羧酸改性HKUST-1提高甲烷吸附容量

doi:10.11949/j.issn.0438-1157.20180604

摘要/Abstract

摘要：

为提高吸附材料对甲烷的吸附容量，采用溶剂热法合成了金属有机骨架材料HKUST-1，并进行了改性研究。HKUST-1的优化合成工艺条件为：原料摩尔比n（Cu（NO₃）₂·3H₂O）：n（H₃BTC）：n（DMF）：n（C₂H₅OH）：n（H₂O）=1.7：1：46：60：100，晶化温度为80℃，晶化时间24 h。合成HKUST-1在25℃、3.5 MPa下的甲烷吸附容量为11.9 mmol/g。乙酸改性HKUST-1可以提高甲烷吸附容量，当反应母液中V_HAc/V_solvent=5.8%时，合成HAc-HK-1（5.8%）的甲烷吸附容量达到12.6 mmol/g。分子模拟结果表明，加入乙酸可以调控HKUST-1晶体孔道结构，增大比表面积和孔容，提高甲烷吸附容量。

关键词: HKUST-1, 金属有机骨架材料, 甲烷, 天然气吸附储存

Abstract:

In order to improve the methane adsorption capacity of adsorbent, the metal-organic frameworks material HKUST-1 was synthesized by solvothermal method and follow by modification research. The optimized synthesis conditions were as follows:n(Cu(NO₃)₂·3H₂O):n(H₃BTC):n(DMF):n(C₂H₅OH):n(H₂O)=1.7:1:46:60:100, the crystallization temperature of 80℃ and the crystallization time of 24 h. The methane adsorption capacity of HKUST-1 was 11.9 mmol/g at 25℃. Acid ligand modification could increase the methane adsorption capacity of HKUST-1. When V_HAc/V_solvent=5.8%, the methane adsorption capacity of HAc-HK-1(5.8%) reached 12.6 mmol/g. Molecular simulation results show that the addition of acetic acid can regulate the pore structure of HKUST-1 crystal, increase the specific surface area and pore volume, and increase the methane adsorption capacity.

Key words: HKUST-1, metal-organic frameworks, methane, natural gas adsorption storage

中图分类号:

TE821

韩强, 程振飞, 刘纪昌, 汪成, 欧苏慧, 汪瑜懿, 简雨培, 杨小娟, 王紫竹, 杨璐彬. 羧酸改性HKUST-1提高甲烷吸附容量[J]. 化工学报, 2018, 69(11): 4902-4909.

HAN Qiang, CHENG Zhenfei, LIU Jichang, WANG Cheng, OU Suhui, WANG Yuyi, JIAN Yupei, YANG Xiaojuan, WANG Zizhu, YANG Lubin. Improving methane adsorption capacity of HKUST-1 by modified with carboxylic acid[J]. CIESC Journal, 2018, 69(11): 4902-4909.

