挥发性有机物(VOCs)吸附材料的研究进展

目前,我国面临严重的挥发性有机物（VOCs）污染问题。吸附法是研究与应用最为广泛的VOCs治理技术。主要介绍了吸附净化VOCs原理和几种常见的VOCs吸附材料,包括活性炭、新型多孔炭材料、沸石分子筛、黏土基吸附剂、金属有机框架和介孔硅。详述了各吸附材料的VOCs吸附能力和优缺点,判断了其应用价值,并指出了为提升大规模工业化应用潜力,后续研发的VOCs吸附材料应满足高吸附量、高疏水性、高热稳定性和再生能力强4个特征。     

活性炭吸附挥发性有机化合物的研究进展

由于挥发性有机化合物(VOCs)对人类健康和生态环境的危害巨大,因此VOCs控制技术的研究显得尤为重要。活性炭吸附法具有技术成熟、操作简单、净化效率高、能耗低以及可回收等优势,是净化VOCs最经济、有效的方法之一。主要综述了活性炭在脱除VOCs方面的研究进展,包括活性炭的制备和改性技术及其对VOCs的吸附性能、活性炭吸附VOCs的影响因素以及活性炭在实际工业中的应用。通过探究不同制备及改性方法对活性炭孔结构、表面化学性质、比表面积的改变与VOCs吸附效果之间的联系,并结合实际应用实例,对活性炭吸附技术在实际应用中的发展方向提出了一些合理见解。     

稀土材料在挥发性有机废气降解中的应用及发展趋势

稀土材料由于富含表面羟基、表面晶格缺陷和具有高温稳定性,结合其强挥发性有机物（VOCs）亲和性以及优异储氧和释放能力等优势,在大气污染控制领域的应用十分广泛。近年来的研究发现,部分稀土基材料在VOCs处理上的效果优于贵金属催化剂,在实际工程中也显示出广泛的应用前景。在文献及工程调研的基础上,综述了稀土基材料在国内外催化领域、吸附领域以及实际工程应用中的现状,分析了稀土材料的优势以及目前面临的难题。从吸附、催化等角度分析了稀土材料在国内外的发展趋势,同时结合我国当前国情指出发展中的关键问题及解决方案,期望能为稀土材料在VOCs治理领域的更好发展提供参考。     

不同配体合成的锆基MOFs吸附VOCs的试验研究

以对苯二甲酸作为基础配体，采用功能化官能团配体2-氨基对苯二甲酸、1,4-萘二甲酸以及长链配体联苯二甲酸，水热合成UIO-66、UIO-66-NH₂、UIO-66-NDC和UIO-67等含有不同配体的锆基MOFs吸附材料。利用XRD、FTIR、BET表征分析了这4种材料，分别考察了其对甲苯和乙酸乙酯的动态吸附容量。结果表明：具有4种不同配体的MOFs均合成成功；在相对湿度为80%时，UIO-66表现出最高的吸附容量，甲苯吸附量高达139.4 mg/g,乙酸乙酯吸附量为60.8 mg/g; UIO-66具有最佳吸附性能归因于其以微孔为主的孔径结构，BET结果显示其微孔分布在0.5～1 nm之间，有利于小分子VOCs的吸附，展示出良好的应用潜力。     

两种介孔分子筛动态吸附VOCs的研究

采用模板剂法制备了孔道规整、大比表面积的2种介孔分子筛MCM-41和SBA-15,并以甲苯、二甲苯、三甲苯为吸附对象,考察了介孔分子筛动态吸附VOCs的性能.结果表明,增加VOCs分子尺寸和浓度,降低床层温度可大幅提高介孔分子筛吸附性能.SBA-15由于介孔壁上的微孔结构适合吸附低浓度、小分子VOCs;MCM-41更适合吸附高浓度、大分子VOCs.TPD脱附试验表明,VOCs在介孔材料表面150℃下就能基本脱附完全.     

