Electron‐Trap Induced “Hot” Microenvironment Boosting Photocatalytic Nitrogen Fixation
Abstract
Abstract Plasmonic photocatalysis aims to develop a highly reactive surface enriched with hot carriers to enable challenging chemical processes, including high‐energy‐barrier nitrogen reduction reactions. In traditional plasmonic photocatalysis, hot carriers often undergo rapid thermalization, leading to suboptimal catalytic efficiency. Moreover, the role of hot carriers in surface reactions is often complex and frequently overlooked. Here, we designed a photocatalyst through loading Au nanoparticles on Mo‐doped W 18 O 49 nanorods (Au‐MWO‐S) to achieve efficient nitrogen reduction to produce ammonia, with a formation rate reaching 571.0 µmol h −1 g −1 and solar‐to‐ammonia (STA) conversion efficiency up to 0.28%. It was revealed through in situ experiments and theoretical simulations that the shallow energy‐level defects in MWO‐S act as electron traps to rapidly capture, store, and release hot electrons, which greatly reduces the thermalization of hot electrons. At the same time, the local electromagnetic field of MWO‐S was enhanced, creating a high‐activity “hot” microenvironment on the surface of the photocatalyst. This, in turn, increased the occupancy of electrons in the anti‐bonding orbitals of N 2 , significantly promoting photocatalytic nitrogen reduction reaction (pNRR). This work unveils the mechanism of hot carrier participation in surface reactions, inspiring the development of catalytic systems with hot‐electron‐active surfaces.
Article Details
Authors (13)
Bing‐Hao Wang
Advanced Catalytic Engineering Research Center of the Ministry of Education State Key Laboratory of Chemo and Biosensing College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P.R. China
Guang‐Hui Chen
Advanced Catalytic Engineering Research Center of the Ministry of Education State Key Laboratory of Chemo and Biosensing College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P.R. China
Sheng Tian
Advanced Catalytic Engineering Research Center of the Ministry of Education State Key Laboratory of Chemo and Biosensing College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P.R. China
Huijuan Wang
Yu‐Yun Liu
Advanced Catalytic Engineering Research Center of the Ministry of Education State Key Laboratory of Chemo and Biosensing College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P.R. China
Xiong Wang
Department of Physics, The University of Hong Kong, Pokfulam Road, Hong Kong, Hong Kong SAR, China
Xing‐Sheng Hu
Advanced Catalytic Engineering Research Center of the Ministry of Education State Key Laboratory of Chemo and Biosensing College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P.R. China
Chao Peng
Jin‐Xin Li
Advanced Catalytic Engineering Research Center of the Ministry of Education State Key Laboratory of Chemo and Biosensing College of Chemistry and Chemical Engineering Hunan University Changsha 410082 P.R. China
Yang Li
Li‐Long Jiang
College of Chemical Engineering Fuzhou University Fuzhou 350002 P.R. China
Lang Chen
Collaborative Innovation Center for Statistical Data Engineering, Technology and Application School of Statistics and Mathematics, Zhejiang Gongshang University
Shuang‐Feng Yin
College of Materials and Energy Central South University of Forestry and Technology Changsha People's Republic of China