物理化学学报 >> 2024, Vol. 40 >> Issue (12): 2405005.doi: 10.3866/PKU.WHXB202405005

所属专题： 太阳燃料制备

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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. 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
  • 收稿日期:2024-05-07 修回日期:2024-05-27 录用日期:2024-05-28 发布日期:2024-06-04
  • 通讯作者: Email: wangzl@chnu.edu.cn (王中辽)
  • 基金资助:
    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)

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

Zhao Lu1, Hu Lv2, Qinzhuang Liu3, Zhongliao Wang3,*()   

  1. 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
  • Received:2024-05-07 Revised:2024-05-27 Accepted:2024-05-28 Published:2024-06-04
  • Contact: Email: wangzl@chnu.edu.cn (Zhongliao Wang)
  • Supported by:
    the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(HZQB-KCZYB-2020083); Shenzhen Science and Technology Program(KCXFZ20211020163816023); Shenzhen Zhongdi Construction Engineering Co., Ltd. cooperation project(22100245); Key Research Project in Natural Sciences for Higher Education Institutions by the Ministry of Education(2022AH050396)

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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

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