催化学报

催化学报 ›› 2026, Vol. 83: 244-257.DOI: 10.1016/S1872-2067(26)64987-X

• 论文 • 上一篇    下一篇

富含氧空位的三嗪基-COF/TiO2 S-型异质结用于高效光催化CO2还原

唐克山a,1, 邓莞沂b,1, 王宁远a, 夏阳a,*(), 吴新鹤d, 杨恒c,*()   

  1. a武汉工程大学化工与制药学院, 绿色化工过程教育部重点实验室, 新型反应器和绿色化学工艺湖北省重点实验室, 湖北武汉 430072
    b武汉工程大学材料科学与工程学院, 湖北武汉 430205
    c武汉轻工大学化学与环境工程学院, 农业废弃物资源化利用湖北省重点实验室, 湖北武汉 430023
    d湖北师范大学化学化工学院, 污染物分析与资源化技术湖北省重点实验室, 湖北黄石 435002
  • 收稿日期:2025-08-02 接受日期:2025-11-04 出版日期:2026-04-18 发布日期:2026-03-04
  • 通讯作者: * 电子信箱: xiayang410@sina.com (夏阳), yhxg666@sina.com (杨恒).
  • 作者简介:1共同第一作者.
  • 基金资助:
    国家自然科学基金(22478308);国家自然科学基金(22108211);国家自然科学基金(22402156);污染物分析与资源化技术湖北省重点实验室开放基金(湖北师范大学PA240204)

Triazine-based COF/TiO2 S-scheme heterojunction with oxygen vacancies for efficient photocatalytic CO2 reduction

Keshan Tanga,1, Wanyi Dengb,1, Ningyuan Wanga, Yang Xiaa,*(), Xinhe Wud, Heng Yangc,*()   

  1. aKey Laboratory of Green Chemical Engineering Process of Ministry of Education, Hubei Key Lab of Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430072, Hubei, China
    bSchool of Materials Science and Engineering, Wuhan Institute of Technology, Wuhan 430205, Hubei, China
    cHubei Key Laboratory of Agricultural Waste Resource Utilization, School of Chemical and Environmental Engineering, Wuhan Polytechnic University, Wuhan 430023, Hubei, China
    dHubei Key Laboratory of Pollutant Analysis and Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, Hubei, China
  • Received:2025-08-02 Accepted:2025-11-04 Online:2026-04-18 Published:2026-03-04
  • Contact: * E-mail: xiayang410@sina.com (Y. Xia), yhxg666@sina.com (H. Yang).
  • About author:1Contributed equally to this work.
  • Supported by:
    National Natural Science Foundation of China(22478308);National Natural Science Foundation of China(22108211);National Natural Science Foundation of China(22402156);Hubei key laboratory of pollutant analysis & reuse Technology(Hubei Normal University PA240204)

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摘要：

能源危机和环境污染已成为人类迫切需要解决的问题. 光催化技术被认为是解决上述问题的有效途径之一. 光催化CO2还原是利用太阳能驱动半导体材料将CO2转化为碳氢燃料, 是减少碳排放生产可再生能源的前瞻性策略. 该过程的实现主要依赖于开发能够实现有效电荷分离、高太阳光利用率和强反应物吸附的高效光催化剂. 然而, 具有高结晶度和有序多孔结构的共价三嗪有机框架材料(CTF)在光催化应用中受限于载流子分离效率低, 氧化还原能力不足等问题. 因此, 利用无机半导体与CTF复合构建S-型异质结以实现高效CO2还原是本文的主要研究思路.
本文首先通过惰性气氛下煅烧法制备富氧空位的一维TiO2纳米带(TN), 随后利用溶剂热法将其与富含电子的二维CTF耦合, 构建了用于光催化CO2还原的高效一维/二维TN/CTF S-型异质结. 所得TN/CTF复合光催化剂表现出卓越的CO2还原性能, 优化后的TN/CTF10复合光催化剂生成CO和CH4的产率分别达到21.4和7.9 μmol g‒1 h‒1, 分别是单一CTF的3.5倍和4.4倍. 相比于单一TN, 其性能则提高了6.5倍和7.2倍. 通过光照开尔文探针力显微镜、原位X射线光电子能谱分析、飞秒超快吸收光谱以及密度泛函理论计算, 明确了S-型异质结中的电荷转移机制; 同时借助电子自旋共振和X射线光电子能谱分析证实了氧空位的形成. 表征结果进一步表明, TN中的氧空位可显著拓宽光吸收范围, 并形成中间能级以加快S-型异质结中的电荷分离, 从而大幅提升光捕获效率并抑制电荷复合. 此外, 缺陷工程与S-型异质结的协同作用能够优化氧化还原能力以及CO2吸附与活化能力, 进而促进CO2还原反应.
综上, 本文通过构建S-型内建电场和氧缺陷, 合理设计了紧密的有机/无机异质结界面, 提高了太阳光的捕获能力和光生载流子分离效率; 同时增强了反应物的吸附和活化, 从而进一步增强光催化活性. 本工作为设计高性能光催化剂提供了新视角.

关键词: 光催化, S-型异质结, 氧缺陷, CO2还原

Abstract:

Solar-driven CO2 conversion into valuable hydrocarbon fuels process primarily depends on the development of efficient photocatalysts capable of achieving effective charge separation, high sunlight utilization, and strong reactant adsorption. In this work, one-dimensional (1D) TiO2 nanobelts with abundant oxygen vacancies (TN) were strategically coupled with a two-dimensional (2D) electron-rich triazine-based covalent organic framework (CTF) to construct a high-efficiency 1D/2D TN/CTF S-scheme heterojunction for photocatalytic CO2 reduction. The resulting TN/CTF composites exhibited impressive CO2 conversion rates toward CO and CH4 generation, with the optimized TN/CTF composite (TN/CTF10) achieving the highest CO and CH4 yields of 21.4 and 7.9 μmol g‒1 h‒1, respectively, which were 3.5- and 4.4-fold higher than those of pristine CTF and represented 6.5- and 7.2-fold enhancements compared to pure TN. The charge-transfer mechanism involved in the S-scheme heterojunction was identified via photo-irradiated Kelvin probe force microscopy, in-situ X-ray photoelectron spectroscopy, and density functional theory calculations, while the formation of oxygen vacancies was confirmed by electron spin resonance and X-ray photoelectron spectroscopy. Further in-depth studies indicate that the oxygen vacancies in TN greatly broaden light absorption and provide an intermediate energy level that accelerates charge separation in the S-scheme heterojunction, thereby significantly improving light-harvesting efficiency and suppressing charge recombination. Meanwhile, the synergistic integration of defect engineering with S-scheme heterojunction design optimizes redox capability and CO2 adsorption strength to enhance the CO2 reduction reaction. This work offers a new perspective on designing high-performance photocatalysts by integrating defect engineering into S-scheme heterojunctions.

Key words: Photocatalysis, S-scheme heterojunction, Oxygen vacancy, CO2 reduction