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固体NMR研究MOFs吸附和分离过程中的主客体相互作用

  • 贺彩艳 ,
  • 肖宇情 ,
  • 李申慧 ,
  • 徐君 ,
  • 邓风
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  • 1.中国科学院精密测量科学与技术创新研究院,波谱与原子分子物理国家重点实验室,武汉磁共振中心,湖北 武汉 430071
    2.中国科学院大学,北京 100049

收稿日期: 2022-10-10

  网络出版日期: 2022-11-03

基金资助

中国科学院磁共振技术联盟功能开发项目(2020gz1007)

Solid-state NMR Investigation of the Host-guest Interactions in Gas Adsorption and Chemical Separation Using MOFs as Adsorbents

  • Caiyan HE ,
  • Yuqing XIAO ,
  • Shenhui LI ,
  • Jun XU ,
  • Feng DENG
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  • 1. Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan 430071, China
    2. University of Chinese Academy of Sciences, Beijing 100049, China

Received date: 2022-10-10

  Online published: 2022-11-03

摘要

固体核磁共振(NMR)因对结构和化学环境敏感,已广泛应用于研究金属有机框架材料(MOFs)在吸附分离应用上的主客体相互作用机制.多核、多维、变温固体NMR实验可以用来研究低碳碳氢化合物、CO2在MOFs孔道内的吸附行为(包括优先吸附位点、动力学性质、扩散快慢等).固体NMR也可用来直接测定低碳烷烃/烯烃在MOFs中的分离选择性,并观测低碳烷烃/烯烃在MOFs孔道内的竞争优先吸附.此外,固体NMR还可用来揭示常见化学品与MOFs的主客体相互作用模式.这些研究的开展将有助于人们理解MOFs在吸附和分离过程中存在的内在构效关系.

本文引用格式

贺彩艳 , 肖宇情 , 李申慧 , 徐君 , 邓风 . 固体NMR研究MOFs吸附和分离过程中的主客体相互作用[J]. 波谱学杂志, 2023 , 40(2) : 192 -206 . DOI: 10.11938/cjmr20223027

Abstract

Due to its sensitivity to the local geometries and chemical environments, solid-state nuclear magnetic resonance (NMR) is widely applied to investigate the host-guest interactions between metal-organic frameworks (MOFs) and guest molecules in the studies of gas adsorption and chemical separation. Multi-nuclear, multi-dimensional and variable temperature solid-state NMR is employed to investigate the adsorption behavior, primary adsorption sites, dynamic property, and self-diffusion coefficients of light hydrocarbons and carbon dioxide inside the MOFs channels. Moreover, solid-state NMR spectroscopy is utilized to determine the adsorption selectivity, visualize the preferential adsorption and uncover the separation mechanism of light alkane/alkene mixtures inside MOFs. Furthermore, solid-state NMR is used to explore the detailed host-guest interaction mechanism between common chemicals and MOFs adsorbents. All these findings provide insights into deep understanding of the structure-property relationship for the application of functional MOFs in gas adsorption and chemical separation.

