Abstract
Nanoscale metal-organic frameworks (NMOFs) have attracted increased attention in recent years for miniaturized and/or biological applications. However, the synthesis of ultrasmall NMOFs with good stability is a great challenge. In this study, sub-5-nm nano-HKUST-1 was prepared for the first time via a mild metal-organic gel route without surfactants or capping agents. Controlling the gelation process via anion–ligand self-assembly is the key to the formation of NMOFs. The Tyndall effect, zeta potential, and liquid adsorption indicated strong stability of the obtained nano-HKUST-1, even in water. Adsorption experiments were performed using different dyes (crystal violet and methylene blue) to demonstrate the size-dependent adsorption thermodynamics and kinetics of this famous MOF. The results of this study provide new insights regarding the synthesis of NMOFs and their efficient applications.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Sung Cho, H.; Deng, H. X.; Miyasaka, K.; Dong, Z. Y.; Cho, M.; Neimark, A. V.; Ku Kang, J.; Yaghi, O. M.; Terasaki, O. Extra adsorption and adsorbate superlattice formation in metal-organic frameworks. Nature 2015, 527, 503–507.
Li, J. R.; Sculley, J.; Zhou, H. C. Metal-organic frameworks for separations. Chem. Rev. 2012, 112, 869–932.
Silva, P.; Vilela, S. M. F.; Tomé, J. P. C.; Almeida Paz, F. A. Multifunctional metal-organic frameworks: From academia to industrial applications. Chem. Soc. Rev. 2015, 44, 6774–6803.
Zhang, J. P.; Zhang, Y. B.; Lin, J. B.; Chen, X. M. Metal azolate frameworks: From crystal engineering to functional materials. Chem. Rev. 2012, 112, 1001–1033.
He, C. T.; Jiang, L.; Ye, Z. M.; Krishna, R.; Zhong, Z. S.; Liao, P. Q.; Xu, J. Q.; Ouyang, G. F.; Zhang, J. P.; Chen, X. M. Exceptional hydrophobicity of a large-pore metal-organic zeolite. J. Am. Chem. Soc. 2015, 137, 7217–7223.
Hou, C.; Zhao, G. F.; Ji, Y. J.; Niu, Z. Q.; Wang, D. S.; Li, Y. D. Hydroformylation of alkenes over rhodium supported on the metal-organic framework ZIF-8. Nano Res. 2014, 7, 1364–1369.
Cadiau, A.; Adil, K.; Bhatt, P. M.; Belmabkhout, Y.; Eddaoudi, M. A metal-organic framework-based splitter for separating propylene from propane. Science 2016, 353, 137–140.
Mahato, P.; Monguzzi, A.; Yanai, N.; Yamada, T.; Kimizuka, N. Fast and long-range triplet exciton diffusion in metalorganic frameworks for photon upconversion at ultralow excitation power. Nat. Mater. 2015, 14, 924–930.
Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C. et al. Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging. Nat. Mater. 2010, 9, 172–178.
Zhang, X. J.; Ballem, M. A.; Hu, Z. J.; Bergman, P.; Uvdal, K. Nanoscale light-harvesting metal-organic frameworks. Angew. Chem., Int. Ed. 2011, 50, 5729–5733.
Zacher, D.; Schmid, R.; Wöll, C.; Fischer, R. A. Surface chemistry of metal–organic frameworks at the liquid–solid interface. Angew. Chem., Int. Ed. 2011, 50, 176–199.
Tsuruoka, T.; Furukawa, S.; Takashima, Y.; Yoshida, K.; Isoda, S.; Kitagawa, S. Nanoporous nanorods fabricated by coordination modulation and oriented attachment growth. Angew. Chem., Int. Ed. 2009, 48, 4739–4743.
Zhao, M. T.; Wang, Y. X.; Ma, Q. L.; Huang, Y.; Zhang, X.; Ping, J. F.; Zhang, Z. C.; Lu, Q. P.; Yu, Y. F.; Xu, H. et al. Ultrathin 2D metal–organic framework nanosheets. Adv. Mater. 2015, 27, 7372–7378.
Liu, C. C.; Zhang, B. X.; Zhang, J. L.; Peng, L.; Kang, X. C.; Han, B. X.; Wu, T. B.; Sang, X. X.; Ma, X. Gas promotes the crystallization of nano-sized metal-organic frameworks in ionic liquid. Chem. Commun. 2015, 51, 11445–11448.
