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    • 专利摘要:
    The present invention relates to a crystalline metal-organic material that is formed by Mg2+ ions that are coordinated with 3,3', 5,5'-azobenzene tetracarboxylic acid ions (H 2 ABTC2-) and N, N-dimethylformamide (DMF), their method of preparation under solvothermal conditions under autogenous pressure, and the use of the material as a catalyst in a conversion process of compounds or to receive or store at least one substance for storage, separation, controlled release or chemical reaction. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2762828A1
    申请号:ES201831141
    申请日:2018-11-23
    公开日:2020-05-25
    发明作者:Rincón Gisela Orcajo；Andrés Helena Montes；Llorente Pedro Leo；Sánchez Carmen Martos；Castillejo Fernando Martínez；Echevarría Juan Angel Botas；Pardo Guillermo Calleja
    申请人:Universidad Rey Juan Carlos；
    IPC主号:
    专利说明:

    [0004] TECHNICAL SECTOR
    [0006] The present invention relates to a crystalline metal-organic material and its synthesis procedure, which has application in the chemical industry, particularly as a catalyst in organic synthesis processes or as a gas adsorbent.
    [0008] BACKGROUND OF THE INVENTION
    [0010] In recent years, advanced porous materials have been developed, called MOF ( Metal-Organic Framework '), which contain metal ions and organic molecular species (ligands) and have generated great interest in a wide variety of applications due to their properties. individuals.
    [0012] MOF materials have great potential in catalytic applications due to their high crystallinity and porosity physico-chemical characteristics and their composition of metal ions and organic ligands, which can act as acidic, basic and redox centers. Additionally, thanks to their high porosity and a large internal surface area, in addition to an extraordinary degree of variability of their organic and inorganic components in their structure 1 , they have great capacity as adsorbents.
    [0014] In recent years, research has been carried out into the development of new MOFs for the storage of gases of high energy and environmental interest, such as CO 2 and H 2 . 23 In addition, their use as heterogeneous catalysts has been investigated, offering clear advantages compared to homogeneous catalysts, by allowing their subsequent recycling and reuse. 4
    [0016] While most MOF materials developed to date are based on transition metals, alkaline earth metal-based MOFs are relatively rare. 5 In this regard, it is pertinent to highlight that alkaline earth metal-based MOF materials offer several advantages compared to lanthanide or transition metal-based MOFs, such as: (i) the high density of Charge and the ionic nature of alkaline earth metal centers lead to strong binding interactions with functional groups such as carboxylate and phosphate, (ii) alkaline earth metals are generally abundant in nature and non-toxic, (iii) porous structures based In the first members of the group of alkaline earth metals they offer gravimetric benefits for high energy and environmental value gas storage applications.
    [0018] As previously mentioned, MOF-type materials have received wide interest as heterogeneous catalysts due to the presence of exposed metal centers in their structure and their high porosity. Specifically, as regards MOFs with alkaline earth metals for such use, the metals possess significant Lewis basicity, which implies activity in base catalyzed reactions. However, as previously discussed, the number of publications of heterogeneous alkaline earth metal catalysts is currently still very limited.6
    [0020] Magnesium is the most widely used metal in the formation of alkaline earth metal-based MOFs.7-9 In fact, until now, gas storage studies have largely focused on magnesium-based MOF (Mg-MOF) materials. The first porous Mg-MOF was synthesized by Dincá and Long, 10 and shows a preferential adsorption of oxygen and hydrogen over nitrogen. Since then, several Mg-MOFs with permanent microporosity have been described for gas storage, 11 with Mg-MOF-74 being the most studied to date. 1213
    [0022] Platero-Prats et al. carried out the synthesis of MOF materials based on alkaline earth metals (magnesium, calcium, strontium) that were used as catalysts in the hydrogenation reaction of styrene to form ethylbenzene under mild conditions.14 Similarly, studies of Heterogeneous catalysis with various MOFs based on magnesium, calcium and barium. 15-18 Of the above, the magnesium-based MOF material proved to be an effective catalyst for the aldol condensation reactions of various aromatic aldehydes and ketones under mild conditions.18 Furthermore, The catalyst was shown to be recyclable and reusable for several cycles without significant loss of activity.
