Diacetylene-bridged covalent organic framework as crystalline graphdiyne analogue for photocatalytic hydrogen evolution

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2024-12-16 DOI:10.1039/d4sc06633b

Zhiqing Lin, Songyao Dai, Shan Yao, Qia-Chun Lin, Mengying Fu, Lai-Hon Chung, Bin Han, Jun He

{"title":"Diacetylene-bridged covalent organic framework as crystalline graphdiyne analogue for photocatalytic hydrogen evolution","authors":"Zhiqing Lin, Songyao Dai, Shan Yao, Qia-Chun Lin, Mengying Fu, Lai-Hon Chung, Bin Han, Jun He","doi":"10.1039/d4sc06633b","DOIUrl":null,"url":null,"abstract":"Graphdiyne (GDY) alone as photocatalyst is unsatisfactory because of low crystallinity, limited regulation of band gap, weak photogenerated charge separation, etc., and heterojunctioning with other materials is necessary to activate the photocatalytic activity of GDY. Through elaborate design, a diacetylene-rich linker (S2) was prepared and allowed to construct crystalline and structurally well-defined GDY-like covalent organic framework (COF, namely S2-TP COF) which merges the merits of both COF and GDY to boost photocatalytic hydrogen evolution reaction (HER). By theoretical prediction on the donor-acceptor (D-A) pair, other two monoacetylene-bridged COFs (S1-TP COF and S3-TP COF) were prepared for comparison. Exhibiting enhanced separation and suppressed recombination of photogenerated excitons, Pt-photodeposited S2-TP COF showed a higher HER rate (10.16 mmol g−1 h−1) than the other two non-GDY-like COFs (3.71 and 1.13 mmol g−1 h−1). The joint experimental-theoretical study suggests appropriate D-A structure for photogenerated charge separation and diacetylene motif as adsorption site to be key accounts for boosted HER. This work opens a new opportunity for the rational design of COF as GDY mimic for photocatalytic application.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"144 1","pages":""},"PeriodicalIF":7.6000,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4sc06633b","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

Graphdiyne (GDY) alone as photocatalyst is unsatisfactory because of low crystallinity, limited regulation of band gap, weak photogenerated charge separation, etc., and heterojunctioning with other materials is necessary to activate the photocatalytic activity of GDY. Through elaborate design, a diacetylene-rich linker (S2) was prepared and allowed to construct crystalline and structurally well-defined GDY-like covalent organic framework (COF, namely S2-TP COF) which merges the merits of both COF and GDY to boost photocatalytic hydrogen evolution reaction (HER). By theoretical prediction on the donor-acceptor (D-A) pair, other two monoacetylene-bridged COFs (S1-TP COF and S3-TP COF) were prepared for comparison. Exhibiting enhanced separation and suppressed recombination of photogenerated excitons, Pt-photodeposited S2-TP COF showed a higher HER rate (10.16 mmol g−1 h−1) than the other two non-GDY-like COFs (3.71 and 1.13 mmol g−1 h−1). The joint experimental-theoretical study suggests appropriate D-A structure for photogenerated charge separation and diacetylene motif as adsorption site to be key accounts for boosted HER. This work opens a new opportunity for the rational design of COF as GDY mimic for photocatalytic application.

查看原文本刊更多论文

Graphdiyne（GDY）由于结晶度低、带隙调节能力有限、光生电荷分离能力弱等原因，单独作为光催化剂的效果并不理想，需要与其他材料进行异质结合才能激活GDY的光催化活性。通过精心设计，制备出了富含二乙炔的连接体（S2），从而构建出了结晶且结构清晰的类 GDY 共价有机框架（COF，即 S2-TP COF），该框架融合了 COF 和 GDY 的优点，可促进光催化氢进化反应（HER）。通过对供体-受体（D-A）对的理论预测，制备了另外两种单乙炔桥接 COF（S1-TP COF 和 S3-TP COF）进行比较。与其他两种非类 GDY COF（3.71 mmol g-1 h-1 和 1.13 mmol g-1 h-1）相比，铂光沉积的 S2-TP COF 表现出更高的 HER 率（10.16 mmol g-1 h-1），增强了光生激子的分离和抑制了光生激子的重组。实验-理论联合研究表明，光生电荷分离的适当 D-A 结构和作为吸附位点的双乙炔基团是提高 HER 的关键因素。这项工作为合理设计 COF 作为光催化应用的 GDY 模拟物提供了新的机遇。

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

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

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.