物理化学学报 >> 2026, Vol. 42 >> Issue (11): 100384.doi: 10.1016/j.actphy.2026.100384

论文 上一篇    

有机/无机5,10,15,20-四(4-磺基苯基)卟啉/Bi2WO6 S型异质结用于增强光催化降解水中抗生素

梁凤兰1, 马德运1, 熊梧琬1, 刘艳萍2, 于欣3, 王小兵4, 杨方5, 刘通6, 郭洋7, 赵再望8, 李世杰2,3   

  1. 1 肇庆学院生命科学学院, 食品与制药工程学院, 环境与化学工程学院, 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 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;
    4 韶关学院化学与土木工程学院, 广东韶关 512005;
    5 上海工程技术大学机械与汽车工程学院, 上海 201620;
    6 武汉工程大学化学工程与制药学院, 绿色化工过程教育部重点实验室, 湖北 武汉 430205;
    7 生态环境部南京环境科学研究所, 国家环境保护土壤环境管理与污染控制重点实验室, 江苏 南京 210000;
    8 内蒙古大学能源材料化学学院, 化学与化工学院, 内蒙古 呼和浩特 010070
  • 收稿日期:2026-06-20 修回日期:2026-07-30 录用日期:2026-08-06 发布日期:2026-09-29
  • 通讯作者: 马德运, 刘艳萍, 于欣, 李世杰 E-mail:mady@zqu.edu.cn;liuyp@zjou.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(LY20E080014和LTGN23E080001)以及河南大学化学科学部开放合作基金(DCSHENU2413)的资助。

An organic/inorganic 5,10,15,20-tetrakis(4-sulfophenyl) porphyrin/Bi2WO6 S-scheme heterojunction for boosted photocatalytic destruction of antibiotics in water

Fenglan Liang1, Deyun Ma1, Wuwan Xiong1, Yanping Liu2, Xin Yu3, Xiaobing Wang4, Fang Yang5, Tong Liu6, Yang Guo7, Zaiwang Zhao8, Shijie Li2,3   

  1. 1 School of Life Sciences, School of Food and Pharmaceutical Engineering, School of Environmental and Chemical 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 State Key Laboratory of Green Chemical Synthesis and Conversion, College of New Energy and Intelligent Manufacturing, Henan University, Zhengzhou 450046, Henan Province, China;
    4 School of Chemistry and Civil Engineering, Shaoguan University, Shaoguan 512005, Guangdong Province, China;
    5 College of Mechanical and Automotive Engineering, Shanghai University of Engineering Science, Shanghai 201620, China;
    6 Key Laboratory of Green Chemical Process, Ministry of Education, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, Hubei Province, China;
    7 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;
    8 College of Energy Materials and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010070, Inner Mongolia Autonomous Region, China
  • Received:2026-06-20 Revised:2026-07-30 Accepted:2026-08-06 Published:2026-09-29
  • Contact: Deyun Ma, Yanping Liu, Xin Yu, Shijie Li E-mail:mady@zqu.edu.cn;liuyp@zjou.edu.cn;xinyu@henu.edu.cn;lishijie@zjou.edu.cn

摘要: 太阳能驱动催化反应提供了一条环境友好且能源可持续的途径,以应对紧迫的全球能源和环境挑战。然而,其实际应用仍受限于现有光催化剂性能不佳。在此,我们报道了一种新型有机/无机异质结光催化剂,即5,10,15,20-四(4-磺基苯基)卟啉(TPPS)/Bi2WO6 (BWO),通过将TPPS锚定在BWO微球上制备而成。这种独特结构显著增强了异质界面处的内建电场(IEF),从而促进两种组分之间高效的电荷载流子迁移。值得注意的是,具有强氧化能力的光生空穴积累在BWO表面,并参与羟基自由基(·OH)的生成。同时,分离在TPPS组分上的强还原性电子被分子氧迅速捕获,将其还原为超氧自由基(·O2-)。这种协同电荷分配加速了系统内最强还原性和氧化性物种的分离及功能化利用。所产生的活性自由基,连同表面积累的空穴,作为主要活性物种,驱动了90.2%的优异四环素降解效率。因此,TPPS/BWO异质结实现了四环素降解速率常数约为原始BWO的3.2倍。机理研究结合实验表征与密度泛函理论(DFT)计算揭示,高活性源于TPPS与BWO之间形成的有机/无机S型异质结。这种构型有效保留了异质结系统的优异氧化还原能力。总体而言,这项工作为光催化环境修复中有机/无机异质界面的合理设计提供了新见解。

关键词: 有机/无机异质结, Bi2WO6, TPPS, 内建电场, S型机制, 水净化

Abstract: Solar-driven catalysis provides an environmentally benign and energy-sustainable pathway to address pressing global energy and environmental challenges. However, its practical application remains hindered by the suboptimal performance of available photocatalysts. Herein, we report a novel organic/inorganic heterojunction photocatalyst, 5,10,15,20-tetrakis(4-sulfophenyl)porphyrin (TPPS)/Bi2WO6 (BWO), fabricated by anchoring TPPS onto BWO microspheres. This unique architecture substantially amplifies the internal electric field (IEF) at the heterointerface, thereby promoting efficient charge carrier migration between the two components. Notably, photogenerated holes with strong oxidizing ability accumulate on the BWO surface and participate in hydroxyl radical (•OH) generation. Concurrently, the highly reductive electrons separated on the TPPS component are rapidly captured by molecular oxygen, reducing it to superoxide radicals (•O2-). This synergistic charge partitioning accelerates both the separation and the functional utilization of the strongest reducing and oxidizing species within the system. The resultant reactive radicals, together with the surface-accumulated holes, serve as the primary active species, driving an exceptional degradation efficiency of 90.2%. Consequently, the TPPS/BWO heterojunction achieves a tetracycline abatement rate constant approximately 3.2 folds greater than that of pristine BWO. Mechanistic investigations, integrating experimental characterization with density functional theory (DFT) calculations, reveal that the elevated activity stems from the formation of an organic/inorganic S-scheme heterojunction between TPPS and BWO. This configuration effectively preserves the superior redox capability of the heterojunction system. Overall, this work offers fresh insights into the rational design of organic/inorganic heterointerfaces for photocatalytic environmental remediation.

Key words: Organic/inorganic heterojunction, Bi2WO6, TPPS, Internal electric field, S-scheme mechanism, Water purification