Modulating NH2 Lewis Basicity in CTF-NH2 through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting

IF 13.5 2区化学 Q1 CHEMISTRY, PHYSICAL 物理化学学报 Pub Date : 2024-12-01 Epub Date: 2024-06-04 DOI:10.3866/PKU.WHXB202405005

Zhao Lu , Hu Lv , Qinzhuang Liu , Zhongliao Wang

{"title":"Modulating NH2 Lewis Basicity in CTF-NH2 through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting","authors":"Zhao Lu , Hu Lv , Qinzhuang Liu , Zhongliao Wang","doi":"10.3866/PKU.WHXB202405005","DOIUrl":null,"url":null,"abstract":"<div><div>Photocatalytic water splitting (PWS) provides an optimal approach for the sustainable production of green hydrogen. NH2-modified covalent triazine frameworks (CTFs-NH2) hold potential in PWS due to robust light uptake, optimal charge separation, and considerable redox potential. However, the high surface reaction barriers hinder the efficiency of PWS owing to the conversion difficulty of intermediate products. Modulating the Lewis basicity of NH2 on CTFs offers a feasible route for addressing this challenge. In this work, electron-donating ethyl (C2H5) and electron-withdrawing 5-fluoroethyl groups (C2F5) are introduced at the para position of amine groups, producing C2H5-CTF-NH2 and C2F5-CTF-NH2, to adjust the Lewis basicity of CTF-NH2. Through DFT calculations, the optical properties, excited states, electronic structures, dipole moments, and surface reaction processes of the CTF-NH2, C2H5-CTF-NH2 and C2F5-CTF-NH2 are simulated. The results indicate that the electron-withdrawing C2F5 group can decrease the electron density and Lewis basicity on NH2, thereby lowering the energy barriers for hydrogen and oxygen evolution reactions, effectively ameliorating the PWS efficiency of CTF-NH2. This work unveils an innovative approach for donor-acceptor-regulated CTFs for the application of PWS.</div><div><figure><img><ol><li>Download: Download high-res image (76KB)</li><li>Download: Download full-size image</li></ol></figure></div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"40 12","pages":"Article 2405005"},"PeriodicalIF":13.5000,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"物理化学学报","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1000681824001851","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/6/4 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

Abstract

Photocatalytic water splitting (PWS) provides an optimal approach for the sustainable production of green hydrogen. NH₂-modified covalent triazine frameworks (CTFs-NH₂) hold potential in PWS due to robust light uptake, optimal charge separation, and considerable redox potential. However, the high surface reaction barriers hinder the efficiency of PWS owing to the conversion difficulty of intermediate products. Modulating the Lewis basicity of NH₂ on CTFs offers a feasible route for addressing this challenge. In this work, electron-donating ethyl (C₂H₅) and electron-withdrawing 5-fluoroethyl groups (C₂F₅) are introduced at the para position of amine groups, producing C₂H₅-CTF-NH₂ and C₂F₅-CTF-NH₂, to adjust the Lewis basicity of CTF-NH₂. Through DFT calculations, the optical properties, excited states, electronic structures, dipole moments, and surface reaction processes of the CTF-NH₂, C₂H₅-CTF-NH₂ and C₂F₅-CTF-NH₂ are simulated. The results indicate that the electron-withdrawing C₂F₅ group can decrease the electron density and Lewis basicity on NH₂, thereby lowering the energy barriers for hydrogen and oxygen evolution reactions, effectively ameliorating the PWS efficiency of CTF-NH₂. This work unveils an innovative approach for donor-acceptor-regulated CTFs for the application of PWS.

Download: Download high-res image (76KB)
Download: Download full-size image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

通过供体-受体基团调节CTF-NH2的NH2刘易斯碱度以优化光催化水裂解

光催化水分解（PWS）为可持续生产绿色氢提供了一种最佳途径。nh2修饰的共价三嗪框架（CTFs-NH2）在PWS中具有强大的光吸收能力，最佳的电荷分离能力和可观的氧化还原电位。然而，由于中间产物的转化困难，高表面反应障碍阻碍了PWS的效率。调节CTFs上NH2的刘易斯碱度为解决这一挑战提供了一条可行的途径。本文在胺基的对位上引入给电子乙基（C2H5）和吸电子5-氟乙基（C2F5），生成C2H5-CTF-NH2和C2F5-CTF-NH2，调节CTF-NH2的路易斯碱度。通过DFT计算，模拟了CTF-NH2、C2H5-CTF-NH2和C2F5-CTF-NH2的光学性质、激发态、电子结构、偶极矩和表面反应过程。结果表明，吸电子C2F5基团可以降低NH2上的电子密度和Lewis碱度，从而降低析氢和析氧反应的能垒，有效提高CTF-NH2的PWS效率。这项工作揭示了一种用于PWS应用的供体-受体调节CTFs的创新方法。下载：下载高清图片（76KB）下载：下载全尺寸图片

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分钟内获得全文去求助

来源期刊