环糊精金属有机框架材料(CD-MOFs)是一种绿色环保的新型金属有机框架材料,但由于其水稳定性差,在实际应用中受到了限制。通过交联CD-MOFs和柠檬酸(CA)来提高环糊精基MOFs的水溶液稳定性。研究制备了CA改性的CA-γ-CD-MOF复合材料,并作为吸附剂从水溶液中去除阳离子染料结晶紫。在15mg CA-γ-CD-MOF用量、20℃、pH 6和60mg/L初始结晶紫浓度下,CA-γ-CD-MOF对结晶紫的平衡吸附能力为79.86mg/g,相应的清除率达到99.83%。此外,CA-γ-CD-MOF在经过3次吸附解吸循环,吸附率仍达第一次的98%以上,表现出良好的再生能力。动力学和吸附等温线研究表明,吸附遵循拟二阶动力学,CA-γ-CD-MOF吸附结晶紫是一种自发的单层吸热过程。因此,CA-γ-CD-MOF是一种高效、绿色、可循环利用的吸附剂。
Cyclodextrin-based MOFs (CD-MOFS) material is a kind of environment-friendly metal organic frame material,but the application is limited due to its poor aqueous stability.Herein,we have developed a novel synthesis method to enhance aqueous stability by crosslinking CD-MOFs and citric acid (CA).In the present study,CA-γ-CD-MOF was prepared and used as an adsorbent to remove crystal violet dye from aqueous solution.The equilibrium adsorption capacity of CA-γ-CD-MOF for crystal violet was 79.86mg/g at 15mg CA-γ-CD-MOF dosage,20℃,pH 6,and 60mg/L initial crystal violet concentration,and the corresponding removal rate reached 99.83%.In addition,CA-γ-CD-MOF showed good regeneration ability and remained the adsorption rate more than 98% of the first one after three adsorption-desorption cycles.Research on the adsorption kinetic and isotherms revealed that the adsorption followed the pseudo-second order kinetics,and the adsorption of crystal violet by CA-γ-CD-MOF occurred via an monolayer heat adsorption process and was spontaneous.Overall,CA-γ-CD-MOF was an efficient,green,and recyclable adsorbent for crystal violet.
[1] Wen Gang,Guo Zhigang.Facile modification of NH2-MIL-125(Ti) to enhance water stability for efficient adsorptive removal of crystal violet from aqueous solution[J].Colloids and Surfaces,A Physicochemical and Engineering Aspects,2018,541:58-67.
[2] Zhihui Z,Yanqing F,Qian Q,et al.Synthesis of magnetic mesoporous metal-organic framework-5 for the effective enrichment of malachite green and crystal violet in fish samples[J].Journal of Chromatography A,2018,1560:19-25.
[3] Satilmis B,Budd P M.Selective dye adsorption by chemically-modified and thermally-treated polymers of intrinsic microporosity[J].Journal of Colloid & Interface Science,2017,492:81-91.
[4] Zhao X,Wang K,Gao Z,et al.Reversing the dye adsorption and separation performance of metal-organic frameworks via introduction of SO3H groups[J].Industrial & Engineering Chemistry Research,2017,56(15):4496-4501.
[5] Li H,Cao X,Zhang C,et al.Enhanced adsorptive removal of anionic and cationic dyes from single or mixed dye solutions using MOF PCN-222[J].RSC Advances,2017,7(27):16273-16281.
[6] Mantasha I,Saleh H,Qasem K,et al.Efficient and selective adsorption and separation of methylene blue (MB) from mixture of dyes in aqueous environment employing a Cu(Ⅱ) based metal organic framework[J].Inorganica Chimica Acta,2020,511:119787.
[7] Yu F,Bai X,Liang M,et al.Recent progress on metal-organic framework-derived porous carbon and its composite for pollutant adsorption from liquid phase[J].Chemical Engineering Journal,2021,405:126960.
[8] Zewde A A,Zhang L,Li Z,et al.A review of the application of sonophotocatalytic process based on advanced oxidation process for degrading organic dye[J].Reviews on Environmental Health,2019,34(4):365-375.
[9] Priti R,Gautam S,Sumit M,et al.Microwave assisted synthesis of polyacrylamide grafted gum ghatti and its application as flocculant[J].Carbohydrate Polymers,2012,89:275-281.
[10] Okesola Babatunde O,Smith David K,et al.Applying low-molecular weight supramolecular gelators in an environmental setting-self-assembled gels as smart materials for pollutant removal[J].Chemical Society Reviews,2016,45(15):4226-4251.
[11] Zhao Y C,Wang J W,Bao Z B,et al.Adsorption separation of acetylene and ethylene in a highly thermostable microporous metal-organic framework[J].Separation and Purification Technology,2017,195:238-243.