    [0024] On the other hand, due to the wide variety of organic molecules that can act as ligands capable of coordinating with metal cations, MOF materials can be pre-designed in a controlled way depending on the type of application that is applied to them. want to give. 3,3,5,5-Azobenzenotetracarboxylic acid (H 4 ABTC), which consists of four carboxylic groups, has been used as a ligand in some MOFs, which can be easily deprotonated to coordinate to the metal, giving rise to a wide variety of crystalline structures with different geometry and with application in different study areas, such as luminescence, magnetism, catalysis and hydrogen storage. 19-29
    [0026] Li et al.30 describe a MOF material synthesized from magnesium nitrate hexahydrate and H 4 ABTC. However, the obtained compound has a totally different crystalline structure from the compound developed in the present invention and is not porous.
    [0028] In this sense, it is evident that despite the continuous evolution of MOF materials, including those formed by magnesium, there is still a need in the state of the art to obtain materials with new structures, resulting from the appropriate choice of metals, ligands and solvents, capable of providing improved performance in various industrial processes. In particular, the design and development of materials with high catalytic activity, selectivity and stability, where their porous structure can additionally provide selectivity, still remains a scientific and technical challenge.
    [0030] Thus, in the present invention, a new MOF material with a monoclinic crystalline structure has been developed, which has basic exposed metallic centers of magnesium and acid centers (protons with Bronsted acidity from the organic ligand). The MOF material of the present invention has a double chemical functionality that gives it great efficiency as a heterogeneous catalyst and as a compound adsorbent.
    [0032] DESCRIPTION OF THE INVENTION
    [0034] In a first aspect, the present invention refers to a crystalline metal-organic material (hereafter the material of the invention or URJC-2), characterized by being formed by Mg 2+ ions that are coordinated with acid ions 3 , 3 ', 5,5'-azobenzene tetracarboxylic (H 2 ABTC 2- ) and N, N-dimethylformamide (DMF) to form a metal-organic structure.
    [0035] In particular, the material of the present invention has the formula C 22 H 22 MgN 4 O io , or Mg (H 2 ABTC) (DMF) 2 . In Figs. 1a and 1b shows the asymmetric unit of the material of the present invention consisting of half an Mg 2+ ion, half an H 2 ABTC 2- ligand and a coordinated DMF molecule. Ligand H 2 ABTC 2- has a center-symmetrical structure, whose inversion center is at the midpoint of the N = N double bond. Mg 2+ ions have an octahedral coordination sphere in which four of the six oxygen atoms come from four 1V-CO 2 groups - from four H 2 ABTC 2- ligands and the other two coordinated oxygens belong to two molecules of DMF terminals.
    [0037] According to single crystal X-ray diffraction, the material of the present invention crystallizes in a monoclinic system, space group P2i / c. The Mg-O bond distance is in the range of 2,000 to 2,200 Á, preferably 2,058 (18) to 2,124 (20) Á, and the O-Mg-O bond angles in the range of 80 to 180 °, preferably from 86.4 (10) to 171.2 (8). In the tetracarboxylate ligand H 2 ABTC 2- , the two phenyl rings are essentially coplanar. The H 2 ABTC 2- ligand provides four donor centers and coordinates four Mg 2+ ions, and each Mg 2+ ion coordinates in turn with four different H 2 ABTC 2- ligands (Fig. 1b), each H 2 anion serving ABTC 2- as a P 4 ligand-bridge to bind four ions. These building units are repeated to form a three-dimensional (3-D) network, the channels of which have an approximate dimension of 4.9 x12.8 Á 2 (including van der Waals radii), assuming the elimination of the coordinated DMF molecules. .
    [0039] The X-ray diffractogram of the material of the invention was obtained in the range 5 <20 <50 ° and using a fixed slot, with a step size of 0.026 ° and an acquisition time of 2.5 seconds per step at a temperature 25 ° C. In a preferred form, the crystalline metal-organic material of the invention is characterized in that the powder X-ray diffraction pattern has peak values of 20 of 7.96 ± 0.09; 12.36 ± 0.05; 16.16 ± 0.13; 18.55 ± 0.08; 21.63 ± 0.12; 22.60 ± 0.12; 23.24 ± 0.07; 24.34 ± 0.17; 27.74 ± 0.13, as seen in Fig. 2b. In Example 4, the powder X-ray diffraction patterns for the material of the invention were measured at different temperatures, which demonstrated the integrity of the crystalline phase up to 250 ° C.
