Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen Evolution
Abstract Spinel‐type nickel ferrite (NixFe3‐xO4, x≤1) is a widely used electrocatalyst for the oxygen evolution reaction (OER). Due to the lower hybridization of metal‐d and oxygen‐p orbitals, the OER process on NixFe3‐xO4 follows the sluggish adsorbate evolution mechanism (AEM). Generally, activati...
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2025-02-01
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| Online Access: | https://doi.org/10.1002/advs.202409024 |
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| author | Yang Peng Xu Zhao Yiqun Shao Xin Yue Zhuofeng Hu Shaoming Huang |
| author_facet | Yang Peng Xu Zhao Yiqun Shao Xin Yue Zhuofeng Hu Shaoming Huang |
| author_sort | Yang Peng |
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| description | Abstract Spinel‐type nickel ferrite (NixFe3‐xO4, x≤1) is a widely used electrocatalyst for the oxygen evolution reaction (OER). Due to the lower hybridization of metal‐d and oxygen‐p orbitals, the OER process on NixFe3‐xO4 follows the sluggish adsorbate evolution mechanism (AEM). Generally, activating the lattice oxygen to trigger the lattice‐oxygen‐mediated mechanism (LOM) can enhance the OER activity. Herein, to trigger the LOM pathway while maintaining high stability, iron foam (IF)‐supported Ni0.75Fe2.25O4 (NiFeO) with geometrical defects of [NiO6] (nickel cation coordinated with six oxygen anions) units and higher ratio of Fe to Ni cations in octahedral sites (d‐NiFeHRO/IF) is prepared by ion‐exchanging with polar aprotic solvent followed by annealing. As a result, as‐synthesized d‐NiFeHRO/IF exhibits excellent activity (at 295 mV overpotential to achieve 100 mA cm−2), fast kinetics (Tafel slope of only 34.6 mV dec−1), and high stability (maintaining a current density of 100 mA cm−2 over 130 h) for the OER. The theoretical calculations reveal that the construction of octahedral defect in NixFe3‐xO4 enhances the overlap of Fe‐d and O‐p orbitals, which can activate the lattice oxygen. Therefore, increasing the ratio of Fe to Ni will further improve the lattice oxygen redox activity, and thus trigger the fast LOM pathway, ultimately facilitating the OER process. |
| format | Article |
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| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-02-01 |
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| spelling | doaj-art-819d61f5c87a4018853a661b096ac4062025-02-04T13:14:55ZengWileyAdvanced Science2198-38442025-02-01125n/an/a10.1002/advs.202409024Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen EvolutionYang Peng0Xu Zhao1Yiqun Shao2Xin Yue3Zhuofeng Hu4Shaoming Huang5Guangzhou Key Laboratory of Low‐Dimensional Materials and Energy Storage Devices Collaborative Innovation Center of Advanced Energy Materials School of Materials and Energy Guangdong University of Technology Guangzhou 510006 ChinaGuangzhou Key Laboratory of Low‐Dimensional Materials and Energy Storage Devices Collaborative Innovation Center of Advanced Energy Materials School of Materials and Energy Guangdong University of Technology Guangzhou 510006 ChinaGuangzhou Key Laboratory of Low‐Dimensional Materials and Energy Storage Devices Collaborative Innovation Center of Advanced Energy Materials School of Materials and Energy Guangdong University of Technology Guangzhou 510006 ChinaGuangzhou Key Laboratory of Low‐Dimensional Materials and Energy Storage Devices Collaborative Innovation Center of Advanced Energy Materials School of Materials and Energy Guangdong University of Technology Guangzhou 510006 ChinaSchool of Environmental Science and Engineering Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology Sun Yat‐sen University Guangzhou 510006 ChinaGuangzhou Key Laboratory of Low‐Dimensional Materials and Energy Storage Devices Collaborative Innovation Center of Advanced Energy Materials School of Materials and Energy Guangdong University of Technology Guangzhou 510006 ChinaAbstract Spinel‐type nickel ferrite (NixFe3‐xO4, x≤1) is a widely used electrocatalyst for the oxygen evolution reaction (OER). Due to the lower hybridization of metal‐d and oxygen‐p orbitals, the OER process on NixFe3‐xO4 follows the sluggish adsorbate evolution mechanism (AEM). Generally, activating the lattice oxygen to trigger the lattice‐oxygen‐mediated mechanism (LOM) can enhance the OER activity. Herein, to trigger the LOM pathway while maintaining high stability, iron foam (IF)‐supported Ni0.75Fe2.25O4 (NiFeO) with geometrical defects of [NiO6] (nickel cation coordinated with six oxygen anions) units and higher ratio of Fe to Ni cations in octahedral sites (d‐NiFeHRO/IF) is prepared by ion‐exchanging with polar aprotic solvent followed by annealing. As a result, as‐synthesized d‐NiFeHRO/IF exhibits excellent activity (at 295 mV overpotential to achieve 100 mA cm−2), fast kinetics (Tafel slope of only 34.6 mV dec−1), and high stability (maintaining a current density of 100 mA cm−2 over 130 h) for the OER. The theoretical calculations reveal that the construction of octahedral defect in NixFe3‐xO4 enhances the overlap of Fe‐d and O‐p orbitals, which can activate the lattice oxygen. Therefore, increasing the ratio of Fe to Ni will further improve the lattice oxygen redox activity, and thus trigger the fast LOM pathway, ultimately facilitating the OER process.https://doi.org/10.1002/advs.202409024adsorbate evolution mechanismlattice‐oxygen‐mediated mechanismoctahedral geometrical defectsoxygen evolution reactionspinel‐type Ni─Fe oxides |
| spellingShingle | Yang Peng Xu Zhao Yiqun Shao Xin Yue Zhuofeng Hu Shaoming Huang Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen Evolution Advanced Science adsorbate evolution mechanism lattice‐oxygen‐mediated mechanism octahedral geometrical defects oxygen evolution reaction spinel‐type Ni─Fe oxides |
| title | Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen Evolution |
| title_full | Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen Evolution |
| title_fullStr | Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen Evolution |
| title_full_unstemmed | Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen Evolution |
| title_short | Triggering Oxygen Redox Cycles in Nickel Ferrite by Octahedral Geometry Engineering for Enhancing Oxygen Evolution |
| title_sort | triggering oxygen redox cycles in nickel ferrite by octahedral geometry engineering for enhancing oxygen evolution |
| topic | adsorbate evolution mechanism lattice‐oxygen‐mediated mechanism octahedral geometrical defects oxygen evolution reaction spinel‐type Ni─Fe oxides |
| url | https://doi.org/10.1002/advs.202409024 |
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