参考文献

[1] FURUKAWA H, CORDOVA K E, O’KEEFFE M, et al. The chemistry and applications of metal-organic frameworks[J]. Science, 2013, 341(6149): 1230444.
[2] ZHOU H C, LONG J R, YAGHI O M. Introduction to metal-organic frameworks[J]. Chem Rev, 2012, 112(2): 673-674.
[3] QI G D, WANG Q, XU J, et al. Solid-state NMR studies of internuclear correlations for characterizing catalytic materials[J]. Chem Soc Rev, 2021, 50(15): 8382-8399.
[4] MARCHETTI A, CHEN J, PANG Z, et al. Understanding surface and interfacial chemistry in functional nanomaterials via solid-state NMR[J]. Adv Mater, 2017, 29(14): 1605895.
[5] FAN B H, XU S T, WEI Y X, et al. Progresses of hyperpolarized 129Xe NMR application in porous materials and catalysis[J]. Magn Reson Lett, 2021, 1(1): 11-27.
[6] YANG W J, HUANG J. Analysis of local structure, acidic property and activity of solid acids by solid-state nuclear magnetic resonance spectroscopy[J]. Chinese J Magn Reson, 2021, 38(4): 460-473.
[6] 杨文杰, 黄骏. 基于固体核磁共振技术的固体酸结构、酸性及活性分析[J]. 波谱学杂志, 2021, 38(4): 460-473.
[7] XIAO Y, XIA C J, YI X F, et al. Progress in the studies on Sn-zeolites by solid-state nuclear magnetic resonance[J]. Chinese J Magn Reson, 2021, 38(4): 571-584.
[7] 肖瑶, 夏长久, 易先锋, 等. 固体核磁共振技术在锡硅分子筛表征中的应用[J]. 波谱学杂志, 2021, 38(4): 571-584.
[8] XU J, LIU Y M, LIPTON A S, et al. Amine dynamics in diamine-appended Mg2 (dobpdc) metal-organic frameworks[J]. J Phys Chem Lett, 2019, 10(22): 7044-7049.
[9] LI X, SHEN W L, SUN H. Solid-state NMR studies of sulfonated SBA-15 and the synergistic catalysis of fructose into 5-hydroxymethylfurfural with dimethyl sulfoxide[J]. Magn Reson Lett, 2022, 2(1): 38-47.
[10] WANG C, DAI W L, WU G J, et al. Application of ammonia probe-assisted solid-state NMR technique in zeolites and catalysis[J]. Magn Reson Lett, 2022, 2(1): 28-37.
[11] GAO X Z, ZHANG Y, WANG X M, et al. Structure and acidity changes in ultra-stable Y zeolites during hydrothermal aging: A solid-state NMR spectroscopy study[J]. Chinese J Magn Reson, 2020, 37(1): 95-103.
[11] 高秀枝, 张翊, 王秀梅, 等. NMR研究超稳Y分子筛水热老化过程中结构与酸性的变化[J]. 波谱学杂志, 2020, 37(1): 95-103.
[12] WANG Y X, WANG Q, XU J, et al. The effects of ammonium hexafluorosilicate post-treatment on the acidity of H-ZSM-5 zeolite studied by solid-state NMR spectroscopy[J]. Chinese J Magn Reson, 2021, 38(4): 514-522.
[12] 王永祥, 王强, 徐君, 等. 六氟硅酸铵后处理对H-ZSM-5分子筛酸性影响的固体NMR研究[J]. 波谱学杂志, 2021, 38(4): 514-522.
[13] WONG Y T A, MARTINS V, LUCIER B E, et al. Solid-state NMR spectroscopy: A powerful technique to directly study small gas molecules adsorbed in metal-organic frameworks[J]. Chem - Eur J, 2019, 25(8): 1848-1853.
[14] BRUNNER E, RAUCHE M. Solid-state NMR spectroscopy: an advancing tool to analyse the structure and properties of metal-organic frameworks[J]. Chem Sci, 2020, 11(17): 4297-4304.
[15] BERTMER M. Solid-state NMR of small molecule adsorption in metal-organic frameworks (MOFs)[M]. ATTAURRAHMAN Ed Annu Rep NMR Spectrosc, 2020: 1-64.
[16] FU Y, GUAN H X, YIN J L, et al. Probing molecular motions in metal-organic frameworks with solid-state NMR[J]. Coord Chem Rev, 2021, 427: 213563.
[17] JAEGERS N R, MUELLER K T, WANG Y, et al. Variable temperature and pressure operando MAS NMR for catalysis science and related materials[J]. Acc Chem Res, 2020, 53(3): 611-619.
[18] WITHERSPOON V J, XU J, REIMER J A. Solid-state NMR investigations of carbon dioxide gas in metal-organic frameworks: Insights into molecular motion and adsorptive behavior[J]. Chem Rev, 2018, 118(20): 10033-10048.
