Huan He, Rongchen Shen, Yuhao Yan, Dejun Chen, Zhixiong Liu, Lei Hao, Xin Zhang, Peng Zhang and Xin Li
{"title":"用于光催化氢气进化的供体-分子-供体共价有机框架中质子化和共轭作用的双重增强","authors":"Huan He, Rongchen Shen, Yuhao Yan, Dejun Chen, Zhixiong Liu, Lei Hao, Xin Zhang, Peng Zhang and Xin Li","doi":"10.1039/D4SC07028C","DOIUrl":null,"url":null,"abstract":"<p >Covalent organic frameworks (COFs) have emerged as highly promising platforms for photocatalytic water splitting. However, exploring the structure–activity relationships in different COF systems remains challenging. In this study, three donor–imine–donor (D–I–D) COFs as relatively pure model materials were carefully selected to investigate the effect of protonation and conjugation on the mechanism of photocatalytic H<small><sub>2</sub></small> evolution. Unlike widely reported donor–acceptor (D–A) COF systems, these three ideal COFs have short electronic channels and lack chemical bond isomerism and heteroatoms in building blocks. These aspects are beneficial for a comprehensive investigation of the underlying mechanisms at the active sites of the imine bond. Both the calculation and experimental results indicate that increasing the conjugation intensity can enhance the efficiency of exciton dissociation and charge transfer rates. Protonation can also dominantly enhance the light absorption capacity and electron transport efficiency of D–I–D COFs. After protonation, the Py-hCOF with optimal conjugation intensity exhibits a remarkable H<small><sub>2</sub></small> evolution rate of 44.2 mmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> under visible light, which is 88.4 times higher than that of Tpe-hCOF. This result highlights the crucial roles of simultaneous enhancement of the protonation and conjugation in improving photocatalytic hydrogen evolution of COFs, providing valuable insights for the design of COF materials to achieve the superior electronic functions in photocatalysis.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 47","pages":" 20002-20012"},"PeriodicalIF":7.6000,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/sc/d4sc07028c?page=search","citationCount":"0","resultStr":"{\"title\":\"Double enhancement of protonation and conjugation in donor–imine–donor covalent organic frameworks for photocatalytic hydrogen evolution†\",\"authors\":\"Huan He, Rongchen Shen, Yuhao Yan, Dejun Chen, Zhixiong Liu, Lei Hao, Xin Zhang, Peng Zhang and Xin Li\",\"doi\":\"10.1039/D4SC07028C\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Covalent organic frameworks (COFs) have emerged as highly promising platforms for photocatalytic water splitting. However, exploring the structure–activity relationships in different COF systems remains challenging. In this study, three donor–imine–donor (D–I–D) COFs as relatively pure model materials were carefully selected to investigate the effect of protonation and conjugation on the mechanism of photocatalytic H<small><sub>2</sub></small> evolution. Unlike widely reported donor–acceptor (D–A) COF systems, these three ideal COFs have short electronic channels and lack chemical bond isomerism and heteroatoms in building blocks. These aspects are beneficial for a comprehensive investigation of the underlying mechanisms at the active sites of the imine bond. Both the calculation and experimental results indicate that increasing the conjugation intensity can enhance the efficiency of exciton dissociation and charge transfer rates. Protonation can also dominantly enhance the light absorption capacity and electron transport efficiency of D–I–D COFs. After protonation, the Py-hCOF with optimal conjugation intensity exhibits a remarkable H<small><sub>2</sub></small> evolution rate of 44.2 mmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> under visible light, which is 88.4 times higher than that of Tpe-hCOF. This result highlights the crucial roles of simultaneous enhancement of the protonation and conjugation in improving photocatalytic hydrogen evolution of COFs, providing valuable insights for the design of COF materials to achieve the superior electronic functions in photocatalysis.</p>\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":\" 47\",\"pages\":\" 20002-20012\"},\"PeriodicalIF\":7.6000,\"publicationDate\":\"2024-11-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/sc/d4sc07028c?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc07028c\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc07028c","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Double enhancement of protonation and conjugation in donor–imine–donor covalent organic frameworks for photocatalytic hydrogen evolution†
Covalent organic frameworks (COFs) have emerged as highly promising platforms for photocatalytic water splitting. However, exploring the structure–activity relationships in different COF systems remains challenging. In this study, three donor–imine–donor (D–I–D) COFs as relatively pure model materials were carefully selected to investigate the effect of protonation and conjugation on the mechanism of photocatalytic H2 evolution. Unlike widely reported donor–acceptor (D–A) COF systems, these three ideal COFs have short electronic channels and lack chemical bond isomerism and heteroatoms in building blocks. These aspects are beneficial for a comprehensive investigation of the underlying mechanisms at the active sites of the imine bond. Both the calculation and experimental results indicate that increasing the conjugation intensity can enhance the efficiency of exciton dissociation and charge transfer rates. Protonation can also dominantly enhance the light absorption capacity and electron transport efficiency of D–I–D COFs. After protonation, the Py-hCOF with optimal conjugation intensity exhibits a remarkable H2 evolution rate of 44.2 mmol g−1 h−1 under visible light, which is 88.4 times higher than that of Tpe-hCOF. This result highlights the crucial roles of simultaneous enhancement of the protonation and conjugation in improving photocatalytic hydrogen evolution of COFs, providing valuable insights for the design of COF materials to achieve the superior electronic functions in photocatalysis.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.