    [0041] Preferably, the material of the present invention has a surface Specific between 100 and 300 m 2 / g, measured by argon adsorption / desorption at 87 K, with pores in the micropores range. Preferably the specific surface is around 130 m 2 / g.
    [0043] In a second aspect, the present invention also provides a method of preparing a crystalline metal-organic material which comprises the reaction step of a compound of magnesium and 3,3 ', 5,5'-azobenzene tetracarboxylic acid (H 4 ABTC) in N, N-dimethylformamide (DMF). The reaction is preferably carried out in the presence of water. The reaction is preferably carried out in acidic medium, which can come from H 4 ABTC itself dissolved in the medium. The method is developed under solvothermal conditions under autogenous pressure in an autoclave container.
    [0045] The magnesium compound, usually in the form of a salt, oxide or other chemical species, is added to the reaction medium. The reaction in the method of the invention to prepare crystalline metal-organic material can be carried out in the classical way in which the magnesium compound is typically a magnesium salt. The magnesium salts are preferably nitrate, sulfate, acetate, and chloride.
    [0047] The molar ratio of magnesium compound (A) to 3,3 ', 5,5'-azobenzene tetracarboxylic acid (B) can vary from 1: 4 to 4: 1, and may have an A: B ratio of 1: 1; 1: 2; 1: 3; 1: 4; 2: 1, 3: 1, 4: 1.
    [0049] Preferably, the method of preparing a crystalline metal-organic material according to the invention is carried out by reacting a compound of magnesium and H 4 ABTC in DMF, optionally in DMF and water, to obtain a solution. Next, the solution is heated to a temperature of 50-250 ° C. The temperature is maintained for a time of 12 to 120 h. After this time, it is allowed to cool slowly to room temperature to obtain the crystalline metal-organic material. The cooling rate can vary from 0.5 ° C / min up to 3 ° C / min. The ambient temperature is typically 25 ° C.
    [0051] The method of preparation may further include solvent washing the crystals obtained. Optionally, the solvent can be an alcohol, for example methanol, ethanol, or iso-propanol, or also another type of solvent, polar or apolar, such as, for example, dichloromethane, acetone, and acetonitrile.
    [0052] The organic H 4 ABTC ligand can be commercially obtained or synthesized as described in the literature, for example, as described by Dhakshinamoorthy et al.31 The synthesized ligand can be purified by recrystallization from N, N- dimethylformamide after use in the method for preparing the crystalline metal-organic material of the invention.
    [0054] A further aspect of the present invention is the use of the crystalline metal-organic material according to the invention as catalyst in a compound conversion process, which comprises contacting a compound or a mixture that compounds with a quantity of material of the invention and other reagents.
    [0056] Optionally, the compound conversion process is a Knoevenagel condensation reaction.
    [0058] The advantage of using the material of the invention as a catalyst is that, being heterogeneous, it allows the catalyst to be separated from the rest of the products, even allowing its reuse, in addition to minimizing residual effluents produced by conventional homogeneous acidic and basic catalysts. Particularly, the use of the material of the present invention as a catalyst has the advantage of obtaining a higher yield of the desired product compared to other MOF materials used for this reaction. Furthermore, the material of the present invention can be reused during a certain number of consecutive reactions, at least five, keeping its crystalline structure and its catalytic activity unchanged.
    [0060] Still another aspect of the invention is the use of the crystalline metal-organic material according to the invention to receive or store at least one compound of a substance for storage, separation, controlled release or chemical reaction of said compound.
    [0062] Preferably, the substance is a gas, a vapor, a mixture of gases, a mixture of vapors, or a mixture of gases and vapors. Preferred compounds are hydrogen, natural gas, coke gas, hydrocarbons, in particular methane, ethane, acetylene, acetylene, propane, n-butane and i-butane, carbon monoxide, carbon dioxide, oxides of nitrogen, oxygen, oxides sulfur, halogens, halogenated hydrocarbons, NF 3 , SF e , ammonia, boranes, phosphines, hydrogen sulfide, amines, formaldehyde, noble gases, in particular helium, neon, argon, krypton and xenon.