[19] LUCIER B E, CHEN S S, HUANG Y N. Characterization of metal-organic frameworks: Unlocking the potential of solid-state NMR[J]. Acc Chem Res, 2018, 51(2): 319-330.
[20] UR REHMAN S, XU S, XU H T, et al. The role of NMR in metal organic frameworks: deep insights into dynamics, structure and mapping of functional groups[J]. Mater Today Adv, 2022, 16: 100287.
[21] HE C Y, LI S H, XIAO Y Q, et al. Application of solid-state NMR techniques for structural characterization of metal-organic frameworks[J]. Solid State Nucl Magn Reson, 2022, 117: 101772.
[22] LI Y X, ZHANG W L, HUANG Y N. Two open metal sites on the same metal: Dynamics of CO2 in MOF UTSA-74[J]. Magn Reson Lett, 2021, 1(2): 121-130.
[23] LI S H, LAFON O, WANG W Y, et al. Recent advances of solid-state NMR spectroscopy for microporous materials[J]. Adv Mater, 2020, 32(44): 2002879.
[24] ASHBROOK S E, DAVIS Z H, MORRIS R E, et al. O-17 NMR spectroscopy of crystalline microporous materials[J]. Chem Sci, 2021, 12(14): 5016-5036.
[25] PAUL G, BISIO C, BRASCHI I, et al. Combined solid-state NMR, FT-IR and computational studies on layered and porous materials[J]. Chem Soc Rev, 2018, 47(15): 5684-5739.
[26] DING S Y, DONG M, WANG Y W, et al. Thioether-based fluorescent covalent organic framework for selective detection and facile removal of mercury(II)[J]. J Am Chem Soc, 2016, 138(9): 3031-3037.
[27] COMOTTI A, BRACCO S, BEN T, et al. Molecular rotors in porous organic frameworks[J]. Angew Chem, 2014, 53(4): 1043-1047.
[28] LUCIER B E, ZHANG Y, LEE K J, et al. Grasping hydrogen adsorption and dynamics in metal-organic frameworks using 2H solid-state NMR[J]. Chem Commun, 2016, 52(48): 7541-7544.
[29] ZHANG Y, LUCIER B E, FISCHER M, et al. A multifaceted study of methane adsorption in metal-organic frameworks by using three complementary techniques[J]. Chem - Eur J, 2018, 24(31): 7866-7881.
[30] CHEN M S, CHEN S S, CHEN W, et al. Analyzing gas adsorption in an amide-functionalized metal organic framework: are the carbonyl or amine groups responsible?[J]. Chem Mater, 2018, 30(11): 3613-3617.
[31] KHUDOZHITKOV A E, ARZUMANOV S S, KOLOKOLOV D I, et al. UiO-66 (Zr) MOF as a promising material for butane isomers separation: Evidence based on the analysis of the adsorbed alkanes mobility by 2H NMR and molecular dynamics simulation[J]. J Phys Chem C, 2021, 125(24): 13391-13400.
[32] LI J, LI S H, ZHENG A M, et al. Solid-state NMR studies of host-guest interaction between UiO-67 and light alkane at room temperature[J]. J Phys Chem C, 2017, 121(26): 14261-14268.
[33] XIAO Y Q, CHU Y Y, LI S H, et al. Primary adsorption sites of light alkanes in multivariate UiO-66 at room temperature as revealed by solid-state NMR[J]. J Phys Chem C, 2020, 124(6): 3738-3746.
[34] DVOYASHKINA N, FREUDE D, ARZUMANOV S S, et al. Monitoring the diffusivity of light hydrocarbons in a mixture by magic angle spinning pulsed field gradient NMR: methane/ethane/ethene in ZIF-8[J]. J Phys Chem C, 2017, 121(45): 25372-25376.
[35] CHMELIK C, FREUDE D, BUX H, et al. Ethene/ethane mixture diffusion in the MOF sieve ZIF-8 studied by MAS PFG NMR diffusometry[J]. Microporous Mesoporous Mater, 2012, 147(1): 135-141.
[36] BANIANI A, CHMELIK C, FORMAN E M, et al. Anomalous relationship between molecular size and diffusivity of ethane and ethylene inside crystals of zeolitic imidazolate framework-11[J]. J Phys Chem C, 2019, 123(27): 16813-16822.
