催化学报

催化学报 ›› 2026, Vol. 87: 126-139.DOI: 10.1016/S1872-2067(26)65106-6

• 论文 • 上一篇    下一篇

Ag/AgBr/C3N5中LSPR增强S型电荷转移促进活性氧物种生成实现高效光催化降解抗生素废水

李世杰a,b,c,d,*(), 李蕊a, 刘艳萍a, 于欣c, 马德运e, 姜建辉f, 周小松g, 庄春强h,*(), 赵再望i, 姜维a,b,*()   

  1. a 浙江海洋大学国家海洋设施养殖工程技术研究中心, 浙江省石油化工环境污染控制重点实验室, 浙江舟山 316022
    b 平阳县科技创新研究院, 浙江温州 325400
    c 河南大学能源科学与技术学院, 河南省废弃物资源能源化工程技术研究中心, 河南郑州 450046
    d 韶关学院化学与土木工程学院， 广东韶关 512005, 中国
    e 肇庆学院食品与制药工程学院, 广东肇庆 526061
    f 塔里木大学化学化工学院, 新疆阿拉尔 843300
    g 岭南师范学院化学化工学院, 广东湛江 524048
    h 北京工业大学先进材料微观结构与性能研究所, 北京 100124
    i 内蒙古大学能源材料化学研究院, 化学化工学院, 内蒙古呼和浩特 010070
  • 收稿日期:2025-07-22 接受日期:2026-02-13 出版日期:2026-08-18 发布日期:2026-06-24
  • 通讯作者: *电子信箱: lishijie@zjou.edu.cn (李世杰),
    chunqiang.zhuang@bjut.edu.cn (庄春强),
    jiangw@zjou.edu.cn (姜维).
  • 基金资助:
    国家重点研发计划(2024YFD2101200);浙江省自然科学基金(LY20E080014);浙江省自然科学基金(LTGN23E080001);河南大学化学科学部开放合作项目(DCSHENU2413)

Augmented reactive oxygen species generation in Ag/AgBr/C3N5 via LSPR-enhanced S-scheme charge transfer for efficient photocatalytic antibiotic wastewater remediation

Shijie Lia,b,c,d,*(), Rui Lia, Yanping Liua, Xin Yuc, Deyun Mae, Jianhui Jiangf, Xiaosong Zhoug, Chunqiang Zhuangh,*(), Zaiwang Zhaoi, Wei Jianga,b,*()   

  1. a Zhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, National Engineering Research Center for Marine Aquaculture, Zhejiang Ocean University, Zhoushan 316022, Zhejiang, China
    b Pingyang Institute of Science and Technology Innovation, Wenzhou 325400, Zhejiang, China
    c Henan Engineering Research Center of Resource & Energy Recovery from Waste, School of Energy Science and Technology, Henan University, Zhengzhou 450046, Henan, China
    d School of Chemistry and Civil Engineering, Shaoguan University, Shaoguan, 512005, China
    e School of Food and Pharmaceutical Engineering, Zhaoqing University, Zhaoqing 526061, Guangdong, China
    f College of Chemistry and Chemical Engineering, Tarim University, Alar 843300, Xinjiang, China
    g School of Chemistry and Chemical Engineering, Lingnan Normal University, Zhanjiang 524048, Guangdong, China
    h Institute of Microstructure and Property of Advanced Materials, Beijing University of Technology, Beijing 100124, China
    i College of Energy Materials and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010070, Inner Mongolia, China
  • Received:2025-07-22 Accepted:2026-02-13 Online:2026-08-18 Published:2026-06-24
  • Supported by:
    National Key R&D Program of China(2024YFD2101200);Natural Science Foundation of Zhejiang Province(LY20E080014);Natural Science Foundation of Zhejiang Province(LTGN23E080001);Open Cooperation Foundation of the Department of Chemical Science of Henan University(DCSHENU2413)

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摘要：

随着抗生素在水体环境中的持续累积, 其生态风险的日益凸显, 开发高效、稳定的水处理技术已成为环境科学领域的重要课题. 光催化氧化技术因其可利用太阳能、反应条件温和且无二次污染等优势, 在抗生素废水治理中展现出广阔前景. 然而, 传统光催化剂在实际应用中仍面临关键瓶颈: 光生电子-空穴对易复合导致量子效率低、单一材料难以同时具备宽光谱响应和强氧化还原能力.

