0010] This application claims the benefit of 62/373,047 filed August 10, 2016, Ignacio Luz, Atty. Dkt. No. 474774US which is hereby incorporated by reference in its entirety.

1. FIELD

[0011] The present disclosure relates to a general method for the solid-state crystallization of metal organic frameworks (MOFs) within the pore spaces of mesoporous materials (MPMs) in the absence of solvent. Additionally, the present disclosure relates to hybrid metal organic framework (MOF) and mesoporous material (MPM) hybrid materials (MOF/MPM) generated therefrom.

2. BACKGROUND

2.1. Introduction

[0012] The "background" description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present disclosure.

[0013] During the last decade, rational design of very sophisticated hybrid materials based on metal organic frameworks (MOFs) as functional species blended with different supports (such as metals, metal oxides, carbon, and polymers) has emerged as a general strategy for integrating their most interesting properties (such as elevated surface areas, well-defined active sites, highly-designed functionality, etc.) while enhancing their weaknesses as single components (such as handling, mechanical/thermal/chemical resistance, conductivity, etc.) and further adding extra synergistic properties which arise from the intimate interactions and complex hierarchical architectures of the resulting composites (such as micro/meso-porosity, multi-functionality, etc.). Thus, hybrid materials in which MOFs are embedded into one continuous matrix have been applied to several applications such as gas adsorption/separation, drug delivery, proton conductivity, sensors, optoelectronics, and heterogeneous catalysis.

[0014] Metal organic frameworks (MOFs) have been widely supported on different surface by the blending method or the solvothermal "in situ" growth method. The blending method consists of the impregnation of pre- synthesized nano-crystalline MOFs on different surfaces while the "in situ" technique requires a pre-modification of the surface of the support by functional groups (i.e. grafting) or the use of tedious techniques (such as atomic layer deposition of metal oxides or layer by layer crystallization) which are difficult to scale up. Nevertheless, these complex techniques are restricted to a few MOF/MPM examples such as MOF-5/Si02, (Mg)MOF-74/SBA-15, SIM-1/γ-Α1203, (Cu)HKUST-l/Si02 and (Cu)HKUST-l/y-Al203 and the growth or the deposition of these MOFs have been done mainly on the external surface (i.e. in a non-porous manner or not inside the pores of the supports) of the supports. Despite these efforts, a universal, efficient, environmental friendly and inexpensive method for loading MOFs on mesoporous materials is highly of interest to meet the industrial demands and the diverse applications of these hybrid materials.

[0015] The following references are incorporated herein by reference in their entirety:

[0016] Doherty, C. M.; Buso, D.; Hill, A. J.; Furukawa, S.; Kitagawa, S.; Falcaro, P.: Using Functional Nano- and Microparticles for the Preparation of Metal-Organic Framework Composites with Novel Properties. Accounts of Chemical Research 2014, 47, 396-405.

[0017] Zhan, G.; Zeng, H. C: Integrated nanocatalysts with mesoporous silica/silicate and microporous MOF materials. Coordination Chemistry Reviews 2016, 320-321, 181-192.

[0018] Zhou, H.-C; Long, J. R.; Yaghi, O. M.: Introduction to Metal-Organic Frameworks. Chemical Reviews 2012, 112, 673-674.

[0019] Li, Z.; Zeng, H. C: Armored MOFs: Enforcing Soft Microporous MOF Nanocrystals with Hard Mesoporous Silica. Journal of the American Chemical Society 2014, 136, 5631-5639.

[0020] Wu, C M.; Rathi, M.; Ahrenkiel, S. P.; Koodali, R. T.; Wang, Z. Q.: Facile synthesis of MOF-5 confined in SBA-15 hybrid material with enhanced hydro stability. Chemical Communications 2013, 49, 1223-1225.

[0021] Yang, L. J.; Tang, B. B.; Wu, P. Y.: Metal-organic framework-graphene oxide composites: a facile method to highly improve the proton conductivity of PEMs operated under low humidity. Journal of Materials Chemistry A 2015, 3, 15838-15842.

[0022] Li, S. Z.; Huo, F. W.: Metal-organic framework composites: from fundamentals to applications. Nanoscale 2015, 7, 7482-7501.

[0023] Furukawa, H.; Cordova, K. E.; O'Keeffe, M.; Yaghi, O. M.: The Chemistry and Applications of Metal- Organic Frameworks. Science 2013, 341, 974-+.

[0024] Silva, P.; Vilela, S. M. F.; Tome, J. P. C; Paz, F. A. A.: Multifunctional metal-organic frameworks: from academia to industrial applications. Chemical Society Reviews 2015, 44, 6774-6803.

[0025] Li, J. R.; Ma, Y. G.; McCarthy, M. C; Sculley, J.; Yu, J. M.; Jeong, H. K.; Balbuena, P. B.; Zhou, H. C: Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks. Coordination Chemistry Reviews 2011, 255, 1791-1823.

[0026] 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. Chemical Reviews 2012, 112, 724-781.

[0027] Li, J. R.; Sculley, J.; Zhou, H. C: Metal-Organic Frameworks for Separations. Chemical Reviews 2012, 112, 869-932.

[0028] Delia Rocca, J.; Liu, D.; Lin, W.: Nanoscale Metal-Organic Frameworks for Biomedical Imaging and Drug Delivery. Accounts of Chemical Research 2011, 44, 957-968.

[0029] Goesten, M. G.; Juan-Alcaniz, J.; Ramos-Fernandez, E. V.; Gupta, K. B. S. S.; Stavitski, E.; van Bekkum, H.; Gascon, J.; Kapteijn, F.: Sulfation of metal-organic frameworks: Opportunities for acid catalysis and proton conductivity. Journal of Catalysis 2011, 281, 177-187.

[0030] Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T.: Metal-Organic Framework Materials as Chemical Sensors. Chemical Reviews 2012, 112, 1105-1125.

[0031] Stavila, V.; Talin, A. A.; Allendorf, M. D.: MOF-based electronic and opto-electronic devices. Chemical Society Reviews 2014, 43, 5994-6010.

[0032] Corma, A.; Garcia, H.; Llabres i Xamena, F. X. L. I.: Engineering Metal Organic Frameworks for Heterogeneous Catalysis. Chemical Reviews 2010, 110, 4606-4655.

[0033] F. X. Llabres i Xamena, J. G.: Metal Organic Frameworks as Heterogeneous Catalysts; The Royal Society of Chemistry (Cambrigde) 2014.

[0034] Stock, N.; Biswas, S.: Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites. Chemical Reviews 2012, 112, 933-969.