[37] FREUDE D, DVOYASHKINA N, ARZUMANOV S S, et al. NMR study of the host structure and guest dynamics investigated with alkane/alkene mixtures in metal organic frameworks ZIF-8[J]. J Phys Chem C, 2018, 123(3): 1904-1912.
[38] WEHRING M, GASCON J, DUBBELDAM D, et al. Self-diffusion studies in CuBTC by PFG NMR and MD simulations[J]. J Phys Chem C, 2010, 114(23): 10527-10534.
[39] KONG X Q, SCOTT E, DING W, et al. CO2 dynamics in a metal-organic framework with open metal sites[J]. J Am Chem Soc, 2012, 134(35): 14341-14344.
[40] WANG W D, LUCIER B E, TERSKIKH V V, et al. Wobbling and hopping: studying dynamics of CO2 adsorbed in metal-organic frameworks via 17O solid-state NMR[J]. J Phys Chem Lett, 2014, 5(19): 3360-3365.
[41] LU Y J, LUCIER B E, ZHANG Y, et al. Sizable dynamics in small pores: CO2 location and motion in the α-Mg formate metal-organic framework[J]. Phys Chem Chem Phys, 2017, 19(8): 6130-6141.
[42] ZHANG Y, LUCIER B E, HUANG Y N. Deducing CO2 motion, adsorption locations and binding strengths in a flexible metal-organic framework without open metal sites[J]. Phys Chem Chem Phys, 2016, 18(12): 8327-8341.
[43] WU B W, WONG Y A, LUCIER B E, et al. Exploring host-guest interactions in the α-Zn3 (HCOO)6 metal-organic framework[J]. ACS Omega, 2019, 4(2): 4000-4011.
[44] CHEN S S, LUCIER B E, BOYLE P D, et al. Understanding the fascinating origins of CO2 adsorption and dynamics in MOFs[J]. Chem Mater, 2016, 28(16): 5829-5846.
[45] GUL-E-NOOR F, MENDT M, MICHEL D, et al. Adsorption of small molecules on Cu3(btc)2 and Cu3-xZnx(btc)2 metal-organic frameworks (MOF) as studied by solid-state NMR[J]. J Phys Chem C, 2013, 117(15): 7703-7712.
[46] DESVEAUX B E, WONG Y A, LUCIER B E, et al. CO2 behavior in a highly selective ultramicroporous framework: insights from single-crystal X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy[J]. J Phys Chem C, 2019, 123(29): 17798-17807.
[47] MILNER P J, SIEGELMAN R L, FORSE A C, et al. A diaminopropane-appended metal-organic framework enabling efficient CO2 capture from coal flue gas via a mixed adsorption mechanism[J]. J Am Chem Soc, 2017, 139(38): 13541-13553.
[48] FORSE A C, MILNER P J, LEE J-H, et al. Elucidating CO2 chemisorption in diamine-appended metal-organic frameworks[J]. J Am Chem Soc, 2018, 140(51): 18016-18031.
[49] SIEGELMAN R L, MILNER P J, FORSE A C, et al. Water enables efficient CO2 capture from natural gas flue emissions in an oxidation-resistant diamine-appended metal-organic framework[J]. J Am Chem Soc, 2019, 141(33): 13171-13186.
[50] DINAKAR B, FORSE A C, JIANG H Z, et al. Overcoming metastable CO2 Adsorption in a bulky diamine-appended metal-organic framework[J]. J Am Chem Soc, 2021, 143(37): 15258-15270.
[51] XIAO Y Q, CHU Y Y, LI S H, et al. Host-guest interaction in ethylene and ethane separation on zeolitic imidazolate frameworks as revealed by solid-state NMR spectroscopy[J]. Chem - Eur J, 2021, 27(44): 11303-11308.
[52] XIAO Y Q, CHU Y Y, LI S H, et al. Preferential adsorption sites for propane/propylene separation on ZIF-8 as revealed by solid-state NMR spectroscopy[J]. Phys Chem Chem Phys, 2022, 24(11): 6535-6543.
[53] SIN M, KAVOOSI N, RAUCHE M, et al. In situ 13C NMR spectroscopy study of CO2/CH4 mixture adsorption by metal-organic frameworks: does flexibility influence selectivity?[J]. Langmuir, 2019, 35(8): 3162-3170.