[12] Yin Q,Li Y L,Li L,et al.Novel hierarchical meso-microporous hydrogen-bonded organic framework for selective separation of acetylene and ethylene versus methane[J].ACS Applied Materials & Interfaces,2019,11(19):17823.
[13] Xue D,Wang Q,Bai J.Amide-functionalized metal-organic frameworks:syntheses,structures and improved gas storage and separation properties[J].Coordination Chemistry Reviews,2017,378:2-16.
[14] Karmakar A,Samanta P,Desai A V,et al.Guest-responsive metal-organic frameworks as scaffolds for separation and sensing applications[J].Accounts of Chemical Research,2017,50(10):2457-2469.
[15] Jiao L,Wang Y,Jiang H L,et al.Metal-organic frameworks as platforms for catalytic applications[J].Advanced Materials,2018,30(37):1703663.1-1703663.23.
[16] Chen R,Zhang J,Chelora J,et al.Ruthenium(Ⅱ) complex incorporated UiO-67 metal-organic frameworks nanoparticles for enhanced two-photon fluorescence imaging and photodynamic cancer therapy[J].ACS Applied Materials & Interfaces,2017,9(7):5699-5708.
[17] Zhou L J,Deng W H,Wang Y L,et al.Lanthanide-potassium biphenyl-3,3′-disulfonyl-4,4′-dicarboxylate frameworks:gas Sorption,Proton Conductivity,and Luminescent Sensing of Metal Ions[J].Inorganic Chemistry,2016:6271-6277.
[18] Guan H Y,Leblanc R J,Xie S Y,et al.Recent progress in the syntheses of mesoporous metal-organic framework materials[J].Coordination Chemistry Reviews,2018,369:76-90.
[19] Siamak J,Malihe P,Hamed H,et al.Carboxymethylcellulose capsulated Cu-based metal-organic framework-drug nanohybrid as a pH-sensitive nanocomposite for ibuprofen oral delivery[J].International Journal of Biological Macromolecules,2018,119:588-596.
[20] Jansook P,Ogawa N,Loftsson T.Cyclodextrins:structure,physicochemical properties and pharmaceutical applications[J].International Journal of Pharmaceutics,2018,535(1-2):272-284.
[21] Li H,Hill M R,Huang R,et al.Facile stabilization of cyclodextrin metal-organic frameworks under aqueous conditions via the incorporation of C60 in their matrices[J].Chemical Communications,2016,52(35):5973-5976.
[22] Zhou Yanbo,Gu Xiaochen,Zhang Ruzhuang,et al.Removal of aniline from aqueous solution using pine sawdust modified with citric acid and β-cyclodextrin[J].Industrial & Engineering Chemistry Research,2014,53(2):887-894.
[23] Kritskiy I,Volkova T,Terekhova I,et al.γ-Cyclodextrin-metal organic frameworks as efficient microcontainers for encapsulation of leflunomide and acceleration of its transformation into teriflunomide[J].Carbohydrate Polymers,2019,216:224-230.
[24] Zhan F P,Meng Y,Repo E,et al.EDTA-cross-linked beta-cyclodextrin:an environmentally friendly bifunctional adsorbent for simultaneous adsorption of metals and cationic dyes[J].Environmental Science & Technology:ES&T,2015,49(17):10570.
[25] Li Yaoyue,Zhou Yanbo,Zhou Yi,et al.Cyclodextrin modified filter paper for removal of cationic dyes/Cu ions from aqueous solutions[J].Water Science and Technology:A Journal of the International Association on Water Pollution Research,2018,78(12):2553-2563.
[26] Zhang H,Li Y X,Wang P L,et al.Synthesis of β-cyclodextrin immobilized starch and its application for the removal of dyestuff from waste-water[J].Journal of Polymers and the Environment,2019,27(5):929-941.
[27] Guo L Y,Lu H Q,Rackemann D,et al.Quaternary ammonium-functionalized magnetic chitosan microspheres as an effective green adsorbent to remove high-molecular-weight invert sugar alkaline degradation products (HISADPs)[J].Chemical Engineering Journal,2021,416:129084.
[28] Fu Q P,Lou J,Zhang R B,et al.Highly effective and fast removal of Congo red from wastewater with metal-organic framework Fe-MIL-88NH2-ScienceDirect[J].Journal of Solid State Chemistry,2020,294:8.
[29] Wang S,Zhu Z H.Characterisation and environmental application of an Australian natural zeolite for basic dye removal from aqueous solution[J].Journal of Hazardous Materials,2006,136(3):946-952.
[30] Sohrabnezhad S,Pourahmad A.Comparison absorption of new methylene blue dye in zeolite and nanocrystal zeolite[J].Desalination,2010,256(1-3):84-89.
基金资助
国家自然科学基金(82173731);上海市科委地方院校能力建设项目(19050502000)
PDF