Zhao, Y. J.; Zhang, J. L.; Han, B. X.; Song, J. L.; Li, J. S.; Wang, Q. Metal–organic framework nanospheres with wellordered mesopores synthesized in an ionic liquid/CO2/surfactant system. Angew. Chem., Int. Ed. 2011, 50, 636–639.
Li, L.; Xiang, S. L.; Cao, S. Q.; Zhang, J. Y.; Ouyang, G. F.; Chen, L. P.; Su, C. Y. A synthetic route to ultralight hierarchically micro/mesoporous Al(III)-carboxylate metalorganic aerogels. Nat. Commun. 2013, 4, 1774.
Liu, Y.-R.; He, L. S.; Zhang, J. Y.; Wang, X. B.; Su, C.-Y. Evolution of spherical assemblies to fibrous networked Pd(II) metallogels from a pyridine-based tripodal ligand and their catalytic property. Chem. Mater. 2009, 21, 557–563.
Xue, C. F.; Tu, B.; Zhao, D. Y. Facile fabrication of hierarchically porous carbonaceous monoliths with ordered mesostructure via an organic organic self-assembly. Nano Res. 2009, 2, 242–253.
Liu, N.; Yao, Y.; Cha, J. J.; McDowell, M. T.; Han, Y.; Cui, Y. Functionalization of silicon nanowire surfaces with metal-organic frameworks. Nano Res. 2012, 5, 109–116.
Lin, W. B.; Rieter, W. J.; Taylor, K. M. L. Modular synthesis of functional nanoscale coordination polymers. Angew. Chem., Int. Ed. 2009, 48, 650–658.
Zhao, X.; Bu, X. H.; Wu, T.; Zheng, S. T.; Wang, L.; Feng, P. Y. Selective anion exchange with nanogated isoreticular positive metal-organic frameworks. Nat. Commun. 2013, 4, 2344.
Li, L.; Liu, X. L.; Geng, H. Y.; Hu, B.; Song, G. W.; Xu, Z. S. A MOF/graphite oxide hybrid (MOF: HKUST-1) material for the adsorption of methylene blue from aqueous solution. J. Mater. Chem. A 2013, 1, 10292–10299.
Zhao, X. L.; Liu, S. L.; Tang, Z.; Niu, H. Y.; Cai, Y. Q.; Meng, W.; Wu, F. C.; Giesy, J. P. Synthesis of magnetic metal-organic framework (MOF) for efficient removal of organic dyes from water. Sci. Rep. 2015, 5, 11849.
Wei, Y. H.; Dong, H. Y.; Wei, C.; Zhang, W.; Yan, Y. L.; Zhao, Y. S. Wavelength-tunable microlasers based on the encapsulation of organic dye in metal–organic frameworks. Adv. Mater. 2016, 28, 7424–7429.
Chaudhari, A. K.; Han, I.; Tan, J. C. Multifunctional supramolecular hybrid materials constructed from hierarchical self-ordering of in situ generated metal-organic framework (MOF) Nanoparticles. Adv. Mater. 2015, 27, 4438–4446.
Xin, C. L.; Zhan, H. J.; Huang, X.; Li, H. G.; Zhao, N.; Xiao, F. K.; Wei, W.; Sun, Y. H. Effect of various alkaline agents on the size and morphology of nano-sized HKUST-1 for CO2 adsorption. RSC Adv. 2015, 5, 27901–27911.
Prestipino, C.; Regli, L.; Vitillo, J. G.; Bonino, F.; Damin, A.; Lamberti, C.; Zecchina, A.; Solari, P. L.; Kongshaug, K. O.; Bordiga, S. Local structure of framework Cu(II) in HKUST-1 metallorganic framework: Spectroscopic characterization upon activation and interaction with adsorbates. Chem. Mater. 2006, 18, 1337–1346.
Jeong, N. C.; Samanta, B.; Lee, C. Y.; Farha, O. K.; Hupp, J. T. Coordination-chemistry control of proton conductivity in the iconic metal-organic framework material HKUST-1. J. Am. Chem. Soc. 2012, 134, 51–54.
Iler, R. K. The Chemistry of Silica: Solubility, Polymerization, Colloid and Surface Properties and Biochemistry of Silica; John Wiley & Sons: New York, 1979.
Wei, S. C.; Pan, M.; Li, K.; Wang, S. J.; Zhang, J. Y.; Su, C. Y. A multistimuli-responsive photochromic metal-organic gel. Adv. Mater. 2014, 26, 2072–2077.
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.
Kim, Y. K.; Hyun, S. M.; Lee, J. H.; Kim, T. K.; Moon, D.; Moon, H. R. Crystal-size effects on carbon dioxide capture of a covalently alkylamine-tethered metal-organic framework constructed by a one-step self-assembly. Sci. Rep. 2016, 6, 19337.
