物理化学学报

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利用漂浮式全有机S型光催化剂实现四环素降解耦合制氢

赵铖山1, 李嘉明1, 朱玉荃2, 徐先燕3, 李湘4, 杨新雨1, 王楷1   

  1. 1 湖北师范大学城市与环境学院, 黄石市土壤污染防治重点实验室, 湖北 黄石 435002;
    2 湖北师范大学化学化工学院, 湖北 黄石 435002;
    3 韶关大学化学与土木工程学院, 广东 韶关 512005;
    4 肇庆学院环境与化学工程学院, 广东 肇庆 526061
  • 收稿日期:2026-08-13 修回日期:2026-09-07 录用日期:2026-09-08
  • 通讯作者: 王楷Kai Wang E-mail:wangkai@hbnu.edu.cn
  • 基金资助:
    本工作得到了国家自然科学基金(22378104)、湖北省自然科学基金(2025AFA093)以及纺织印染清洁生产教育部工程研究中心开放课题(2025GCZX003)的资助。

Coupling tetracycline degradation and hydrogen evolution with a floating all-organic S-scheme photocatalyst

Chengshan Zhao1, Jiaming Li1, Yuquan Zhu2, Xianyan Xu3, Xiang Li4, Xinyu Yang1, Kai Wang1   

  1. 1 Huangshi Key Laboratory of Prevention and Control of Soil Pollution, College of Urban and Environmental Sciences, Hubei Normal University, Huangshi 435002, Hubei Province, China;
    2 College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, Hubei Province, China;
    3 School of Chemistry and Civil Engineering, Shaoguan University, Shaoguan 512005, Guangdong Province, China;
    4 School of Environmental and Chemical Engineering, Zhaoqing University, Zhaoqing 526061, Guangdong Province, China
  • Received:2026-08-13 Revised:2026-09-07 Accepted:2026-09-08

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摘要： 浮动光催化技术可以缓解传统悬浮光催化剂在催化剂回收、光利用和传质方面的局限性。然而，当前的浮动构型往往依赖于被动固定化，而未解决体相载流子复合这一关键问题。在此，我们原位构建了S型全有机石墨相氮化碳(g-C3N4)/有机共价框架材料(iCOF)异质结，并将其固定在退火三聚氰胺海绵(AMS)基底上，用于可见光驱动的四环素(TC)降解耦合析氢反应。优化后的复合材料(CNCF50)在60 min内实现了99.8%的TC去除率，表观速率常数为0.062 min-1，析氢速率为16.5 mmol g-1 h-1。当作为宏观浮动催化剂使用时，CNCF50/AMS系统保持了12.6 mmol g-1 h-1的析氢速率和80.3%的TC去除效率。利用电子顺磁共振(EPR)、捕获实验、光电化学表征和飞秒瞬态吸收(fs-TA)光谱进行的机理研究表明，S型界面改变了光生电荷载流子的弛豫路径，从而促进了其高效分离和界面转移。这项工作通过分子尺度的电荷调控和宏观尺度的界面工程，展示了污染物氧化与太阳能燃料生产的集成。

关键词: 漂浮光催化剂, 四环素降解, 光催化产氢, g-C3N4/iCOF异质结, S型电荷转移

Abstract: Floating photocatalysis can mitigate the catalyst-recovery, light-utilization and mass-transfer limitations of conventional suspended photocatalysts. However, current floating configurations often rely on passive immobilization without addressing the critical issue of bulk carrier recombination. Here, an S-scheme all-organic graphitic carbon nitride (g-C3N4)/covalent organic framework (iCOF) heterojunction was constructed in situ and immobilized on an annealed melamine sponge (AMS) substrate for visible-light-driven tetracycline (TC) degradation coupled with hydrogen evolution. The optimized composite (CNCF50) achieved 99.8% removal of TC within 60 min, yielding an apparent rate constant of 0.062 min-1, and a hydrogen evolution rate of 16.5 mmol g-1 h-1. When deployed as a macroscopic floating catalyst, the CNCF50/AMS system maintained a hydrogen evolution rate of 12.6 mmol g-1 h-1 and a TC removal efficiency of 80.3%. Mechanistic studies using electron paramagnetic resonance (EPR), trapping experiments, photoelectrochemical characterization, and femtosecond transient absorption (fs-TA) spectroscopy indicate that the S-scheme interface modifies the relaxation pathways of photogenerated charge carriers, thereby promoting their efficient separation and interfacial transfer. This work demonstrates the integration of pollutant oxidation and solar fuel production through molecular-scale charge regulation and macroscopic-scale interface engineering.

Key words: Floating photocatalysts, Tetracycline degradation, Photocatalytic hydrogen evolution, g-C3N4/iCOF heterojunction, S-scheme charge transfer