物理化学学报 >> 2026, Vol. 42 >> Issue (11): 100376.doi: 10.1016/j.actphy.2026.100376

论文 上一篇    

Co掺杂诱导S型CoCdS/石墨炔异质结不对称电荷分布及其宽光谱光催化析氢

郝旭强1,2, 何沅瑾1,2, 王学1,2, 郝宇强1,2, 靳治良1,2   

  1. 1 北方民族大学化学与化学工程学院, 宁夏 银川 750021;
    2 北方民族大学宁夏太阳能化学转化技术重点实验室, 国家民委化学工程与技术重点实验室, 宁夏 银川 750021
  • 收稿日期:2026-07-01 修回日期:2026-07-25 录用日期:2026-07-26 发布日期:2026-09-29
  • 通讯作者: 郝旭强 E-mail:haoxuqiang@nun.edu.cn
  • 基金资助:
    本研究得到宁夏回族自治区自然科学基金(2025AAC050004)资助。

Co-doping-induced asymmetric charge distribution in S-scheme CoCdS/graphdiyne heterojunction for broad-spectrum photocatalytic hydrogen evolution

Xuqiang Hao1,2, Yuanjin He1,2, Xue Wang1,2, Yuqiang Hao1,2, Zhiliang Jin1,2   

  1. 1 School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, Ningxia Hui Autonomous Region, China;
    2 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 Hui Autonomous Region, China
  • Received:2026-07-01 Revised:2026-07-25 Accepted:2026-07-26 Published:2026-09-29
  • Contact: Xuqiang Hao E-mail:haoxuqiang@nun.edu.cn

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摘要： 杂原子掺杂能够打破金属硫化物的本征电子对称性，是促进电荷分离的有效策略。本研究通过水热法合成了钴掺杂硫化镉(CoCdS)纳米颗粒，并将其与二维石墨炔(GDY)耦合构建GDY/CoCdS S型异质结，用于高效宽光谱光催化产氢。钴掺杂诱导CdS中局部不对称电荷分布，削弱S-H相互作用并降低氢脱附能垒，从而加速表面析氢反应。同时，钴掺杂还产生局部内建电场，显著增强CdS内部的本征电荷分离，并协同促进S型异质结中的界面电荷转移。原位X射线光电子能谱(XPS)分析与差分电荷密度计算证实了GDY/CoCdS异质界面的S型电荷转移机制，该机制极大加速了光生载流子的分离与迁移。此外，GDY凭借其宽光谱捕获能力和光热效应，赋予复合材料更宽的光响应范围并增强析氢反应动力学。因此，15%GDY/CoCdS在可见光照射下4 h内产氢量达4.8 mmol g-1，分别是纯CoCdS和GDY的约9.6倍和48倍。本研究为通过钴掺杂诱导S型异质结中不对称电荷调控实现高效宽光谱光催化产氢提供了可行策略。

关键词: S型异质结, 光催化析氢, 石墨炔, 光热效应, 不对称电荷再分布

Abstract: Heteroatom doping-induced breaking of the intrinsic electronic symmetry in metal sulfides is an attractive strategy for promoting charge separation. In this work, Co-doped CdS (CoCdS) nanoparticles were synthesized via a hydrothermal method and coupled with 2D graphdiyne (GDY) to construct GDY/CoCdS S-scheme heterojunctions for efficient broad-spectrum photocatalytic hydrogen evolution. Co doping induces local asymmetric charge redistribution in CdS, weakens S-H interaction, and lowers the hydrogen desorption energy barrier, thereby accelerating the surface hydrogen evolution reaction. Meanwhile, Co doping also creates a local built-in electric field that significantly enhances the intrinsic charge separation within CdS and synergistically facilitates interfacial charge transfer in the S-scheme heterojunction. In situ X-ray Photoelectron Spectroscopy (XPS) analysis and differential charge density calculations confirm the S-scheme charge transfer mechanism at the GDY/CoCdS heterointerface, which greatly accelerates the separation and migration of photogenerated carriers. Moreover, GDY endows the composite with extended light response and enhanced reaction kinetics owing to its broad-spectrum light harvesting and photothermal effect. As a result, the 15%GDY/CoCdS exhibits a prominent hydrogen evolution amount of 4.8 mmol g-1 within 4 h under visible light irradiation, which is approximately 9.6 and 48 times higher than that of pure CoCdS and GDY. This work offers a reliable strategy of Co-doping induced asymmetric charge modulation in S-scheme heterojunction toward highly efficient broad-spectrum photocatalytic hydrogen evolution.

Key words: S-scheme heterojunction, Photocatalytic hydrogen evolution, Graphdiyne, Photothermal effect, Asymmetric charge redistribution