Functionalization of Mono- and Bimetallic MIL-100(Al,Fe) MOFs by Ethylenediamine: Postfunctionalization, Brønsted Acido-Basicity, and Unusual CO2 Sorption Behavior
[en] The metal sites of MIL-100(Fe), MIL-100(Fe,Al), and MIL-100(Al) metal–organic frameworks (MOFs) were decorated with ethylenediamine (EN). Interestingly, the Al-containing MOFs presented hierarchized porosity, and their structural integrity was maintained upon functionalization. Solution and solid-state NMR confirmed the grafting efficiency in the case of MIL-100(Al) and the presence of a free amine group. It was shown that MIL-100(Al) can be functionalized by only one EN molecule in each trimeric Al3O cluster unit, whereas the other two aluminum sites are occupied by a hydroxyl and a water molecule. The −NH2 sites of the grafted ethylenediamine can be used for further postfunctionalization through amine chemistry and are responsible for the basicity of the functionalized material as well as increased affinity for CO2. Furthermore, the presence of coordinated water molecules on the Al-MOF is responsible for simultaneous Brønsted acidity. Finally, the Al-containing MOFs show an unusual carbon dioxide sorption mechanism at high pressures that distinguishes those materials from their iron and chromium counterparts and is suspected to be due to the presence of polarized Al–OH bonds.
Disciplines :
Chemical engineering Materials science & engineering
Author, co-author :
Steenhaut, Thimoty
Fusaro, Luca
Robeyns, Koen
Lacour, Seraphin
Li, Xiao
Mahy, Julien ; Université de Liège - ULiège > Department of Chemical Engineering > Nanomaterials, Catalysis, Electrochemistry
Functionalization of Mono- and Bimetallic MIL-100(Al,Fe) MOFs by Ethylenediamine: Postfunctionalization, Brønsted Acido-Basicity, and Unusual CO2 Sorption Behavior
Senkovska, I.; Barea, E.; Navarro, J. A. R.; Kaskel, S. Adsorptive Capturing and Storing Greenhouse Gases Such as Sulfur Hexafluoride and Carbon Tetrafluoride Using Metal-Organic Frameworks. Microporous Mesoporous Mater. 2012, 156, 115-120, 10.1016/j.micromeso.2012.02.021
Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Carbon Dioxide Capture in Metal-Organic Frameworks. Chem. Rev. 2012, 112, 724-781, 10.1021/cr2003272
Li, H.; Wang, K.; Sun, Y.; Lollar, C. T.; Li, J.; Zhou, H. C. Recent Advances in Gas Storage and Separation Using Metal-Organic Frameworks. Mater. Today 2018, 21, 108-121, 10.1016/j.mattod.2017.07.006
Wu, M. X.; Yang, Y. W. Metal-Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy. Adv. Mater. 2017, 29, 1606134 10.1002/adma.201606134
Liu, Y.; Xie, X. Y.; Cheng, C.; Shao, Z. S.; Wang, H. S. Strategies to Fabricate Metal-Organic Framework (MOF)-Based Luminescent Sensing Platforms. J. Mater. Chem. C 2019, 7, 10743-10763, 10.1039/c9tc03208h
Wang, H. H.; Shi, W. J.; Hou, L.; Li, G. P.; Zhu, Z.; Wang, Y. Y. A Cationic MOF with High Uptake and Selectivity for CO2 Due to Multiple CO2-Philic Sites. Chem.-Eur. J. 2015, 21, 16525-16531, 10.1002/chem.201502532
