金属-有机骨架对苯二甲酸酯-铝吸附水中酚类化合物动力学和热力学

doi:10.11944/j.issn.1000-0518.2016.09.160211

摘要/Abstract

摘要：

以吸附等温线、动力学和热力学等方法研究了金属-有机骨架对苯二甲酸酯-铝[MIL-53(Al),MIL:Materials of Institut Lavoisier]对水中邻硝基苯酚、苯酚和邻苯二酚的吸附行为。 MIL-53(Al)对上述酚类化合物的吸附符合准二级吸附动力学模型,且包含表面吸附和孔内扩散两个过程。吸附热力学结果表明,MIL-53(Al)对酚类化合物的吸附是自发的,且为吸热和熵增加过程。在40 ℃条件下,MIL-53(Al)对邻硝基苯酚、苯酚和邻苯二酚的吸附量分别为78.6、30.5和16.5 mg/g。

关键词: 金属-有机骨架, 吸附, 酚类化合物, 对苯二甲酸酯-铝

Abstract:

Adsorption of phenols such as o-nitrophenol, phenol, and catechol on metal-organic framework aluminum terephthalate[MIL-53(Al), MIL:Materials of Institut Lavoisier] was investigated in detail in terms of adsorption isotherms, thermodynamics, and kinetics. The adsorption of the phenols on MIL-53(Al) follows a pseudo-second order kinetic model. Intraparticle diffusion model analysis reveals that the adsorption of the phenols on MIL-53(Al) proceeds by two phases, surface sorption and intraparticle/pore diffusion. The adsorption of phenols fits well with the Freundlich model. In addition, the results indicate that the adsorption of the phenols on MIL-53(Al) is a thermodynamically spontaneous process with positive enthalpy change and positive entropy change. The adsorption capacities for o-nitrophenol, phenol, and catechol at 40 ℃ are 78.6, 30.5, and 16.5 mg/g, respectively.

Key words: metal-organic framework, adsorption, phenols, aluminum terephthalate

杨成雄, 王士伟, 严秀平. 金属-有机骨架对苯二甲酸酯-铝吸附水中酚类化合物动力学和热力学[J]. 应用化学, 2016, 33(9): 1040-1046.

YANG Chengxiong, WANG Shiwei, YAN Xiuping. Adsorption Thermodynamics and Kinetics of Phenols on Metal-Organic Framework Aluminum Terephthalate in Water[J]. Chinese Journal of Applied Chemistry, 2016, 33(9): 1040-1046.

