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高效磁性 MnFeO/ZIF-67 催化剂催化香草醛的强化臭氧化:协同作用和机理研究。

Enhanced ozonation of vanillin catalyzed by highly efficient magnetic MnFeO/ZIF-67 catalysts: Synergistic effects and mechanism insights.

机构信息

College of Environment, Zhejiang University of Technology, Hangzhou, China.

Zhejiang Yiwu Water Supply Company Limited, Yiwu, China.

出版信息

Water Environ Res. 2024 Apr;96(4):e11027. doi: 10.1002/wer.11027.

Abstract

In this study, we synthesized magnetic MnFeO/ZIF-67 composite catalysts using a straightforward method, yielding catalysts that exhibited outstanding performance in catalyzing the ozonation of vanillin. This exceptional catalytic efficiency arose from the synergistic interplay between MnFeO and ZIF-67. Comprehensive characterization via x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), Fourier transform infrared spectrometer (FT-IR), Brunauer-Emmett-Teller (BET), field emission scanning electron microscopy (FE-SEM), and energy dispersive spectroscopy (EDS) confirmed that the incorporation of MnFeO promoted the creation of oxygen vacancies, resulting in an increased presence of l adsorbed oxygen (O) and the generation of additional ·OH groups on the catalyst surface. Utilizing ZIF-67 as the carrier markedly enhanced the specific surface area of the catalyst, augmenting the exposure of active sites, thus improving the degradation efficiency and reducing the energy consumption. The effects of different experimental parameters (catalyst type, initial vanillin concentration, ozone dosage, initial pH value, and catalyst dosage) were also investigated, and the optimal experimental parameters (300 mg/L1.0-MnFeO/ZIF-67, vanillin concentration = 250 mg/L, O concentration = 12 mg/min, pH = 7) were obtained. The vanillin removal efficiency of MnFeO/ZIF-67 was increased from 74.95% to 99.54% after 30 min of reaction, and the magnetic separation of MnFeO/ZIF-67 was easy to be recycled and stable, and the vanillin removal efficiency of MnFeO/ZIF-67 was only decreased by about 8.92% after 5 cycles. Additionally, we delved into the synergistic effects and catalytic mechanism of the catalysts through kinetic fitting, reactive oxygen quenching experiments, and electron transfer analysis. This multifaceted approach provides a comprehensive understanding of the enhanced ozonation process catalyzed by MnFeO/ZIF-67 composite catalysts, shedding light on their potential applications in advanced oxidation processes. PRACTITIONER POINTS: A stable and recyclable magnetic composite MnFeO/ZIF-67 catalyst was synthesized through a simple method. The synergistic effect and catalytic mechanism of the MnFeO/ZIF-67 catalyst were comprehensively analyzed and discussed. A kinetic model for the catalytic ozone oxidation of vanillin was introduced, providing valuable insights into the reaction dynamics.

摘要

在这项研究中,我们采用简便的方法合成了磁性 MnFeO/ZIF-67 复合催化剂,该催化剂在催化香草醛的臭氧氧化方面表现出卓越的性能。这种出色的催化效率源于 MnFeO 和 ZIF-67 之间的协同作用。通过 X 射线光电子能谱 (XPS)、X 射线衍射 (XRD)、傅里叶变换红外光谱 (FT-IR)、BET、场发射扫描电子显微镜 (FE-SEM) 和能谱 (EDS) 进行的全面表征证实,MnFeO 的掺入促进了氧空位的形成,从而增加了 l 吸附氧 (O) 的存在,并在催化剂表面产生了更多的·OH 基团。利用 ZIF-67 作为载体显著提高了催化剂的比表面积,增加了活性位点的暴露,从而提高了降解效率并降低了能耗。还研究了不同实验参数(催化剂类型、初始香草醛浓度、臭氧用量、初始 pH 值和催化剂用量)的影响,并获得了最佳实验参数(300mg/L1.0-MnFeO/ZIF-67、香草醛浓度=250mg/L、O 浓度=12mg/min、pH=7)。反应 30 分钟后,MnFeO/ZIF-67 对香草醛的去除效率从 74.95%提高到 99.54%,MnFeO/ZIF-67 的磁性分离易于回收和稳定,MnFeO/ZIF-67 的香草醛去除效率仅降低约 8.92%经过 5 次循环。此外,我们通过动力学拟合、活性氧猝灭实验和电子转移分析深入探讨了催化剂的协同作用和催化机制。这种多方面的方法提供了对 MnFeO/ZIF-67 复合催化剂增强臭氧氧化过程的全面理解,为其在高级氧化过程中的潜在应用提供了启示。从业者要点:通过简单的方法合成了一种稳定且可回收的磁性复合 MnFeO/ZIF-67 催化剂。全面分析和讨论了 MnFeO/ZIF-67 催化剂的协同作用和催化机制。引入了催化臭氧氧化香草醛的动力学模型,为反应动力学提供了有价值的见解。

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