    [0064] BRIEF DESCRIPTION OF THE FIGURES
    [0066] Fig. 1a. Asymmetric unit of the URJC-2 material.
    [0067] Fig. 1 b. Representation of the 3-D structure through the coordinate axis c of the crystal structure. Magnesium: green, carbon: gray, nitrogen: blue and oxygen: red. Fig. 2a. X-ray diffraction pattern simulated from the crystallographic data of the material of the invention. Y axis: Relative intensity of DRX (arbitrary units), X axis: angle (degrees).
    [0068] Fig. 2b. Experimental X-ray diffraction pattern of the material of the invention. Y axis: Relative intensity of DRX (arbitrary units), X axis: angle (degrees).
    [0069] Fig. 3a. Argon adsorption-desorption isotherms at 87 K of the material of the invention. The filled points represent the adsorption branch and the empty points the desorption branch. Y axis: Amount of adsorbed Ar (cm 3 g -1 STP), X axis: relative pressure.
    [0070] Fig. 3b. Pore size distribution in the material of the invention. Y axis. Pore volume (cm 3 Á -1 g -1 ), X axis: pore diameter (Á).
    [0071] Fig. 4. X-ray diffraction patterns of the material of the invention at different temperatures. Y axis: Relative intensity of DRX (arbitrary units), X axis: angle (degrees).
    [0072] Fig. 5 Thermogravimetric analysis of the material of the invention in an air atmosphere. Y axis: Weight percentage (%), X axis: Temperature (° C).
    [0073] Fig. 6 X-ray diffraction patterns of the material of the invention after immersion in different organic solvents. Y axis: Relative intensity of DRX (arbitrary units), X axis: angle (degrees).
    [0074] Fig. 7a Catalytic activity of the blank assay (without catalyst), of the URJC-2 material and its components in the Knoevenagel condensation of benzaldehyde and malononitrile; conversion of BZ (columns without filling), yields to the product 2-benzylidenemalononitrile (2-BM) (packed columns).
    [0075] Fig. 7b Catalytic activity of URJC-2 material against other catalysts in Knoevenagel condensation of benzaldehyde (BZ) and malononitrile (MN); conversion of BZ (columns without filling), yields to the product 2-benzylidenemalononitrile (2-BM) (packed columns).
    [0076] Fig. 8 X-ray diffraction patterns of URJC-2, IRMOF-3, UÍO-66-NH 2 and MIL-101-NH 2 catalysts before and after the Knoevenagel reaction of benzaldehyde (BZ) and malononitrile (MN ). Y axis: Relative intensity of DRX (arbitrary units), X axis: angle (degrees).
    [0077] Fig. 9a Catalytic activity of the URJC-2 material in consecutive reaction cycles; conversion of BZ (columns without filling), yields to the product 2-benzylidenemalononitrile (2-BM) (packed columns).
    [0078] Fig. 9b X-ray diffraction patterns of the URJC-2 material after several consecutive reaction cycles. Y axis: Relative intensity of DRX (arbitrary units), X axis: angle (degrees).
    [0079] Fig. 10a CO 2 adsorption-desorption isotherms in mmol / g at different temperatures. The filled points represent the adsorption branch and the empty points the desorption branch. Y axis: CO 2 amount (mmol / g), X axis: absolute pressure (bar).
    [0080] Fig. 10b CO 2 adsorption-desorption isotherms in% by weight at different temperatures. The filled points represent the adsorption branch and the empty points the desorption branch. Y axis: CO 2 quantity (% weight), X axis: absolute pressure (bar).
    [0082] EXAMPLES
    [0084] The examples set forth herein are intended to illustrate the invention, without thereby limiting its scope.
    [0086] Example 1: Synthesis of 3,3 ', 5,5'-azobenzene tetracarboxylic acid (H 4 ABTC) H 4 ABTC was synthesized in the following way: 2.5 g of 5- acid were mixed in a round bottom flask. nitroisophthalic, 6.6 g of sodium hydroxide and 33 ml of distilled water and kept under stirring at 60 ° C for 1 hour. In parallel, 13.2 g of glucose was dissolved in 20 ml of distilled water. The glucose solution was added dropwise to the mixture contained in the flask, causing an immediate color change from pale yellow to dark brown. The reaction mixture was allowed to cool slowly to room temperature. Subsequently, it is bubbled with air overnight, applying constant agitation at 400 rpm. The resulting mixture was cooled on ice and the solid was recovered by filtration. The obtained product was dissolved in 40 ml of distilled water and this solution was acidified to a pH of 1, by adding 37% w / w hydrochloric acid, in such a way that a solid precipitated. The precipitated solid was filtered, washed with distilled water, recrystallized from DMF and finally dried in vacuo. The product was obtained with a 75% yield and is bright orange.
