Achieving Photocatalytic Overall Nitrogen Fixation via an Enzymatic Pathway on a Distorted CoP4 Configuration
Corresponding Author
Xin Wang
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055 China
Shenzhen University of Advanced Technology, Shenzhen, 518107 China
These authors contributed equally to this work.
Search for more papers by this authorYuqi Zhao
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055 China
School of Materials Science and Engineering, Shan-dong University of Science and Technology, Qingdao, 266590 China
These authors contributed equally to this work.
Search for more papers by this authorXi Wu
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055 China
Shenzhen Institute of Translational Medicine, The First Affiliated Hospital of Shenzhen University, Shenzhen Second People's Hospital, Shenzhen, 518035 China
Search for more papers by this authorBin Zhang
Shenzhen Institute of Translational Medicine, The First Affiliated Hospital of Shenzhen University, Shenzhen Second People's Hospital, Shenzhen, 518035 China
Search for more papers by this authorJian Tian
School of Materials Science and Engineering, Shan-dong University of Science and Technology, Qingdao, 266590 China
Search for more papers by this authorCorresponding Author
Wai-Yeung Wong
Department of Applied Biology and Chemical Technology and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, China
Search for more papers by this authorCorresponding Author
Fuxiang Zhang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian, 116023 China
Search for more papers by this authorCorresponding Author
Xin Wang
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055 China
Shenzhen University of Advanced Technology, Shenzhen, 518107 China
These authors contributed equally to this work.
Search for more papers by this authorYuqi Zhao
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055 China
School of Materials Science and Engineering, Shan-dong University of Science and Technology, Qingdao, 266590 China
These authors contributed equally to this work.
Search for more papers by this authorXi Wu
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055 China
Shenzhen Institute of Translational Medicine, The First Affiliated Hospital of Shenzhen University, Shenzhen Second People's Hospital, Shenzhen, 518035 China
Search for more papers by this authorBin Zhang
Shenzhen Institute of Translational Medicine, The First Affiliated Hospital of Shenzhen University, Shenzhen Second People's Hospital, Shenzhen, 518035 China
Search for more papers by this authorJian Tian
School of Materials Science and Engineering, Shan-dong University of Science and Technology, Qingdao, 266590 China
Search for more papers by this authorCorresponding Author
Wai-Yeung Wong
Department of Applied Biology and Chemical Technology and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong, China
Search for more papers by this authorCorresponding Author
Fuxiang Zhang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian, 116023 China
Search for more papers by this authorAbstract
Photocatalytic nitrogen (N2) fixation over semiconductors has always suffered from poor conversion efficiency owing to weak N2 adsorption and the difficulty of N≡N triple bond dissociation. Herein, a Co single-atom catalyst (SAC) model with a C-defect-evoked CoP4 distorted configuration was fabricated using a selective phosphidation strategy, wherein P-doping and C defects co-regulate the local electronic structure of Co sites. Comprehensive experiments and theoretical calculations revealed that the distorted CoP4 configuration caused a strong charge redistribution between the Co atoms and adjacent C atoms, minimizing their electronegativity difference. Consequently, the N2 adsorption pattern switched from an “end-on” to a “side-on” mode with a high N2 adsorption energy of −1.40 eV and an elongated N−N bond length of 1.20 Å, notably decreasing the N2 adsorption/activation energy barrier. In the absence of sacrificial agents, the Co SAC achieved excellent photocatalytic overall N2 fixation performance via an enzymatic pathway. The NH3 yielding rate peaked at 1249.5 μmol h−1 g−1 with an apparent quantum yield of 3.51 % at 365 nm. Moreover, the selective phosphidation strategy has universality for synthesizing other SACs, such as those containing Ni and Fe. This study offers new insight into co-regulating the electronic structure of SACs for efficient photocatalytic overall N2 fixation.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
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