MCC/MOF-5/RhB三元纳米复合材料的制备及其荧光性能
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摘要
采用原位生长法在微晶纤维素(MCC)表面沉积金属有机骨架化合物(MOF-5),通过改变有机配体与金属离子的比例,调控MOF-5尺寸,然后采用溶剂扩散法将荧光染料负载到MOF-5和纤维素的复合物上,制备出具有荧光发光性质的三元纳米复合材料.通过FTIR、TGA、XRD、SEM、UV、PL表征复合材料组分的相互作用方式、形貌尺寸、MOF-5在纤维素上的聚集行为及荧光发光能力等.结果表明:通过调控有机配体和金属离子比例可实现MOF-5尺寸的控制,当有机配体与金属离子配比为10∶1时,尺寸为纳米级别,约为20nm左右;当RhB浓度位于10~(-2)～10~(-4) mol/L时,随着染料浓度的递减,复合材料的发光强度依次增大.
The metal-organic framework composites(MOF-5)were deposited on the surface of microcrystalline cellulose(MCC)by in-situ growth method,and size of MOF-5 was regulated by varying the molar ratio of organic ligands and metal ions.Then,a fluorescent dye,RhB,was loaded onto the composites of MOF-5 and cellulose by solvent diffusion method to prepare ternary nanocomposites with fluorescent properties.The FTIR,TGA,XRD,SEM,UV and PL were used to characterize the interaction of the composite components,the morphology,the aggregation behavior of MOF-5 on cellulose,and the characteristics of fluorescence luminescence.The results showed that the size of MOF-5 can be controlled by adjusting the molar ratio of organic ligand and metal ion.When the molar ratio of organic ligand and metal ion was 10∶1,MOF-5 with the size of 20 nm can be obtained;When the RhB concentration is between 10~(-2) and 10~(-4) mol/L,the luminescence intensity of the composite increases with the decrease of the dye concentration.
The metal-organic framework composites(MOF-5)were deposited on the surface of microcrystalline cellulose(MCC)by in-situ growth method,and size of MOF-5 was regulated by varying the molar ratio of organic ligands and metal ions.Then,a fluorescent dye,RhB,was loaded onto the composites of MOF-5 and cellulose by solvent diffusion method to prepare ternary nanocomposites with fluorescent properties.The FTIR,TGA,XRD,SEM,UV and PL were used to characterize the interaction of the composite components,the morphology,the aggregation behavior of MOF-5 on cellulose,and the characteristics of fluorescence luminescence.The results showed that the size of MOF-5 can be controlled by adjusting the molar ratio of organic ligand and metal ion.When the molar ratio of organic ligand and metal ion was 10∶1,MOF-5 with the size of 20 nm can be obtained;When the RhB concentration is between 10~(-2) and 10~(-4) mol/L,the luminescence intensity of the composite increases with the decrease of the dye concentration.
引文
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[4]陈颂.罗丹明荧光染料的TICT作用机制及荧光探针的应用研究[D].长沙:中南大学,2013.
[5]S Yang,J A Ramirez Cuesta,R Newby,et al.Supramolecular binding and separation of hydrocarbons within a functionalized porous metal-organic framework[J].Nature Chemistry,2015,7(2):121-129.
[6]Yang Q,Zhang M,Song S,et al.Surface modification of PCC filled cellulose paper by MOF-5(Zn3(BDC)2)metalorganic frameworks for use as soft gas adsorption composite materials[J].Cellulose,2017,28:1-10.
[7]He Y,Zhou W,Qian G,et al.Methane storage in metalorganic frameworks[J].Chem.Soc.Rev.,2014,43(16):5 657-5 678.
[8]S Xiang,Y He,Z Zhang,et al.Microporous metal-organic framework with potential for carbon dioxide capture at ambient conditions[J].Nature Communications,2012,3:954-956.
[9]Li J,Cheng S,Zhao Q,et al.Synthesis and hydrogen-storage behavior of metal-organic framework MOF-5[J].International Journal of Hydrogen Energy,2009,34(3):1 377-1 382.
[10]王海君,朱广山,张可勇,等.金属有机骨架复合材料RhB/MOF-5的制备及其发光性质[J].高等学校化学学报,2009,30(1):11-13.
[11]王海君.金属-有机骨架化合物的组装及膜的制备[D].长春:吉林大学,2008.
[12]Wilkinson F,Leicester P A,Ferreira L F V,et al.Photochemistry on surfaces triplet-triplet energy transfer on microcrystalline cellulose studied by diffuse reflectance transient absorption and emission spectroscopy[J].Photochemistry&Photobiology,2010,54(4):599-608.
[13]Pujiasih S,Kurnia,Masykur A,et al.Silylation and characterization of microcrystalline cellulose isolated from indonesian native oil palm empty fruit bunch[J].Carbohydrate Polymers,2018,184:74-81.
[14]Kanemitsu S,Li Fuhuo,Kamata Y,et al.Mathematical foundations of fluid dynamics[J].Basic Sciences Journal of Textile Universities,2016,29(3):275-285.
[15]许碧琼,吴玉通.新型发光材料[J].华侨大学学报(自然科学版),1995,16(3):333-337.
[16]Abuzalat O,Wong D,Elsayed M,et al.Sonochemical fabrication of Cu(II)and Zn(II)metal-organic framework films on metal substrates[J].Ultrasonics Sonochemistry,2018,45:180-188.
[17]徐娜,李菁,冯占恒,等.金属-有机框架MOF-5的制备与表征[J].实验技术与管理,2012,29(1):49-50.
[18]贺良灿.金属-金属有机骨架化合物杂化材料的合成及性能研究[D].北京:清华大学,2013.
[19]强丹丹.杂多酸选择性水解纤维素技术与机理的研究[D].西安:陕西科技大学,2016.
[20]Kaye S S,Dailly A,Yaghi O M,et al.Impact of preparation and handling on the hydrogen storage properties of Zn4O(1,4-benzenedicarboxylate)3(MOF-5)[J].Journal of the American Chemical Society,2007,129(46):14 176-14 177.
[21]宋秋生,徐园好,朱小飞.微乳液法SiO2/罗丹明B荧光杂化纳米微球的制备与表征[J].发光学报,2011,32(8):798-820.