物理化学学报 >> 2025, Vol. 41 >> Issue (12): 100152.doi: 10.1016/j.actphy.2025.100152

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构建S型异质结：通过将共价有机框架与过渡金属硫化物结合实现高效无贵金属光催化制氢

赵鑫婉1,†, 曹越2,†, 雷敏军1,†, 靳治良1,*(), TsubakiNoritatsu3   

  1. 1 北方民族大学化学与化学工程学院, 宁夏太阳能化学转化技术重点实验室, 国家民族事务委员会化工技术基础重点实验室, 宁夏 银川 750021
    2 宁夏大学化学化工学院, 宁夏 银川 750021
    3 Department of Applied Chemistry, Graduate School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan
  • 收稿日期:2025-06-26 修回日期:2025-08-01 录用日期:2025-08-06 发布日期:2025-10-23
  • 通讯作者: Email: zl-jin@nun.edu.cn (靳治良)
  • 作者简介:

    †These authors contributed equally to this work.

  • 基金资助:
    国家自然科学基金(22062001)

Constructing S-scheme heterojunctions by integrating covalent organic frameworks with transition metal sulfides for efficient noble-metal-free photocatalytic hydrogen evolution

Xinwan Zhao1, Yue Cao2, Minjun Lei1, Zhiliang Jin1,*(), Tsubaki Noritatsu3   

  1. 1 School of Chemistry and Chemical Engineering, Ningxia Key Laboratory of Solar Chemical Conversion Technology, Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan 750021, Ningxia Autonomous Region, China
    2 School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia Autonomous Region, China
    3 Department of Applied Chemistry, Graduate School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan
  • Received:2025-06-26 Revised:2025-08-01 Accepted:2025-08-06 Published:2025-10-23
  • Contact: Email: zl-jin@nun.edu.cn (Zhiliang Jin)
  • Supported by:
    the National Natural Science Foundation of China(22062001)

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摘要：

二维共价有机框架(COFs)被认为是最具太阳能驱动制氢潜力的晶态多孔材料之一，但通常需要引入贵金属助催化剂来提升其析氢能力。本研究通过简单溶剂热合成法，在典型二维共价有机框架TtTfp-COF表面生长金属硫化物，成功构建了独特的S型异质结结构TtTfp-COF/NiS复合材料。该结构中，棒状NiS的线性结构更稳定且便于后续表面修饰，同时提供关键活性位点并促进电子高效转移，显著提升析氢效率。共价有机框架通过控制前驱体与配体的空间排布，增强了载流子传输效率。实验结果表明，NT-20样品析氢速率可达5978 μmol·g−1·h−1，较原始TtTfp-COF (520 μmol·g−1·h−1)提升约11.5倍。此外，该材料在420 nm光照下表现出1.96%的显著量子效率。实验结果与理论分析共同证实了光催化析氢速率的提升，并深入阐明了S型异质结内的电荷转移机制。本文为非贵金属COF基光催化剂的设计开发提供了新思路，通过无机与有机材料在光催化中的协同组合，为S型异质结的构建提供了新见解。

关键词: 共价有机框架, 光催化析氢, S型异质结, 密度泛函理论

Abstract:

Two-dimensional covalent organic frameworks (COFs) are considered among the most potential crystalline porous materials for solar-driven hydrogen production. However, it is usually necessary to introduce noble metal cocatalysts to boost the hydrogen evolution capacity of COFs. In this work, a unique S-scheme heterojunction structured TtTfp-COF/NiS composite material was effectively developed by growing metal sulfide on the typical two-dimensional covalent organic framework TtTfp-COF through a simple solvothermal synthesis method. In this structure, linear structure of rod-like NiS is more stable and convenient for further surface modification. It also provides key active sites and promotes efficient electron transfer, significantly enhancing the hydrogen evolution efficiency. The covalent organic framework enhances charge carrier transport efficiency by controlling the spatial organization of precursors and ligands. It is indicated by the experimental findings that a hydrogen evolution rate of 5978 μmol·g−1·h−1 can be achieved for the NT-20 sample, which about 11.5 times higher than that of the initial TtTfp-COF (520 μmol·g−1·h−1). In addition, the material exhibits a notable quantum efficiency of 1.96% when exposed to 420 nm illumination. Both experimental results and theoretical analyses have been confirmed to improve the hydrogen evolution rate via photocatalysis and the charge transfer mechanism within the S-scheme heterojunction has been thoroughly elucidated. The design and development of non-precious metal COF-based photocatalysts are provided with new insights in this article, and new ideas for the construction of S-scheme heterojunctions are offered by the synergistic combination of inorganic and organic materials in photocatalysis.

Key words: Covalent organic framework, Photocatalytic hydrogen evolution, S-scheme heterojunction, DFT