Zhou Ji-Li, Mu Yan-Fei, Qiao Meng, Zhang Meng-Ran, Yuan Su-Xian, Zhang Min, Lu Tong-Bu
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.
Angew Chem Int Ed Engl. 2025 Jul 7;64(28):e202506963. doi: 10.1002/anie.202506963. Epub 2025 May 15.
The indirect two-step two-electron oxygen reduction reaction (2e ORR) dominates photocatalytic HO synthesis but suffers from sluggish kinetics, •O -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 ZnInS (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 O 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 O activation pathway from indirect to direct 2e ORR process, delivering an exceptional HO production rate of 3121 µmol g h in pure water under simulated AM 1.5G illumination (100 mW cm)-an 11-fold enhancement over ZnInS. The system achieves an unprecedented apparent quantum yield of 49.8% at 365 nm for HO photosynthesis among inorganic semiconducting photocatalysts, and can continuously produce medical-grade HO (3 wt%). This work provides insights for designing efficient HO photocatalysts and beyond.
间接两步双电子氧还原反应（2e ORR）主导着光催化合成HO，但存在动力学迟缓、•O诱导的催化剂降解以及时空载流子-中间体失配等问题。在此，我们开创了一种金属-准金属双位点策略来开启直接一步2e ORR途径，通过具有In-B双活性位点的硼工程化ZnInS（B-ZnInS）光催化剂得以证明。In-B双位点构型通过电荷互补创建了一个电荷平衡电子库，通过双齿配位和双通道电子转移实现适度的O吸附，防止过度的O─O键活化。同时，硼掺杂诱导晶格极化以建立内建电场，使光生载流子寿命相对于原始ZnInS提高了五倍。这些协同作用将O活化途径从间接2e ORR过程转变为直接2e ORR过程，在模拟AM 1.5G光照（100 mW cm）下，在纯水中实现了3121 µmol g h的优异HO生成速率，比ZnInS提高了11倍。该系统在无机半导体光催化剂中，对于365 nm处的HO光合作用实现了前所未有的49.8%表观量子产率，并且能够连续生产医用级HO（3 wt%）。这项工作为设计高效的HO光催化剂及其他方面提供了见解。