[0035] Buso, D.; Nairn, K. M.; Gimona, M.; Hill, A. J.; Falcaro, P.: Fast Synthesis of MOF-5 Microcrystals Using Sol-Gel Si02 Nanoparticles. Chemistry of Materials 2011, 23, 929-934.

[0036] Chakraborty, A.; Maji, T. K.: Mg-MOF-74@SBA-15 hybrids: Synthesis, characterization, and adsorption properties. Apl Materials 2014, 2.

[0037] Aguado, S.; Canivet, J.; Farrusseng, D.: Engineering structured MOF at nano and macroscales for catalysis and separation. Journal of Materials Chemistry 2011, 21, 7582-7588.

[0038] Yan, X. L.; Hu, X. Y.; Komarneni, S.: Facile synthesis of mesoporous MOF/silica composites. Rsc Advances 2014, 4, 57501-57504.

[0039] Ulker, Z.; Erucar, I.; Keskin, S.; Erkey, C: Novel nanostructured composites of silica aerogels with a metal organic framework. Microporous and Mesoporous Materials 2013, 170, 352-358.

[0040] Qin, L.; Zhou, Y.; Li, D.; Zhang, L.; Zhao, Z.; Zuhra, Z.; Mu, C: Highly Dispersed HKUST-1 on Milimeter- Sized Mesoporous γ-Α1203 Beads for Highly Effective Adsorptive Desulfurization. Industrial & Engineering Chemistry Research 2016, 55, 7249-7258.

[0041] Sanchez-Sanchez, M.; Getachew, N.; Diaz, K.; Diaz-Garcia, M.; Chebude, Y.; Diaz, I.: Synthesis of metal-organic frameworks in water at room temperature: salts as linker sources. Green Chemistry 2015, 17, 1500-1509.

[0042] Klimakow, M.; Klobes, P.; Thunemann, A. F.; Rademann, K.; Emmerling, F.: Mechanochemical Synthesis of Metal-Organic Frameworks: A Fast and Facile Approach toward Quantitative Yields and High Specific Surface Areas. Chemistry of Materials 2010, 22, 5216-5221.

[0043] Tranchemontagne, D. J.; Hunt, J. R.; Yaghi, O. M.: Room temperature synthesis of metal-organic frameworks: MOF-5, MOF-74, MOF-177, MOF-199, and IRMOF-0. Tetrahedron 2008, 64, 8553-8557.

[0044] Chen, Y.; Yang, C. Y.; Wang, X. Q.; Yang, J. F.; Ouyang, K.; Li, J. P.: Kinetically controlled ammonia vapor diffusion synthesis of a Zn(II) MOF and its H20/NH3 adsorption properties. Journal of Materials Chemistry A 2016, 4, 10345-10351.

[0045] Luz, I.; Loiudice, A.; Sun, D. T.; Queen, W. L.; Buonsanti, R.: Understanding the Formation Mechanism of Metal Nanocrystal® MOF-74 Hybrids. Chemistry of Materials 2016, 28, 3839-3849

3. SUMMARY OF THE DISCLOSURE

[0046] According to a first aspect, the present disclosure relates to a method, comprising i) contacting an aqueous solution of an organic ligand salt of the formula AX(L~X) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula AX(L~X)/MPM where A is a counter ion, x is a whole number, and L is an organic ligand, ii) treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula HX(L~X)/MPM where H is hydrogen, iii) contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Hx(L~x)]/MPM where M is a metal, y is a whole number, and B is an anion; and iv) at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL"x)/MPM, wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

[0047] According to a second aspect, the present disclosure relates to a hybrid material comprising i) a mesoporous material comprising mesopores and ii) a nano-crystalline metal organic framework comprising micropores, wherein the nano-crystalline metal organic framework is homogeneously dispersed and substantially present within the mesopores or void spaces of the mesoporous material, and wherein the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material.

[0048] The foregoing paragraphs have been provided by way of general introduction, and are not intended to limit the scope of the following claims. The described embodiments, together with further advantages, will be best understood by reference to the following detailed description taken in conjunction with the accompanying drawings. It is to be understood, that both the foregoing general description and the following detailed description are exemplary, but are not restrictive.

4. BRIEF DESCRIPTION OF THE FIGURES

[0049] A more complete appreciation of the disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the

following detailed description when considered in connection with the accompanying drawings, wherein:

[0050] Table 1 is an example of the versatility and scope of the solid-state crystallization of MOFs within Silica(A) (HyperMOF-X).

[0051] Table 2 is an example of the versatility and scope of the solid-state crystallization of MOFs within different mesoporous supports.

[0052] Fig. 1 is an exemplary schematic representation of the general 'solid-state' crystallization of metal organic frameworks (MOFs) on mesoporous materials (MPMs) via multistep impregnation/evacuation to form hybrid materials (MOF/MPM), AX(L"X) is the salt of the MOF ligand and M+y(B)y is the metal precursor.

[0053] Fig. 2 is the Fourier transform infrared (FT-IR) spectra of two hybrid materials HyperMOF with different MOF loadings (20% and 40%), bulk MOF, the MOF ligand on Si02 and both MOF precursors on Si02 as salt.

[0054] Fig. 3 is the X-ray diffraction (XRD) spectra of the hybrid material HyperMOF with a

MOF loading of 20% (dotted lower line) and bulk MOF (solid upper line).

[0055] Fig. 4A is a Z-polarized confocal microscope image of bare Si02.

[0056] Fig. 4B is a Z-polarized confocal microscope image of the 20% HyperMOF hybrid material.

[0057] Fig. 4C is a Z-polarized confocal microscope image of the 40% HyperMOF hybrid material.

[0058] Fig. 5A is a scanning electron microscopy (SEM) image of the 20% HyperMOF hybrid material at 100 μιη scale.

[0059] Fig. 5B is a SEM image of the 20% HyperMOF hybrid material at 1 μιη scale.

[0060] Fig. 5C is a SEM image of the 20% HyperMOF hybrid material at 1 μιη scale after grinding the particles.

[0061] Fig. 6A is a transmission electron microscopy (TEM) image of bare Si02.

[0062] Fig. 6B is a TEM image of the 20% HyperMOF hybrid material.

[0063] Fig. 6C is a histogram showing the MOF particle distribution.

[0064] Fig. 7 is the energy-dispersive X-ray spectroscopy (EDS) spectrum of the 20% HyperMOF hybrid material.

[0065] Fig. 8 are the type IV N2 isotherms of two hybrid materials HyperMOF with different MOF loadings (20% and 40%), bulk MOF, and bare Si02.

