多孔氢键金属-有机框架材料对乙炔和二氧化碳的吸附分离

doi:10.11949/j.issn.0438-1157.20161055

摘要/Abstract

摘要：

以腺嘌呤和溴化铜（氯化铜）为原料，采用慢扩散合成法，合成多孔氢键金属-有机框架材料MPM-1-Br和MPM-1-Cl。采用SEM、PXRD、TGA及比表面积分析等技术对材料进行综合表征，并测定了此二种同构多孔氢键金属-有机框架材料对乙炔和二氧化碳单组分气体的吸附等温线。实验结果表明，MPM-1-Br和MPM-1-Cl的比表面积分别为373 m²·g^-1和417 m²·g^-1，且在<240℃的温度范围内有良好的稳定性；在298 K和总压100 kPa下，通过IAST理论计算得到其对C₂H₂/CO₂混合气体（体积比50：50）的吸附选择性分别达到了3.8和3.0，与HKUST-1（4.7）和UTSA-30（3.3）等金属-有机框架材料有相当的分离性能。

关键词: 氢键金属-有机框架材料, 慢扩散合成法, 吸附, 分离, 乙炔, 二氧化碳

Abstract:

Two porous hydrogen-bonded organometallic frameworks, termed as MPM-1-Br and MPM-1-Cl, were synthesized from adenine and CuBr₂(or CuCl₂) at room temperature by slow diffusion method.The synthesized materials were characterized by analysis techniques including SEM, PXRD, TGA and specific surface area analysis.Single-component adsorption isotherms for acetylene and carbon dioxide on these materials were also determined.The experimental results revealed that MPM-1-Br and MPM-1-Cl have moderately high BET surface(373 m²·g^-1, 417 m²·g^-1), and they show good thermo stability at temperature up to 240℃.The calculations were performed using the ideal adsorbed solution theory(IAST) based on the single-component adsorption isotherms, obtaining the adsorption selectivity of MPM-1-Br and MPM-1-Cl for binary mixture of acetylene and carbon dioxide(50:50, volume ratio) to be 3.8 and 3.0 at temperature of 298 K and total pressure of 100 kPa, respectively, which are comparable to those on HKUST-1 and UTSA-30.

Key words: hydrogen-bonded organometallic framework, low diffusion method, adsorption, separation, acetylene, carbon dioxide

中图分类号:

TQ021.4

谢丹妍, 邢华斌, 张治国, 杨启炜, 杨亦文, 任其龙, 鲍宗必. 多孔氢键金属-有机框架材料对乙炔和二氧化碳的吸附分离[J]. 化工学报, 2017, 68(1): 154-162.

XIE Danyan, XING Huabin, ZHANG Zhiguo, YANG Qiwei, YANG Yiwen, REN Qilong, BAO Zongbi. Porous hydrogen-bonded organometallic frameworks for adsorption separation of acetylene and carbon dioxide[J]. CIESC Journal, 2017, 68(1): 154-162.

