金属有机骨架MIL-101(Fe)吸附As(Ⅲ)的性能
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摘要
以对苯二甲酸为有机配体,Fe(Ⅲ)为中心金属,采用溶剂热法合成了金属有机骨架材料MIL-101(Fe),通过XRD,SEM对其结构进行了表征.用MIL-101(Fe)吸附溶液中的As(Ⅲ),考察了溶液pH值、反应时间、溶液浓度及温度对吸附的影响.结果表明:溶液pH对吸附影响明显,pH=9时,吸附效果最佳;MIL-101(Fe)对As(Ⅲ)的吸附速率较快,吸附过程符合拟二级动力学;等温吸附实验数据用Langmuir和TemKin模型拟合良好,303 K条件下,MIL-101(Fe)对As(Ⅲ)的最大吸附量为211.42 mg·g~(-1);热力学参数ΔG、ΔH均小于0,吸附过程为自发放热反应;MIL-101(Fe)的中心金属Fe与亚砷酸根的配位作用在吸附过程中起主要作用.
In this study,metal-organic framework MIL-101 was prepared by hydrothermal method using terephthalic acid as the organic ligand and Fe(Ⅲ) as the central metal ion. The obtained MIL-101(Fe) was characterized by XRD,SEM and employed for the adsorption of As(Ⅲ). The effects of pH value,reaction time,solution concentration and temperature on the adsorption of As(Ⅲ) were investigated. The results showed that the effect of solution pH on adsorption was significant and the best adsorptive effect could be achieved at pH=9.The adsorption of As(Ⅲ) by MIL-101(Fe) was rapid and the process followed pseudo-second order kinetics. The experimental data of isothermal adsorption were fitted with the Langmuir and TemKin models,and the maximum adsorption capacity was 211.42 mg·g~(-1) at 303 K. Since its ΔG and ΔH were both less than zero,the adsorption process was a spontaneous exothermic reaction. The coordination interaction between the central metal Fe and arsenous anion in MIL-101(Fe) played a major role in the adsorption process.
In this study,metal-organic framework MIL-101 was prepared by hydrothermal method using terephthalic acid as the organic ligand and Fe(Ⅲ) as the central metal ion. The obtained MIL-101(Fe) was characterized by XRD,SEM and employed for the adsorption of As(Ⅲ). The effects of pH value,reaction time,solution concentration and temperature on the adsorption of As(Ⅲ) were investigated. The results showed that the effect of solution pH on adsorption was significant and the best adsorptive effect could be achieved at pH=9.The adsorption of As(Ⅲ) by MIL-101(Fe) was rapid and the process followed pseudo-second order kinetics. The experimental data of isothermal adsorption were fitted with the Langmuir and TemKin models,and the maximum adsorption capacity was 211.42 mg·g~(-1) at 303 K. Since its ΔG and ΔH were both less than zero,the adsorption process was a spontaneous exothermic reaction. The coordination interaction between the central metal Fe and arsenous anion in MIL-101(Fe) played a major role in the adsorption process.
引文
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[5] OLAH Z,KREMMER T,VOGG A T,et al. Novel ion exchange chromatography method for nca arsenic separation[J].Appl Radiat Isot,2017,122: 111-115.
[6] SAHU U K,SAHU S,MAHAPATRA S S,et al. Cigarette soot activated carbon modified with Fe3O4 nanoparticles as aneffective adsorbent for As(Ⅲ) and As(V): Material preparation,characterization and adsorption mechanism study[J]. J Mol Liq,2017,243: 395-405.
[7] LIU Z M,CHEN J C,WU Y C,et al. Synthesis of magnetic orderly mesoporous alpha-Fe2O3 nanocluster derived from MIL-100(Fe) for rapid and efficient arsenic(Ⅲ,V) removal[J].J Hazard Mater,2018,343: 304-314.
[8] XIONG Y Y,LI J Q,GONG L L,et al. Using MOF-74 for Hg2+ removal from ultra-low concentration aqueous solution[J]. J Solid State Chem,2017,246: 16-22.
[9] WANGD K,HUANG R K,LIU W J,et al. Fe-based MOFs for photocatalytic CO2 reduction: role of coordination unsaturated sites and dual excitation pathways[J]. ACS Catal,2014,4(12): 4254-4260.
[10] LI Z Q,YANG J C,SUI K W,et al. Facile synthesis of metal-organic framework MOF-808 for arsenic removal[J]. Mater Lett,2015,160:412-414.
[11] LIU B,JIAN M,LIU R,et al. Highly efficient removal of arsenic(Ⅲ) from aqueous solution by zeolitic imidazolate frameworks with different morphology[J]. Colloid Surface A,2015,481: 358-366.
[12] BARBOSA A D S,JULI?O D,FERNANDES D M,et al. Catalytic performance and electrochemical behaviour of Metal-organic frameworks: MIL-101(Fe) versus NH2 -MIL-101(Fe) [J]. Polyhedron,2017,127: 464-470.
[13] KAYRANLI B. Adsorption of textile dyes onto iron based waterworks sludge from aqueous solution; isotherm,kinetic and thermodynamic study [J]. Chem Eng J,2011,173(3): 782-791.
[14] TANHAEI B,AYATI A,LAHTINEN M,et al. Preparation and characterization of a novel chitosan/Al2O3/magnetite nanoparticles composite adsorbent for kinetic,thermodynamic and isotherm studies of Methyl Orange adsorption[J]. Chem Eng J,2015,259: 1-10.
[15] SINGH T S,PANT K K. Equilibrium,kinetics and thermodynamic studies for adsorption of As(Ⅲ) on activated alumina[J]. Sep Purif Technol,2004,36(2):139-147.
[16] HU T,JIA Q,HE S,et al. Novel functionalized metal-organic framework MIL-101 adsorbent for capturing oxytetracycline[J]. J Alloys Compd,2017,727:114-122.
[17] 崔龙哲,刘瑾,汪卓,等.磁性沸石的制备及吸附溶液中氨氮[J].中南民族大学学报(自然科学版),2017,36(3):10-13.
[18] SONG L J,YOU Q L,CHENG Q R,et al. Electrospun core-shell polyamide 6/chitosan-Fe3+ composite fibers: An efficient and recyclable adsorbent for removal of antibiotic[J]. Mater Lett,2016,185: 286-289.
[19] CHENG Z H,FU F L,DIONYSIOU D D,et al. Adsorption,oxidation,and reduction behavior of arsenic in the removal of aqueous As(Ⅲ) by mesoporous Fe/Al bimetallic particles[J]. Water Res,2016,96: 22-31.