H_6P_2Mo_(18)O_(62)/MIL-101(Cr)-NH_2的制备及其吸附性能的研究
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摘要
采用水热法将磷钼酸H_6P_2Mo_(18)O_(62)与金属有机骨架MIL-101(Cr)-NH_2负载,制备出新型吸附剂H_6P_2Mo_(18)O_(62)/MIL-101(Cr)-NH_2,通过XRD、BET、FT-TR、SEM、N2吸附-脱附表征手段测试分析,对该材料负载杂多酸前后的各种物理化学性质进行表征.并探究了H_6P_2Mo_(18)O_(62)/MIL-101(Cr)-NH_2对MB的吸附性能,结果表明H_6P_2Mo_(18)O_(62)/MIL-101(Cr)-NH_2对亚甲基蓝的吸附率比纯的金属有机骨架MIL-101(Cr)-NH_2高,进一步探究了温度、接触时间、初始pH和MB初始浓度对吸附实验的影响.吸附热力学和动力学研究表明,热力学实验数据符合langmiur等温曲线,动力学符合拟二级动力学.热力学参数-20 <ΔG <0说明该吸附是自发进行的物理吸附过程,ΔH> 0说明该吸附过程吸热.
Phosphorus molybdate H_6P_2Mo_(18)O_(62) was loaded with metal organic framework MIL-101( Cr)-NH_2 by hydrothermal synthesis method. The novel absorbent H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 had been prepared. The chemical structure and surface properties of the MIL-101( Cr)-NH_2 before and after loading heteropoly acid were characterized by XRD、BET、FT-TR、SEM、N2 adsorption-desorption isotherms. The adsorption of methylene blue( MB) onto H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 in aqueous solution was studied.The results showed that the removal rate of H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 was greater than that of MIL-101( Cr)-NH_2. And the effects of the experimental parameters including temperature,reaction time,the initial pH value and initial concentration of methylene blue solution were discussed. The kinetic study and The thermodynamic indicated that the experiment data could be well described by the Langmuir equations and pseudo-second-order kinetic model. Thermodynamic parameters-20 < ΔG < 0、ΔH > 0 illustrated that the MB adsorption onto H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 was spontaneous and endothermic physical adsorption.
Phosphorus molybdate H_6P_2Mo_(18)O_(62) was loaded with metal organic framework MIL-101( Cr)-NH_2 by hydrothermal synthesis method. The novel absorbent H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 had been prepared. The chemical structure and surface properties of the MIL-101( Cr)-NH_2 before and after loading heteropoly acid were characterized by XRD、BET、FT-TR、SEM、N2 adsorption-desorption isotherms. The adsorption of methylene blue( MB) onto H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 in aqueous solution was studied.The results showed that the removal rate of H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 was greater than that of MIL-101( Cr)-NH_2. And the effects of the experimental parameters including temperature,reaction time,the initial pH value and initial concentration of methylene blue solution were discussed. The kinetic study and The thermodynamic indicated that the experiment data could be well described by the Langmuir equations and pseudo-second-order kinetic model. Thermodynamic parameters-20 < ΔG < 0、ΔH > 0 illustrated that the MB adsorption onto H_6P_2Mo_(18)O_(62)/MIL-101( Cr)-NH_2 was spontaneous and endothermic physical adsorption.
引文
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[23]艾伦弘,蒋静,唐娟.活性碳/Co Fe2O4复合物的制备及其对亚甲基蓝的吸附性能[J].应用化学,2010,27(6):710-715.
[24] Shen TT,Luo J M,Zhang S Y,et al. Hierarchically mesostructured MIL-101 metal-organic frameworks with different mineralizing agents for adsorptive removal of methyl orange and methylene blue from aqueous solution[J]. Journal of Environmental Chemical Engineering,2014,3(2):1372-1383.
[25]Haque E,Jun J W,Jhung S H. Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material,iron terephthalate(MOF-235)[J]. Journal of Hazqrdous Materials,2011,185(1):507-511.
[26]Liu T H,Li Y H,Du Q J,et al. Adsorption of methylene blue from aqueous solution by grapheme[J]. Colloids and Surfaces B:Biointerfaces,2012,90(1):197-203.
[2]Crini G. Non-conventional low-cost adsorbents for dye removal:a review[J]. Bioresource Technology,2006,97(9):1061-1085.
[3] Srinivasan M, White T. Degradation of methylene blue by three-dimensionally ordered macroporous titania[J].Environmental Science Technology,2007,41(12):4405-4409.
[4]Gross A F,Sherman E,Mahoney S L. Reversible ligand exchange in a metal-organic framework(MOF):toward MOF-based dynamic combinatorial chemical systems[J]. Journal Physical Chemistry A,2013,117(18):3771-3776.
