二价铬/钼/镍空配位MOFs的CH4/N2吸附分离研究

doi:10.11949/j.issn.0438-1157.20180302

摘要/Abstract

摘要：

基于金属有机骨架材料中金属空配位对气体的强吸附作用，利用具有较高活性的二价金属Cr²⁺/Mo²⁺/Ni²⁺与均苯三酸（H₃BTC）配位合成了HKUST-1（Cu-BTC）同构系列材料M-BTC（M=Cr、Mo、Ni），并与Cu-BTC对比分析了该类型材料中不同金属空配位对甲烷和氮气的吸附性能。实验结果显示，此三种材料均具有较好的甲烷选择吸附性，其中含Ni²⁺金属空位的Ni-BTC以其尤为突出的甲烷吸附热值而呈现较好的CH₄/N₂分离潜力；Cr²⁺空配位虽具有较强活性，但是对于甲烷的选择性吸附性能却低于含Cu²⁺空位的Cu-BTC材料。结合吸附选择性IAST计算分析得到此三种含较高活性不饱和金属空配位的MOFs材料对于甲烷选择性吸附作用能顺序为：Ni-BTC > Mo-BTC > Cu-BTC > Cr-BTC。

关键词: 甲烷, 氮气, 吸附, 吸附剂, 不饱和金属空配位

Abstract:

Based on the strong interaction energy between the coordinatively unsaturated metal sites (UMSs) and the gas molecules, M-BTC(M=Cr, Mo, Ni), isostructural with HKUST-1 (Cu-BTC), were successfully synthesized via the coordination reaction of the high activity divalent metal (Cr²⁺/Mo²⁺/Ni²⁺) and organic ligand (H₃BTC), and then to gain insight into the impact of gas-metal interactions on the selective adsorption of CH₄ from N₂ by comparing with classical materials (Cu-BTC). The results show the good CH₄ selective adsorption properties of M-BTC (M=Cr, Mo, Ni) with UMSs. Among these materials, Ni-BTC with unsaturated Ni²⁺ sites presents the highest adsorption heat value for CH₄, leading to the excellent CH₄/N₂ adsorption separation properties; but the Cr-BTC with high Cr²⁺ activity shows the lower ability for CH₄/N₂ separation than Cu-BTC. Combined the IAST calculation results, we verified the ability for the selective adsorption of CH₄ molecules on M-BTC (M=Cr, Mo, Ni) and Cu-BTC followed as Ni-BTC > Mo-BTC > Cu-BTC > Cr-BTC.

Key words: methane, nitrogen, adsorption, adsorbents, coordinatively unsaturated metal sites

中图分类号:

TQ028.8

贾晓霞, 王丽, 元宁, 杨江峰, 李晋平. 二价铬/钼/镍空配位MOFs的CH₄/N₂吸附分离研究[J]. 化工学报, 2018, 69(9): 3896-3904.

JIA Xiaoxia, WANG Li, YUAN Ning, YANG Jiangfeng, LI Jinping. CH₄/N₂ adsorption separation research of MOFs with divalent Cr/Mo/Ni unsaturated metal sites[J]. CIESC Journal, 2018, 69(9): 3896-3904.

