铁钴双金属有机框架/稻谷壳复合材料的制备及其染料脱色性能

doi:10.13475/j.fzxb.20241000601

摘要/Abstract

摘要： 为改善金属有机框架(MOFs)材料的重复回收和连续操作性能,通过溶剂热原位生长法制备了FeCo-1,4-苯二甲酸/稻谷壳复合材料FeCo-BDC/RH。借助扫描电子显微镜、X射线衍射仪和红外光谱仪等分析了FeCo-BDC/RH的形貌及结构;评估了复合材料活化过一硫酸盐(PMS)对罗丹明B(RhB)的脱色效果,并通过猝灭实验和电子顺磁共振谱揭示了脱色过程的关键活性物种及其产生机制。结果表明:FeCo-BDC/RH能高效激活PMS,实现RhB的快速脱色;5 min内FeCo-BDC/RH+PMS体系对RhB的脱色率高达99%;该体系在不同pH值的溶液及天然水质条件下均表现出稳定的脱色性能,且对多种染料具有良好的普适性;在固定床反应器中以 32 h^-1 液时空速连续反应 300 min,FeCo-BDC/RH 复合材料对 RhB 的脱色率仍近100%,显示出良好的稳定性和高活性;¹O₂是参与染料脱色的主要活性物种,SO₄¹·次之,复合材料中的双金属位点Fe(Ⅲ)/Fe(Ⅱ)和Co(Ⅲ)/Co(Ⅱ)是产生这些活性物种的关键活性位点。

关键词: 金属有机框架, 废弃生物质, 稻谷壳, 高级氧化, 染料脱色, 印染废水, 废水处理

Abstract:

Objective With the progression of the global textile industry, a substantial quantity of wastewater containing toxic and non-biodegradable synthetic dyes may impose considerable threats to public health and the environment. Peroxymonosulfate (PMS)-based advanced oxidation processes have garnered significant attention in the remediation of organic dye wastewater because of their high degradation efficiency and non-selective oxidation. As promising catalysts for PMS activation, metal-organic frameworks (MOFs) often face limitations because of particle agglomeration and challenges in recovery during liquid-phase reactions, attributed to their powdery nature. Therefore, constructing macroscopic structures from powdered MOFs is highly significant for expanding their practical applications.

Method FeCo-benzenedicarboxylate/rice husk (FeCo-BDC/RH) composite material was fabricated via solvothermal in-situ growth strategy. The morphology and structure of FeCo-BDC/RH were analyzed by scanning electron microscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The decolorization performance of the composite material for activating PMS on Rhodamine B (RhB) was evaluated, and the key active species in the decolorization process were revealed through quenching experiments and electron paramagnetic resonance (EPR) spectroscopy.

Results The scanning electron microscopy images confirmed that the FeCo-BDC, which was grown in-situ on the surface of RH, exhibited a highly dispersed state. This is significantly different from the spindle-shaped morphology of pure FeCo-BDC, thereby highlighting the importance of the carrier. Moreover, the composite material FeCo-BDC/RH was of centimeter-scale size and easily recovered from the liquid phase after the reaction. The analytical results of FT-IR, XPS, and XRD further confirmed the successful preparation of the FeCo-BDC/RH composite material. FeCo-BDC/RH was capable of efficiently activating PMS and facilitating rapid decolorization of RhB. The decolorization rate of RhB by the FeCo-BDC/RH+PMS system reached as high as 99% within 5 min. The FeCo-BDC/RH+PMS system demonstrated stable decolorization effects under various solution pH volues and natural water quality conditions and possesses universality for the decolorization of multiple dyes. In a fixed-bed reactor with a continuous reaction for 300 min, the decolorization rate of RhB by the FeCo-BDC/RH composite material remained nearly 100%, indicating the potential for large-scale continuous treatment of organic dye wastewater. The results of quenching experiments and EPR technology indicated that the degradation of RhB included both radical (S${O}_{4}^{-}$O4-·) and non-radical (¹O₂) pathways, with ¹O₂ being the dominant one. In addition, the results of the EPR spectra confirmed the existence of these key reactive oxygen species. The variable valence state of iron and cobalt metal sites plays an indispensable role in the process of activating PMS to generate these key species. The interaction between the bimetals accelerates the redox process of Fe(Ⅲ)/Fe(Ⅱ) and Co(Ⅲ)/Co(Ⅱ) through electron transfer between metals, thereby promoting the generation of reactive oxygen species.

Conclusion The FeCo-BDC/RH composite catalyst was successfully prepared through the in-situ growth of FeCo-BDC on waste RH. This composite material demonstrated outstanding performance in activating PMS. The decolorization rate of the RhB dye reached 99% within just 5 min. Additionally, the FeCo-BDC/RH composite catalyst showed good recoverability and remarkable anti-interference ability in the face of different pH values and natural water matrices. The composite material demonstrated versatility in degrading a range of organic dyes and achieved continuous and efficient dye decolorization in a fixed-bed reactor. This study offers a low-cost waste biomass carrier for the construction of three-dimensional macroscopic structures of MOFs, thereby helping to lower the economic cost of wastewater treatment. The fabricated composite material significantly expands the potential for large-scale continuous treatment of organic dye wastewater.

Key words: metal-organic framework, waste biomass, rice husk, advanced oxidation, dye decolorization, dyeing wastewater, wastewater treatment

中图分类号:

O643.3

项文龙, 杨静冉, 肖晓珍. 铁钴双金属有机框架/稻谷壳复合材料的制备及其染料脱色性能[J]. 纺织学报, 2025, 46(06): 178-186.

XIANG Wenlong, YANG Jingran, XIAO Xiaozhen. Preparation of Fe-Co bimetallic organic framework/rice husk composite material and its performance in dye decolorization[J]. Journal of Textile Research, 2025, 46(06): 178-186.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20241000601

http://www.fzxb.org.cn/CN/Y2025/V46/I06/178

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