[0066] Fig. 9 is the Barrett- Joyner-Halenda (BJH) adsorption dV/dD pore volume plots of two hybrid materials HyperMOF with different MOF loadings (20% and 40%) and bare Si02.

[0067] Fig. 10 is the thermogravimetric analysis (TGA) plots of two hybrid materials HyperMOF with different MOF loadings (20% and 40%) and bare Si02.

[0068] Fig. 11 is a plot depicting initial particle size distribution and final particle size distribution for the 20% HyperMOF hybrid material by the Jet Cup attrition index.

[0069] Fig. 12A is a Z-polarized confocal microscope image of a hybrid material obtained by a conventional solvothermal approach.

[0070] Fig. 12B is a SEM image of a hybrid material obtained by a conventional solvothermal approach.

[0071] Fig. 13 is example of the excellent C02 adsorption capacity during 250 cycles and stability of a fluidized HyperMOF containing polyamine in a packed-bed reactor under realistic flue gas conditions (C02=15 vol%, 02 = 4.5 vol%, and H20 = 5.6 vol% in balance with N2 at 50 °C for the adsorption step, and H20 = 5.6 vol% in balance with N2 at 120 °C for regeneration step).

[0072] Fig. 14 is an example of superior catalytic activity of HyperMOFs for esterification of alcohols showing the turnover frequency (TOF) for HyperMOF catalysts containing varying loading of MOF nanocrystals within a mesoporous silica compared to bulk MOF (100 wt.%).

[0073] Fig.15 is the Fourier Transform Infrared (FTIR) spectra of the hybrid material HyperMOF (Mg2(dobpdc)) (upper line) and bulk MOF (lower line) prepared by alternative method C (Fig. 16C).

[0074] Fig. 16A is a scheme describing alternative method A for the solid-state crystallization and preparation of MOF/MPMs.

[0075] Fig. 16B is a scheme describing alternative method B for the solid-state crystallization and preparation of MOF/MPMs.

[0076] Fig. 16C is a scheme describing alternative method C for the solid-state crystallization and preparation of MOF/MPMs.

[0077] Fig. 17 is a scheme describing one embodiment of the solid-state crystallization approach. First step, ligand salt impregnation (a). Second step, gas phase acidification (b). Third step, metal salt impregnation (c). Final step, application of synthesis conditions and crystallization of MOF nanocrystals (d).

5. DETAILED DESCRIPTION OF THE DISCLOSURE

[0078] Referring now to the drawings, embodiments of the present disclosure will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all of the embodiments of the disclosure are shown.

[0079] In one embodiment of the present disclosure, several hybrid materials have been prepared by a novel approach which consists of the 'in situ' crystallization of metal organic frameworks (MOFs) within mesoporous materials via self-assembly of pre-impregnated MOF precursors (metal and organic ligand) on the cavities of MPMs under the absence of solvent. This novel and inexpensive approach is provided for efficient, scalable and environmentally friendly synthesis of hybrid compounds based on nano-crystalline metal organic frameworks (MOFs) embedded within mesoporous materials (MPMs). These hybrid materials can be highly designed to exhibit elevated MOF loading (up to 35-40%), excellent MOF dispersion and homogeneity, tunable hierarchical micro (MOF; ranging from 0.5-5.0 nm) and meso (MPM; ranging from 2-50 nm) pore size distribution, elevated surface areas (up to 900-1200 m2/g), nano-metric MOF particles (below 30 nm), enhanced attrition resistance, good fluidizability as well as handling (100-500 μπι).

[0080] Herein, the present disclosure describes the first promising discovery of a 'solid phase' crystallization technique which allows homogeneous growth of different MOF structures with a series of commercially available mesoporous materials regardless of their nature (silica, alumina, zeolite, carbon, polymer, etc.), pore architecture (size, pore distribution, etc.) or surface functionality (acidic, basic, etc.). The absence of solvent during the crystallization restricts the crystal growth, size, and mobility to just the void space (inside the pores) where the precursors were previously confined, thus overcoming the limitations found when typical solvothermal methods are applied, even when using grafted functional groups (i.e. carboxylic or amine). In particular, typical solvothermal methods are limited by formation of extra MOF crystallites out of the pore system which can be washed out or remain as aggregates on the outer surface, and therefore reduce the yield of the synthesis and the resulting MOF loading on the MPMs. Thus,

more mechanically stable, well-defined, highly designed and multifunctional materials can be provided by the general approach described in the present disclosure in order to meet the emergence of novel hybrid MOF/MPM applications.

[0081] Furthermore, the use of the novel approach of the present disclosure provides high and homogeneous loading of MOF nanocrystals within MPMs achieved via a "multistep" impregnation of saturated aqueous solutions containing the MOF precursors: metal salt, and in the present disclosure ligand salt, instead of the acid form. The acid form of the organic ligands is widely used for MOF synthesis, but it exhibits very low solubility in either water or even organic solvents (i.e. terephthalic or trimesic acid), which prevents the high loading of MOF precursors required for the 'in-situ' growth of MOFs within the pores of the MPMs in the 'solid-state' crystallization described herein. An acidification step between the initial impregnation of the ligand salt solution and the metal salt solution within the MPM cavities is performed to prevent the formation of non-porous coordination polymers due to the fast polymerization rates upon addition of the metal salts in solution even at room temperature. Although the preparation of freestanding (or bulk) MOFs under dry conditions has been demonstrated, the present disclosure provide the first 'solid phase' or 'dry' crystallization of MOFs on MPMs using water soluble ligand salts.

[0082] According to a first aspect, the present disclosure relates to a method, comprising i) contacting an aqueous solution of an organic ligand salt of the formula AX(L~X) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula AX(L~X)/MPM, ii) treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula HX(L~X)/MPM, iii) contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y] [Hx(L"x)]/MPM, and iv) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent to form a hybrid material of the formula (M+yL"x)/MPM, wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

[0083] In a first step, an aqueous solution of an organic ligand salt of the formula AX(L~X) is contacted with a mesoporous material (MPM) present at a concentration in the range of 10-300

mg/niL, preferably 25-275 mg/niL, preferably 50-250 mg/niL to form an impregnated mesoporous salt material of the formula AX(L~X)/MPM. Exemplary salts include, but are not limited to, mineral or organic acid salts of basic groups such as amines, and alkali or organic salts of acidic groups such as carboxylic acids. The salts include, but are not limited to, the conventional non-toxic salts or the quaternary ammonium salts of the parent compound formed, for example, from non-toxic inorganic or organic acids. Salts of carboxylic acid containing ligands may include cations such as lithium, sodium, potassium, magnesium, additional alkali metals, and the like. The salts include, but are not limited to, the conventional non-toxic salts or the quaternary ammonium salts of the parent compound formed, for example, from non-toxic inorganic or organic acids. In a preferred embodiment, the salts are alkali metal salts, most preferably sodium salts. In a preferred embodiment, the contacting is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a contacting time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2-12 hours, preferably 2.5-8 hours, preferably 3-6 hours. In some embodiments, the ligand (i.e. acid form; 2,6-dihydoxyterephthalic acid) may be dissolved and impregnated in water or organic solvents. Exemplary organic solvents include, but are not limited to, methanol, ethanol, tetrahydrofuran, Ν,Ν-dimethylformamide, acetonitrile, acetone, and the like.