石墨烯量子点辅助合成Cu-MOFs及CO2吸附行为

选用一种成本低、可大规模合成的Cu基MOFs（Cu-MOFs）材料作为CO₂吸附剂,在原位合成过程中添加石墨烯量子点以调控其晶体结构.结果表明：适量石墨烯量子点的添加有利于提高Cu-MOFs的比表面积和孔体积,相比未改性MOFs材料,改性后的CO₂吸附性能有所提高,25℃,100kPa时提高了4.5%.随着温度升高,吸附容量提升越明显.改性后的MOFs对于N₂的吸附量则比未改性时更低,因此计算得到的CO₂/N₂吸附选择性也更高,增加了近一倍.综合等量吸附热的考察结果发现,尤其添加适量含N石墨烯量子点的Cu-MOFs吸附剂不仅具备了较高的吸附容量、吸附选择性,还展现了较理想的吸附热,因此兼具了较优CO₂吸附性能和较低脱附能耗的特点,为MOFs吸附剂的改性提供了一点参考价值.     

TiO_2光催化降解VOCs工艺参数研究进展

半导体材料TiO_2光催化降解室内VOCs技术存在降解工艺参数千差万别、可见光利用率低、难以产业化等问题。目前国内外有大量研究以期明确光催化进程的机理、寻求合适的工艺参数从而提高光催化降解效率。VOCs特性、环境条件、光催化剂特性是影响反应进行的主要因素。研究发现,对于室内VOCs浓度水平,提高催化剂的吸附能力是关键,且VOCs之间的吸附竞争可以忽略不计。由于VOCs分子结构不同,不同VOC对空气湿度的响应不同;氧气浓度与温度均在接近室内环境时效率最高;在可见光范围内,降解率较低;接触时间越长,光催化效率越高。对TiO_2进行改性后可以解决光催化效率低的问题,但需要研究经济性与实用性以期实现产业化。     

金属有机框架ZIF-8/聚二乙烯基苯纳米复合材料的合成及其吸附VOCs的性能

在常温常压下的甲醇溶液体系中,将COOH功能化的介孔材料聚二乙烯基苯(PDVB)与微孔材料金属有机框架(MOFs)ZIF-8进行复合,获得了一种新型的多孔纳米复合材料ZIF-8/PDVB,采用XRD、FTIR、SEM和氮气吸附-脱附等方法对ZIF-8/PDVB进行表征,并考察了其吸附甲苯、乙酸乙酯的性能.XRD谱图表明,所合成的ZIF-8以晶体形式存在;FTIR和XRD的结果表明,ZIF-8与PDVB的复合是通过Zn2+与PDVB上的COOH形成配位,未配位饱和的Zn~(2+)再与2-甲基咪唑进行配位,从而形成纳米复合材料ZIF-8/PDVB;SEM结果显示,ZIF-8晶体分散在PDVB的表面上;氮气吸附-脱附表征结果显示,ZIF-8/PDVB的比表面积达到1301 m~2·g~(-1),材料同时具有介孔与微孔结构.吸附性能评价结果表明,ZIF-8/PDVB对甲苯、乙酸乙酯均具有优良的吸附性能,ZIF-8/PDVB在吸附VOCs性能上显示出潜在的巨大优势.     

基于机器学习的金属有机框架吸附水中重金属性能预测

为了能准确预测金属有机框架材料(MOFs)对水中重金属的吸附性能,收集了48篇文献中的MOFs结构特征和成分特性,以及吸附水中重金属的实验参数建立数据集,训练并评价了6种回归模型,包括支持向量回归(SVR)、K-最近邻(KNN)、提升法(AdaBoost)、梯度提升树(GBDT)、随机森林(RF)和袋装法(Bagging).结果表明:基于树的集成学习模型的预测性能表现优异,其中以GBDT算法训练的模型性能最佳;进一步应用该模型,证明了机器学习方法可以准确预测MOFs对水中重金属的吸附性能;排列重要性与部分依赖图(PDP)显示,除了可控的实验参数外,影响吸附量的重要因素是MOFs的孔径、比表面积、孔体积.本研究中的方法不仅能预测MOFs结构和性能的关系,还可以基于有效的实验参数模拟水中重金属的去除,进而为吸附材料的筛选优化提供参考.     

