氧化石墨烯-纤维素复合物的制备及其对钚的吸附性能
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摘要
采用NaOH/尿素混合水溶液作为溶剂完全溶解纤维素(FB),再与Hummers法合成的氧化石墨烯(GO)进行复合来制备复合型吸附剂GO-FB,利用红外光谱(FTIR)、扫描电镜(SEM)和拉曼谱图(Raman)对其结构和形貌进行表征。GO-FB的SEM形貌表征可见其表面布满颗粒物的条状物或者团聚体,表明有大量GO附着在FB表面。以钚溶液作为研究对象,考察了溶液pH、吸附剂投加量、吸附时间、钚初始活度以及温度等参数对吸附效果的影响,旨为核工业放射性废水的处理工艺提供理论基础和新的技术途径。结果表明,对于30 Bq·L~(-1)的含钚溶液,GO和GO-FB的最佳吸附条件分别为:pH均为8;投加量0.05,0.10 g·L~(-1);吸附时间均为<1 min,最大去钚率分别为98.65%和98.67%。由此可见,GO-FB可以作为优良的吸附剂对放射性含钚废水进行有效净化处理。根据热力学参数吉布斯自由能(ΔG~0)、焓变(ΔH~0)和熵变(ΔS~0)在不同温度下的计算结果可知,GO-FB对溶液中钚的吸附过程为自发的放热反应,低温有利于反应的进行;同时,吸附过程以物理吸附为主。
Cellulose( FB) was completely resolved in the mixture solution of NaOH/urea,and then reacted with graphene oxide( GO) synthesized by modified Hummers method. Thus,the composite adsorbent graphene oxide-cellulose( GO-FB) was prepared successfully and characterized by Fourier transform infrared spectroscopy( FTIR),scanning electron microscope( SEM) and Raman spectra. It could be seen from the SEM image that there were lots of particles or aggregates on the surface of GO-FB,which indicated that plenty of GO molecular adhered to the surface of GO-FB. The products were used to study the adsorption of plutonium from aqueous solution. The solution pH,adsorbent dosage,contact time,initial plutonium activity and temperature were investigated to estimate the adsorption properties in order to supply theory basic and new technique method for the treatment of industry radioactive wastewater.The results showed that for the plutonium solution with initial activity of 30 Bq·L~(-1),the optimum adsorption conditions of GO and GOFB were pH of 8,the dosages of 0. 05 and 0. 10 g·L~(-1),adsorption time of less than 1 min,and the maximum removal rate of plutonium of 98. 65% and 98. 67%,respectively. Therefore,GO-FB had favorable adsorption property for the efficiency treatment of radioactive plutonium wastewater. According to the calculated thermodynamic parameters such as Gibbs free energy( ΔG~0),standard enthalpy change( ΔH~0) and standard entropy change( ΔS~0) at various temperatures the adsorption of uranium onto GO-FB was spontaneous and feasible endothermal reaction. Moreover,the adsorption of uranium on GO-FB was physisorption process and less favorable at higher temperature.
Cellulose( FB) was completely resolved in the mixture solution of NaOH/urea,and then reacted with graphene oxide( GO) synthesized by modified Hummers method. Thus,the composite adsorbent graphene oxide-cellulose( GO-FB) was prepared successfully and characterized by Fourier transform infrared spectroscopy( FTIR),scanning electron microscope( SEM) and Raman spectra. It could be seen from the SEM image that there were lots of particles or aggregates on the surface of GO-FB,which indicated that plenty of GO molecular adhered to the surface of GO-FB. The products were used to study the adsorption of plutonium from aqueous solution. The solution pH,adsorbent dosage,contact time,initial plutonium activity and temperature were investigated to estimate the adsorption properties in order to supply theory basic and new technique method for the treatment of industry radioactive wastewater.The results showed that for the plutonium solution with initial activity of 30 Bq·L~(-1),the optimum adsorption conditions of GO and GOFB were pH of 8,the dosages of 0. 05 and 0. 10 g·L~(-1),adsorption time of less than 1 min,and the maximum removal rate of plutonium of 98. 65% and 98. 67%,respectively. Therefore,GO-FB had favorable adsorption property for the efficiency treatment of radioactive plutonium wastewater. According to the calculated thermodynamic parameters such as Gibbs free energy( ΔG~0),standard enthalpy change( ΔH~0) and standard entropy change( ΔS~0) at various temperatures the adsorption of uranium onto GO-FB was spontaneous and feasible endothermal reaction. Moreover,the adsorption of uranium on GO-FB was physisorption process and less favorable at higher temperature.
引文
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[29]Zohuriaan-Mehr M J,Pourjavadi A,Salehi-Rad M.Modified CMC.2.Novel carboxymethylcellulose-based poly(amidoxime)chelating resin with high metal sorption capacity[J].Reactive and Functional Polymers,2004,61(1):23.