Vaidhyanathan, R.; Iremonger, S. S.; Dawson, K. W.; Shimizu, G. K. H. An Amine-Functionalized Metal Organic Framework for Preferential CO 2 Adsorption at Low Pressures. Chem. Commun. 2009, 5230-5232, 10.1039/b911481e
Ma, W.; Xu, L.; Li, Z.; Sun, Y.; Bai, Y.; Liu, H. Post-Synthetic Modification of an Amino-Functionalized Metal-Organic Framework for Highly Efficient Enrichment of N-Linked Glycopeptides. Nanoscale 2016, 8, 10908-10912, 10.1039/c6nr02490d
Lin, Y.; Kong, C.; Chen, L. Amine-Functionalized Metal-Organic Frameworks: Structure, Synthesis and Applications. RSC Adv. 2016, 6, 32598-32614, 10.1039/c6ra01536k
Montoro, C.; García, E.; Calero, S.; Pérez-Fernández, M. A.; López, A. L.; Barea, E.; Navarro, J. A. R. Functionalisation of MOF Open Metal Sites with Pendant Amines for CO 2 Capture. J. Mater. Chem. 2012, 22, 10155-10158, 10.1039/c2jm16770k
Zhong, R.; Yu, X.; Meng, W.; Han, S.; Liu, J.; Ye, Y.; Sun, C.; Chen, G.; Zou, R. A Solvent ‘Squeezing' Strategy to Graft Ethylenediamine on Cu3(BTC)2 for Highly Efficient CO2/CO Separation. Chem. Eng. Sci. 2018, 184, 85-92, 10.1016/j.ces.2017.12.040
Yeon, J. S.; Lee, W. R.; Kim, N. W.; Jo, H.; Lee, H.; Song, J. H.; Lim, K. S.; Kang, D. W.; Seo, J. G.; Moon, D.; Wiers, B.; Hong, C. S. Homodiamine-Functionalized Metal-Organic Frameworks with a MOF-74-Type Extended Structure for Superior Selectivity of CO2 over N2. J. Mater. Chem. A 2015, 3, 19177-19185, 10.1039/c5ta02357b
Choi, S.; Watanabe, T.; Bae, T. H.; Sholl, D. S.; Jones, C. W. Modification of the Mg/DOBDC MOF with Amines to Enhance CO 2 Adsorption from Ultradilute Gases. J. Phys. Chem. Lett. 2012, 3, 1136-1141, 10.1021/jz300328j
Bai, Z. Q.; Yuan, L. Y.; Zhu, L.; Liu, Z. R.; Chu, S. Q.; Zheng, L. R.; Zhang, J.; Chai, Z. F.; Shi, W. Q. Introduction of Amino Groups into Acid-Resistant MOFs for Enhanced U(vi) Sorption. J. Mater. Chem. A 2015, 3, 525-534, 10.1039/c4ta04878d
Cabello, C. P.; Berlier, G.; Magnacca, G.; Rumori, P.; Palomino, G. T. Enhanced CO2 Adsorption Capacity of Amine-Functionalized MIL-100(Cr) Metal-Organic Frameworks. CrystEngComm 2015, 17, 430-437, 10.1039/c4ce01265h
Wang, L.; Zhang, F.; Wang, C.; Li, Y.; Yang, J.; Li, L.; Li, J. Ethylenediamine-Functionalized Metal Organic Frameworks MIL-100(Cr) for Efficient CO2/N2O Separation. Sep. Purif. Technol. 2020, 235, 116219 10.1016/j.seppur.2019.116219
Sepehrmansouri, H.; Zarei, M.; Ali, M. et al. Multilinker Phosphorous Acid Anchored En / MIL-100 (Cr) as a Novel Nanoporous Catalyst for the Synthesis of New N-Heterocyclic Pyrimido [4, 5-b] Quinolines. Mol. Catal. 2020, 110303 10.1016/j.mcat.2019.01.023
Pertiwi, R.; Oozeerally, R.; Burnett, D. L.; Chamberlain, T. W.; Cherkasov, N.; Walker, M.; Kashtiban, R. J.; Krisnandi, Y. K.; Degirmenci, V.; Walton, R. I. Replacement of Chromium by Non-Toxic Metals in Lewis-Acid MOFs: Assessment of Stability as Glucose Conversion Catalysts. Catalysts 2019, 9, 437 10.3390/catal9050437
Bartlett, L.; Vesilind, P. A. Chemistry and Controversy: The Regulation of Environmental Chromium. Environ. Eng. Policy 1998, 1, 81-86, 10.1007/s100220050008