[0084] In a second step, the impregnated mesoporous salt material present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL is treated with an aqueous acidic solution of 0.05-10.0 M in concentration, preferably 0.1-9.0 M, preferably 1.0-8.0M, preferably 2.0-6.0 M, or about 4.0 M to form an impregnated mesoporous acid material of the formula HX(L~X)/MPM. Strong acids including, but not limited to, HC1, H2SO4, and HNO3 are preferred, but organic acids and weak acids (i.e. acetic acid) may also be used in the treating, most preferably HC1. In a preferred embodiment, the treating is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a treating time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2-12 hours, preferably 2.5-8 hours, preferably 3-6 hours.

[0085] In a third step, the impregnated mesoporous acid material present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL is contacted with an aqueous solution of a metal precursor of the formula M+y(B)y to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Hx(L~x)]/MPM. In a

preferred embodiment, the contacting is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a contacting time of up to 48 hours, preferably 0.5-36 hours, preferably 1-24 hours, preferably 2-12 hours, preferably 2.5-8 hours, preferably 3-6 hours.

[0086] In a final step the impregnated mesoporous metal organic framework precursor present at a concentration in the range of 10-300 mg/mL, preferably 25-275 mg/mL, preferably 50-250 mg/mL is heated in the absence of a solvent or exposed to a volatile vapor (i.e. and amine such as methylamine or controlled moisture such as steam) in the absence of a solvent to form a hybrid material of the formula (M+yL"x)/MPM, or hereafter called MOF/MPM. In this step, the metal ions form coordinate bonds with the one or more organic ligands, preferably multidentate organic ligands to form a nano-crystalline metal organic framework in the pore spaces of the mesoporous material. In a preferred embodiment, the heating is performed at a temperature of up to 300 °C, preferably 40-250 °C, preferably 60-220 °C, preferably 100-200 °C, preferably 120-190 °C, and has a heating time of up to 60 hours, preferably 12-48 hours, preferably 24-36 hours. In a preferred embodiment, the exposing to a vapor is performed at a temperature of up to 80 °C, preferably 10-80 °C, preferably 15-60 °C, preferably 20-40 °C, preferably 22-30 °C, or about room temperature and has a heating time of up to 48 hours, preferably 6-36 hours, preferably 12-24 hours. In certain embodiments, a catalytic amount of a specific additive including (preferably 15 %), but not limited to, methanol, ethanol, tetrahydrofuran, Ν,Ν-dimethylformamide, and the like may be employed to assist the crystal formation within the hybrid material.

[0087] In certain embodiments, the nano-crystalline metal organic framework is present only within the mesopores or void spaces of the mesoporous material and homogeneously dispersed within the mesopores or void spaces of the mesoporous material. As used herein, "disposed on", "embedded" or "impregnated" describes being completely or partially filled throughout, saturated, permeated and/or infused. The nano-crystalline MOF may be affixed substantially within the pore space of the mesoporous material. The nano-crystalline MOF may be affixed to the mesoporous material in any reasonable manner, such as physisorption or chemisorption and mixtures thereof. In one embodiment, greater than 10% of the pore spaces of the mesoporous material is covered by the nano-crystalline MOF, preferably greater than 15%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%, preferably greater than 45%, preferably greater than 50%, preferably greater than 55%, preferably greater than 60%, preferably greater than 65%, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 96%, preferably greater than 97%, preferably greater than 98%, preferably greater than 99%. In certain embodiments, the nano-crystalline metal organic framework is substantially present only within the mesopores or void spaces of the mesoporous material and homogeneously dispersed within the mesopores or void spaces of the mesoporous material, preferably greater than 60% of the nano-crystalline MOF is located in the pore spaces and not at the surface of the mesoporous material, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 96%, preferably greater than 97%, preferably greater than 98%, preferably greater than 99%. As used herein, homogeneous dispersion refers to dispersion in a similar or the same manner and may refer to uniform structure and composition. In a preferred embodiment, the hybrid material is substantially free of MOF aggregates or an amorphous MOF phase and substantially comprises MOF particles as a nano-crystalline phase dispersed in a uniform manner throughout the pore spaces of the mesoporous material.

[0088] In certain embodiments, the method further comprises drying at least one selected from the group consisting of the impregnated mesoporous salt material, the impregnated mesoporous acid material, the impregnated mesoporous metal organic framework precursor, and the hybrid material at a temperature in the range of 25-160 °C, preferably 85-150 °C, preferably 90-140 °C, preferably 100-130 °C, or about 120 °C under a vacuum and with a drying time of up to 24 hours, preferably 0.5-18 hours, preferably 1-12 hours, preferably 1.5-6 hours, or about 2 hours.

[0089] In certain embodiments, the method further comprises washing the hybrid material with distilled water or other polar protic solvent, and extracting water from the hybrid material in a Soxhlet system recycling methanol or other polar protic solvent.

[0090] In a preferred embodiment, the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide (aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.), a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate, etc.). As used herein, a mesoporous material may refer to a material containing pores with diameters between 2-50 nm, porous materials are classified into several kinds by their pore size. In a preferred embodiment, the mesoporous material has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%

[0091] In a preferred embodiment, the organic ligand (L"x) of the organic ligand salt is at least one selected from the group consisting of polycarboxylate ligands, azaheterocyclic ligands, and derivatives thereof. As used herein, "ligand" refers to a mono-dentate or polydentate compound that bind a transition metal or a plurality of transition metals, respectively. Generally a linking moiety comprises a substructure covalently linked to an alkyl or cycloalkyl group, comprising 1 to 20 carbon atoms, an aryl group comprising 1 to 5 phenyl rings, or an alkyl or aryl amine comprising alkyl or cycloalkyl groups having from 1 to 20 carbon atoms or aryl groups comprising 1 to 5 phenyl rings, and in which a linking cluster (e.g., a multidentate function groups) are covalently bound to the substructure. A cycloalkyl or aryl substructure may comprise 1 to 5 rings that comprise either of all carbon or a mixture of carbon with nitrogen, oxygen, sulfur, boron, phosphorus, silicon and/or aluminum atoms making up the ring. Typically the linking moiety will comprise a substructure having one or more carboxylic acid linking clusters covalently attached.

