Unlocking One-Step Two-Electron Oxygen Reduction via Metalloid Boron-Modified Zn3In2S6 for Efficient H2O2 Photosynthesis
Ji-Li Zhou
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorCorresponding Author
Dr. Yan-Fei Mu
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu, 225002 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorMeng Qiao
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorMeng-Ran Zhang
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorSu-Xian Yuan
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorCorresponding Author
Dr. Min Zhang
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorCorresponding Author
Prof. Dr. Tong-Bu Lu
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorJi-Li Zhou
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorCorresponding Author
Dr. Yan-Fei Mu
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu, 225002 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorMeng Qiao
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorMeng-Ran Zhang
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorSu-Xian Yuan
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
Search for more papers by this authorCorresponding Author
Dr. Min Zhang
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorCorresponding Author
Prof. Dr. Tong-Bu Lu
MOE International Joint Laboratory of Materials Microstructure, Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorGraphical Abstract
A boron-modified Zn3In2S6 photocatalyst is engineered, featuring In-B dual-active sites that establish dual-channel carrier transfer pathways and substantially prolong photogenerated carrier lifetimes five-fold. These synergistic effects enable direct one-step 2e− ORR for efficient H2O2 production from O2 in pure water, achieving a record apparent quantum yield of 49.8% at 365 nm among inorganic semiconductor photocatalysts.
Abstract
The indirect two-step two-electron oxygen reduction reaction (2e− ORR) dominates photocatalytic H2O2 synthesis but suffers from sluggish kinetics, •O2−-induced catalyst degradation, and spatiotemporal carrier-intermediate mismatch. Herein, we pioneer a metal-metalloid dual-site strategy to unlock the direct one-step 2e− ORR pathway, demonstrated through boron-engineered Zn3In2S6 (B-ZnInS) photocatalyst with In-B dual-active sites. The In-B dual-site configuration creates a charge-balanced electron reservoir by charge complementation, which achieves moderate O2 adsorption via bidentate coordination and dual-channel electron transfer, preventing excessive O─O bond activation. Simultaneously, boron doping induces lattice polarization to establish a built-in electric field, quintupling photogenerated carrier lifetimes versus pristine ZnInS. These synergies redirect the O2 activation pathway from indirect to direct 2e− ORR process, delivering an exceptional H2O2 production rate of 3121 µmol g−1 h−1 in pure water under simulated AM 1.5G illumination (100 mW cm−2)—an 11-fold enhancement over ZnInS. The system achieves an unprecedented apparent quantum yield of 49.8% at 365 nm for H2O2 photosynthesis among inorganic semiconducting photocatalysts, and can continuously produce medical-grade H2O2 (3 wt%). This work provides insights for designing efficient H2O2 photocatalysts and beyond.
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.
Supporting Information
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Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
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