催化学报

催化学报 ›› 2026, Vol. 89: 258-268.DOI: 10.1016/S1872-2067(26)65049-8

• 论文 • 上一篇    下一篇

界面Cu‒S键和局域表面等离子体共振协同调控的Cu3P@Cu/Mn0.3Cd0.7S S型异质结用于高效光催化析氢

张瑞琪a,1, 姚欣彤a,1, 刘君昌a, 陈智b, 张大凤a, 蒲锡鹏a,*()   

  1. a聊城大学材料科学与工程学院,山东省化学储能与新型电池技术重点实验室,山东聊城 252000
    b中国计量大学材料与化学学院,浙江杭州 310018
  • 收稿日期:2025-10-21 接受日期:2025-12-04 出版日期:2026-10-18 发布日期:2026-09-01
  • 通讯作者: *电子信箱: xipengpu@hotmail.com (蒲锡鹏).
  • 作者简介:

    1共同第一作者.

  • 基金资助:
    山东省自然科学基金(ZR2022ME179)

Interfacial Cu‒S bond and localized surface plasmon resonance modulated Cu3P@Cu/Mn0.3Cd0.7S S-scheme heterojunction for efficient photocatalytic hydrogen evolution

Ruiqi Zhanga,1, Xintong Yaoa,1, Junchang Liua, Zhi Chenb, Dafeng Zhanga, Xipeng Pua,*()   

  1. aSchool of Materials Science and Engineering, Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, Liaocheng University, Liaocheng 252000, Shandong, China
    bCollege of Materials and Chemistry, China Jiliang University, Hangzhou 310018, Zhejiang, China
  • Received:2025-10-21 Accepted:2025-12-04 Online:2026-10-18 Published:2026-09-01
  • Contact: *E-mail:xipengpu@hotmail.com(X. Pu).
  • About author:

    1 Contributed equally to this work.

  • Supported by:
    Shandong Provincial Natural Science Foundation, China(ZR2022ME179)

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摘要：

化石燃料的过度消耗导致能源危机和环境污染, 对全球经济和生态构成严峻挑战. 氢气(H2)具有高能量密度和零碳排放等优势被认为是最具前景的化石燃料替代品之一. 在诸多制氢路径中, 利用可再生太阳能驱动光催化剂分解水制备H2是最有效的方法之一. 近年来, Mn0.3Cd0.7S(MCS)纳米棒因其合适的能带结构、优越的可见光吸收能力以及丰富的活性位点而备受关注. 然而, 单一MCS的光催化性能仍然受到载流子复合严重和界面反应动力学缓慢的限制. 因此, 亟需设计一种有效策略来提高MCS的光催化析氢性能.

本文采用超声自组装的方法合成了界面Cu‒S键和局域表面等离子体共振协同调控的Cu3P@Cu/MCS S型异质结. 在该体系中, 界面Cu‒S键的形成促进了界面上的电荷传输, 不仅有利于内建电场的建立, 而且加速了光生载流子的空间分离. 与此同时, Cu3P@Cu的局域表面等离子体共振效应拓宽了可见光响应波长范围, 提高了催化剂表面的局部温度, 从而提升了光催化反应动力学. S型异质结的形成有效地促进了Cu3P@Cu/MCS复合材料内光生载流子的分离和迁移. 拉曼测试结果表明, Cu3P@Cu/MCS复合材料中存在Cu‒S键, 为界面Cu‒S键的形成提供了有力的证据. 此外, 通过紫外-可见漫反射光谱、Tauc曲线和莫特-肖特基图谱等研究了Cu3P@Cu和MCS的能带结构, 发现两种材料的能级交错, 有利于形成S型异质结. 通过原位X射线光电子能谱和密度泛函理论计算揭示了S型异质结的电荷转移机制. 值得注意的是, 在可见光照下, 优化后的5%-Cu3P@Cu/MCS复合材料的光催化产氢速率为93.25 mmol g‒1 h‒1, 是MCS(12.69 mmol g‒1 h‒1)的7.3倍. 5%-Cu3P@Cu/MCS光催化剂也表现出优异的循环稳定性.

综上, 本研究通过合理构建S型异质结, 并协同界面化学键和局域表面等离子体共振, 实现了光生载流子的快速分离, 增强了光催化析氢活性, 为合理构建高效稳定的光催化剂提供了一种有效策略.

关键词: S型异质结, 界面Cu-S键, 局域表面等离子体共振, 光催化析氢

Abstract:

Photocatalytic hydrogen evolution is an economically viable and environmentally friendly synthesis method. However, its photocatalytic efficiency is hindered by the sluggish reaction kinetics and rapid recombination of photogenerated charge carriers. Herein, an interfacial Cu‒S bond and localized surface plasmon resonance (LSPR)-synchronously mediated Cu3P@Cu/Mn0.3Cd0.7S (Cu3P@Cu/MCS) S-scheme heterojunction was designed and synthesized for accelerated photogenerated electron transfer. Under light illumination, the optimized 5%-Cu3P@Cu/MCS composite exhibited a photocatalytic hydrogen production rate of 93.25 mmol g-1 h-1, representing a 7.3-fold increase compared to that of pristine MCS (12.69 mmol g-1 h-1). Experimental results revealed that the interfacial Cu‒S bonds between MCS and Cu3P@Cu accelerated charge separation, thereby enhancing the reaction kinetics. Simultaneously, Cu-induced LSPR converted long-wavelength photons into localized heat, thereby increasing the interfacial temperature and accelerating the transfer of charge carriers. The synergistic effect of this chemical bond established in the S-scheme heterojunction with the LSPR effect provides new insights into photocatalytic H2 evolution.

Key words: S-scheme heterojunction, Interface Cu-S bond, Localized surface plasmon resonance, Photocatalytic hydrogen evolution