[0092] In a preferred embodiment, the organic ligand (L"x) of the organic ligand salt is at least one selected from the group consisting of, terephthalate, benzene- 1, 3, 5-tricarboxylate, 2,5-dioxibenzene dicarboxylate, biphenyl-4,4'-dicarboxylate and derivatives thereof. In a preferred embodiment, the organic ligand (L"x) of the organic ligand salt is at least one selected from the group consisting of imidazolate, pyrimidine-azolate, triazolate, tetrazolate and derivatives thereof. Additional suitable exemplary ligands include, but are not limited to, bidentate carboxylics (i.e. oxalic acid, malonic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terepthalic acid), tridentate carboxylates (i.e. citric acid, trimesic acid), azoles (i.e. 1,2,3-triazole, pyrrodiazole), squaric acid and mixtures thereof.

[0093] In preferred embodiments, the metal (M+y) of the metal precursor is at least one transition metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga. As used herein, "metal ion" is selected from the group consisting of elements of groups la, Ila, Ilia, IVa to Villa and IB to VIb of the periodic table of the elements. In certain other embodiments, the metal precursor may comprise clusters of metal oxides.

[0094] In a preferred embodiment, the metal organic framework is at least one selected from the group consisting of MIL-101, MIL-100, MIL-53, MOF-74, UiO-66, UiO-67, ZIF-8, ZIFs,

HKUST-1, M2(dobpdc), NU-1000, PCN-222, PCN-224, and derivatives thereof. As used herein, a metal organic framework may refer to compounds consisting of metal ions or clusters coordinated to organic ligands to form one-, two- or three-dimensional structures, with the special feature of porosity. More formally, a metal organic framework is a coordination network with organic ligands containing potential voids. In a preferred embodiment, the nano-crystalline MOF has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%. MOFs are composed of two major components: a metal ion or cluster of metal ions and an organic molecule often termed a linker. The organic units are typically mono-, di-, tri-, or tetravalent ligands. The choice of metal and linker will dictate the structure and hence properties of the MOF. For example, the metal's coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal and in which orientation.

[0095] In a preferred embodiment, the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material, preferably 15-45%, preferably 25-40%, preferably 30-35%, or at least 20%, preferably at least 25%, preferably at least 30%, preferably at least 35%, preferably at least 40%, preferably at least 45%.

[0096] In a preferred embodiment, the hybrid material comprises mesopores with an average diameter in the range of 2-50 nm, preferably 4-45 nm, preferably 6-40 nm and micropores with an average diameter in the range of 0.5-5.0 nm, preferably 1.0-4.5 nm, preferably 2.0-4.0 nm. In a preferred embodiment, the mesopores, the micropores, or both are monodisperse having a coefficient of variation of less than 10%, preferably less than 8%, preferably less than 6%, preferably less than 5%, preferably less than 4%, preferably less than 3%. In a preferred embodiment, the hybrid material has a percent porosity of greater than 10%, preferably greater than 20%, preferably greater than 25%, preferably greater than 30%, preferably greater than 35%, preferably greater than 40%. In a preferred embodiment, the hybrid material has a reduced mesoporosity relative to the bare mesoporous material and an increased microporosity relative to the bare mesoporous material.

[0097] In a preferred embodiment, the nano-crystalline metal organic framework has an average longest linear dimension of less than 40 nm, preferably less than 35 nm, preferably less than 30 nm, preferably less than 25 nm.

[0098] In a preferred embodiment, the hybrid material has a surface area in the range of 200-1200 m2/g, preferably 300-1100 m2/g, preferably 400-1000 m2/g, preferably 500-950 m2/g, preferably 600-900 m2/g, preferably 700-850 m2/g, or at least 400 m2/g, preferably at least 600 m2/g, preferably at least 800 m2/g, preferably at least 1000 m2/g. In a preferred embodiment, the hybrid material has a surface area in the range of 105-500% that of the surface area of the impregnated mesoporous salt material, preferably 150-450%, preferably 175-400%, preferably 200-350%, preferably 225-350% that of the surface area of the impregnated mesoporous salt material. In a preferred embodiment, the hybrid material has a surface area in the range of 125-500% that of the surface area of the bare mesoporous material, preferably 150-450%, preferably 175-400%, preferably 200-350%, preferably 225-350% that of the surface area of the bare mesoporous material.

[0099] In a preferred embodiment, the hybrid material has an average longest linear dimension of 100-500 μιη, preferably 125-450 μιη, preferably 150-400 μιη, preferably 175-350 μιη, preferably 200-300 μιη.

[00100] In some embodiments, with the calculated average particle size and particle apparent density values, the fluidization regime of the hybrid material particles of the present disclosure can be determined using Geldart's powder classification chart. Geldart groups powders into four "Geldart Groups" or "Geldart Classes". The groups are defined by solid-fluid density difference and particle size. Design methods for fluidized beds can be tailored based upon a particle's Geldart Group. For Geldart Group A the particle size is between 20 and 100 μηι and the particle density is typically less than 1.4 g/cm3. For Geldart Group B the particle size lies between 40 and 500 μηι and the particle density is between 1.4-4 g/cm3. For Geldart Group C the group contains extremely fine and consequently the most cohesive particles with a particle size of 20 to 30 μηι. The hybrid material particles of the present disclosure are preferably fluidizable and may be classified as a Geldart Group A powder, a Geldart Group B powder, a Geldart Group C powder or a Geldart Group D powder, preferably as a Geldart Group B powder or a Geldart Group A powder, preferably a Geldart Group B powder. In at least one preferred embodiment, the hybrid material particles display a Geldart Group B powder property, which is highly fluidizable.

[00101] According to a second aspect, the present disclosure relates to a hybrid material comprising i) a mesoporous material comprising mesopores and ii) a nano-crystalline metal organic framework comprising micropores, wherein the nano-crystalline metal organic framework

is homogeneously dispersed and substantially present within the mesopores or void spaces of the mesoporous material, and wherein the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material.

