSTRACT Understanding and regulating the electronic states of single‐atom sites near the Fermi energy level are essential for developing effective electrocatalysts for lithium–oxygen batteries (LOBs). In this study, we introduce an axial oxygen ligand at the metal center of cobalt porphyrin (CoPP) to adjust the electronic state of the Co center. Theoretical calculations and experimental findings show that this axial interaction disrupts the planar tetragonal crystal field of CoPP, resulting in enhanced spin polarization and electronic rearrangement. This rearrangement of d orbitals causes an upward shift in the frontier orbitals, which facilitates electron exchange during reactions. Additionally, the increased number of unpaired electrons in the d orbitals enhances the adsorption of CoPP‐O‐MXene to various oxygen species, promoting the formation of a thin film‐like Li2O2. These thin film‐like discharge products improve contact with the electrode surfaces, leading to easier decomposition during the charging process. Consequently, CoPP‐O‐MXene‐based LOBs demonstrate a high discharge capacity of 11035 mAh g−¹, a low overpotential of 0.76 V, and remarkable cycling stability (445 cycles). |
| format | Article |
| id | doaj-art-ec79be33aeb44aa49b6f2ac2d9aea581 |
| institution | OA Journals |
| issn | 2692-4552 |
| language | English |
| publishDate | 2025-06-01 |
| publisher | Wiley |
| record_format | Article |
| series | SusMat |
| spelling | doaj-art-ec79be33aeb44aa49b6f2ac2d9aea5812025-08-20T02:36:27ZengWileySusMat2692-45522025-06-0153n/an/a10.1002/sus2.70007Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen BatteriesPengfei Liu0Chuan Wang1Chenrui Zeng2Shuhan Wang3Xudong Yu4Haoruo Xiao5Yan Huang6Yang Zhang7Ying Zeng8Chaozhu Shu9Zhenxing Liang10College of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaCollege of Materials and Chemistry & Chemical Engineering Chengdu University of Technology Chengdu Sichuan ChinaGuangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering South China University of Technology Guangzhou ChinaABSTRACT Understanding and regulating the electronic states of single‐atom sites near the Fermi energy level are essential for developing effective electrocatalysts for lithium–oxygen batteries (LOBs). In this study, we introduce an axial oxygen ligand at the metal center of cobalt porphyrin (CoPP) to adjust the electronic state of the Co center. Theoretical calculations and experimental findings show that this axial interaction disrupts the planar tetragonal crystal field of CoPP, resulting in enhanced spin polarization and electronic rearrangement. This rearrangement of d orbitals causes an upward shift in the frontier orbitals, which facilitates electron exchange during reactions. Additionally, the increased number of unpaired electrons in the d orbitals enhances the adsorption of CoPP‐O‐MXene to various oxygen species, promoting the formation of a thin film‐like Li2O2. These thin film‐like discharge products improve contact with the electrode surfaces, leading to easier decomposition during the charging process. Consequently, CoPP‐O‐MXene‐based LOBs demonstrate a high discharge capacity of 11035 mAh g−¹, a low overpotential of 0.76 V, and remarkable cycling stability (445 cycles).https://doi.org/10.1002/sus2.70007axial ligandselectrocatalystlithium–oxygen batteryoxygen electrode reactionsingle‐atom sites |
| spellingShingle | Pengfei Liu Chuan Wang Chenrui Zeng Shuhan Wang Xudong Yu Haoruo Xiao Yan Huang Yang Zhang Ying Zeng Chaozhu Shu Zhenxing Liang Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen Batteries SusMat axial ligands electrocatalyst lithium–oxygen battery oxygen electrode reaction single‐atom sites |
| title | Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen Batteries |
| title_full | Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen Batteries |
| title_fullStr | Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen Batteries |
| title_full_unstemmed | Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen Batteries |
| title_short | Single‐Atom Sites With Axial Ligand‐Induced d Orbital Rearrangement as Efficient Electrocatalysts for Lithium–Oxygen Batteries |
| title_sort | single atom sites with axial ligand induced d orbital rearrangement as efficient electrocatalysts for lithium oxygen batteries |
| topic | axial ligands electrocatalyst lithium–oxygen battery oxygen electrode reaction single‐atom sites |
| url | https://doi.org/10.1002/sus2.70007 |
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