碳基材料与挥发性有机污染物相互作用行为和机制研究进展

挥发性有机物(VOCs)是常见的污染物，可通过工农业生产活动进入环境，并对生态环境和人类健康构成潜在威胁。碳基材料具有多种优点且极具工程应用潜力，被广泛应用于VOCs污染防治的研究中。因此明确碳基材料与VOCs间的作用机制有着切实的环境意义。首先综述了VOCs的主要来源、危害。并以碳基材料为主要关注对象，论述了各种改性或未改性碳基材料对VOCs的吸附和降解效率；详细介绍了吸附和降解过程中两者间可能发生的作用机制；然后从碳基材料和VOCs本身的物理化学性质以及环境因素角度出发，探讨碳基材料吸附或降解VOCs过程中的影响因素；最后阐明了两者之间的关联和区别，总结出判定去除VOCs过程中相互作用的方法。基于此，碳基材料在VOCs治理过程中起到重要作用，具有重要的环境意义。研究成果可为碳基材料的结构调控方向、应用性能评价及其在VOCs吸附或降解中的应用提供参考。     

Potential applications of porous organic polymers as adsorbent for the adsorption of volatile organic compounds

Volatile organic compounds (VOCs) with high toxicity and carcinogenicity are emitted from kinds of industries, which endanger human health and the environment. Adsorption is a promising method for the treatment of VOCs due to its low cost and high efficiency. In recent years, activated carbons, zeolites, and mesoporous materials are widely used to remove VOCs because of their high specific surface area and abundant porosity. However, the hydrophilic nature and low desorption rate of those materials limit their commercial application. Furthermore, the adsorption capacities of VOCs still need to be improved. Porous organic polymers (POPs) with extremely high porosity, structural diversity, and hydrophobic have been considered as one of the most promising candidates for VOCs adsorption. This review generalized the superiority of POPs for VOCs adsorption compared to other porous materials and summarized the studies of VOCs adsorption on different types of POPs. Moreover, the mechanism of competitive adsorption between water and VOCs on the POPs was discussed. Finally, a concise outlook for utilizing POPs for VOCs adsorption was discussed, noting areas in which further work is needed to develop the next-generation POPs for practical applications.     

Development of metal organic fromwork-199 immobilized zeolite foam for adsorption of common indoor VOCs

Reticulated foam shaped adsorbents are more efficient for the removal of volatile organic compounds(VOCs),particularly from low VOC-concentration indoor air streams. In this study composite structure of zeolite and metal organic frameworks(MOFs),referred as ZMF,has been fabricated by immobilization of fine MOF-199 powder on foam shaped Zeolite Socony Mobil-5(ZSM-5)Zeolitic structure,referred as ZF. The ZMF possess a uniform and well-dispersed coating of MOF-199 on the porous framework of ZF. It shows higher surface area,pore volume,and VOCs adsorption capacity,as compared to ZF-structure.Post-fabrication changes in selective adsorption properties of ZMF were studied with three common indoor VOCs(benzene,n-hexane,and cyclohexane),using gravimetric adsorption technique. The adsorption capacity of ZMF with different VOCs follow the order of benzene n-hexane cyclohexane. In comparison with MOF-199 and ZF,the composite structure ZMF shows improvement in selectivity for benzene from other two VOCs. Further,improvement in efficiency and stability of prepared ZMF was found to be associated with its high MOF loading capacity and unique morphological and structural properties. The developed composite structure with improved VOCs removal and recyclability could be a promising material for small to limited scale air pollution treatment units.     

Development of metal organic framework-199 immobilized zeolite foam for adsorption of common indoor VOCs

Reticulated foam shaped adsorbents are more efficient for the removal of volatile organic compounds (VOCs), particularly from low VOC-concentration indoor air streams. In this study composite structure of zeolite and metal organic frameworks (MOFs), referred as ZMF, has been fabricated by immobilization of fine MOF-199 powder on foam shaped Zeolite Socony Mobil-5 (ZSM-5) Zeolitic structure, referred as ZF. The ZMF possess a uniform and well-dispersed coating of MOF-199 on the porous framework of ZF. It shows higher surface area, pore volume, and VOCs adsorption capacity, as compared to ZF-structure. Post-fabrication changes in selective adsorption properties of ZMF were studied with three common indoor VOCs (benzene, n-hexane, and cyclohexane), using gravimetric adsorption technique. The adsorption capacity of ZMF with different VOCs follow the order of benzene > n-hexane > cyclohexane. In comparison with MOF-199 and ZF, the composite structure ZMF shows improvement in selectivity for benzene from other two VOCs. Further, improvement in efficiency and stability of prepared ZMF was found to be associated with its high MOF loading capacity and unique morphological and structural properties. The developed composite structure with improved VOCs removal and recyclability could be a promising material for small to limited scale air pollution treatment units.     