Férey, G.; Serre, C.; Mellot-Draznieks, C.; Millange, F.; Surblé, S.; Dutour, J.; Margiolaki, I. A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction. Angew. Chem., Int. Ed. 2004, 43, 6296-6301, 10.1002/anie.200460592
Horcajada, P.; Surble, S.; Serre, C.; Hong, D.; Seo, Y.; Chang, J.; Grene, J. et al. Synthesis and Catalytic Properties of MIL-100 (Fe), an Iron (III) Carboxylate with Large Pores. Chem. Commun. 2007, 100, 2820-2822, 10.1039/b704325b
Morcombe, C. R.; Zilm, K. W. Chemical Shift Referencing in MAS Solid State NMR. J. Magn. Reson. 2003, 162, 479-486, 10.1016/S1090-7807(03)00082-X
Bertani, P.; Raya, J.; Bechinger, B. 15N Chemical Shift Referencing in Solid State NMR. Solid State Nucl. Magn. Reson. 2014, 61-62, 15-18, 10.1016/j.ssnmr.2014.03.003
Steenhaut, T.; Hermans, S.; Filinchuk, Y. Green Synthesis of a Large Series of Bimetallic MIL-100(Fe,M) MOFs. New J. Chem. 2020, 44, 3847-3855, 10.1039/d0nj00257g
Kim, D.; Ma, D.; Kim, M.; Jung, Y.; Kim, N. H.; Lee, C.; Cho, S. W.; Park, S.; Huh, Y.; Jung, J.; Ahn, K. H. Fluorescent Labeling of Protein Using Blue-Emitting 8-Amino-BODIPY Derivatives. J. Fluoresc. 2017, 27, 2231-2238, 10.1007/s10895-017-2164-5
Zhang, H.; Wen, J.; Fang, Y.; Zhang, S.; Zeng, G. Influence of Fulvic Acid on Pb(II)Removal from Water Using a Post-Synthetically Modified MIL-100(Fe). J. Colloid Interface Sci. 2019, 551, 155-163, 10.1016/j.jcis.2019.05.016
Mutyala, S.; Yakout, S. M.; Ibrahim, S. S.; Jonnalagadda, M.; Mitta, H. Enhancement of CO2 Capture and Separation of CO2/N2 Using Post-Synthetic Modified MIL-100(Fe). New J. Chem. 2019, 43, 9725-9731, 10.1039/c9nj02258a
Seoane, B.; Dikhtiarenko, A.; Mayoral, A.; Tellez, C.; Coronas, J.; Kapteijn, F.; Gascon, J. Metal Organic Framework Synthesis in the Presence of Surfactants: Towards Hierarchical MOFs?. CrystEngComm 2015, 17, 1693-1700, 10.1039/c4ce02324b
Qiu, M.; Guan, Q.; Li, W. Controllable Assembly of Al-MIL-100 via an Inducing Occupied Effect and Its Selective Adsorption Activity. Cryst. Growth Des. 2016, 16, 3639-3646, 10.1021/acs.cgd.6b00103
Yang, J.; Wang, J.; Deng, S.; Li, J. Improved Synthesis of Trigone Trimer Cluster Metal Organic Framework MIL-100Al by a Later Entry of Methyl Groups. Chem. Commun. 2016, 52, 725-728, 10.1039/c5cc08450d
Benzaqui, M.; Pillai, R. S.; Sabetghadam, A.; Benoit, V.; Normand, P.; Marrot, J.; Menguy, N.; Montero, D.; Shepard, W.; Tissot, A.; Martineau-Corcos, C.; Sicard, C.; Mihaylov, M.; Carn, F.; Beurroies, I.; Llewellyn, P. L.; De Weireld, G.; Hadjiivanov, K.; Gascon, J.; Kapteijn, F.; Maurin, G.; Steunou, N.; Serre, C. Revisiting the Aluminum Trimesate-Based MOF (MIL-96): From Structure Determination to the Processing of Mixed Matrix Membranes for CO2 Capture. Chem. Mater. 2017, 29, 10326-10338, 10.1021/acs.chemmater.7b03203
Loiseau, T.; Volkringer, C.; Haouas, M.; Taulelle, F.; Férey, G. Crystal Chemistry of Aluminium Carboxylates: From Molecular Species towards Porous Infinite Three-Dimensional Networks. C. R. Chim. 2015, 18, 1350-1369, 10.1016/j.crci.2015.08.006
Haouas, M.; Volkringer, C.; Loiseau, T.; Férey, G.; Taulelle, F. Monitoring the Activation Process of the Giant Pore MIL-100(Al) by Solid State NMR. J. Phys. Chem. C 2011, 115, 17934-17944, 10.1021/jp206513v