Rodenas, T.; Luz, I.; Prieto, G.; Seoane, B.; Miro, H.; Corma, A.; Kapteijn, F.; Llabrés i Xamena, F. X.; Gascon, J. Metal-organic framework nanosheets in polymer composite materials for gas separation. Nat. Mater. 2015, 14, 48–55.
Campbell, M. G.; Liu, S. F.; Swager, T. M.; Dinca, M. Chemiresistive sensor arrays from conductive 2D metalorganic frameworks. J. Am. Chem. Soc. 2015, 137, 13780–13783.
Talin, A. A.; Centrone, A.; Ford, A. C.; Foster, M. E.; Stavila, V.; Haney, P.; Kinney, R. A.; Szalai, V.; El Gabaly, F.; Yoon, H. P. et al. Tunable electrical conductivity in metalorganic framework thin-film devices. Science 2014, 343, 66–69.
Yoon, M.; Srirambalaji, R.; Kim, K. Homochiral metal-organic frameworks for asymmetric heterogeneous catalysis. Chem. Rev. 2012, 112, 1196–1231.
Dhakshinamoorthy, A.; Asiri, A. M.; García, H. Metal–organic framework (MOF) compounds: Photocatalysts for redox reactions and solar fuel production. Angew. Chem., Int. Ed. 2016, 55, 5414–5445.
Mahdavinia, G. R.; Aghaie, H.; Sheykhloie, H.; Vardini, M. T.; Etemadi, H. Synthesis of CarAlg/MMt nanocomposite hydrogels and adsorption of cationic crystal violet. Carbohydr. Polym. 2013, 98, 358–365.
Zhu, Y.; Wang, Y. M.; Zhao, S. Y.; Liu, P.; Wei, C.; Wu, Y. L.; Xia, C. K.; Xie, J. M. Three N–H functionalized metal-organic frameworks with selective CO2 uptake, dye capture, and catalysis. Inorg. Chem. 2014, 53, 7692–7699.
Mahdavinia, G. R.; Hasanpour, J.; Rahmani, Z.; Karami, S.; Etemadi, H. Nanocomposite hydrogel from grafting of acrylamide onto HPMC using sodium montmorillonite nanoclay and removal of crystal violet dye. Cellulose 2013, 20, 2591–2604.
Sun, J. W.; Yan, P. F.; An, G. H.; Sha, J. Q.; Li, G. M.; Yang, G. Y. Immobilization of polyoxometalate in the metalorganic framework rht-MOF-1: Towards a highly effective heterogeneous catalyst and dye scavenger. Sci. Rep. 2016, 6, 25595.
Yang, Q. Y.; Vaesen, S.; Ragon, F.; Wiersum, A. D.; Wu, D.; Lago, A.; Devic, T.; Martineau, C.; Taulelle, F.; Llewellyn, P. L. et al. A water stable metal–organic framework with optimal features for CO2 capture. Angew. Chem., Int. Ed. 2013, 52, 10316–10320.
Howarth, A. J.; Liu, Y. Y.; Li, P.; Li, Z. Y.; Wang, T. C.; Hupp, J. T.; Farha, O. K. Chemical, thermal and mechanical stabilities of metal–organic frameworks. Nat. Rew. Mater. 2016, 1, 15018.
Zhang, J.-P.; Chen, X.-M. Exceptional framework flexibility and sorption behavior of a multifunctional porous cuprous triazolate framework. J. Am. Chem. Soc. 2008, 130, 6010–6017.
Salles, F.; Bourrelly, S.; Jobic, H.; Devic, T.; Guillerm, V.; Llewellyn, P.; Serre, C.; Ferey, G.; Maurin, G. Molecular insight into the adsorption and diffusion of water in the versatile hydrophilic/hydrophobic flexible MIL-53(Cr) MOF. J. Phys. Chem. C 2011, 115, 10764–10776.
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 21571193), Open Funds of the state key Laboratory of Rare Earth Resource Utilization (No. RERU2013012), Science Foundation of Guangdong Province (No. 2015A030312007) and National Postdoctoral Program for Innovative Talents (No. BX201600195).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Qi, Y., He, CT., Lin, J. et al. Mild metal-organic-gel route for synthesis of stable sub-5-nm metal-organic framework nanocrystals. Nano Res. 10, 3621–3628 (2017). https://doi.org/10.1007/s12274-017-1539-x
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12274-017-1539-x