参考文献 30

[1]	XUAN W, ZHU C, LIU Y, et al. Mesoporous metal-organic framework materials[J]. Chemical Society Reviews, 2012, 41(5):1677-1695.
[2]	LI H, EDDAOUDI M, O'KEEFFE M, et al. Design and synthesis of an exceptionally stable and highly porous metal-organic framework[J]. Nature, 1999, 402(6759):276-279.
[3]	KONDO M, YOSHITOMI T, SEKI K, et al. Three-dimensional framework with channeling cavities for small molecules:{M2(4,4'-bpy)3(NO3)4·xH2O}n(M=Co, Ni, Zn)[J]. Angewandte Chemie International Edition, 1997, 36(16):1725-1727.
[4]	KRISTINA K, THERESA O, YUNXIA Y, et al. Methane storage in metal organic frameworks[J]. Journal of Materials Chemistry, 2012, 22:16698-16708.
[5]	YABING H, WEI Z, GUODONG Q, et al. Methane storage in metal-organic frameworks[J]. Chemical Society Reviews, 2014, 43:5657-5678.
[6]	JARAD A M, MIKE V, JEFFREY R L. Evaluating metal-organic frameworks for natural gas storage[J]. Chemical Science, 2014, 5:32-51.
[7]	WEI Z. Methane storage in porous metal-organic frameworks:current records and future perspectives[J]. The Chemical Record, 2010, 10:200-204.
[8]	冯英子. 几种金属有机骨架材料的合成及其吸附性能的研究[D]. 广州:华南理工大学, 2010. FENG Y Z. Study on the synthesis and adsorption properties of several metallic organic framework materials[D]. Guangzhou:South China University of Technology, 2010.
[9]	吴华伟. 微孔材料的甲烷吸附研究[D]. 太原:太原理工大学, 2009. WU H W. Study on methane adsorption of microporous materials[D]. Taiyuan:Taiyuan University of Technology, 2009.
[10]	周丽姣. MOF-5的合成及Ru(Pd)/AC掺杂研究[D]. 长沙:中南大学, 2012. ZHOU L J. Study on synthesis of MOF-5 and Ru(Pd)/AC doping[D]. Changshai:Central South University, 2012.
[11]	王明雪. 金属有机骨架化合物MOF-5的合成及其耐水性能研究[D]. 长沙:中南大学, 2014. WANG M X. Study on the synthesis and water resistance of metal organic skeleton compound MOF-5[D]. Changshai:Central South University, 2014.
[12]	BAICHUAN S, SIBNATH K, ANUTOSH C. Study of HKUST (copper benzene-1,3,5-tricarboxylate, Cu-BTC MOF)-1 metal organic frameworks for CH4 adsorption:an experimental investigation with GCMC (grand canonical Monte-Carlo) simulation[J]. Energy, 2014, 76:419-427.
[13]	YANG P, VAIVA K, IBRAHIM E, et al. Methane storage in metal-organic frameworks:current records, surprise findings, and challenges[J]. Journal of the American Chemical Society, 2013, 135:11887-11894.
[14]	JUNCONG J, HIROYASU F, YUEBIAO Z, et al. High methane storage working capacity in metal-organic frameworks with acrylate links[J]. Journal of the American Chemical Society, 2016, 138:10244-10251.
[15]	HOW W B, ANUTOSH C, SIBNATH K. Evaluation of CH4 and CO2 adsorption on HKUST-1 and MIL-101(Cr) MOFs employing Monte Carlo simulation and comparison with experimental data[J]. Applied Thermal Engineering, 2017, 110:891-900.
[16]	PRAJWAL B P, AYAPPA K G. Evaluating methane storage targets:from powder samples to onboard storage systems[J]. Adsorption, 2014, 20:769-776.
[17]	JUERGEN G, IRENA S, DIRK W, et al. Methane storage mechanism in the metal-organic framework Cu3(btc)2:an in situ neutron diffraction study[J]. Microporous and Mesoporous Materials, 2010, 136:50-58.
[18]	ZHIYONG G, HUI W, GADIPELLI S, et al. A metal-organic framework with optimized open metal sites and pore spaces for high methane storage at room temperature[J]. Angewandte Chemie International Edition, 2011, 50:3178-3181.
[19]	阳庆元, 刘大欢, 仲崇立. 金属有机骨架材料的计算化学研究[J]. 化工学报, 2009, 60(4):805-819. YANG Q Y, LIU D H, ZHONG C L. Computational chemistry of metallic organic framework materials[J]. CIESC Journal, 2009, 60(4):805-819.
[20]	WEI M, DAHUAN L, QINGYUAN Y, et al.Computational study of the effect of organic linkers on natural gas upgrading in metal-organic frameworks[J]. Microporous and Mesoporous Materials, 2010, 130:76-82.
[21]	JIA F, YUN T, JIANZHONG W. Classical density functional theory for methane adsorption in metal-organic framework materials[J]. AIChE Journal, 2015, 61(9):3012-3021.
[22]	仲崇立, 刘大欢, 阳庆元. 金属-有机骨架材料的构效关系及设计[M]. 北京:科学出版社, 2013:104-105. ZHONG C L, LIU D H, YANG Q Y. Structure-Activity Relationship and Design of Metal-Organic Framework Materials[M]. Beijing:Science Press, 2013:104-105.
[23]	张伊, 顾奕奕, 陈云琳, 等. 掺杂金属离子对MOF-5吸附甲烷分子的影响[J]. 化工新型材料, 2015, 43(2):93-96. ZHANG Y, GU Y Y, CHEN Y L, et al. Influence of doped metal ions on MOF-5 adsorption of methane molecules[J]. New Chemical Materials, 2015, 43(2):93-96.
[24]	朱晨明, 王保登, 张中正, 等. 金属-有机骨架复合材料的制备及其二氧化碳吸附性能[J]. 化工进展, 2016, 35(9):2875-2884. ZHU C M, WANG B D, ZHANG Z Z, et al. Preparation of metal-organic matrix composites and their carbon dioxide adsorption properties[J]. Chemical Industry and Engineering Progress, 2016, 35(9):2875-2884.
[25]	SEO Y K, AHREUM K, JUNG W Y, et al. Creation of mesoporous defects in a microporous metal-organic framework by an acetic acid-fragmented linker co-assembly and its remarkable effects on methane uptake[J]. Chemical Engineering Journal, 2018, 335:94-100.
[26]	BARIN G, KRUNGLEVICIUTE V, GUTOV O, et al. Defect creation by linker fragmentation in metal-organic frameworks and its effects on gas uptake properties[J]. Inorganic Chemistry, 2014, 53(13):6914-6919.
[27]	FANG Z L, BUEKEN B, DEVOS D E, et al. Defect-engineered metal-organic frameworks[J]. Angewandte Chemie International Edition, 2015, 54:7234-7254.
[28]	LI B, WEN H M, ZHOU W, et al. Porous metal-organic frameworks:promising materials for methane storage[J]. Chemistry, 2016, 1:557-580.
[29]	ZHANG W, KAUER M, GUO P, et al. Impact of synthesis parameters on the formation of defects in HKUST-1[J]. European Journal of Inorganic Chemistry, 2017, 5:925-931.
[30]	PARK J, WANG Z Y, SUN L B, et al. Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly[J]. Journal of the American Chemical Society, 2012, 134(49):20110-20116.