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    BiOCl/g-C3N4异质结压电催化降解四环素的性能和机理研究

    Performance and Mechanism of BiOCl/g-C3N4 Heterojunction for Piezocatalytic Degradation of Tetracycline

    • 摘要: 随着抗生素等难降解有机污染物在水环境中的持续累积,开发兼具高效性与可持续性的污染物去除技术已成为当前环境催化领域的重要研究方向。然而,传统压电催化体系普遍存在本征压电响应弱、界面载流子复合严重以及活性氧物种(ROS)生成效率有限等问题,严重制约了其实际应用性能。为了构建具有高效压电催化性能的异质结体系以实现水中抗生素的快速降解和过氧化氢的绿色合成,采用水热法制备了BiOCl/g-C3N4(BOC/CN)复合材料,通过界面调控成功构筑了紧密耦合的Z-scheme异质结,对材料的物相结构、微观形貌、界面特性及压电催化性能进行了系统研究。结果表明,BOC纳米片与CN之间形成了紧密且连续的异质结界面,有效促进了界面电荷的定向迁移与分离,显著增强了复合材料的压电响应性能。在超声波振动下,BOC/CN对四环素的压电催化降解速率显著提升,30 min内降解速率达0.189 min−1,分别是纯CN和纯BOC的11.8倍和5.7倍,活性物种空穴(h+)、羟基自由基(·OH)和超氧阴离子自由基(·O 2)协同主导了降解过程。BOC/CN在压电催化合成H2O2反应中表现出优异的性能,生成速率达280 μmol/(L·h),远高于纯BOC和纯CN(均接近20 μmol/(L·h)),充分体现了Z-scheme异质结在压电催化中的协同优势。该研究为开发高效压电催化剂应用于环境修复和能源转化提供了新思路。

       

      Abstract: With the continuous accumulation of refractory organic pollutants and antibiotics in aquatic environments, the development of efficient and sustainable water treatment technologies has become an important research focus in the field of environmental catalysis. Among emerging advanced oxidation technologies, piezocatalysis has attracted increasing attention because it can directly convert ubiquitous mechanical energy into chemical energy for reactive oxygen species (ROS) generation without requiring external light irradiation or additional oxidants. However, conventional piezocatalytic materials generally suffer from several intrinsic limitations, including weak piezoelectric polarization, rapid recombination of charge carriers, insufficient active sites, and sluggish interfacial reaction kinetics, which severely restrict their practical catalytic efficiency. In particular, although heterojunction engineering has been widely considered an effective strategy to improve charge separation, constructing highly efficient piezoelectric heterojunction systems with directional charge-transfer pathways and strong redox capability remains a major challenge. To address these issues, BiOCl/g-C3N4 (BOC/CN) composites were successfully synthesized via a hydrothermal method, and a tightly coupled Z-scheme heterojunction was rationally constructed through interfacial engineering. The phase structure, morphology, interfacial characteristics, charge-transfer behavior, and piezocatalytic performance of the composites were systematically investigated. The results demonstrate that BOC nanosheets are uniformly anchored onto the CN surface, forming an intimate and continuous heterointerface that effectively promotes interfacial charge migration and spatial charge separation. More importantly, the Z-scheme charge-transfer pathway preserves the strong oxidation ability of holes in the valence band of BOC and the high reduction ability of electrons in the conduction band of CN, thereby significantly enhancing the generation efficiency of ROS under ultrasonic stimulation. Benefiting from the synergistic effect between piezoelectric polarization and interfacial charge redistribution, the BOC/CN composite exhibits remarkably enhanced piezocatalytic activity toward tetracycline (TC) degradation. Under ultrasonic vibration, the degradation efficiency rate reaches 0.189 min−1, which is 11.8 and 5.7 times higher than that of pure CN and BOC, respectively. Radical trapping experiments confirmed that holes (h+), hydroxyl radicals (·OH), and superoxide radicals (·O 2) synergistically dominated the degradation process. In addition, BOC/CN displays excellent performance in piezocatalytic H2O2 synthesis, achieving a generation rate of 280 μmol/(L·h), which is significantly higher than those of pure BOC and CN (both close to 20 μmol/(L·h)). This enhanced H2O2 production is mainly attributed to the efficient two-electron oxygen reduction pathway enabled by the Z-scheme heterojunction and piezo-induced charge separation. This work deepens the understanding of piezoelectric Z-scheme interfacial mechanisms and provides a promising strategy for the design of highly efficient piezocatalysts for environmental remediation and sustainable energy conversion.

       

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