Synergizing Mass Transfer and Exciton Dissociation in Nanoscale COFs for Efficient H <sub>2</sub> O <sub>2</sub> Photosynthesis
Abstract
ABSTRACT Covalent organic frameworks (COFs) are promising photocatalysts for solar H 2 O 2 production, but their efficiencies remain insufficient for practical application. A primary limitation stems from the coupled proton–electron transfer in the two‐electron oxygen reduction reaction (2e − ORR), which demands photoinduced charge generation and rapid proton delivery—features rarely optimized simultaneously in existing COF architectures. Here we address these bottlenecks by combining nanoscale morphological control with pore‐wall functionalization. Bottom‐up colloidal synthesis produces highly crystalline COF nanospheres that reduce exciton‐diffusion losses and enhance light harvesting and charge generation versus bulk COFs. Meanwhile, carboxylic acid groups incorporated into 1D nanopores tune the microenvironment to promote proton delivery. This unified design delivers an exceptional H 2 O 2 evolution rate of 11246 µmol g −1 h −1 (>sevenfold enhancement over pristine bulk COF), and a solar‐to‐chemical conversion efficiency of 2.18% in pure water under air (AM 1.5G, 100 mW cm −2 ), among the highest reported for COF‐based photocatalysts. Experimental investigations and theoretical calculations reveal the carboxylated pore walls template continuous, oriented hydrogen‐bond chains in confined water, lowering the kinetic barrier for the 2e − ORR pathway. This work establishes a generalizable paradigm for orchestrating coupled proton–electron transfer in porous photocatalysts for efficient solar energy conversion.
Article Details
Authors (18)
Xinman Liu
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
Xiyin Zhan
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
Guanhua Ren
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Centre for Computational Chemistry and Research Institute of Industrial Catalysis
Zhaoxia Wu
Zhihua Li
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
Kaicheng Xu
Tengwu Zeng
School of Physical Science and Technology, Shanghai Key Laboratory of High-Resolution Electron Microscopy, State Key Laboratory of Advanced Medical Materials and Devices
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
Shiqiang Cheng
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering
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
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
Minghui Zhu
Mingyang Xing
Haifeng Wang
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