参考文献 45

[1]	ZHAO X, XING H, YANG Q, et al. Differential solubility of ethylene and acetylene in room-temperature ionic liquids:a theoretical study[J]. J. Phys. Chem. B, 2012, 116(13):3944-53.
[2]	EGUCHI R, UCHIDA S, MIZUNO N. Inverse and high CO2/C2H2 sorption selectivity in flexible organic-inorganic ionic crystals[J]. Angewandte Chemie International Edition, 2012, 51(7):1635-1639.
[3]	LI P, HE Y, ZHAO Y, et al. A rod -packing microporous hydrogen-bonded organic framework for highly selective separation of C2H2/CO2 at room temperature[J]. Angewandte Chemie International Edition, 2015, 54(2):574-577.
[4]	RAO X, CAI J, YU J, et al. A microporous metal-organic framework with both open metal and Lewis basic pyridyl sites for high C2H2 and CH4 storage at room temperature[J]. Chemical Communications, 2013, 49(60):6719-6721.
[5]	DUAN J, JIN W, KRISHNA R. Natural gas purification using a porous coordination polymer with water and chemical stability[J]. Inorganic Chemistry, 2015, 54(9):4279-4284.
[6]	YOON J W, LEE J S, LEE S, et al. Adsorptive separation of acetylene from light hydrocarbons by mesoporous iron trimesate MIL-100(Fe)[J]. Chemistry-A European Journal, 2015, 21(50):18431-18438.
[7]	CHANG G, LI B, WANG H, et al. Control of interpenetration in a microporous metal-organic framework for significantly enhanced C2H2/CO2 separation at room temperature[J]. Chemical Communications, 2016, 52(17):3494-3496.
[8]	DAVIS M E. Ordered porous materials for emerging applications[J]. Nature, 2002, 417(6891):813-821.
[9]	ZHANG Z, ZHAO Y, GONG Q, et al. MOFs for CO2 capture and separation from flue gas mixtures:the effect of multifunctional sites on their adsorption capacity and selectivity[J]. Chemical Communications, 2013, 49(7):653-661.
[10]	HE Y, ZHOU W, QIAN G, et al. Methane storage in metal-organic frameworks[J]. Chemical Society Reviews, 2014, 43(16):5657-5678.
[11]	FURUKAWA H, CORDOWA K E, O'KEEFFE M, et al. The chemistry and applications of metal-organic frameworks[J]. Science, 2013, 341(6149):1230444.
[12]	李亮莎, 王可可, 黄宏亮, 等. 高稳定铪金属-有机骨架材料的合成及二氧化碳捕获性能[J]. 化工学报, 2014, 65(5):1706-1715. LI L S, WANG K K, HUANG H L, et al. Synthesis of exceptional stable Hf-based metal-organic frameworks:characterization, stability and CO2 adsorption performance[J]. CIESC Journal, 2014, 65(5):1706-1715.
[13]	LI J R, KUPPLER R J, ZHOU H C. Selective gas adsorption and separation in metal-organic frameworks[J]. Chemical Society Reviews, 2009, 38(5):1477-1504.
[14]	CHUI S S Y, LO S M F, CHARMANT J P H, et al. A chemically functionalizable nanoporous material[Cu3(TMA)2(H2O)3]n[J]. Science, 1999, 283(5405):1148-1150.
[15]	乔智威, 杨仁党, 王海辉, 等. 面向生物甲烷分离的不同金属配位金属-有机骨架材料的分子设计[J]. 化工学报, 2014, 65(5):1729-1735. QIAO Z W, YANG R D, WANG H H, et al. Molecular design of metal-organic frameworks with different metal ligands for bio-methane separation[J]. CIESC Journal, 2014, 65(5):1729-1735.
[16]	HE Y, KRISHNA R, CHEN B. Metal-organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons[J]. Energy & Environmental Science, 2012, 5(10):9107-9120.
[17]	杨宵, 刘晶, 胡建波. 氢气在共价有机骨架材料中的吸附机理[J]. 化工学报, 2015, 66(7):2540-2546. YANG X, LIU J, HU J B. Adsorption mechanism of H2 on covalent organic frameworks[J]. CIESC Journal, 2015, 66(7):2540-2546.
[18]	MILLWARD A R, YAGHI O M. Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature[J]. Journal of the American Chemical Society, 2005, 127(51):17998-17999.
[19]	MATSUDA R, KITAULA R, KITAGAWA S, et al. Highly controlled acetylene accommodation in a metal-organic microporous material[J]. Nature, 2005, 436(7048):238-241.
[20]	TIAN J, THALLAPALLY P K, MCGRAIL B P. Porous organic molecular materials[J]. CrystEngComm, 2012, 14(6):1909-1919.
[21]	HISAKI I, NAKAGAWA S, TOHNAI N, et al. A C3-symmetric macrocycle-based, hydrogen-bonded, multiporous hexagonal network as a motif of porous molecular crystals[J]. Angewandte Chemie International Edition, 2015, 54(10):3008-3012.
[22]	LI P, HE Y, ZHAO Y, et al. A rod-packing microporous hydrogen-bonded organic framework for highly selective separation of C2H2/CO2 at room temperature[J]. Angewandte Chemie International Edition, 2015, 54(2):574-577.
[23]	LI P, HE Y, ARMAN H D, et al. A microporous six-fold interpenetrated hydrogen-bonded organic framework for highly selective separation of C2H4/C2H6[J]. Chemical Communications, 2014, 50(86):13081-13084.