本研究设计并构建了一种新型等离子体增强S-型异质结光催化剂Ag/AgBr/C3N5, 旨在通过协同效应提升光生电荷分离效率并保留强氧化还原能力. 采用沉淀-光沉积法将Ag/AgBr纳米颗粒均匀负载于C3N5纳米片表面, 通过调控组分比例优化了异质结界面接触. 系统的表征手段(X-射线衍射、扫描电镜、透射电镜、X-射线光电子能谱、紫外-可见光漫反射光谱、紫外光电子能谱、Mott-Schottky、电化学抗阻谱、瞬态光电流、电子顺磁共振(EPR))和密度泛函理论计算揭示了材料的结构、光吸收、能带位置、界面电荷转移机制及活性物种生成能力. 光催化性能评估显示, 最优质量比的Ag/AgBr/C3N5 (AAN-2)在可见光照射下50 min内对左氧氟沙星的降解率达87.9%, 表观速率常数达0.0391 min‒1, 分别是纯AgBr, C3N5和AgBr/C3N5的1.76, 11.2和1.35倍, 且对多种抗生素(土霉素、诺氟沙星、恩诺沙星)均表现出高效降解能力. 在连续流固定床反应器中, AAN-2可稳定运行24 h, 去除率保持85%以上. 自由基捕获和EPR测试证实, 超氧自由基(•O2‒)和空穴(h+)是主要活性物种, 羟基自由基(•OH)起辅助作用. 液相色谱-质谱联用分析提出了左氧氟沙星的两种主要降解路径, 毒性评估软件预测表明中间产物毒性较原药显著降低. 机理研究表明, AgBr与C3N5功函差异(5.64 vs. 5.05 eV)在界面形成内建电场, 驱动S型电荷转移: AgBr导带弱还原性电子与C3N5价带弱氧化性空穴复合, 而强还原性电子保留在C3N5导带、强氧化性空穴保留在AgBr价带, 分别用于还原O2生成•O2‒和氧化H2O/OH‒生成•OH.同时, Ag纳米颗粒的局域表面等离子体共振(LSPR)效应不仅拓宽了可见光吸收范围, 还产生热电子注入C3N5导带, 进一步促进电荷分离.

综上, 提出一种基于S型异质结和LSPR协同增效的催化剂设计策略, 旨在通过能带工程和界面调控实现光生电荷的高效分离与活性物种的定向强化生成, 为抗生素污染水体的绿色治理提供新思路, 在抗生素污染水处理领域具有广阔应用前景.

关键词: 活性氧物种生成增强, 局域表面等离子体共振效应, C3N5, S-型异质结, Ag/AgBr, 内建电场, 抗生素去除

Abstract:

The efficacy of photocatalytic pollutant degradation is fundamentally governed by charge carrier separation dynamics and redox potential preservation. To address these critical factors, we developed a plasmon-enhanced Ag/AgBr/C3N5 S-scheme heterojunction through a facile assembly approach. Systematic characterization and theoretical calculations reveal the establishment of a robust interfacial electric field that simultaneously promotes efficient charge separation while maintaining the strong inherent redox capabilities of individual components. The incorporation of plasmonic Ag nanoparticles introduces localized surface plasmon resonance, significantly broadening visible light absorption and generating energetic hot electrons. This synergistic integration of S-scheme charge transfers and plasmonic effects contributes to reinforced production of reactive species and yields exceptional photocatalytic performance, achieving 87.9% degradation of levofloxacin within 50 min under visible light irradiation. This performance surpasses those of pristine AgBr, AgBr/C3N5 and C3N5 by factors of approximately 1.76, 1.35 and 11.2, respectively. Mechanistic investigations through intermediate analysis elucidate a plausible levofloxacin degradation process, while eco-toxicological assessments confirm the environmentally benign nature of the final products. This work establishes a novel design paradigm for designing plasmon-enhanced S-scheme photocatalysts, offering a sustainable solution for antibiotic remediation in aqueous systems.

Key words: Reinforced ROS generation, Localized surface plasmon resonance effect, C3N5, S-scheme heterojunction, Ag/AgBr, Internal electric field, Antibiotic removal