Tailored Surface Microenvironment of Molecular Nanophotocatalysts for Boosting Photocatalytic Hydrogen Evolution
Abstract
ABSTRACT Organic photocatalysts are an attractive platform for solar‐to‐chemical energy conversion, but their performance is often constrained by bulk aggregation, poor light penetration, and rapid exciton recombination. Although surfactant‐assisted nanostructuring can help alleviate aggregation, surfactants are generally treated as passive stabilizers with little direct influence on photocatalytic function. Here we show that surfactants can actively engineer the interfacial microenvironment of organic nanophotocatalysts, leading to substantially enhanced photocatalytic hydrogen evolution. A donor–acceptor small molecule, CNP90, is co‐assembled with either hydrophilic polyethylene glycol (PEG) or amphiphilic Tween surfactants (Tween 20, T20; Tween 80, T80) via nanoprecipitation to afford a series of tailored nanophotocatalysts. Although all surfactants improve colloidal stability, T20/CNP90 exhibits markedly enhanced photoluminescence quantum yield and charge generation, leading to a more than 16‐fold increase in the hydrogen evolution rate to 520.17 mmol g −1 h −1 , among the highest values reported for organic photocatalysts. Spectroscopic studies combined with molecular dynamics simulations reveal that T20 constructs an amphiphilic interfacial microenvironment around CNP90, comprising a hydrophobic inner shell that suppresses nonradiative recombination and a hydrophilic outer corona that promotes water access to catalytic sites. These insights establish surfactant‐driven microenvironment engineering as a powerful, low‐cost, and generalizable paradigm for maximizing the performance of organic photocatalysts.
Article Details
Authors (19)
Xueyan Liu
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry
Ke Wang
Tianjin Medical University Cancer Institute and Hospital Tianjin China
Haiyang Huang
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering
Miaojie Yu
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Shanghai Key Laboratory of Functional Materials Chemistry, Center of Photosensitive Chemicals Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai China
Chao Li
Chengyang Jiang
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis Key Laboratory for Advanced Materials and Institute of Fine Chemicals Shanghai Key Laboratory of Functional Materials Chemistry Center of Photosensitive Chemicals Engineering Feringa Nobel Prize Scientist Joint Research Center School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai China
Hongxu Gu
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Shanghai Key Laboratory of Functional Materials Chemistry, Center of Photosensitive Chemicals Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai China
Jing Qi
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering
Guowei Shi
Long Hu
School of Materials Science and Engineering, University of New South Wales, Sydney, New South Wales, 2052, Australia
Fuxing Chu
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis Key Laboratory for Advanced Materials and Institute of Fine Chemicals Shanghai Key Laboratory of Functional Materials Chemistry Center of Photosensitive Chemicals Engineering Feringa Nobel Prize Scientist Joint Research Center School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai China
Shiqiang Cheng
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering
Kunchi Xie
School of Materials Science and Engineering Huazhong University of Science and Technology Wuhan Hubei P. R. China
Xiaobo Li
Teng‐Teng Chen
Department of Chemistry The Hong Kong University of Science and Technology Hong Kong China
Yongzhen Wu
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Shanghai Key Laboratory of Functional Materials Chemistry, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering
Zhen Song
State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Engineering Research Center of Large-Scale Reactor Engineering and Technology (Ministry of Education)
Wei‐Hong Zhu
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering Shanghai Key Laboratory of Functional Materials Chemistry Feringa Nobel Prize Scientist Joint Research Center Institute of Fine Chemicals Frontiers Science Center For Materiobiology and Dynamic Chemistry School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai China
Weiwei Zhang
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering