摘要
在避免母体结构坍塌的前提下,通过缺陷工程对金属有机骨架(MOFs)进行处理可有效提升其去除水体污染物的性能。目前,通过调整合成条件(温度、金属/配体比例等)、添加调制剂、热处理和金属节点取代等方式可制备缺陷MOFs。粉末X射线衍射(PXRD)、比表面积分析、热重-差热分析(TGA-DSC)、电子顺磁共振(EPR)、X射线光电子能谱(XPS)、高分辨率透射电子显微镜(HR-TEM)、球差校正透射电镜(AC-TEM)和X射线吸收光谱(XAS)表征技术可证实MOFs中缺陷的特征。相比原始MOFs,从光催化等高级氧化的角度来看,构造缺陷型MOFs可促进电子转移、减小带隙以提升其高级氧化降解去除污染物的性能。此外,缺陷型MOFs还可为污染物提供更多吸附位点,进一步提升吸附剂的吸附容量和吸附速率。本文系统总结缺陷MOFs的制备方法、现有常见表征技术及其在水处理领域中的应用。同时,本文还根据缺陷MOFs用于去除水中污染物的研究现状对其今后发展予以展望。
Defect engineering is an effective strategy for modulating the structure of metal-organic frameworks(MOFs)to boost their performance in water treatment.The defect can be formed when the regular periodic arrange-ment of atoms or ions in the crystalline parent framework is broken due to the missing or dislocation of atoms orions.In the field of defective MOFs,the types of defects are divided into(ⅰ)missing linker defects,(ⅰⅰ)modified link-er defects,(ⅰⅰⅰ)missing node defects,and(ⅳ)modified node defects.Although the construction of defective MOFs hasreceived continuous attention,which remains challenging today.Up to now,there are two synthetic pathways tofabricate defective MOFs:the modulation during the synthesis process and the post-synthetic treatment methods.Specifically,defective MOFs can be fabricated by adjusting the synthesis conditions(temperature,the ratio of metal/ligand,etc.),introducing modulators,thermal activation,metal node substitution,and so on.Many advanced tech-niques like X-ray diffraction(XRD),specific surface area analysis,thermogravimetric analyses-differential scanning calorimetry(TGA-DSC),electron paramagnetic resonance(EPR),X-ray photoelectron spectra(XPS),high-resolutiontransmission electron microscopy(HR-TEM),spherical aberration-corrected transmission electron microscope(AC-TEM),and X-ray absorption spectroscopy(XAS)can effectively affirm the defective structure of MOFs.In thefield of water remediation,the construction of defective MOFs can boost their performance of advanced oxidationprocesses like photocatalysis,persulfate(PS)activation,and photo-Fenton by enhancing separation rates of photoin-duced electron-hole,promoting the photo-electron transfer and narrowing the band gap compared with pristineMOFs.Moreover,because the defective sites are introduced in the framework,they act as dominant active sites inthe PS system,promoting the generation of radicals and creating a nonradical degradation pathway.Meanwhile,defective MOFs with rich unsaturated coordination centers can provide more adsorption sites toward pollutants,further enhancing the adsorption capacities and rates of sorbents.This review summarized the fabrications,charac-terizations,and applications in the water treatment of defective MOFs.Meanwhile,the prospects of defective MOFsfor pollutant removal from water are proposed in this review.
作者
李渝航
王鹏
王崇臣
刘艳彪
LI Yu-Hang;WANG Peng;WANG Chong-Chen;LIU Yan-Biao(Beijing Key Laboratory of Functional Materials for Building Structure and Environment Remediation,School of Environmental and Energy Engineering,Beijing University of Civil Engineering and Architecture,Beijing 100044,China;College of Environmental Science and Engineering,Donghua University,Shanghai 201620,China)
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2022年第12期2342-2362,共21页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金(No.51878023)
北京自然科学基金(No.8202016)
北京市属高等学校长城学者培养计划(No.CIT&TCD20180323)
北京市百千万人才工程(No.2020A27)资助。
关键词
金属有机骨架
缺陷工程
高级氧化
吸附
水体污染物
metal-organic frameworks
defect engineering
advanced oxidation process
adsorption
aqueous pollutants