[00102] According to a third aspect, the present disclosure relates to a gas adsorbent comprising the hybrid material. According to a fourth aspect, the present disclosure relates to a method of adsorbing, separating, storing or sequestering at least one gas, comprising contacting the gas adsorbent with the at least one gas and wherein the at least one gas is selected from the group consisting of hydrogen (H2), hydrogen sulfide (H2S), sulfur dioxide (S02), methane (CH4) and carbon dioxide (C02) [example of application 1]. According to a fifth aspect, the present disclosure relates to a catalyst comprising the hybrid material, preferably a heterogeneous catalyst that may be used in gas phase and liquid phase reactions. According to a sixth aspect, the present disclosure relates to a method of catalyzing a reaction, comprising reacting a substrate in the presence of the catalyst. Exemplary types of reactions include, but are not limited to, hydrogenation, methanol synthesis, oxidation, addition to carbonyls, epoxidation, transesterification, alcoholysis (methanolysis) of epoxides, cyanosilylation, C-C coupling, isomerization, cyclization, rearrangement, and the like [example of application 2] . According to a seventh aspect, the present disclosure relates to a reactor configuration comprising a hybrid material described above. Exemplary types of reactor method include, but are not limited to, packed-bed, fluidized-bed, batch-bed, and the like. According to an eighth aspect, the present disclosure relates to a device or material comprising a hybrid material described above wherein the device or material is at least one selected from the group consisting of a drug delivery carrier, biomedical imaging material, a proton conductive material, a sensor and an optoelectronic device. According to a ninth aspect, the present disclosure relates to a method for liquid/gas chromatography. Exemplary types of chromatographic method include, but are not limited to, high-performance liquid chromatography (HPLC), chiral chromatography, gas chromatography, and the like. According to a tenth aspect, the present disclosure relates to the use of a dispositive comprising a hybrid material described above for sensing, capture and catalytic degradation of harmful gases and vapors.

[00103]

[00104] In another aspect, there is provided a method, comprising i) contacting an aqueous solution of an organic ligand salt of the formula AX(L"X) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula AX(L"X)/MPM where A is a counter

ion, x is a whole number, and L is an organic ligand, ii) treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula HX(L"X)/MPM where H is hydrogen, iii) contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y] [Hx(L~ X)]/MPM where M is a metal, y is a whole number, and B is an anion; and iv) at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the presence of a catalytic amount of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the presence of a catalytic amount of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL~x)/MPM.

[00105] In this aspect, the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material, the nano-crystalline metal organic framework is homogeneously dispersed and substantially present only within the mesopores or void spaces of the mesoporous material; and the solvent is at least one selected from the group consisting of water, ethanol, methanol, tetrahydrofuran, and Ν,Ν-dimethylformamide and is present in a weight amount of less than 75% of the weight amount of the hybrid material formed.

[00106] The examples below are intended to further illustrate protocols for preparing and characterizing the metal organic framework and mesoporous material hybrid materials of the present disclosure. Further, they are intended to illustrate assessing the properties and applications of these metal organic framework and mesoporous material hybrid materials. They are not intended to limit the scope of the claims.

5.1. Definitions

[00107] While the following terms are believed to be well understood by one of ordinary skill in the art, the following definitions are set forth to facilitate explanation of the presently disclosed subject matter.

[00108] Throughout the present specification, the terms "about" and/or "approximately" may be used in conjunction with numerical values and/or ranges. The term "about" is understood to mean those values near to a recited value. For example, "about 40 [units]" may mean within + 25% of 40 (e.g., from 30 to 50), within + 20%, + 15%, + 10%, + 9%, + 8%, + 7%, + 6%, + 5%, +

4%, + 3%, + 2%, + 1%, less than + 1%, or any other value or range of values therein or there below. Furthermore, the phrases "less than about [a value]" or "greater than about [a value]" should be understood in view of the definition of the term "about" provided herein. The terms "about" and "approximately" may be used interchangeably.

[00109] Throughout the present specification, numerical ranges are provided for certain quantities. It is to be understood that these ranges comprise all subranges therein. Thus, the range "from 50 to 80" includes all possible ranges therein (e.g., 51-79, 52-78, 53-77, 54-76, 55-75, 60-70, etc.). Furthermore, all values within a given range may be an endpoint for the range encompassed thereby (e.g. , the range 50-80 includes the ranges with endpoints such as 55-80, 50-75, etc.).

[00110] As used herein, the verb "comprise" as is used in this description and in the claims and its conjugations are used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.

[00111] Throughout the specification the word "comprising," or variations such as "comprises" or "comprising," will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps. The present disclosure may suitably "comprise", "consist of, or "consist essentially of, the steps, elements, and/or reagents described in the claims.

[00112] It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as "solely", "only" and the like in connection with the recitation of claim elements, or the use of a "negative" limitation.

[00113] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Preferred methods, devices, and materials are described, although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure. All references cited herein are incorporated by reference in their entirety.

[00114] The following Examples further illustrate the disclosure and are not intended to limit the scope. In particular, it is to be understood that this disclosure is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.

6. EXAMPLES

6.1. Materials and Methods

[00115] Chemicals. All chemicals were used as received from Sigma-Aldrich without further purification. Cr(N0 ) -9H20, CrCl3-6H20, Α1(Ν0 ) ·9Η20, AlCl xH20, Co(N0 )2-6H20, Ni(N03)2-6H20, ZrOCl2- 8H20, RuCl3 xH20, Ζη(Ν03)3·9Η20, 1,4-benzenedicarboxylic acid (H2BDC), 1,3,5-benzenetricarboxylic acid (H BTC), 2-aminoterephthalic acid (H2BDC(NH2)), monosodium 2-sulfoterephthalate (H2BDC(S03Na)), 2,5-dihydroxyterephthalic acid (H4DOBDC), 2,2'-Bipyridine-5,5'-dicarboxylic acid (H2BpyDC), 2-methylimidazol (HMelM), tetrakis(4-carboxy-phenyl)-porphyrin (H4TCPP). l,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) was synthetized according to the published procedure. See Deria, P.; Bury, W.; Hupp, J. T.; Farha, O. K.: Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation. Chem. Commun. 2014, 50, 1965-1968. Triethylamine (TEA), N,N-dimethylformamide (DMF), tetrahydrofuran (THF) and methanol (MeOH) were of analytical grade (Sigma-Aldrich).

[00116] Mesoporous materials. Silica(A) [75-250 μιη], Silica(B) [200-500 μιη], Silica(C) [75-200 μιη] and Silica(D) [75-150 μm] were kindly supplied by our commercial partner. SBA-15 was prepared according to the published procedure. Zhao, D. Y.; Feng, J. L.; Huo, Q. S.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D.: Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 1998, 279, 548-552. MCM-41 was provided by Claytec, γ-Α1203 by Sasol, Ti02 by Sachtleben and Zr02 by Mel Chemicals. Mesoporous carbon and HayeSep A (Supelco) [100-120 μιη] were supplied by Sigma-Aldrich. All mesoporous materials were degassed at 120 °C overnight under vacuum to remove the adsorbed water.