[24]	LUO X Z, JIA X J, DENG J H, et al. A microporous hydrogen-bonded organic framework:exceptional stability and highly selective adsorption of gas and liquid[J]. Journal of the American Chemical Society, 2013, 135(32):11684-11687.
[25]	WANG H, LI B, WU H, et al. A flexible microporous hydrogen-bonded organic framework for gas sorption and separation[J]. Journal of the American Chemical Society, 2015, 137(31):9963-9970.
[26]	YANG W, LI B, WANG H, et al. A microporous porphyrin-based hydrogen-bonded organic framework for gas separation[J]. Crystal Growth & Design, 2015, 15(4):2000-2004.
[27]	CHEN T H, POPOV I, KAVEEVIVITCHAI W, et al. Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCs[J]. Nature Communications, 2014, 5(1):5131.
[28]	ZENTNER C A, LAI H W H, GREENFIELD J T, et al. High surface area and Z' in a thermally stable 8-fold polycatenated hydrogen-bonded framework[J]. Chemical Communications, 2015, 51(58):11642-11645.
[29]	ZHOU D D, XU Y T, LIN R B, et al. High-symmetry hydrogen-bonded organic frameworks:air separation and crystal-to-crystal structural transformation[J]. Chemical Communications, 2016, 52(28):4991-4994.
[30]	THOMAS-GIPSON J, BEOBIDE G, CASTILLO O, et al. Paddle-wheel shaped copper (Ⅱ)-adenine discrete entities as supramolecular building blocks to afford porous supramolecular metal-organic frameworks (SMOFs)[J]. Crystal Growth & Design, 2014, 14(8):4019-4029.
[31]	THOMAS-GIPSON J, BEOBIDE G, CASTILLO O, et al. Porous supramolecular compound based on paddle-wheel shaped copper (Ⅱ)-adenine dinuclear entities[J]. CrystEngComm, 2011, 13(10):3301-3305.
[32]	NUGENT P S, RHODUS V L, PHAM T, et al. A robust molecular porous material with high CO2 uptake and selectivity[J]. Journal of the American Chemical Society, 2013, 135(30):10950-10953.
[33]	LEE J M, PALGUNADI J, KiIM J H, et al. Selective removal of acetylenes from olefin mixtures through specific physicochemical interactions of ionic liquids with acetylenes[J]. Physical Chemistry Chemical Physics, 2010, 12(8):1812-1816.
[34]	ZHAO X, XING H, YANG Q, et al. Differential solubility of ethylene and acetylene in room-temperature ionic liquids:a theoretical study[J]. The Journal of Physical Chemistry B, 2012, 116(13):3944-3953.
[35]	PALGUNADI J, HONG S Y, LEE J K, et al. Correlation between hydrogen bond basicity and acetylene solubility in room temperature ionic liquids[J]. The Journal of Physical Chemistry B, 2011, 115(5):1067-1074.
[36]	BURD S D, MA S, PERMAN J A, et al. Highly selective carbon dioxide uptake by[Cu(bpy-n)2(SiF6)](bpy-1=4,4'-Bipyridine; bpy-2=1,2-bis (4-pyridyl) ethene)[J]. Journal of the American Chemical Society, 2012, 134(8):3663-3666.
[37]	MOHAMED M H, ELSAIDI S K, WOJTAS L, et al. Highly selective CO2 uptake in uninodal 6-connected "mmo" nets based upon MO42-(M=Cr, Mo) pillars[J]. Journal of the American Chemical Society, 2012, 134(48):19556-19559.
[38]	XU H, HE Y, ZHANG Z, et al. A microporous metal-organic framework with both open metal and Lewis basic pyridyl sites for highly selective C2H2/CH4 and C2H2/CO2 gas separation at room temperature[J]. Journal of Materials Chemistry A, 2013, 49(60):77-81.
[39]	HE Y, XIANG S, ZHANG Z, et al. A microporous lanthanide-tricarboxylate framework with the potential for purification of natural gas[J]. Chemical Communications, 2012, 48(88):10856-10858.
[40]	XIANG S, ZHOU W, GALLENGOS J M, et al. Exceptionally high acetylene uptake in a microporous metal-organic framework with open metal sites[J]. Journal of the American Chemical Society, 2009, 131(34):12415-12419.
[41]	SUMIDA K, ROGOW D L, MASON J A, et al. Carbon dioxide capture in metal-organic frameworks[J]. Chemical Reviews, 2011, 112(2):724-781.
[42]	CUI XL, CHEN K J, XING H B, et al. Pore chemistry and size control in by brid porous materials for acetylene capture from ethylene[J]. Science, 2016, 353(6295):141-144.
[43]	LI P, HE Y, GUANG J, et al. A homochiral microporous hydrogen-bonded organic framework for highly enantioselective separation of secondary alcohols[J]. Journal of the American Chemical Society, 2014, 136(2):547-549.
[44]	LU J, PEREZ-KRAP C, SUYETIN M, et al. A robust binary supramolecular organic framework (SOF) with high CO2 adsorption and selectivity[J]. Journal of the American Chemical Society, 2014, 136(37):12828-12831.
[45]	ELSAIDI S K, MOHAMED M H, SCHAEL H T, et al. Hydrophobic pillared square grids for selective removal of CO2 from simulated flue gas[J]. Chemical Communications, 2015, 51(94):15530-15533.