参考文献 38

[1]	胡江亮, 孙天军, 刘小伟, 等. CH4-N2在MOFs结构材料中的吸附分离性能[J]. 化工学报, 2015, 66(9):3518-3528. HU J L, SUN T J, LIU X W, et al. Adsorption and separation of CH4-N2 with different structural MOFs[J]. CIESC Journal, 2015, 66(9):3518-3528.
[2]	张倬铭, 杨江峰, 陈杨, 等. 一维直孔道MOFs对CH4/N2 和CO2/CH4 的分离[J]. 化工学报, 2015, 66(9):3549-3555. ZHANG Z M, YANG J F, CHEN Y, et al. Separation of CH4/N2 and CO2/CH4 mixtures in one dimension channel MOFs[J]. CIESC Journal, 2015, 66(9):3549-3555.
[3]	杨江峰, 赵强, 于秋红, 等. 煤层气回收及CH4/N2分离PSA材料的研究进展[J]. 化工进展, 2011, 30(4):793-801. YANG J F, ZHAO Q, YU Q H, et al. Progress of recovery of coal bed methane and adsorption materials for separation of CH4/N2 by pressure swing adsorption[J]. Chemical Industry and Engineering Progress, 2011, 30(4):793-801.
[4]	PERRY R H, GREEN D W. Perry's Chemical Engineers' Handbook[M]. New York:McGraw-Hill, 1999.
[5]	DAVID C B, JOHN L B, ARASH A. Nitrogen Removal from Natural Gas:Phase Ⅱ[M]. Washington, DC:U.S. Department of Energy, 1999.
[6]	SIMONE C, CARLOS A G, ALIRIO E R, et al. Separation of CH4/CO2/N2 mixtures by layered pressure swing adsorption for upgrade of natural gas[J]. Chem. Eng. Sci., 2006, 61(12):3893-3906.
[7]	TAGLIABUE M, FARRUSSENG D, VALENCIA S, et al. Natural gas treating by selective adsorption:material science and chemical engineering interplay[J]. Chem. Eng. J., 2009, 155(3):553-566.
[8]	刘克万, 辜敏, 鲜学福, 等. 变压吸附浓缩甲烷/氮气中甲烷的研究进展[J]. 现代化工, 2007, 27(12):15-18. LIU K W, GU M, XIAN X F, et al. Research progress in concentration of methane from CH4/N2 by PSA[J]. Mod. Chem. Ind., 2007, 27(12):15-18.
[9]	EDDAOUDI M, KIM J, ROSI N, et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage[J]. Science, 2002, 295:469-472.
[10]	HWANG Y K, HONG D Y, CHANG J S, et al. Amine grafting on coordinatively unsaturated metal centers of MOFs:consequences for catalysis and metal encapsulation[J]. Angew. Chem. Int. Ed., 2008, 47:4144-4148.
[11]	LLEWELLYN P L, BOURRELLY S, SERRE C, et al. High uptakes of CO2 and CH4 in mesoporous metal organic frameworks MIL-100 and MIL-101[J]. Langmuir, 2008, 24:7245-7250.
[12]	DIETZEL P D C, BESIKIOTIS V, BLOM R, et al. Application of metal-organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide[J]. J. Mater. Chem., 2009, 19:7362-7370.
[13]	YAGHI O M, O'KEEFFE M, OCKWIG N W, et al. Reticular synthesis and the design of new materials[J]. Nature, 2003, 423:705-714.
[14]	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, 402:276-279.
[15]	STOCK N, BISWAS S, et al. Synthesis of metal-organic frameworks (MOFs):routes to various MOF topologies, morphologies, and composites[J]. Chem. Rev., 2012, 112:933-969.
[16]	JANIAK C, VIETH J K, et al. MOFs, MILs and more:concepts, properties and applications for porous coordination networks (PCNs)[J]. New J. Chem., 2010, 34:2366-2388.
[17]	YU D, YAZAYDIN A O, LANE J R, et al. A combined experimental and quantum chemical study of CO2 adsorption in the metal-organic framework CPO-27 with different metals[J]. Chem. Sci., 2013, 4:3544-3556.
[18]	PENG Y, KRUNGLEVICIUTE V, ERYAZICI I, et al. Methane storage in metal-organic frameworks:current records, surprise findings, and challenges[J]. J. Am. Chem. Soc., 2013, 135:11887-11894.
[19]	LI B, WEN H M, WANG H, et al. A porous metal-organic framework with dynamic pyrimidine groups exhibiting record high methane storage working capacity[J]. J. Am. Chem. Soc., 2014, 136:6207-6210.
[20]	HE Y, ZHOU W, YILDIRIM T, et al. A series of metal-organic frameworks with high methane uptake and an empirical equation for predicting methane storage capacity[J]. Energy Environ. Sci., 2013, 6:2735-2744.
[21]	MA S, SUN D, SIMMONS J M, et al. Metal-organic framework from an anthracene derivative containing nanoscopic cages exhibiting high methane uptake[J]. J. Am. Chem. Soc., 2008, 130:1012-1016.
[22]	ELSAIDI S K, MOHAMED M H, WOJTAS L, et al. Putting the squeeze on CH4 and CO2 through control over interpenetration in diamondoid nets[J]. J. Am. Chem. Soc., 2014, 136:5072-5077.
[23]	ROSI N L, KIM J, EDDAOUDI M, et al. Rod packings and metal-organic frameworks constructed from rod-shaped secondary building units[J]. J. Am. Chem. Soc. 2005, 127:1504-1518.
[24]	DIETZEL P D C, PANELLA B, HIRSCHER M, et al. Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework[J]. Chem. Commun., 2006, (9):959-961.
[25]	DIETZEL P D C, MORITA Y, BLOM R, et al. An in situ high-temperature single-crystal investigation of a dehydrated metal-organic framework compound and field-induced magnetization of one-dimensional metal-oxygen chains[J]. Angew. Chem. Int. Ed., 2005, 44:6354-6358.
[26]	ZHOU W, WU H, YILDIRIM T, et al. Enhanced H2 adsorption in isostructural metal-organic frameworks with open metal sites:strong dependence of the binding strength on metal ions[J]. J. Am. Chem. Soc., 2008, 130:15268-15269.
[27]	DIETZEL P D C, BLOM R, FJELLVAG H, et al. Base-induced formation of two magnesium metal-organic framework compounds with a bifunctional tetratopic ligand[J]. Eur. J. Inorg. Chem., 2008, 23:3624-3632.
[28]	BLOCH E D, MURRAY L J, QUEEN W L, et al. Selective binding of O2 over N2 in a redox-active metal-organic framework with open iron (Ⅱ) coordination sites[J]. J. Am. Chem. Soc., 2011, 133:14814-14822.
[29]	VISHNYAKOV A, RAVIKOVITCH P I, NEIMARK A V. Nanopore structure and sorption properties of Cu-BTC metal-organic framework[J]. Nano Letters, 2003, 3:713-718.
[30]	MURRAY L J, DINCA M, YANO J, et al. Highly-selective and reversible O2 binding in Cr3(1, 3, 5-benzenetricarboxylate)2[J]. J. Am. Chem. Soc., 2010, 132:7856-7857.
[31]	MANIAM P, STOCK N, et al. Investigation of porous Ni-based metal-organic frameworks containing paddle-wheel type inorganic building units via high-throughput methods[J]. Inorg. Chem., 2011, 50:5085-5097.
[32]	KRAMER M, ULRICH S B, KASKEL S, et al. Synthesis and properties of the metal-organic framework Mo3(BTC)2 (TUDMOF-1)[J]. J. Mater. Chem., 2006, 16:2245-2248.
[33]	ZHANG Z, ZHANG L, WOJTAS L, et al. Template-directed synthesis of nets based upon octahemioctahedral cages that encapsulate catalytically active metalloporphyrins[J]. J. Am. Chem. Soc., 2012, 134:928-933.
[34]	BHUNIA M K, HUGHES J T, FETTINGER J C, et al. Thermochemistry of paddle wheel MOFs:Cu-HKUST-1 and Zn-HKUST-1[J]. Langmuir, 2013, 29, 8140-8145.
[35]	LI L B, YANG J F, CHEN Y, et al. Separation of CO2/CH4 and CH4/N2 mixtures by M/DOBDC:a detailed dynamic comparison with MIL-100(Cr) and activated carbon[J]. Microporous and Mesoporous Materials, 2014, 198:236-246.
[36]	LI J M, YANG J F, LI L B. Separation of CO2/CH4 and CH4/N2 mixtures using MOF-5 and Cu3(BTC)2[J]. Journal of Energy Chemistry, 2014, 23:453-460.
[37]	MARKUS K, ULRICH S, STEFAN K. Synthesis and properties of the metal-organic framework Mo3(BTC)2 (TUDMOF-1)[J]. J. Mater. Chem., 2006, 16:2245-2248.
[38]	WANG X Q, LI L B, WANG Y. Exploiting the pore size and functionalization effects in UiO topology structures for the separation of light hydrocarbons[J]. Cryst. Eng. Comm., 2017, 19:1729-1737.