    [0088] Example 2: Synthesis of crystalline metal-organic material
    [0089] 0.0256 mg (0.1 mmol) of magnesium nitrate hexahydrate and 0.0716 mg (0.2 mmol) of H4ABTC were dissolved in 5 ml of DMF and 0.33 ml of distilled water in a Teflon autoclave. The autoclave was sealed and heated to 100 ° C for 72 hours. Subsequently, it was slowly cooled to 0.5 ° C / min to room temperature and orange crystals were obtained. The suspension was decanted and the crystals were washed in methanol, immersing them for 3 days and replacing 3 times with fresh solvent. Crystals were obtained in 70% yield. The crystalline information of the crystalline metal-organic material obtained is as follows: molecular weight = 526.73 gmol-1; monoclinic structure, P2i / c; a = 11,2106 (2) Á, b = 22,0370 (3) Á, c = 9,6241 (10) Á; a = 90 °, = 103.6100 ° (10), y = 90 °; V = 2310.85 Á3; Z = 4. Fig. 2a shows the simulated powder X-ray diffraction pattern that was obtained from the crystallographic data.
    [0091] Fig. 2b shows the experimental powder X-ray diffraction pattern corresponding to the material obtained by the described method. The X-ray diffractogram of the material of the invention was obtained in the range 5 <20 <50 ° and using a fixed slot, with a step size of 0.026 ° and an acquisition time of 2.5 seconds per step at a temperature 25 ° C. The main peaks coincide in both patterns, which demonstrates the high purity of the crystalline phase in the obtained material, as well as the correct resolution of its crystalline structure by means of single crystal X-ray diffraction.
    [0093] Crystallographic data for the metal-organic material is included in Table 1.
    [0095] Table 1. Crystallographic data of the metal-organic material.
    [0097]
    [0098]
    [0101] Example 3: Porosity
    [0102] The porosity of the crystalline metal-organic material of the invention was measured by adsorption / desorption of argon at 87 K (see Fig. 3a), after degassing the sample at high vacuum and temperature. This material shows a BET specific surface area of 130 m 2 / g and a pore volume of 0.054 cm 3 / g at P / P 0 of 0.998. Additionally, a narrow pore size distribution, centered on 9.5 Á, was obtained using the Non-Local DFT method, applied for an Ar-carbon kernel at 87 K based on the grid model (Fig. 3b) , as described in Jagiello et al.32 Said pore size agrees with the dimensions found crystallographically. The experimental density of the activated material was 1.46 g / cm 3 , measured by helium pycnometry.
    [0104] Example 4: Thermal stability
    [0105] Fig. 4 shows the powder X-ray diffraction patterns at different temperatures of the material of the invention (TDRX). The acquired standards indicate the integrity of the crystalline phase of the material up to 250 ° C.
    [0107] For its part, Fig. 5 shows an analysis of thermogravimetry in an oxidizing atmosphere for the material of the invention. In the thermogravimetric profile, three marked weight losses are evident. The first and smallest of approximately 1.3% in the range of 30 to 175 ° C, corresponding to the elimination of adsorbed water in the shows. The second weight loss is approximately 21.9% in the range of 180 to 250 ° C and is attributable to the removal of the coordinated DMF molecules. Finally, the third loss occurs between 250 and 500 ° C, due to the degradation of the organic ligand, which implies the collapse of the structure, coinciding with the result obtained using the TDRX technique in Fig. 4.
    [0109] Example 5: Chemical stability
    [0110] The stability of the crystalline metal-organic material of the invention was evaluated by immersing a sample of said material for 72 hours at room temperature in three different solvents: dichloromethane, acetone and methanol. Fig. 6 shows the X-ray diffraction patterns of the sample after treatment with each solvent, where it is observed that the crystalline structure remains present in all cases, which shows great chemical stability.