[54] ROZTOCKI K, RAUCHE M, BON V, et al. Combining in situ techniques (XRD, IR, and 13C NMR) and gas adsorption measurements reveals CO2-induced structural transitions and high CO2/CH4 selectivity for a flexible metal-organic framework JUK-8[J]. ACS Appl Mater Interfaces, 2021, 13(24): 28503-28513.
[55] LI S H, LI J, TANG J, et al. Host-guest interaction of styrene and ethylbenzene in MIL-53 studied by solid-state NMR[J]. Solid State Nucl Magn Reson, 2018, 90: 1-6.
[56] XU J, TERSKIKH V V, HUANG Y N. 25Mg solid-state NMR: a sensitive probe of adsorbing guest molecules on a metal center in metal-organic framework CPO-27-Mg[J]. J Phys Chem Lett, 2013, 4(1): 7-11.
[57] GUL-E-NOOR F, JEE B, P?PPL A, et al. Effects of varying water adsorption on a Cu3(BTC)2 metal-organic framework (MOF) as studied by 1H and 13C solid-state NMR spectroscopy[J]. Phys Chem Chem Phys, 2011, 13(17): 7783-7788.
[58] GIOVINE R, POURPOINT F, DUVAL S, et al. The surprising stability of Cu3(btc)2 metal-organic framework under steam flow at high temperature[J]. Cryst Growth Des, 2018, 18(11): 6681-6693.
[59] GUL-E-NOOR F, MICHEL D, KRAUTSCHEID H, et al. Time dependent water uptake in Cu3(btc)2 MOF: Identification of different water adsorption states by 1H MAS NMR[J]. Microporous Mesoporous Mater, 2013, 180: 8-13.
[60] MCHUGH L N, MCPHERSON M J, MCCORMICK L J, et al. Hydrolytic stability in hemilabile metal-organic frameworks[J]. Nat Chem, 2018, 10(11): 1096-1102.
[61] GUL-E-NOOR F, JEE B, MENDT M, et al. Formation of mixed metal Cu3-xZnx(btc)2 frameworks with different zinc contents: Incorporation of Zn2+ into the metal-organic framework structure as studied by solid-state NMR[J]. J Phys Chem C, 2012, 116(39): 20866-20873.
[62] NANDY A, FORSE A C, WITHERSPOON V J, et al. NMR spectroscopy reveals adsorbate binding sites in the metal-organic framework UiO-66 (Zr)[J]. J Phys Chem C, 2018, 122(15): 8295-8305.
[63] TANG J, CHU Y Y, LI S H, et al. Breathing effect via solvent inclusions on the linker rotational dynamics of functionalized MIL-53[J]. Chem - Eur J, 2021, 27(59): 14711-14720.
[64] XU J, TERSKIKH V V, CHU Y Y, et al. 13C chemical shift tensors in MOF α-Mg3(HCOO)6: Which component is more sensitive to host-guest interaction?[J]. Magn Reson Chem, 2020, 58(11): 1082-1090.
[65] HOSSAINá KHAN A, AMANZADEHá SALOUT S, SHUPLETSOV L, et al. Solid-state NMR insights into alcohol adsorption by metal-organic frameworks: adsorption state, selectivity, and adsorption-induced phase transitions[J]. Chem Commun, 2022, 58(28): 4492-4495.
[66] XU X H, LI S H, LIU Q, et al. Isolated π-interaction sites in mesoporous MOF backbone for repetitive and reversible dynamics in water[J]. ACS Appl Mater Interfaces, 2018, 11(1): 973-981.
[67] WITTMANN T, MONDAL A, TSCHENSE C B, et al. Probing interactions of N-donor molecules with open metal sites within paramagnetic Cr-MIL-101: a solid-state NMR spectroscopic and density functional theory study[J]. J Am Chem Soc, 2018, 140(6): 2135-2144.
[68] VENEL F, VOLKRINGER C, LAFON O, et al. Probing adsorption of water and DMF in UiO-66 (Zr) using solid-state NMR[J]. Solid State Nucl Magn Reson, 2022, 120: 101797-101797.
[69] BAE J, CHOI J S, HWANG S, et al. Multiple coordination exchanges for room-temperature activation of open-metal sites in metal-organic frameworks[J]. ACS Appl Mater Interfaces, 2017, 9(29): 24743-24752.
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