参考文献

[1]	Snyder S A,Westerhoff P,Yoon Y. Pharmaceuticals, Personal Care Products and Endocrine Disrupters in Water:Implications for the Water Industry[J]. Environ Eng Sci,2003,20(5):449-469.
[2]	WU Yongmin,LI Fu,HUANG Xianyu,et al.New Techniques for Treatment of Phenol-Containing Wastewater and Prospect of Them[J]. Environ Sci Manage,2007,32(3):150-153(in Chinese). 吴勇民,李甫,黄咸雨,等. 含酚废水处理新技术及其发展前景[J]. 环境科学与管理,2007,32(3):150-153.
[3]	Annagiev M K,Rustamova D T,Bairamova S S. Study of Phenol Adsorption on Modified Forms of Zeolite[J]. Russ J Appl Chem,2012,85(4):684-685.
[4]	Liu C,Chen Z,Ni C,et al.Adsorption of Phenol from Aqueous Solution by a Hierarchical Micro-nano Porous Carbon Material[J]. Rare Met,2012,31(5):582-589.
[5]	Kumar K,Porkodi K. Comments on “Adsorption of 4-Chlorophenol from Aqueous Solutions by xad-4 Resin:Isotherm, Kinetic, and Thermodynamic Analysis”[J]. J Hazard Mater,2007,143(1/2):598-599.
[6]	Eddaoudi M,Moler D B,Li H L,et al.Modular Chemistry: Secondary Building Units as a Basis for the Design of Highly Porous and Robust Metal-organic Carboxylate Frameworks[J]. Acc Chem Res,2001,34(4):319-330.
[7]	Férey G,Mellot-Draznieks C,Serre C,et al.Crystallized Frameworks with giant Pores:Are There Limits to the Possible[J]. Acc Chem Res,2005,38(4):217-225.
[8]	Kitagawa S,Kitaura R,Noro S. Functional Porous Coordination Polymers[J]. Angew Chem Int Ed,2004,43(18):2334-2375.
[9]	HAN Yitong,LIU Min,LI Keyan,et al.Preparation and Application of High Stability Metal-organic Framework UiO-66[J]. Chinese J Appl Chem,2016,33(4):367-378(in Chinese). 韩易潼,刘民,李克艳,等. 高稳定性金属有机骨架UiO-66的合成与应用[J]. 应用化学,2016,33(4):367-378.
[10]	ZHAO Wenpeng,Li Aiqin,DING Sanyuan. Application of Porous Organic Polymers in Water Contaminants Removal[J]. Chinese J Appl Chem,2016,33(5):513-523(in Chinese). 赵文鹏,李爱琴,丁三元. 多孔有机聚合物在水处理中的应用[J]. 应用化学,2016,33(5):513-523.
[11]	Gu Z Y,Yang C X,Chang N,et al.Metal-organic Frameworks for Analytical Chemistry: from Sample Collection to Chromatographic Separation[J]. Acc Chem Res,2012,45(5):734-745.
[12]	Suh M P,Park H J,Prasad T K,et al.Hydrogen Storage in Metal-organic Frameworks[J]. Chem Rev,2012,112(2):782-835.
[13]	Yoon M,Srirambalaji R,Kim K. Homochiral Metal-organic Frameworks for Asymmetric Heterogeneous Catalysis[J]. Chem Rev,2012,112(2):1196-1231.
[14]	Cui Y,Yue Y,Qian G,et al.Luminescent Functional Metal-organic Frameworks[J]. Chem Rev,2012,112(2):1126-1162.
[15]	Li J R,Sculley J,Zhou H C. Metal-organic Frameworks for Separations[J]. Chem Rev,2012,112(2):869-932.
[16]	Horcajada P,Gref R,Baati T,et al.Metal-organic Frameworks in Biomedicine[J]. Chem Rev,2012,112(2):1232-1268.
[17]	Cychosz K A,Ahmad R,Matzger A J. Liquid Phase Separations by Crystalline Microporous Coordination Polymers[J]. Chem Sci,2010,1(3):293-302.
[18]	Haque E,Lee J E,Jang I T,et al.Adsorptive Removal of Methyl Orange from Aqueous Solution with Metal-organic Frameworks, Porous Chromium-benzenedicarboxylates[J]. J Hazard Mater,2010,181(1/2/3):535-542.
[19]	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]. J Hazard Mater,2011,185(1):507-511.
[20]	Cychosz K A,Matzger A J. Water Stability of Microporous Coordination Polymers and the Adsorption of Pharmaceuticals from Water[J]. Langmuir,2010,26(22):17198-17202.
[21]	Hasan Z,Jeon J,Jhung S H. Adsorptive Removal of Naproxen and Clofibric Acid from Water Using Metal-organic Frameworks[J]. J Hazard Mater,2012,209/210:151-157.
[22]	Yang C X,Yan X P. Selective Adsorption and Extraction of C70 and Higher Fullerenes on a Reusable Metal-organic Framework MIL-101(Cr)[J]. J Mater Chem,2012,22(34):17833-17841.
[23]	Huo S H,Yan X P. Metal-organic Framework MIL-100(Fe) for the Adsorption of Malachite Green from Aqueous Solution[J]. J Mater Chem,2012,22(15):7449-7455.
[24]	Huo S H,Yan X P. Facile Magnetization of Metal-organic Framework MIL-101 for Magnetic Solid-phase Extraction of Polycyclic Aromatic Hydrocarbons in Environmental Water Samples[J]. Analyst,2012,137(15):3445-3451.
[25]	Loiseau T,Serre C,Huguenard C,et al.A Pationale for the Large Breathing of the Porous Aluminum Terephthalate(MIL-53) upon Hydration[J]. Chem -Eur J,2004,10(6):1373-1382.
[26]	Yang C X,Liu S S,Wang H F,et al.High-performance Liquid Chromatographic Separation of Position Isomers Using Metal-organic Framework MIL-53(Al) as the Stationary Phase[J]. Analyst,2012,137(1):133-139.
[27]	Liu S S,Yang C X,Wang S W,et al.Metal-organic Frameworks for Reverse-phase High-performance Liquid Chromatography[J]. Analyst,2012,137(4):816-818.
[28]	Hameed B. Rahman A. Removal of Phenol from Aqueous Solutions by Adsorption onto Activated Carbon Prepared from Biomass[J]. J Hazard Mater,2008,160(2/3):576-581.
[29]	Wang S,Li H,Xu L. Application of Zeolite MCM-22 for Basic Dye Removal from Wastewater[J]. J Colloid Interface Sci,2006,295(1):71-78.
[30]	Ho Y, McKay G. Pseudo-second Order Model for Sorption Processes[J]. Process Biochem,1999,34(5):451-465.