    [0112] Example 6. Catalytic tests
    [0113] A catalytic study was carried out using a typical Knoevenagel condensation reaction of benzaldehyde (BZ) with malononitrile (MN) to obtain 2-benzylidenemalononitrile (2-BM), using the crystalline metal-organic material of the invention as the basic catalyst. With the objective of knowing the catalytic activity of the components that are part of the crystalline metal-organic material (basic centers of Mg 2+ and nitrogen atoms of the organic ligand), four reactions were carried out: without catalyst (blank test) , with the magnesium salt, with magnesium oxide and with the H 4 ABTC ligand, using concentrations equivalent to those existing within the URJC-2 structure. In Fig. 7a, it is evident that the URJC-2 material shows a better catalytic behavior, compared with the results achieved by its components separately. On the other hand, at the end reaction time (240 min), both homogeneous Mg 2+ from nitrate salt and MgO show higher catalytic activity compared to organic ligand, showing better BZ conversions and yield at 2- BM. This shows the important catalytic contribution of the basic magnesium centers compared to the organic part of the crystalline metal-organic material. It is worth noting the poor results obtained without a catalyst, which confirms the importance of the URJC-2 catalyst in the reaction system.
    [0114] Example 7. Performance of the material against other catalysts
    [0115] For the same reaction of benzaldehyde (BZ) with malononitrile (MN) to obtain 2-benzylidenemalononitrile (2-BM), the catalytic behavior of the MOF URJC-2 was evaluated against other MOFs of the state of the art containing amino groups, and They have high porosity and are widely known, such as the microporous IRMOF-3 and UiO-66-NH 2 , and the mesoporous MIL-101-NH 2 . IRMOF-3 was synthesized according to Tanabe et al.33; UiO-66-NH 2 was synthesized according to Garibay et al.34; MIL-101-NH 2 was synthesized according to Serra-Crespo et al.35. In addition, for comparative purposes, the performance of the beta zeolite (purchased from Zeolyst International) impregnated with sodium was evaluated following the procedure of Seung-Tae et al.36, as it is widely used in base catalyzed reactions. The amount of catalyst employed was set to have 5 mmol of metal in all cases. In the case of beta zeolite, said concentration was fixed taking sodium as a reference. Fig. 7b shows the conversion of BZ and the yield to 2-BM for all the catalysts used.
    [0117] It is observed that with the URJC-2 material and the sodium exchanged beta zeolite similar BZ conversions are obtained at final reaction times (240 min). However, URJC-2 outperforms zeolite in terms of yield to the 2-BM product, being 85% for URJC-2 versus 77% for zeolite, demonstrating higher selectivity to 2-BM. Compared with UiO-66-NH 2 and MIL-101-NH 2 materials , better performance of URJC-2 material is demonstrated. Regarding IRMOF-3, the BZ conversion achieved is comparable to that obtained by URJC-2 at 240 min of reaction. The good results obtained for this Zn material (IRMOF-3) can be attributed to its high specific surface area (2,298 m 2 / g) and its highly accessible 3-D structure. However, the X-ray diffraction pattern of IRMOF-3 after the reaction showed an irreversible degradation of its crystal structure, while for the rest of the tested materials its crystal structure remained unchanged (Fig. 8). Furthermore, the structural stability of URJC-2 was verified by analyzing the reaction medium using the induction coupled plasma atomic emission spectroscopy (ICP) technique. The absence of dissolved magnesium (magnesium concentration less than 0.02 ppm), further demonstrated the preservation of the URJC-2 structure after its use in the reaction.
    [0119] Example 8. Material performance in consecutive reaction cycles
    [0120] The performance of the URJC-2 material as a heterogeneous catalyst was evaluated in several Consecutive reaction cycles in the reaction of benzaldehyde (BZ) with malononitrile (MN) to obtain 2-benzylidenemalononitrile (2-BM) described in Example 5. The results showed the same conversion of BZ and yield to the 2-BM product after five reaction cycles, being 95% and 85%, respectively (Fig. 9a). Furthermore, the crystalline phase of URJC-2 also remained unchanged after several cycles (Fig. 9b), ruling out degradation of the catalyst in the reaction medium.