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[31]Zhao G X,Li J X,Ren X M,Chen C L,Wang X K.Few-layered graphene oxide nanosheets as superior sorbents for heavy metal ion pollution management[J].Environmental Science and Technology,2011,45(24):10454.
[32]Wu Y,Luo H J,Wang H,Zhang L,Liu P P,Feng L Q.Fast adsorption of nickel ions by porous graphene oxide/sawdust composite and reuse for phenol degradation from aqueous solutions[J].Journal of Colloid and Interface Science,2014,(436):90.
[33]Romanchuk A Y,Slesarev A S,Kalmykov S N,Kosynkin D V,Tour J M.Graphene oxide for effective radionuclide removal[J].Physical Chemistry Chemical Physics,2013,15(7):2321.
[34]Cui R P,Li Y L,Jing C.Adsorption of uranium from aqueous solution on illite[J].Environmental Chemistry,2015,34(2):314.(崔瑞萍,李义连,景晨.伊利石对水溶液中低浓度铀的吸附[J].环境化学,2015,34(2):314.)
[2]Zhang H X,Zhao X,Wei J Y,Li F Z.Removal of cesium from low-level radioactive wastewaters using magnetic potassium titanium hexacyanoferrate[J].Chemical Engineering Journal,2015,(275):262.
[3]Shao D D,Ren X M,Wen J,Hu S,Xiong J,Jiang T,Wang X L,Wang X K.Immobilization of uranium by biomaterial stabilized Fe S nanoparticles:effects of stabi-lizer and enrichment mechanism[J].Journal of Hazardous Materials,2016,(302):1.
[4]GB8973-1996.Sewage integrate emission criteria[S].Beijing:Chinese Standard Publishing Company,1997.(GB8973-1996.污水综合排放标准[S].北京:中国标准出版社,1997.)
[5]Wu L Y,Zhang G H,Wang Q Z,Wu L Y,Zhang G H,Wang Q Z,Hou L A,Gu P.Removal of strontium from liquid waste using a hydraulic pellet co-precipitation microfiltration(HPC-MF)process[J].Desalination,2014,349(5):31.
[6]Zou W H,Zhao L,Han R P.Removal of uranium(VI)by fixed bed ion-exchange column using natural zeolite coated with manganese oxide[J].Chinese Journal of Chemical Engineering,2009,17(4):585.
[7]Aytas S,Yurtlu M,Donat R.Adsorption characteristic of U(VI)ion onto thermally activated bentonite[J].Journal of Hazardous Materials,2009,172(2-3):667.
[8]Crane R A,Dickinson M,Scott T B.Nanoscale zerovalent iron particles for the remediation of plutonium and uranium contaminated solutions[J].Chemical Engineering Journal,2015,262(3):319.
[9]Liu H Y,Wang J L.Treatment of radioactive wastewater using direct contact membrane distillation[J].Journal of Hazardous Materials,2013,261(20):307.
[10]Liu Y,Deng L,Liu L,Zhou Y Z,Chang Y L.Adsorption of Re from electrolyte of superalloy by using D296 resin[J].Chinese Journal of Rare Metals,2017,41(6):678.(刘洋,邓丽,刘莉,周亦胄,常云龙.D296树脂对高温合金电解液中Re的吸附研究[J].稀有金属,2017,41(6):678.)
[11]Zhang L,Wei J Y,Zhao X,Li F Z,Jiang F,Zhang M,Cheng X Z.Competitive adsorption of strontium and cobalt onto tin antimonite[J].Chemical Engineering Journal,2016,(285):679.
[12]Yang A L,Zhang H,Yang P,Jiang L,Deng H F,Yang S Y.Treatment of low-level radioactivity wastewater containing plutonium using PAM[J].Journal of Nuclear and Radiochemistry,2011,33(3):179.(杨爱丽,张灏,杨鹏,姜玲,邓恒凤,杨胜亚.聚丙烯酰胺絮凝处理低放含钚废水技术[J].核化学与放射化学,2011,33(3):179.)
[13]Macaskie L E,Jeong B C,Tolley M R.Enzymically accelerated biomineralization of heavy metals:application to the removal of americium and plutonium from aqueous flows[J].FEMS Microbiology Reviews,1994,14(4):351.
[14]Villalobos-Rodríguez R,Montero-Cabrera M E,EsparzaPonce H E,Herrera-Peraza E F,Ballinas-Casarrubias M L.Uranium removal from water using cellulose triacetate membranes added with activated carbon[J].Applied Radiation and Isotopes,2012,70(5):872.
[15]SzabóT,Berkesi O,ForgóP,Josepovits K,Sanakis Y,Petridis D,Dékány I.Evolution of surface functional groups in a series of progressively oxidized GOs[J].Chemistry of Materials,2006,18(11):2740.
