Plasma‐Engineered Covalent Organic Frameworks With Tunable Electronic Structures for Selective Superoxide Generation
- 1Department of Chemical Engineering National Taiwan University of Science and Technology Taipei Taiwan
Abstract
Covalent organic frameworks (COFs) are promising metal‐free photocatalysts; however, direct strategies for modulating their electronic structure and controlling reactive oxygen species (ROS) pathways remain limited. Here, we report an atmospheric‐pressure microplasma strategy for engineering COFs with microplasma‐induced electronic‐structure modulation and selective superoxide generation in aqueous media. In this non‐equilibrium process, microplasma simultaneously promotes framework formation, surface functionalization, and interfacial electronic modulation, thereby establishing favorable band alignment and charge–transfer pathways for selective superoxide generation. Among the synthesized materials, the microplasma‐engineered TAPB_BTCA COF exhibits a favorable combination of framework ordering, accessible porosity, enhanced light harvesting, and band alignment that thermodynamically supports O2 reduction to •O2−. Consequently, the optimized COF achieves 99% degradation of bisphenol A within 60 min under simulated solar irradiation, with an apparent pseudo‐first‐order rate constant of 0.0575 min−1, while also exhibiting efficient degradation of representative cationic dyes. Band‐structure analysis, radical‐scavenging experiments, mass spectrometry, and total organic carbon measurements consistently support a superoxide‐dominated photocatalytic pathway, followed by progressive oxidation, bond cleavage, ring opening, and partial mineralization. Overall, this work establishes atmospheric‐pressure microplasma as a green and versatile platform for engineering the electronic structure and ROS pathways of metal‐free framework photocatalysts.
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BibTeX
@article{huang2026plasmaengineered,
title = {{Plasma‐Engineered Covalent Organic Frameworks With Tunable Electronic Structures for Selective Superoxide Generation}},
author = {Cheng You Huang and Chia‐Hung Lin and You‐Jia Zhang and Shuo‐Wei Wang and Yi‐An Chen and Darwin Kurniawan and Wei‐Hung Chiang},
journal = {Small Structures},
year = {2026},
month = oct,
doi = {10.1002/sstr.70623},
url = {https://doi.org/10.1002/sstr.70623},
note = {CC BY},
}
RIS
TY - JOUR
TI - Plasma‐Engineered Covalent Organic Frameworks With Tunable Electronic Structures for Selective Superoxide Generation
AU - Cheng You Huang
AU - Chia‐Hung Lin
AU - You‐Jia Zhang
AU - Shuo‐Wei Wang
AU - Yi‐An Chen
AU - Darwin Kurniawan
AU - Wei‐Hung Chiang
PY - 2026
DA - 2026/10/25
JO - Small Structures
DO - 10.1002/sstr.70623
UR - https://doi.org/10.1002/sstr.70623
AB - Covalent organic frameworks (COFs) are promising metal‐free photocatalysts; however, direct strategies for modulating their electronic structure and controlling reactive oxygen species (ROS) pathways remain limited. Here, we report an atmospheric‐pressure microplasma strategy for engineering COFs with microplasma‐induced electronic‐structure modulation and selective superoxide generation in aqueous media. In this non‐equilibrium process, microplasma simultaneously promotes framework formation, surface functionalization, and interfacial electronic modulation, thereby establishing favorable band alignment and charge–transfer pathways for selective superoxide generation. Among the synthesized materials, the microplasma‐engineered TAPB_BTCA COF exhibits a favorable combination of framework ordering, accessible porosity, enhanced light harvesting, and band alignment that thermodynamically supports O2 reduction to •O2−. Consequently, the optimized COF achieves 99% degradation of bisphenol A within 60 min under simulated solar irradiation, with an apparent pseudo‐first‐order rate constant of 0.0575 min−1, while also exhibiting efficient degradation of representative cationic dyes. Band‐structure analysis, radical‐scavenging experiments, mass spectrometry, and total organic carbon measurements consistently support a superoxide‐dominated photocatalytic pathway, followed by progressive oxidation, bond cleavage, ring opening, and partial mineralization. Overall, this work establishes atmospheric‐pressure microplasma as a green and versatile platform for engineering the electronic structure and ROS pathways of metal‐free framework photocatalysts.
SN - 2688-4062
ER -