Engineering intermolecular C–F···C=O interactions in covalent organic framework promotes dual-path H2O2 photosynthesis for sustainable disinfection

IF 11.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2025-06-26 DOI:10.1016/j.watres.2025.124112

Yuxin He , Guocheng Huang , Xuejian Guo , Shaokui Chen , Qiaoshan Chen , Wenjun Yang , Weikang Peng , Xiaoying Xu , Jie Ye , Jinhong Bi , Po Keung Wong

{"title":"Engineering intermolecular C–F···C=O interactions in covalent organic framework promotes dual-path H2O2 photosynthesis for sustainable disinfection","authors":"Yuxin He , Guocheng Huang , Xuejian Guo , Shaokui Chen , Qiaoshan Chen , Wenjun Yang , Weikang Peng , Xiaoying Xu , Jie Ye , Jinhong Bi , Po Keung Wong","doi":"10.1016/j.watres.2025.124112","DOIUrl":null,"url":null,"abstract":"<div><div>The urgent need to address the high prevalence of waterborne diseases in underdeveloped regions necessitates the development of economically viable, decentralized, and sunlight-assisted disinfection techniques. An encouraging solution lies in the utilization of photosynthesized H2O2 to initiate advanced oxidation processes (AOPs). However, challenges persist in the quest to develop efficient photocatalysts and reactor designs. Herein, we present the rational design and synthesis of a metal-free supramolecular photocatalyst achieved via the post-functionalization of fluorine-substituted covalent organic frameworks (FCOFs) with polyvinylpyrrolidone (PVP). The resulting FCOF/PVP composite establishes intermolecular C–F···C=O interactions at the interface, which facilitate accelerated charge separation and transfer, as well as promote efficient intersystem crossing to enhance the formation of molecular triplet excitons. These photophysical enhancements enable dual-pathway H₂O₂ generation mediated by superoxide radicals (•O2−) and singlet oxygen (1O2), yielding a H2O2 production rate of 1763.50 μmol/g/h from pure water and atmospheric oxygen. The photosynthesized H2O2 is subsequently catalyzed by Fe(II) to generate hydroxyl radicals (•OH), achieving effective inactivation of pathogenic bacteria and viruses. A continuous-flow system was further developed to couple photocatalytic H2O2 production with Fenton disinfection, combining the benefits of heterogeneous and homogeneous catalysis while addressing limitations in photocatalyst recovery and light dependency. This system exhibited robust disinfection performance under real water matrices and intermittent light conditions. Economic analysis supports the feasibility of the system for deployment in resource-limited settings, offering a novel material-based approach for decentralized water treatment and global efforts to mitigate waterborne diseases.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"285 ","pages":"Article 124112"},"PeriodicalIF":11.4000,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Water Research","FirstCategoryId":"93","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0043135425010206","RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, ENVIRONMENTAL","Score":null,"Total":0}

引用次数: 0

Abstract

The urgent need to address the high prevalence of waterborne diseases in underdeveloped regions necessitates the development of economically viable, decentralized, and sunlight-assisted disinfection techniques. An encouraging solution lies in the utilization of photosynthesized H₂O₂ to initiate advanced oxidation processes (AOPs). However, challenges persist in the quest to develop efficient photocatalysts and reactor designs. Herein, we present the rational design and synthesis of a metal-free supramolecular photocatalyst achieved via the post-functionalization of fluorine-substituted covalent organic frameworks (FCOFs) with polyvinylpyrrolidone (PVP). The resulting FCOF/PVP composite establishes intermolecular C–F···C=O interactions at the interface, which facilitate accelerated charge separation and transfer, as well as promote efficient intersystem crossing to enhance the formation of molecular triplet excitons. These photophysical enhancements enable dual-pathway H₂O₂ generation mediated by superoxide radicals (•O₂⁻) and singlet oxygen (¹O₂), yielding a H₂O₂ production rate of 1763.50 μmol/g/h from pure water and atmospheric oxygen. The photosynthesized H₂O₂ is subsequently catalyzed by Fe(II) to generate hydroxyl radicals (•OH), achieving effective inactivation of pathogenic bacteria and viruses. A continuous-flow system was further developed to couple photocatalytic H₂O₂ production with Fenton disinfection, combining the benefits of heterogeneous and homogeneous catalysis while addressing limitations in photocatalyst recovery and light dependency. This system exhibited robust disinfection performance under real water matrices and intermittent light conditions. Economic analysis supports the feasibility of the system for deployment in resource-limited settings, offering a novel material-based approach for decentralized water treatment and global efforts to mitigate waterborne diseases.

