物理化学学报

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构筑有机-无机四(4-羧基苯基)卟啉/Bi4O5Br2 S型异质界面以实现高效光生载流子分离和抗生素降解

梁凤兰1, 刘艳萍2, 王小兵3, 于欣4, 杨方5, 郭洋6, 马德运1, 李世杰2   

  1. 1 肇庆学院生命科学学院, 食品与制药工程学院, 广东 肇庆 526061;
    2 浙江海洋大学国家海洋设施养殖工程技术研究中心, 全省临港石化污染控制重点实验室, 浙江 舟山 316022;
    3 韶关学院化学与土木工程学院, 广东 韶关 512005;
    4 河南大学, 新能源与智能制造学院, 绿色化学合成与转化技术全国重点实验室, 河南 郑州 450046;
    5 上海工程技术大学机械与汽车工程学院, 上海 201600;
    6 国家环境保护土壤环境管理与污染控制重点实验室, 生态环境部南京环境科学研究所, 江苏 南京 210000
  • 收稿日期:2026-06-30 修回日期:2026-08-05 录用日期:2026-08-06
  • 通讯作者: 刘艳萍, 马德运, 于欣, 李世杰 E-mail:liuyp@zjou.edu.cn;mady@zqu.edu.cn;xinyu@henu.edu.cn;lishijie@zjou.edu.cn
  • 基金资助:
    本工作得到了浙江省自然科学基金(LTGN23E080001)的资助。

Engineering organic-inorganic tetra (4-carboxyphenyl) porphyrin/Bi4O5Br2 S-scheme interfaces for efficient photoinduced carrier separation and antibiotic degradation

Fenglan Liang1, Yanping Liu2, Xiaobing Wang3, Xin Yu4, Fang Yang5, Yang Guo6, Deyun Ma1, Shijie Li2   

  1. 1 School of Life sciences, School of Food and Pharmaceutical Engineering, Zhaoqing University, Zhaoqing 526061, Guangdong Province, China;
    2 Zhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, National Engineering Research Center for Marine Aquaculture, Zhejiang Ocean University, Zhoushan 316022, Zhejiang Province, China;
    3 School of Chemistry and Civil Engineering, Shaoguan University, Shaoguan 512005, Guangdong Province, China;
    4 State Key Laboratory of Green Chemical Synthesis and Conversion, College of New Energy and Intelligent Manufacturing, Henan University, Zhengzhou 450046, Henan Province, China;
    5 College of Mechanical and Automotive Engineering, Shanghai University of Engineering Science, Shanghai 201600, China;
    6 State Environmental Protection Key Laboratory of Soil Environmental Management and Pollution Control, Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environment, Nanjing 210000, Jiangsu Province, China
  • Received:2026-06-30 Revised:2026-08-05 Accepted:2026-08-06
  • Contact: Yanping Liu, Deyun Ma, Xin Yu, Shijie Li E-mail:liuyp@zjou.edu.cn;mady@zqu.edu.cn;xinyu@henu.edu.cn;lishijie@zjou.edu.cn

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摘要： 水体中的药物污染构成了日益严重的环境威胁，亟需能够完全去除污染物的高级氧化技术。光催化提供了一种可持续的解决方案，但其更广泛的应用受到电荷载流子利用效率低下的阻碍。在此，我们通过将四(4-羧基苯基)卟啉(TCPP)界面接枝到Bi4O5Br2(BB)纳米片上，构建了一种有机-无机S型异质结(TCPP/BB)。优化后的TCPP/BB异质结展现出优异的光氧化活性，在可见光照射60 min内实现了92.7%的四环素(TC)降解效率，相较于原始BB (54.8%)提升了0.69倍。系统的实验表征和密度泛函理论(DFT)计算揭示，TCPP/BB异质界面上的内建电场引导了稳健的S型电荷迁移路径。至关重要的是，这种构型不仅促进了光生载流子的空间分离，还保存了其高能氧化还原能力，从而确保了高效的表面催化反应。机理研究，包括原位电子顺磁共振(EPR)和自由基捕获实验，确定了·O2-和h+为主要活性物种。这些结果凸显了有机-无机S型异质结构概念在水体高效净化中的变革潜力，为水污染提供了可持续的解决方案。

关键词: 有机-无机异质结, Bi4O5Br2, 四(4-羧基苯基)卟啉(TCPP), 内建电场, S型机制, 光催化

Abstract: Pharmaceutical contamination of water bodies poses a growing environmental threat, calling for advanced oxidation technologies capable of complete pollutant removal. Photocatalysis offers a sustainable solution, yet its broader application is hindered by inefficient utilization of charge-carrier. Here, we construct an organic-inorganic S-scheme heterojunction, tetrakis(4-carboxyphenyl)porphyrin/ Bi4O5Br2 (TCPP/BB), via interfacial grafting of TCPP onto BB nanosheets. The optimized TCPP/BB heterojunction delivers superior photo-oxidative activity, achieving a tetracycline (TC) degradation efficiency of 92.7% within 60 min of visible-light illumination and marking a 0.69-fold enhancement over pristine BB (54.8%). Systematic experimental characterizations and density functional theory (DFT) computations reveal that the built-in electric field across the TCPP/BB heterointerface steers a robust S-scheme charge-migration pathway. Crucially, this configuration not only facilitates the spatial isolation of photogenerated carriers but also safeguards their high-energy redox capacities, thereby ensuring efficient surface reactions. Mechanistic studies, including in situ electron paramagnetic resonance (EPR) and radical scavenging assays, identify ·O2- and h+ as the dominant reactive species. These results highlight the transformative potential of organic-inorganic S-scheme heterostructure concept for efficient water cleanup, offering a sustainable solution to water contamination.

Key words: Organic-inorganic heterojunction, Bi4O5Br2, Tetrakis (4-carboxyphenyl) porphyrin (TCPP), Internal electric field, S-scheme mechanism, Photocatalysis