Drawing inspiration from the biological nitrogenase mechanism,bionic photocatalytic nitrogen fixation technology plays a significant role in activating nitrogen molecules and promoting the nitrogen reduction reaction....Drawing inspiration from the biological nitrogenase mechanism,bionic photocatalytic nitrogen fixation technology plays a significant role in activating nitrogen molecules and promoting the nitrogen reduction reaction.However,developing effective semiconductor photocatalysts remains a considerable challenge in the field of bionic nitrogen fixation.Herein,a novel bionic“FeV-cofactor”system for performing photocatalytic nitrogen reduction was proposed for the first time based on an Fe-doped BiVO_(4) photocatalyst decorated with few-layer 2D black phosphorus(BP).As expected,Fe doping and BP decoration significantly improved the NH_(3) yield of BiVO_(4).With an NH_(3) yield of 337.9μmol g^(−1) h^(−1)(6.83 times that of BiVO_(4)),FeBiVO_(4)-0.05BP ranks among the top-performing nitrogen-fixing materials in oxide-based photocatalysts.DFT calculations show that N_(2) molecules can be adsorbed and activated by Fe doping,thus forming the in-built bionic“FeV-cofactor”.The experimental results further confirm that introducing a bionic“FeV-cofactor”system enhances the electron transfer between redox couples(V^(5+)/V^(4+)&Fe^(3+)/Fe^(2+))and N_(2),thus improving the carrier separation efficiency.Oxygen vacancies coupled with V4+ions also contribute to increasing light absorption.The 2D BP decoration plays a crucial role in the whole process of nitrogen reduction due to its exceptional electron transfer ability while increasing the active sites of the reaction.展开更多
基金supported by the Natural Science Foundation of Guangxi Province(No.2021GXNSFAA220108,2020GXNSFBA297122)Specific Research Project of Guangxi for Research Bases and Talents(No.AD20297134)+2 种基金National Key Research and Development Program(No.2022YFEO134600,2021YFA0715404)Guangxi Key Research and Development Program(No.2021AB05083)Science,Education and Industry Integration of Basic Research Projects of Qilu University of Technology(Grant No.2022PY062).
文摘Drawing inspiration from the biological nitrogenase mechanism,bionic photocatalytic nitrogen fixation technology plays a significant role in activating nitrogen molecules and promoting the nitrogen reduction reaction.However,developing effective semiconductor photocatalysts remains a considerable challenge in the field of bionic nitrogen fixation.Herein,a novel bionic“FeV-cofactor”system for performing photocatalytic nitrogen reduction was proposed for the first time based on an Fe-doped BiVO_(4) photocatalyst decorated with few-layer 2D black phosphorus(BP).As expected,Fe doping and BP decoration significantly improved the NH_(3) yield of BiVO_(4).With an NH_(3) yield of 337.9μmol g^(−1) h^(−1)(6.83 times that of BiVO_(4)),FeBiVO_(4)-0.05BP ranks among the top-performing nitrogen-fixing materials in oxide-based photocatalysts.DFT calculations show that N_(2) molecules can be adsorbed and activated by Fe doping,thus forming the in-built bionic“FeV-cofactor”.The experimental results further confirm that introducing a bionic“FeV-cofactor”system enhances the electron transfer between redox couples(V^(5+)/V^(4+)&Fe^(3+)/Fe^(2+))and N_(2),thus improving the carrier separation efficiency.Oxygen vacancies coupled with V4+ions also contribute to increasing light absorption.The 2D BP decoration plays a crucial role in the whole process of nitrogen reduction due to its exceptional electron transfer ability while increasing the active sites of the reaction.