[00117] Ligand salt precursors. Na2BDC and Na3BTC ligand salt precursors were prepared from their acid form in water with the stoichiometric amount of NaOH necessary to deprotonate the carboxylic acid of the organic linker followed by a purification step via precipitation in acetone. Alternatively, ligand salt precursor solutions for H2BDC(NH2), H2BpyDC, H4TCPP and H4TBAPy were directly prepared with the stoichiometric amount of TEA, thereby skipping the step of isolating the ligand salt. H2BDC(S03Na) and HMelM were directly dissolved in water.

H4DOBDC was dissolved in hot THF due to the insolubility in water of sodium 2,5-dioxyterephthalate coordination polymers and the use of triethylammonium salts did not give rise the targeted MOF-74 structure.

[00118] Bulk-type MOFs. For comparison purposes, the following MOFs were prepared and activated according to the reported literature: (Cr)MIL-lOl(Ferey, G.; Mellot-Draznieks, C; Serre, C; Millange, F.; Dutour, J.; Surble, S.; Margiolaki, I.: A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science 2005, 309, 2040-2042 and Serre, C; Millange, F.; Thouvenot, C; Nogues, M.; Marsolier, G.; Louer, D.; Ferey, G.: Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids: MIL-53 or CrIII(OH) {02C-C6H4-C02} {H02C-C6H4-C02H}x H20y. J. Am. Chem. Soc. 2002, 124, 13519-13526), (Cr)MIL-lOO (Long, P. P.; Wu, H. W.; Zhao, Q.; Wang, Y. X.; Dong, J. X.; Li, J. P.: Solvent effect on the synthesis of MIL-96(Cr) and MIL-lOO(Cr). Microporous Mesoporous Mater. 2011, 142, 489-493), (Cr)MIL-101(SO3H)( Juan-Alcaniz, J.; Gielisse, R.; Lago, A. B.; Ramos-Fernan-dez, E. V.; Serra-Crespo, P.; Devic, T.; Guillou, N.; Serre, C; Kapteijn, F.; Gascon, J.: Towards acid MOFs - catalytic performance of sulfonic acid functionalized architectures. Catal. Sci. Technol. 2013, 3, 2311-2318), (Al)MIL-lOO(Volkringer, C; Popov, D.; Loiseau, T.; Ferey, G.; Burghammer, M.; Riekel, C; Haouas, M.; Taulelle, F.: Synthesis, Single-Crystal X-ray Microdiffraction, and NMR Characterizations of the Giant Pore Metal-Organic Framework Aluminum Trimesate MIL- 100. Chem. Mater. 2009, 21, 5695-5697), (Al)MIL-53(NH2)(Couck, S.; Denayer, J. F. M.; Baron, G. V.; Remy, T.; Gas-con, J.; Kapteijn, F.: An Amine-Functionalized MIL-53 Metal-Organic Framework with Large Separation Power for C02 and CH4. . Am. Chem. Soc. 2009, 131, 6326-+), (Co, Ni)MOF-74 (Dietzel, P. D. C; Morita, Y.; Blom, R.; Fjellvag, H.: 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. Angew. Chem., Int. Ed. 2005, 44, 6354-6358 and Dietzel, P. D. C; Panella, B.; Hirscher, M.; Blom, R.; Fjell-vag, H.: Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated frame-work. Chem. Commun. 2006, 959-961), (Zr)UiO-66(H,NH2)( Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Ols-bye, U.; Tilset, M.; Larabi, C; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P.: Synthesis and Stability of Tagged UiO-66 Zr-MOFs. Chem. Ma-ter. 2010, 22, 6632-6640), (Zr)UiO-67(Bpy)(Fei, H.; Cohen, S. M.: A robust, catalytic metal-organic framework with open 2,2-bipyridine sites. Chem.

Commun. 2014, 50, 4810-4812), (Ru)HKUST-l(Kozachuk, O.; Luz, I.; Llabres i Xamena, F. X.; Noei, H.; Kauer, M.; Albada, H. B.; Bloch, E. D.; Marler, B.; Wang, Y.; Muhler, M.; Fischer, R. A.: Multifunctional, Defect-Engineered Metal-Organic Frameworks with Ruthenium Centers: Sorption and Catalytic Proper-ties. Angew. Chem., Int. Ed. 2014, 53, 7058-7062), (Zn)ZIF-8(Cravillon, J.; Miinzer, S.; Lohmeier, S.-J.; Feldhoff, A.; Hu-ber, K.; Wiebcke, M.: Rapid Room-Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework. Chem. Mater. 2009, 21, 1410-1412), (Zr)PCN-222(Dawei Feng; Zhi-Yuan Gu; Jian-Rong Li; Hai-Long Jiang; ZhangwenWei; Zhou, H.-C: Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts. Angew. Chem., Int. Ed. 2012, 51, 10307 -10310), (Zr)NU-1000 (Deria et al. 2014) and Co2(dobpdc)(McDonald et al. Cooperative insertion of C02 in diamine-appended metal-organic frameworks. Nature 2015, 519, 303-+). FTIR spectra of these MOFs was used as reference for MOF/MPM hybrid materials. N2 isotherms and pore distribution for (Cr)MIL-101(SO3H) were included in Figures.

CLAIMS

1. A method, comprising:

contacting an aqueous solution of an organic ligand salt of the formula AX(L~X) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula Ax(L"x)/MPM where A is a counter ion, each x is independently a whole number, and L is an organic ligand;

treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula HX(L~X)/MPM where H is hydrogen;

contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Hx(L~x)]/MPM where M is a metal, each y is independently a whole number, and B is an anion; and

at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL"x)-MPM;

wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

2. A method, comprising: contacting an aqueous solution of an organic ligand salt of the formula AX(L~X) with a mesoporous material (MPM) to form an impregnated mesoporous salt

material of the formula Ax(L-x)/MPM where A is a counter ion, each x is independently a whole number, and L is an organic ligand;

contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous salt material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Ax(L~x)]/MPM where M is a metal, each y is independently a whole number, and B is an anion; and at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL~x)-MPM; wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

3. A method, comprising: contacting an aqueous suspension of a metal oxide nanoparticles of the formula M+y(0)y with a mesoporous material (MPM) to form a metal oxide impregnated mesoporous material of the formula M+y(0)y /MPM where M is a metal and each y is independently a whole number;

contacting the metal oxide impregnated mesoporous material with (i) an aqueous solution of an organic ligand salt of the formula AX(L~X) to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(0)y][Ax(L~x)]/MPM or (ii) an organic solvent of solution of a ligand HX(L~X) to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(0)y][Hx(L~x)]/MPM, where L is a ligand, A is a counter ion and each x is independently a whole number; and

at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework

precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL"x)-MPM;

wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

4. The method of any of claims 1-3, wherein the nano-crystalline metal organic framework is present only within the mesopores or void spaces of the mesoporous material and

homogeneously dispersed within the mesopores or void spaces of the mesoporous material.