[16]Depan D,Girase B,Shah J S,Misra R D K.Strctureprocess-property relationship of the polar graphene oxidemediated cellular response and stimulated growth of osteoblasts on hybrid chitosan network structure nanocomposite scaffolds[J].Acta Biomaterialia,2011,7(9):3432.
[17]Yu B W,Xu J,Liu J H,Yang S T,Luo J B,Zhou Q H,Wan J,Liao R,Wang H F,Liu Y F.Adsorption behavior of copper ions on graphene oxide-chitosan aerogel[J].Journal of Environmental Chemical Engineering,2013,1(4):1044.
[18]Lavoine N,Desloges I,Dufresne A,Bras J.Microfibrillated cellulose—its barrier properties and applications in cellulosic materials:a review[J].Carbohydrate Polymers,2012,90(2):735.
[19]Liu L P,Yang X N,Ye L,Xue D D,Liu M,Jia S R,Hou Y,Chu L Q,Zhong C.Preparation and characterization of a photocatalytic antibacterial material:graphene oxide/Ti O2/bacterial cellulose nanocomposite[J].Carbohydrate Polymers,2017,(174):1078.
[20]Kim C J,Khan W,Kim D H,Cho K S,Park S Y.Graphene oxide/cellulose composite using NMMO monohydrate[J].Carbohydrate Polymers,2011,86(2):903.
[21]Zhang X M,Yu H W,Yang H J,Wan Y C,Hu H,Zhai Z,Qin J M.Graphene oxide caged in cellulose microbeads for removal of malachite green dye from aqueous solution[J].Journal of Colloid and Interface Science,2015,437(437):277.
[22]Huang Q B,Xu M M,Sun R C,Wang X H.Large scale preparation of graphene oxide/cellulose paper with improved mechanical performance and gas barrier properties by conventional papermaking method[J].Industrial Crops and Products,2016,(85):198.
[23]Kafy A,Sadasivuni K K,Akther A,Min S K,Kim J.Cellulose/graphene nanocomposite as multifunctional electronic and solvent sensor material[J].Materials Letter,2015,(159):20.
[24]Sadasivuni K K,Kafy A,Kim H C,Ko H U,Mun S,Kim J.Reduced graphene oxide filled cellulose films for flexible temperature sensor application[J].Synthetic Metals,2015,(206):154.
[25]Wang Z M,Ning A M,Xie P H,Gao G Q,Xie L X,Li X,Song A D.Synthesis and swelling behaviors of carboxymethyl cellulose-based superabsorbent resin hybridized with graphene oxide[J].Carbohydrate Polymers,2017,(157):48.
[26]Zhang Y L,Liu Y,Wang X R,Sun Z M,Ma J K,Wu T,Xing F B,Gao J P.Porous graphene oxide/carboxymethyl cellulose monoliths,with high metal ion adsorption[J].Carbohydrate Polymers,2014,101(1):392.
[27]Ma J,Liu C H,Li R,Wang J.Properties and structural characterization of oxide starch/chitosan/graphene oxide biodegradable nanocomposites[J].Journal of Applied Polymer Science,2012,123(5):2933.
[28]Fan L L,Luo C N,Li X J,Lu F G,Qiu H M,Sun M.Fabrication of novel magnetic chitosan grafted with graphene oxide to enhance adsorption properties for methyl blue[J].Journal of Hazardous Materials,2012,215-216(10):272.
[29]Zohuriaan-Mehr M J,Pourjavadi A,Salehi-Rad M.Modified CMC.2.Novel carboxymethylcellulose-based poly(amidoxime)chelating resin with high metal sorption capacity[J].Reactive and Functional Polymers,2004,61(1):23.
[30]Chen S P,Hong J X,Yang H X,Yang J Z.Adsorption of uranium(VI)from aqueous solution using a novel graphene oxide-activated carbon felt composite[J].Journal of Environmental Radioactivity,2013,126(4):253.
[31]Zhao G X,Li J X,Ren X M,Chen C L,Wang X K.Few-layered graphene oxide nanosheets as superior sorbents for heavy metal ion pollution management[J].Environmental Science and Technology,2011,45(24):10454.
[32]Wu Y,Luo H J,Wang H,Zhang L,Liu P P,Feng L Q.Fast adsorption of nickel ions by porous graphene oxide/sawdust composite and reuse for phenol degradation from aqueous solutions[J].Journal of Colloid and Interface Science,2014,(436):90.
[33]Romanchuk A Y,Slesarev A S,Kalmykov S N,Kosynkin D V,Tour J M.Graphene oxide for effective radionuclide removal[J].Physical Chemistry Chemical Physics,2013,15(7):2321.
[34]Cui R P,Li Y L,Jing C.Adsorption of uranium from aqueous solution on illite[J].Environmental Chemistry,2015,34(2):314.(崔瑞萍,李义连,景晨.伊利石对水溶液中低浓度铀的吸附[J].环境化学,2015,34(2):314.)