二价铬/钼/镍空配位MOFs的CH₄/N₂吸附分离研究

CH₄/N₂ adsorption separation research of MOFs with divalent Cr/Mo/Ni unsaturated metal sites

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 38

相关文章 15

编辑推荐

Metrics

本文评价

[1]	晁京伟, 许嘉兴, 李廷贤. 基于无管束蒸发换热强化策略的吸附热池的供热性能研究[J]. 化工学报, 2023, 74(S1): 302-310.
[2]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[3]	高燕, 伍鹏, 尚超, 胡泽君, 陈晓东. 基于双流体喷嘴的磁性琼脂糖微球的制备及其蛋白吸附性能探究[J]. 化工学报, 2023, 74(8): 3457-3471.
[4]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.
[5]	张瑞航, 曹潘, 杨锋, 李昆, 肖朋, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析[J]. 化工学报, 2023, 74(8): 3386-3393.
[6]	陈吉, 洪泽, 雷昭, 凌强, 赵志刚, 彭陈辉, 崔平. 基于分子动力学的焦炭溶损反应及其机理研究[J]. 化工学报, 2023, 74(7): 2935-2946.
[7]	牛超, 沈胜强, 杨艳, 潘泊年, 李熠桥. 甲烷BOG喷射器流动过程计算与性能分析[J]. 化工学报, 2023, 74(7): 2858-2868.
[8]	刘晓洋, 喻健良, 侯玉洁, 闫兴清, 张振华, 吕先舒. 螺旋微通道对掺氢甲烷爆轰传播的影响[J]. 化工学报, 2023, 74(7): 3139-3148.
[9]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[10]	周小文, 杜杰, 张战国, 许光文. 基于甲烷脉冲法的Fe₂O₃-Al₂O₃载氧体还原特性研究[J]. 化工学报, 2023, 74(6): 2611-2623.
[11]	王新悦, 王俊杰, 曹思贤, 王翠, 李灵坤, 吴宏宇, 韩静, 吴昊. 玻璃内包材界面修饰对机械应力诱导的单克隆抗体聚集体形成的影响[J]. 化工学报, 2023, 74(6): 2580-2588.
[12]	王蕾, 王磊, 白云龙, 何柳柳. SA膜状锂离子筛的制备及其锂吸附性能[J]. 化工学报, 2023, 74(5): 2046-2056.
[13]	蔺彩虹, 王丽, 吴瑜, 刘鹏, 杨江峰, 李晋平. 沸石中碱金属阳离子对CO₂/N₂O吸附分离性能的影响[J]. 化工学报, 2023, 74(5): 2013-2021.
[14]	李辰鑫, 潘艳秋, 何流, 牛亚宾, 俞路. 基于碳微晶结构的炭膜模型及其气体分离模拟[J]. 化工学报, 2023, 74(5): 2057-2066.
[15]	陈韶云, 徐东, 陈龙, 张禹, 张远方, 尤庆亮, 胡成龙, 陈建. 单层聚苯胺微球阵列结构的制备及其吸附性能[J]. 化工学报, 2023, 74(5): 2228-2238.