MOFs材料在废水污染物吸附治理中的应用研究进展

介绍了国内外MOFs材料吸附去除废水中各种污染物的研究进展,主要针对重金属离子(Hg²⁺、U⁶⁺、Cr⁶⁺、Cd²⁺、Pb²⁺、Co²⁺、Sb⁵⁺、Sr²⁺)及类金属离子(As³⁺、As⁵⁺)、有机污染物(染料分子、芳香化合物)等的去除,分析了MOFs及改性MOFs材料对废水中污染物的吸附性能;展望了MOFs材料在废水污染物吸附治理中的应用前景,提出高稳定性及具有催化性质的MOFs材料是用于废水中污染物吸附治理的理想材料。     

金属有机框架材料吸附去除水中有机砷的研究进展

有机砷作为饲料添加剂在家禽养殖中被广泛使用,并伴随着家禽粪便大量进入环境中. 进入环境后有机砷容易被生物降解或(光)化学氧化转化为剧毒的无机砷,危害环境和人体健康. 因此,高效处理有机砷污染受到广泛关注. 金属有机框架(metal organic frameworks, MOFs)材料因其具有孔隙率和比表面积大、孔道尺寸可调、易功能化改性和材料性能可定制等特点,在水体污染物的去除中展现了良好的应用前景. 本文综述了目前MOFs材料作为吸附剂去除水环境中有机砷的最新研究进展,介绍了吸附有机砷MOFs材料的种类、制备方法和吸附性能,总结了MOFs材料吸附有机砷的关键影响因素,并归纳了不同类型MOFs材料吸附的再生方法和稳定性. 最后,指出了当前MOFs存在的技术缺陷及限制工程应用的关键因素,并提出相对应的建议及解决措施.      

VOCs气体在活性炭上的二元吸附过程研究

采用穿透曲线法研究了4种VOCs在活性炭上的的二元吸附过程。研究表明:对于甲苯-苯、甲苯-丙酮、甲苯-乙酸乙酯、苯-丙酮、丙酮-乙酸乙酯二元吸附体系,吸附过程存在置换作用,即随着高沸点组分在床层内吸附量的逐渐增加,相对挥发性大的低沸点组分重新汽化而脱附,出现高沸点组分置换低沸点组分的现象,表现为被置换组分的穿透曲线上出现峰值。之后随着高沸点组分吸附趋于饱和,置换作用停止,低沸点组分吸附也趋于平衡。但对于沸点相近的苯-乙酸乙酯二元体系,吸附过程没有明显的置换现象。吸附量的计算结果表明,有机物在二元体系中的吸附量较同等条件时的单组分吸附量均有不同程度的降低,其中被置换组分降低程度较大,但总吸附量可近似按照浓度为二元组分总浓度低沸点组分的平衡吸附量的近似法计算,平均误差为7.9%。     

高分子树脂与介孔分子筛吸附-脱附VOCs性能对比

采用溶剂热法制备介孔聚二乙烯基苯(PDVB)树脂,并以介孔分子筛MCM-41、SBA-15为参照,从吸附-脱附甲苯、邻二甲苯、均三甲苯性能和高湿度下的疏水性能方面对其进行对比研究.结果表明,PDVB具有最大的比表面积1219.1m2/g,其对低浓度甲苯吸附量约为介孔分子筛的2倍,同时吸附性能几乎不受水汽影响.随着VOCs分子尺寸增加,3种吸附剂对VOCs的饱和吸附量均有所增加,但PDVB的穿透吸附量明显高于分子筛.热重分析表明,在200℃以下3种吸附剂上吸附的有机分子均能脱附完全,具有优良的脱附再生性能.     

Environmental application of three-dimensional graphene materials as adsorbents for dyes and heavy metals: Review on ice-templating method and adsorption mechanisms

The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.