水热反应前驱液pH对钨酸铋形貌结构及光催化性能调控

Mechanism of morphology regulation and photocatalytic performance of bismuth tungstate by precursor pH in hydrothermal reactions

  • 摘要: 氟伐他汀作为常用的降血脂药物,常随人体排泄物排入水体. 环境水体中的氟伐他汀很难被自然光所降解,长期累积会对环境构成一定的威胁. 本研究采用钨酸铋(Bi2WO6)可见光催化降解氟伐他汀,研究不同水热反应前驱液pH制备Bi2WO6的形貌结构及光电性能变化规律,结合活性自由基及中间产物解析揭示氟伐他汀降解机理. 结果表明,前驱液pH由酸性转向中性时Bi2WO6晶体发育过程被破坏引起纳米片堆叠,前驱液pH为碱性时形成无序的八面体物相高聚体. 随着pH升高,Bi2WO6的比表面积和孔径逐渐减小. 当pH值为0.5时,Bi2WO6呈现有序的三维纳米化球结构,具有最佳光催化性能,光照120 min后氟伐他汀降解率达69.84%. 经过四轮循环实验后,催化剂性能仍较为稳定. 电化学实验结果表明,当前驱液pH值为0.5时,Bi2WO6具有最佳的光生电子–空穴分离性能,进而促进活性自由基高效产生. 自由基实验结果表明,在降解过程中h+发挥主要的氧化作用,·OH和·\mathrmO_2^- 起辅助作用. Bi2WO6降解氟伐他汀的机理是以h+为主,·OH和·\mathrmO_2^- 为辅,联合攻击氟伐他汀分子的C—C键,形成小分子环状有机物、直链有机物和羟基化衍生物,进而将其矿化为CO2和H2O.

     

    Abstract: Fluvastatin, a widely used lipid-lowering drug, is frequently released into water bodies via human excreta. Due to its resistance to natural light degradation, its prolonged accumulation in the environment may pose significant ecological risks. Semiconductor photocatalysis has gained increasing attention as an eco-friendly and versatile method for removing refractory pollutants. Among various photocatalysts, bismuth tungstate (Bi2WO6) has emerged as a promising photocatalyst due to its strong visible-light response and high chemical stability. However, its application remains limited by its energy band structure, low separation efficiency of photogenerated carriers, and small specific surface area. In this study, Bi2WO6 was utilized for the visible-light driven photocatalytic degradation of fluvastatin. The research investigates the influence of precursor pH during hydrothermal synthesis on the morphological structure and photoelectric properties of Bi2WO6. Additionally, reactive radicals and intermediates analyses were conducted to elucidate the degradation mechanism of fluvastatin. The morphology, crystal phase, optical absorption performance, specific surface area, electrochemical performance, and carrier separation ability of the synthesized Bi2WO6 photocatalyst were characterized using an electrochemical workstation and steady-state fluorescence spectroscopy. Its performance and stability were evaluated through degradation and cyclic experiments, and the effects of different pH conditions on photocatalytic efficiency were also examined. Additionally, active species analysis and intermediate product identification were employed to elucidate the degradation mechanism of fluvastatin. The results indicate that as the precursor pH shifts from acidic to neutral, the crystal growth of Bi2WO6 is disrupted, leading to the stacking of nanosheets. Under alkaline conditions, disordered octahedral phase polymers are formed. The optimal precursor pH was found to be 0.5, yielding an ordered, three-dimensional nanoflower morphology. Although variations in precursor pH did not significantly affect the light absorption capacity of Bi2WO6, increasing the pH resulted in a decrease in specific surface area and pore volume, from 57 m2·g–1–1 and 0.045 cm3·g–1–1 –1 to 3.5 m2·g–1–1–1 and 0.002 cm3·g–1–1–1, respectively. Electrochemical experiments and steady-state fluorescence spectra further revealed that the efficiency of photogenerated carrier separation gradually decreases with increasing precursor pH. At pH 0.5, Bi2WO6 exhibited the highest photocatalytic performance, achieving 69.84% fluvastatin degradation after 120 min of illumination. Moreover, after four cycles of testing, the catalyst demonstrated stable performance, with the degradation rate remaining nearly unchanged. Free radical experiments demonstrated that h+ ions play the primary oxidative role in the degradation process, with ·OH and ·\mathrmO_2^- radicals contributing as supplementary effects. These reactive species attack the C–C bonds in fluvastatin molecule, breaking them down into small cyclic organics, straight-chain organics, and hydroxylated derivatives, which are ultimately converted into CO2 and H2O.

     

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