Abstract Image

查看原文本刊更多论文

共价有机框架中C- f…C=O分子间相互作用促进双程H2O2光合作用，实现可持续消毒

迫切需要解决不发达地区水传播疾病的高流行率，因此必须开发经济上可行的、分散的和阳光辅助的消毒技术。一个令人鼓舞的解决方案是利用光合作用的H2O2来启动高级氧化过程（AOPs）。然而，在开发高效光催化剂和反应器设计方面，挑战依然存在。在此，我们提出了合理的设计和合成一种无金属的超分子光催化剂，通过氟取代共价有机框架（FCOFs）与聚乙烯吡咯烷酮（PVP）的后功能化实现。得到的fof /PVP复合材料在界面处建立了分子间的C- f···C=O相互作用，加速了电荷的分离和转移，促进了有效的系统间交叉，促进了分子三重态激子的形成。这些光物理增强实现了由超氧自由基（•O2−）和单线态氧（1O2）介导的双途径H2O2生成，从纯水和大气氧中产生H2O2的速率为1763.50 μmol/g/ H。光合作用后的H2O2被Fe（II）催化生成羟基自由基（•OH），有效灭活致病菌和病毒。研究人员进一步开发了一种连续流系统，将光催化生产H2O2与Fenton消毒结合起来，结合了多相催化和均相催化的优点，同时解决了光催化剂回收和光依赖的局限性。该系统在真实水基质和间歇光照条件下表现出强大的消毒性能。经济分析支持在资源有限的环境中部署该系统的可行性，为分散的水处理和减轻水传播疾病的全球努力提供了一种新的基于材料的方法。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Water Research 环境科学-工程：环境

CiteScore

20.80

自引率

9.40%

发文量

1307

审稿时长

38 days

期刊介绍： Water Research, along with its open access companion journal Water Research X, serves as a platform for publishing original research papers covering various aspects of the science and technology related to the anthropogenic water cycle, water quality, and its management worldwide. The audience targeted by the journal comprises biologists, chemical engineers, chemists, civil engineers, environmental engineers, limnologists, and microbiologists. The scope of the journal include: •Treatment processes for water and wastewaters (municipal, agricultural, industrial, and on-site treatment), including resource recovery and residuals management; •Urban hydrology including sewer systems, stormwater management, and green infrastructure; •Drinking water treatment and distribution; •Potable and non-potable water reuse; •Sanitation, public health, and risk assessment; •Anaerobic digestion, solid and hazardous waste management, including source characterization and the effects and control of leachates and gaseous emissions; •Contaminants (chemical, microbial, anthropogenic particles such as nanoparticles or microplastics) and related water quality sensing, monitoring, fate, and assessment; •Anthropogenic impacts on inland, tidal, coastal and urban waters, focusing on surface and ground waters, and point and non-point sources of pollution; •Environmental restoration, linked to surface water, groundwater and groundwater remediation; •Analysis of the interfaces between sediments and water, and between water and atmosphere, focusing specifically on anthropogenic impacts; •Mathematical modelling, systems analysis, machine learning, and beneficial use of big data related to the anthropogenic water cycle; •Socio-economic, policy, and regulations studies.