[5]Liu Y,Liu J,Lin Y S. Strong binding site molarity of MOFs and its effect on CO2adsorption[J]. Microporous and Mesoporous Materials,2015,214:242-245.
[6]Alesaadi S J,Sabzi F. Hydrogen storage in a series of Zn-based MOFs studied by Sanchez-Lacombe equation of state[J].International Journal of Hydrogen Energy,2014,39(36):21076-21082.
[7]周晶晶,刘开宇,孔春龙,等.金属有机骨架材料MIL-101(Cr)-NH2的合成及其气体吸附性能[J].过程工程学报,2013,13(1):146-151.
[8] Ferey G,M-Draznieks G,Serre C,et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area[J]. Science,2005,309(5743):2040-2042.
[9]Jiang D,Keenan LL,Burrows A D,et al. Synthesis and post-synthetic modification of MIL-101(Cr)-NH2via a tandem diazotisation process[J]. Chemical Communication,2012,48(99):12053-12055.
[10]Lin Y C,Kong C L,Chen L. Direct synthesis of amine-functionalized MIL-101(Cr)nanoparticles and application for CO2capture[J]. Rsc Advances,2012,2(16):6417-6419.
[11]Tian N,Jia Q M,Su H Y,et al. The synthesis of mesostructured NH2-MIL-101(Cr)and kinetic and thermodynamic study in tetracycline aqueous solutions[J]. Journal of Porous Materials,2016,23:1269-1278.
[12]王恩波,高丽华,刘景福,等.具有Dawson结构的钼钒磷杂多酸的制备和性质研究[J].化学学报,1988,46(8):757-762.
[13]于克生,冯豫川,周永恒,等. Dawson型磷钼酸及钒修饰Dawson型磷钼酸的制备及其活性研究[J].西南民族大学学报,2011,37(2):257-262.
[14] Yi F Y,Zhu W,Dang S,et al. Polyoxometalates-based heterometallic organic-inorganic hybrid materials for rapid adsorption and selective separation of methylene blue from aqueous solutions[J]. Chemical Communication,2015,51(16):3336-3339.
[15]Gokmen V,Serpen A. Equilibrium and kinetic studies on the adsorption of dark colored compounds from apple juice using adsorbent resin[J]. Journal of Food Engineering,2002,53(3):221-227.
[16]赵旭,王毅力,郭瑾珑,等.颗粒物微界面吸附模型的分形修正—朗格缪尔(Langmuir)、弗伦德利希(Freundlich)和表面络合模型[J].环境科学学报,2005,25(1):52-57.
[17]吴子豹,黄妙良,杨媛媛,等.负载型TOi2复合材料对甲基橙的吸附行为及光催化降解动力学[J].精细化工,2007,24(1):21-26.
[18]Sun C Y,Wang X L,Qin C,et al. Solvatochromic behavior of chiral mesoporous metal-organic frameworks and their applications for sensing small molecules and separating cationic dyes[J]. Chemistry,2013,19(11):3639-3645.
[19]龚文朋,杜晓刚,田超强,等.基于H3PMo12O40修饰一例MOF复合材料及对染料的吸附[J].精细化工,2016,33(4):467-480.
[20]Liu X X,Luo J,Chen X Y,et al. Selective adsorption performance of H6P2Mo15W3O62-based Cu3(BTC)2composite in treatment of simulated cationic dye wastewater[J]. Chemistry Research in Chinese Universities,2017,33(2),268-273.
[21] Lin S,Song Z L,Che G B,et al. Adsorption behavior of metal-organic frameworks for methylene blue from aqueous solution[J]. Microporous and Mesoporous Materials,2014,193:27-34.
[22] Agarwal S,Sadegh H,Monajjemi M,et al. Efficient removal of toxic bromothymol blue and methylene blue from wastewater by polyvinyl alcohol[J]. Journal of Molecular Liquids,2016,218:191-197.
[23]艾伦弘,蒋静,唐娟.活性碳/Co Fe2O4复合物的制备及其对亚甲基蓝的吸附性能[J].应用化学,2010,27(6):710-715.
[24] Shen TT,Luo J M,Zhang S Y,et al. Hierarchically mesostructured MIL-101 metal-organic frameworks with different mineralizing agents for adsorptive removal of methyl orange and methylene blue from aqueous solution[J]. Journal of Environmental Chemical Engineering,2014,3(2):1372-1383.
[25]Haque E,Jun J W,Jhung S H. Adsorptive removal of methyl orange and methylene blue from aqueous solution with a metal-organic framework material,iron terephthalate(MOF-235)[J]. Journal of Hazqrdous Materials,2011,185(1):507-511.
[26]Liu T H,Li Y H,Du Q J,et al. Adsorption of methylene blue from aqueous solution by grapheme[J]. Colloids and Surfaces B:Biointerfaces,2012,90(1):197-203.