Work

Microdroplet Interfacial Electric Field Triggers Hydroxyl Radical Coupling Toward Efficient H 2 O 2 Photosynthesis

Year: 2026

Type: article

Abstract: ABSTRACT The two‐electron water oxidation reaction (2e − WOR) via ·OH coupling offers a direct route for H 2 O 2 photosynthesis, but conventional bulk systems remain rigidly limited by high thermodynamic barriers, short‐lived ·OH, and disordered H‐bond networks. Inspired by the potential of reaction microenvironments to drive thermodynamically unfavorable pathways, we developed a microdroplet photocatalytic platform using hydrophilic nitrogen‐rich COFs (Tp‐DAPd and Tp‐DAPm), achieving H 2 O 2 photosynthesis rates of 11.12 and 12.15 mmol·L −1 ·g −1 , with 11.6‐ and 7.9‐fold enhancements over their bulk counterparts, respectively. Product‐labeling fluorescence imaging microscopy (PLFIM) at the single‐microdroplet scale visualized size‐dependent acceleration and inward expansion of the interfacial reactive zone. Multiscale mechanistic investigations reveal that the intrinsic microdroplet interfacial electric field actively regulates the 2e − WOR process by restructuring the H‐bond network into a low‐entropy state, stabilizing partially solvated ·OH, and inducing a favorable trans‐gauche configuration. These effects work together to create a unique microenvironment that promotes water dissociation and ·OH coupling, thereby lowering the thermodynamic barrier for 2e − WOR under operational conditions. This work represents a microenvironment‐oriented strategy to overcome intrinsic thermodynamic limitations and inspires new strategies for the rational design of microdroplet‐assisted photosynthetic systems.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.9181115

Authors: Yanchi Yao, Chao Zhu, Qile Fang, Shuang Song, Baoliang Chen, Yi Shen

Institutions: Zhejiang University of Technology, Beijing Normal University, Beijing Normal University, Zhuhai, Zhejiang University

Language: English

Topic: Advanced Photocatalysis Techniques

Subfield: Renewable Energy, Sustainability and the Environment

Field: Energy

Domain: Physical Sciences

SDG: Affordable and clean energy

Open Access status: bronze

Funders: National Natural Science Foundation of China, Fundamental Research Funds for the Provincial Universities of Zhejiang