通过给体-受体基团调节CTF-NH<sub>2</sub>中NH<sub>2</sub>的Lewis碱性优化光催化水分解性能

引用本文: 陆钊, 吕虎, 刘亲壮, 王中辽. 通过给体-受体基团调节CTF-NH₂中NH₂的Lewis碱性优化光催化水分解性能[J]. 物理化学学报, 2024, 40(12): 240500. doi: 10.3866/PKU.WHXB202405005 shu

Citation: Zhao Lu, Hu Lv, Qinzhuang Liu, Zhongliao Wang. Modulating NH₂ Lewis Basicity in CTF-NH₂ through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting[J]. Acta Physico-Chimica Sinica, 2024, 40(12): 240500. doi: 10.3866/PKU.WHXB202405005 shu

通过给体-受体基团调节CTF-NH₂中NH₂的Lewis碱性优化光催化水分解性能

陆钊 ^1, ,
吕虎 ^2, ,
刘亲壮 ^3, ,
王中辽 ^{3,
,}

1.
香港科技大学深港协同创新研究院, 广东深圳 518000
2.
建筑工程学院, 深圳职业技术大学, 广东深圳 518000
3.
安徽省陶铝新材料产业共性技术研究中心, 安徽省污染物敏感材料与环境修复重点实验室, 物理与电子信息学院, 淮北师范大学, 安徽淮北 235000

通讯作者: 王中辽, wangzl@chnu.edu.cn

基金项目:
河套深港科技创新合作区项目 HZQB-KCZYB-2020083

深圳市科技计划项目 KCXFZ20211020163816023

深圳市中地建设工程有限公司合作项目 22100245

教育部高等学校自然科学重点研究项目 2022AH050396

摘要: 光催化水分解(PWS)为可持续生产绿色氢气提供了理想方案。NH₂修饰的共价三嗪框架(CTF-NH₂)由于其强的光吸收能力、优化的电荷分离效率和强的氧化还原电位，在PWS中具有潜在的应用价值。然而，由于中间产物的转化困难，高的表面反应势垒制约了PWS的效率。调节CTF上NH₂的路易斯碱性为解决这一挑战提供了一条可行的途径。本工作在胺基的对位引入给电子基团乙基(C₂H₅)和吸电子基团5氟乙基(C₂F₅)，生成C₂H₅-CTF-NH₂和C₂F₅-CTF- NH₂，以调节CTF-NH₂的路易斯碱性。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上的电子密度和路易斯碱性，从而降低了析氢和析氧反应的能垒，有效提高了CTF-NH₂的PWS效率。这项工作揭示了一种给体-受体调控CTF改性PWS性能的新颖方法。

关键词:

给体
/ 受体
/ 水分解
/ CTF
/ 路易斯碱性

English

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

1.
HKUST Shenzhen-Hong Kong Collaborative Innovation Research Institute, Shenzhen 518000, Guangdong Province, China
2.
School of Construction Engineering, Shenzhen Polytechnic University, Shenzhen 518000, Guangdong Province, China
3.
Anhui Province Industrial Generic Technology Research Center for Alumics Materials, Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000, Anhui Province, China

Corresponding author: Zhongliao Wang, Email: wangzl@chnu.edu.cn

Received Date: 07 May 2024
Accepted Date: 28 May 2024
Revised Date: 27 May 2024
Available Online: 15 December 2024
Fund Project:
the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone

Shenzhen Science and Technology Program

Shenzhen Zhongdi Construction Engineering Co., Ltd. cooperation project

Key Research Project in Natural Sciences for Higher Education Institutions by the Ministry of Education

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.

Key words:

Donor
/ Acceptor
/ Water splitting
/ CTFs
/ Lewis basicity

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

通过给体-受体基团调节CTF-NH₂中NH₂的Lewis碱性优化光催化水分解性能

通讯作者: 王中辽, wangzl@chnu.edu.cn

English

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

Corresponding author: Zhongliao Wang, Email: wangzl@chnu.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

通过给体-受体基团调节CTF-NH2中NH2的Lewis碱性优化光催化水分解性能

通讯作者: 王中辽, wangzl@chnu.edu.cn

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

Corresponding author: Zhongliao Wang, Email: wangzl@chnu.edu.cn

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