{"title":"Photosynthesis of H2O2 using Phenothiazine-Based Covalent-Organic Frameworks Mimicking Coenzyme Q","authors":"Yaoyao Peng, Lewang Yuan, Kang-Kai Liu, Zong-Jie Guan, Shangbin Jin, Yu Fang","doi":"10.1002/anie.202423055","DOIUrl":null,"url":null,"abstract":"Mimicking natural enzymes through artificial enzyme engineering represents a powerful strategy to fine-tune the performance of photocatalysts, while the manipulation of electron transfer systems through atomic precision control is challenging. Herein, we reported a series of covalent organic frameworks (COFs) based on progressively oxidized phenothiazine (PTH) core as the platform for emulating Coenzyme Q, achieved through meticulous stepwise adjustments of their redox states. Compared to the original PTH-S-COF, the COFs with incrementally oxidized sulfur sites exhibited enhanced charge transfer efficiencies, facilitating efficient electron donation to O2 and thereby providing a favorable pathway for H2O2 synthesis. Notably, the PTH-SO2-COF achieved a remarkable synthesis rate of 7755 μmol g-1 h-1, marking a 720% improvement over the PTH-S-COF baseline. Furthermore, in the presence of a sacrificial agent, this rate soared to an impressive 13565 μmol g-1 h-1, surpassing the most reported photo-active COFs. In situ characterizations and simulations verified that three H2O2 evolution pathways (2e- ORR, 4e- OER, and 4e- ORR) all involved in the H2O2 production process. As a result, our findings introduce a novel pathway for the development of high-performance COF-based photocatalysts through the innovative application of artificial enzyme-mimicking techniques.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202423055","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Mimicking natural enzymes through artificial enzyme engineering represents a powerful strategy to fine-tune the performance of photocatalysts, while the manipulation of electron transfer systems through atomic precision control is challenging. Herein, we reported a series of covalent organic frameworks (COFs) based on progressively oxidized phenothiazine (PTH) core as the platform for emulating Coenzyme Q, achieved through meticulous stepwise adjustments of their redox states. Compared to the original PTH-S-COF, the COFs with incrementally oxidized sulfur sites exhibited enhanced charge transfer efficiencies, facilitating efficient electron donation to O2 and thereby providing a favorable pathway for H2O2 synthesis. Notably, the PTH-SO2-COF achieved a remarkable synthesis rate of 7755 μmol g-1 h-1, marking a 720% improvement over the PTH-S-COF baseline. Furthermore, in the presence of a sacrificial agent, this rate soared to an impressive 13565 μmol g-1 h-1, surpassing the most reported photo-active COFs. In situ characterizations and simulations verified that three H2O2 evolution pathways (2e- ORR, 4e- OER, and 4e- ORR) all involved in the H2O2 production process. As a result, our findings introduce a novel pathway for the development of high-performance COF-based photocatalysts through the innovative application of artificial enzyme-mimicking techniques.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.