    [0122] Example 9. CO adsorption 2
    [0123] A sample of URJC-2 material was activated at 150 ° C and high vacuum (10 -6 mbar) for 18 hours. After activation, the CO 2 adsorption properties were measured in the commercial Hiden Analytical Intelligent Gravimetric Analyzer (IGA-003) in a pressure range of 0 to 20 bar and under temperature conditions of 273 K, 288 K and 308 K. It was generally observed that the amount of adsorbed gas decreased with increasing temperature as a result of the increased thermal energy of the CO 2 molecules at higher temperatures. As observed in Fig. 10, the adsorption capacity of the URJC-2 material at 20 bar and 273 K is 1.34 mmol / g (6.03% by weight), higher than that of other materials such as MOF -5, UCMC-1, SNU-31, ZIF-8 or MIL-101 (Cr), measured under similar conditions of pressure and temperature 37 .
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    权利要求:
    Claims (16)
    [1]
    1. A crystalline metal-organic material characterized in that it is formed by Mg 2+ ions that are coordinated with 3,3 ', 5,5'-azobenzene tetracarboxylic acid ions (H 2 ABTC 2- ) and N, N-dimethylformamide ( DMF).
    [2]
    2. The material of claim 1 characterized in that it crystallizes in the monoclinic system, space group P 2 i / c , with formula Mg (H 2 ABTC) (DMF) 2 .
    [3]
    3. The material of any of claims 1 or 2 characterized in that the Mg-O bond distance is in the range of 2,000 to 2,200 Á.
    [4]
    4. The material of any of claims 1 to 3 characterized in that the O-Mg-O bond angles are in the range of 80 to 180 °.
    [5]
    5. The material of any one of claims 1 to 4 characterized in that it has a powder X-ray diffraction pattern at 25 ° C having characteristic peak values at 20 of 7.96 ± 0.09; 12.36 ± 0.05; 16.16 ± 0.13; 18.55 ± 0.08; 21.63 ± 0. 12; 22.60 ± 0.12; 23.24 ± 0.07; 24.34 ± 0.17; 27.74 ± 0.13.
    [6]
    6. The material of any of claims 1 to 5 characterized in that it has a porosity between 100 and 300 m 2 / g.
    [7]
    7. A method of preparing a crystalline metal-organic material consisting of Mg 2+ ions that are coordinated with 3,3 ', 5,5'-azobenzene tetracarboxylic acid and N, N-dimethylformamide ions, characterized in that it comprises:
    1. react a compound of magnesium and 3,3 ', 5,5'-azobenzene tetracarboxylic acid in N, N-dimethylformamide and water, to obtain a solution;
    ii. heat the solution to a temperature between 50 and 250 ° C, maintaining the temperature for 12 to 120 h;
    iii. cool to room temperature.
    [8]
    8. The method of claim 7, characterized in that the reaction medium in i. it is acidic.
    [9]
    9. The method of any one of claims 7 or 8, characterized in that the molar ratio of magnesium compound to 3,3 ', 5,5'-azobenzene tetracarboxylic acid at i. it is from 1: 4 to 4: 1.
    [10]
    10. The method of any of claims 7 to 9, characterized in that the magnesium compound is a magnesium salt or a magnesium oxide.
    [11]
    11. The method of any one of claims 7 to 10, characterized in that the magnesium salt is selected from the group consisting of magnesium nitrate, magnesium sulfate, magnesium acetate, and magnesium chloride.
    [12]
    12. Use of the crystalline metal-organic material of any of claims 1 to 6 as a catalyst in a chemical process.
    [13]
    13. Use of claim 12, characterized in that the chemical process is a Knoevenagel condensation reaction.
    [14]
    14. Use of the crystalline metal-organic material of any one of claims 1 to 6 as an adsorbent of a compound in a substance for storage, separation, controlled release or chemical reaction of said compound.
    [15]
    15. Use of claim 14, characterized in that the substance is a gas, a vapor, a mixture of gases, a mixture of vapors or a mixture of gases and vapors.
    [16]
    16. Use of claim 15, characterized in that the compound is carbon dioxide.
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    公开号 | 公开日
    ES2762828B2|2020-11-13|
    WO2020104720A1|2020-05-28|
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    PCT/ES2019/070784| WO2020104720A1|2018-11-23|2019-11-15|Crystalline metal-organic material based on magnesium, synthesis method and uses|
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