文献类型：期刊文献

英文题名：Clarifying the Direct Generation of ?OH Radicals in Photocatalytic O2 Reduction: Theoretical Prediction Combined with Experimental Validation

作者：Cheng, Qian[1];Wei, Hehe[1];Wang, Jinling[1];Wang, Zhi-Qiang[1];Gong, Xue-Qing[2];Wang, Dong[1]

机构：[1]East China Univ Sci & Technol, Res Inst Ind Catalysis, Ctr Computat Chem, Sch Chem & Mol Engn,State Key Lab Green Chem Engn, Shanghai 200237, Peoples R China;[2]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, 800 Dongchuan Rd, Shanghai 200240, Peoples R China

年份：2024

卷号：15

期号：34

起止页码：8650

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY LETTERS

收录：;EI(收录号：20243516948787);WOS:【SCI-EXPANDED(收录号:WOS:001293334300001)】；

基金：This work was financially supported by the National Key Research and Development Program of China (2021YFB3501900), National Natural Science Foundation of China (22273021), and Shanghai Science and Technology Development Funds (22QA1402900).

语种：英文

外文关键词：Bioremediation - Electron resonance - Electron spin resonance spectroscopy - Hydrogenation - Paramagnetic resonance - Photocatalytic activity - Photodegradation - Photooxidation - Redox reactions

摘要：This work systematically studied thermocatalytic and photocatalytic pathways of formaldehyde degradation and H-assisted O-2 reduction over a Pt-13/anatase-TiO2(101) composite via DFT calculations together with constrained molecular dynamics (MD) simulations. We show that photocatalytic O-2 reduction on Pt/TiO2 can directly generate center dot OH radicals (*O-2 -> *OOH -> center dot OH) via two hydrogenation steps with small barriers, and the product selectivity (*H2O2 or center dot OH) is decided by the relative position between catalyst Fermi level and center dot OH/*H2O2 redox potential (theoretical determination of 0.07 V referencing to the SHE). Such a novel reaction channel was furthermore validated at the liquid-solid interface via constrained MD simulations and experimental electron paramagnetic resonance detections, and a wide range of H resources, e.g., *HCHO, *HCO, *H (H+ + e (-) ), can always drive the direct center dot OH generation. The additional portion of e (-) -triggered center dot OH radicals are prone to diffuse into solution or the TiO2 surface and furthermore cooperate with the conventional h + -driven photooxidations.