5. The method any of claims 1-4, further comprising drying at least one selected from the group consisting of the impregnated mesoporous salt material, the impregnated mesoporous acid material, the impregnated mesoporous metal organic framework precursor, and the hybrid material at a temperature in the range of 25-160 °C under a vacuum.

6. The method any of claims 1-5, further comprising:

washing the hybrid material with distilled water; and

extracting water from the hybrid material in a Soxhlet system recycling methanol.

7. The method any of claims 1-6, wherein the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide (aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.), a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate.

8. The method any of claims 1-7, wherein the organic ligand (L"x) of the organic ligand salt is at least one selected from the group consisting of polycarboxylate ligands, azaheterocyclic ligands, and derivatives thereof.

9. The method of claim 8, wherein the organic ligand (L"x) of the organic ligand salt is at least one selected from the group consisting of, terephthalate, benzene- 1, 3, 5-tricarboxylate, 2,5-dioxibenzene dicarboxylate, biphenyl-4,4'-dicarboxylate and derivatives thereof.

10. The method any of claims 1-9, wherein the organic ligand (L"x) of the organic ligand salt is at least one selected from the group consisting of imidazolate, pyrimidinazolate, triazolate, and derivatives thereof.

11. The method any of claims 1-2, wherein the metal (M+y) of the metal precursor is at least one transition metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga.

12. The method any of claims 1-11, wherein the metal organic framework is at least one selected from the group consisting of MIL-101, MIL-100, MIL-53, MOF-74, UiO-66, UiO-67, ZIF-8, ZIFs, HKUST-1, M2(dobpdc), NU-1000, PCN-222, PCN-224, and derivatives thereof.

13. The method any of claims 1-12, wherein the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material.

14. The method any of claims 1-13, wherein the hybrid material comprises mesopores with an average diameter in the range of 2-50 nm and micropores with an average diameter in the range of 0.5-5.0 nm.

15. The method of claim 14, wherein the mesopores, the micropores, or both are

monodisperse having a coefficient of variation of less than 10%.

16. The method any of claims 1-15, wherein the nano-crystalline metal organic framework has an average longest linear dimension of less than 40 nm.

17. The method any of claims 1-16, wherein the hybrid material has a surface area in the range of 200-1200 m2/g.

18. The method of claim 1, wherein the hybrid material has a surface area in the range of 105-500% that of the surface area of the impregnated mesoporous salt material.

19. The method of claim 1, wherein the hybrid material has an average longest linear dimension of 100-500 μιη.

20. A hybrid material, comprising:

a mesoporous material comprising mesopores; and

a nano-crystalline metal organic framework comprising micropores;

wherein the nano-crystalline metal organic framework is homogeneously dispersed and substantially present only within the mesopores or void spaces of the mesoporous material; and wherein the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material.

21. The hybrid material of claim 20, wherein the nano-crystalline metal organic framework is homogeneously dispersed and only present within the mesopores or void spaces of the mesoporous material.

22. The hybrid material of claim 20, wherein the mesopores have an average diameter in the range of 2-50 nm and the micropores have an average diameter in the range of 0.5-5.0 nm.

23. The hybrid material of claim 20, wherein the mesopores, the micropores, or both are monodisperse having a coefficient of variation of less than 10%.

24. The hybrid material of claim 20, wherein the nano-crystalline metal organic framework has an average longest linear dimension of less than 40 nm.

25. The hybrid material of claim 20, which has a surface area in the range of 200-1200 m2/g.

26. The hybrid material of claim 20, wherein the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide (aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.), a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate.

27. The hybrid material of claim 20, wherein the metal organic framework, comprises at least one metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga.

28. The hybrid material of claim 20, wherein the metal organic framework comprises at least one organic ligand selected from the group consisting of polycarboxylate ligands,

azaheterocyclic ligands, and derivatives thereof.

29. The hybrid material of claim 20, wherein the metal organic framework is at least one selected from the group consisting of MIL-101, MIL-100, MIL-53, MOF-74, UiO-66, UiO-67, ZIF-8, ZIFs, HKUST-1, M2(dobpdc) NU-1000, PCN-222, PCN-224, and derivatives thereof.

30. The hybrid material of claim 20, which has an average longest linear dimension of 100-500 μιη.

31. A gas adsorbent comprising the hybrid material of claim 20.

32. A method of adsorbing, separating, storing or sequestering at least one gas, comprising: contacting the gas adsorbent of claim 29 with the at least one gas;

wherein the at least one gas is selected from the group consisting of hydrogen (H2), hydrogen sulfide (H2S), sulfur dioxide (S02), methane (CH4) and carbon dioxide (C02).

33. A catalyst comprising the hybrid material of claim 18.

34. A method of catalyzing a reaction, comprising:

reacting a substrate in the presence of the catalyst of claim 31.

35. A device or material comprising the hybrid material of claim 18, wherein the device or material is at least one selected from the group consisting of a drug delivery carrier, a proton conductive material, a sensor and an optoelectronic device.

36. A method, comprising:

contacting an aqueous solution of an organic ligand salt of the formula AX(L~X) with a

mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula Ax(L"x)/MPM where A is a counter ion, x is a whole number, and L is an organic ligand;

treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula HX(L~X)/MPM where H is hydrogen;

contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Hx(L~x)]/MPM where M is a metal, y is a whole number, and B is an anion; and

at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the presence of a catalytic amount of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the presence of a catalytic amount of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL"x)/MPM; wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material;

wherein the nano-crystalline metal organic framework is homogeneously dispersed and substantially present only within the mesopores or void spaces of the mesoporous material; and wherein the solvent is at least one selected from the group consisting of water, ethanol, methanol, tetrahydrofuran, and Ν,Ν-dimethylformamide and is present in a weight amount of less than 75% of the weight amount of the hybrid material formed.