Thommes, M.; Kaneko, K.; Neimark, A. V.; Olivier, J. P.; Rodriguez-Reinoso, F.; Rouquerol, J.; Sing, K. S. W. Physisorption of Gases, with Special Reference to the Evaluation of Surface Area and Pore Size Distribution (IUPAC Technical Report). Pure Appl. Chem. 2015, 87, 1051-1069, 10.1515/pac-2014-1117
Koo, J.; Hwang, I. C.; Yu, X.; Saha, S.; Kim, Y.; Kim, K. Hollowing out MOFs: Hierarchical Micro-and Mesoporous MOFs with Tailorable Porosity via Selective Acid Etching. Chem. Sci. 2017, 8, 6799-6803, 10.1039/c7sc02886e
Jaźwiński, J.; Kamieński, B.; Sadlej, A. Polymeric Adducts of Rhodium(II) Tetraacetate with Aliphatic Diamines: Natural Abundance 13C and 15N CPMAS NMR Investigations. Magn. Reson. Chem. 2013, 51, 788-794, 10.1002/mrc.4017
Martineau, C.; Taulelle, F.; Haouas, M. The Use of 27Al NMR to Study Aluminum Compounds: A Survey of the Last 25 Years. In The Chemistry of Organoaluminum Compounds (PATAI'S Chemistry of Functional Groups); Micouin, L.; Marek, I.; Rappoport, Z., Eds.; John Wiley & Sons, Ltd.: Chichester, 2016; pp 1-51.
Smith, M. E. Application Of27Al NMR Techniques to Structure Determination in Solids. Appl. Magn. Reson. 1993, 4, 1-64, 10.1007/BF03162555
Kim, D.; Yamamoto, K.; Ahn, K. H. A BODIPY-Based Reactive Probe for Ratiometric Fluorescence Sensing of Mercury Ions. Tetrahedron 2012, 68, 5279-5282, 10.1016/j.tet.2012.01.091
Marfin, Y. S.; Usoltsev, S. D.; Rumyantsev, E. V. Decomposition Mechanisms of BODIPY Dyes. In BODIPY Dyes-A Privilege Molecular Scaffold with Tunable Properties; IntechOpen, 2019.
Soto-Cantu, E.; Cueto, R.; Koch, J.; Russo, P. S. Synthesis and Rapid Characterization of Amine-Functionalized Silica. Langmuir 2012, 28, 5562-5569, 10.1021/la204981b
Volkringer, C.; Leclerc, H.; Lavalley, J. C.; Loiseau, T.; Férey, G.; Daturi, M.; Vimont, A. Infrared Spectroscopy Investigation of the Acid Sites in the Metal-Organic Framework Aluminum Trimesate MIL-100(Al). J. Phys. Chem. C 2012, 116, 5710-5719, 10.1021/jp210671t
Lyle, S. J.; Flaig, R. W.; Cordova, K. E.; Yaghi, O. M. Facilitating Laboratory Research Experience Using Reticular Chemistry. J. Chem. Educ. 2018, 95, 1512-1519, 10.1021/acs.jchemed.8b00265
Cai, J.; Mao, X.; Song, W. G. Adsorption Behavior and Structure Transformation of Mesoporous Metal-Organic Frameworks towards Arsenates and Organic Pollutants in Aqueous Solution. Mater. Chem. Front. 2018, 2, 1389-1396, 10.1039/c8qm00002f
Hamon, L.; Heymans, N.; Llewellyn, P. L.; Guillerm, V.; Ghoufi, A.; Vaesen, S.; Maurin, G.; Serre, C.; De Weireld, G.; Pirngruber, G. D. Separation of CO 2-CH 4 Mixtures in the Mesoporous MIL-100(Cr) MOF: Experimental and Modelling Approaches. Dalton Trans. 2012, 41, 4052-4059, 10.1039/c2dt12102f
Billemont, P.; Heymans, N.; Normand, P.; De Weireld, G. IAST Predictions vs Co-Adsorption Measurements for CO2 Capture and Separation on MIL-100 (Fe). Adsorption 2017, 23, 225-237, 10.1007/s10450-016-9825-6
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. Chem. Rev. 2018, 118, 10033-10048, 10.1021/acs.chemrev.7b00695
