ZnIn2S4/MOF S-scheme photocatalyst for H2 production and its femtosecond transient absorption mechanism

Jiajie Cai ¹Bowen Liu ¹Shumin Zhang ²Linxi Wang ³Zhen Wu ⁴Jianjun Zhang ³Bei Cheng¹

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作者信息

1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,Wuhan University of Technology,Wuhan 430070,China
2. Hunan Key Laboratory of Applied Environmental Photocatalysis,Changsha University,Changsha 410022,China
3. Laboratory of Solar Fuel,Faculty of Materials Science and Chemistry,China University of Geosciences,68 Jincheng Street,Wuhan 430078,China
4. Department of Chemical Engineering,Ordos Institute of Technology,Ordos 017000,China
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Abstract

Photocatalytic water splitting is a popular pathway for H2 evolution,but the slow water oxidation greatly hampers the overall activity.To harness photogenerated holes in an efficient and lucrative way,the wa-ter oxidation reaction is replaced by selective oxidation of organic compounds to achieve simultaneous production of H2 and value-added chemicals.Herein,an alternative tactic is reported where an organic compound(benzylamine,BA)not only serves as the precursor for N-benzylidene-benzylamine(NBBA)production but also provides hydrogen sources for H2 evolution,achieving the goal under anhydrous conditions.This process is realized using an S-scheme photocatalyst composed of ZnIn2S4 and the UiO-66-NH2(U6N)metal-organic framework(MOF).The S-scheme carrier transfer mechanism was validated by in-situ irradiated X-ray photoelectron spectroscopy(ISI-XPS)and femtosecond transient absorption(fs-TA)spectroscopy.With increased carrier efficiency and reinforced redox power endowed by the S-scheme heterojunction,the composite performed better than ZnIn2S4 and MOF.The performance was further ameliorated by Pt-cocatalyst modification,achieving an H2 production rate of 5275 μmol h-1 g-1 as well as BA conversion of 94.3％with 99.3％NBBA selectivity.Mechanistic studies reveal that BA is ini-tially oxidized to carbon-centered radicals and further to imines along with the release of protons.The imine reacts with another BA molecule to form NBBA,while the protons are reduced to H2.This work provides new insights into concurrent photocatalytic H2 production and selective organic oxidation from organic amines using S-scheme photocatalysts.

Key words

Photocatalysis/S-scheme heterojunction/Hydrogen production/Selective oxidation/Benzylamine/Femtosecond transient absorption

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基金项目

National Key Research and Development Program of China(2022YFB3803600)

National Key Research and Development Program of China(2022YFE0115900)

National Natural Science Foundation of China(22208332)

National Natural Science Foundation of China(22278324)

National Natural Science Foundation of China(52073223)

National Natural Science Foundation of China(22238009)

National Natural Science Foundation of China(51932007)

National Natural Science Foundation of China(22361142704)

Natural Science Foundation of Hubei Province of China(2022CFA001)

Key R&D Program Projects in Hubei Province(2023BAB113)

出版年

2024

材料科学技术(英文版)

中国金属学会中国材料研究学会中国科学院金属研究所

材料科学技术(英文版)

CSTPCD

影响因子：0.657

ISSN：1005-0302

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