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    • 专利摘要:
    Titanium heteromethalic metal-organic solids, procedure for obtaining and their uses. The present invention relates to a new family of heteromethalic titanium structured metal-organic materials (MOFs) that have, among other features, high porosity, stability in aqueous medium and photocatalytic activity against visible light and UV radiation. The new family of materials presents a structural unit that combines tretavalent titanium with multiple combinations of divalent metals with a homogeneous distribution at the atomic level in the structure of the MOF. The invention also relates to methods for obtaining them with high yields as well as their uses in the generation of solar fuels, photoactivated degradation, CO2 photoreduction, heterogeneous catalysis, as a component or part of an electronic component and/or as a porous or photoactive coating for the control of contaminants, among others. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2732803A1
    申请号:ES201830496
    申请日:2018-05-23
    公开日:2019-11-26
    发明作者:Gastaldo Carlos Marti；Gil Javier Castells；Padial Natalia Munoz
    申请人:Universidad de Granada；Universitat de Valencia；
    IPC主号:
    专利说明:

    [0001]
    [0002] Titanium metal heteromic organic heterom solids, procedure for obtaining and using them
    [0003]
    [0004] The present invention relates to a new family of heteromethalic titanium structured metal-organic materials (MOFs) that have, among others, high porosity, stability in aqueous medium and photocatalytic activity with visible light and UV radiation.
    [0005]
    [0006] The invention also relates to methods for obtaining it as well as its uses in catalysis, adsorption, separation, gas storage and photocatalysis, among others.
    [0007]
    [0008] Background of the invention
    [0009]
    [0010] Metal-organic networks or Metal-Organic Frameworks, acronym in English (MOF), constitute a class of porous solids, consisting of metal atoms or associations of metal atoms as active centers coordinated with organic ligands to create open crystalline structures with a permanent porosity . Given the great variety of both metal atoms and organic ligands, there is a constant interest in the search for new metal-organic structures with different properties.
    [0011]
    [0012] Among the most important aspects of MOFs can be highlighted the high adsorption capacity, the ability to generate active centers of different chemical stability in their structure, the uniform size of their channels and cavities that are in the same order of magnitude as many molecules of industrial interest, excellent ion exchange capacity, photoactivity and interesting electronic properties that vary from insulators to conductors and semiconductors.
    [0013]
    [0014] In the context of catalysis, the metal ions present in the structure of the MOFs can act as active centers when they have available coordination positions, or the organic ligands can be the active centers where the desired reaction takes place, that is, both ligands Organic as metal ions can act as active centers. The active center can be introduced into the MOFs both during their synthesis and in a post-synthesis treatment process, which generally involves a metal exchange procedure using a preformed MOF to obtain the same material with a random distribution of different metal ions or organic ligands in their structure. In addition, both the organic part and the inorganic part of the MOFs can be functionalized to introduce other catalytic centers inside the pores of the material (metal nanoparticles, oxides or metal complexes, etc.).
    [0015]
    [0016] The main problem facing many of the MOFs that are known to date is their low stability in aqueous media, which in many cases limits their transfer to industrially relevant applications. This limitation is set by the low stability of the metal-ligand coordination links that define its connectivity, structure and intrinsic porosity for most of the metals used (mainly lanthanides and metals of the first transition series). These coordination links are usually not robust enough from a thermodynamic point of view to prevent hydrolysis processes (bond breakage in aqueous media) or in the presence of acids or bases. To solve this problem, metals in high oxidation state have been used, such as Ti (IV), which entails M-O bond energies of up to 750 kJ.mol1, giving the MOFs resulting from a much higher chemical stability.
    [0017]
    [0018] However, to date, a very small number of titanium MOFs have been described, and in all cases they are based on processes limited to specific combinations of relatively high-cost synthetic organic ligands and Ti (IV) metal precursors. The MOFs described can only be prepared from certain combinations of these two components and cannot be obtained as crystals in a scalable way, nor can they be adapted to different synthesis processes. This difficulty lies in the high reactivity of Ti (IV) in solution, which tends to form amorphous solids of titanium oxide, thus hindering the synthesis of porous and crystalline materials.
    [0019]
    [0020] Many efforts have been made to increase the chemical stability of MOFs, either through the post-synthetic modification of preformed materials or by the creation of new structures with high oxidation metals capable of forming more robust bonds with the ligand organic such as Ti, Zr or Hf (IV).
    [0021]
    [0022] It is known that Ti (IV) has advantages over Zr or Hf (IV) due to its low cost, low toxicity and photoactive properties. However, the high reactivity of Ti (IV) makes it very difficult to achieve crystalline systems. Ti-IV metal-organic systems such as MIL-125, PCN-22, NTU-9, Ti-CAT-5, MIL-91, MOF-901 or COK-69 are known. However, these systems incorporate titanium exclusively as the only metal forming part of the unit Structural of the MOF.
    [0023]
    [0024] Thus, the international patent application WO2010 / 094889 describes a method of preparation of the MIL-125 material. However, the inorganic part of the material is always based solely on homometallic titanium clusters that make it difficult to synthesize crystalline and porous materials based on combinations of titanium with other metals. The methodology used requires multiple chemical reactions to prepare the ligands of interest, which results in a notable increase in production costs.
    [0025]
    [0026] International patent application WO2017211923A1 and US patent US8940392B2 also describe the preparation of Ti (IV) MOF materials from tetradentate ligands with a high number of Ti atoms forming the metal cluster or inorganic part of the MOF. US patent US8940392B2 describes a method for doping the MOF system with metals in oxidation state 3, which achieves doping percentages of up to 20%. However, none of these procedures describe a method of synthesis applicable to the large-scale production of these materials.
    [0027]
    [0028] In the heteromethalic MOFs described in the literature, the incorporation of a second metal proceeds by post-synthetic modification of a pre-formed material. This greatly conditions the homogeneity of the resulting MOF that usually has variable distributions of both metals in its structure, with the second incorporated metal concentrated mainly on the surface of the glass as a result of the kinetic problems associated with the chemical equilibrium that controls the substitution of metals.
    [0029]
    [0030] Hong, K. & Chun, H. in "Unprecedented and highly symmetric (6.8) -connected topology in a porous metal-organic framework through a Zn-T and hetemmetallic approach", Chem. Commun.
    [0031] 2013, 49, 10953 describes an MOF system that uses nitrogenous ligands of the dabco type (1,4-diazabicyclo [2.2.2] octane) and Zn as the active center. However, the system decomposes easily in aqueous medium, so it is not suitable for photocatalysis, nor does it show activity against visible light. The low stability of this system is due to the fact that the coordination bonds based on nitrogenous monodentate ligands are usually not robust enough from the thermodynamic point of view to prevent hydrolysis processes (bond breakage in aqueous medium) or in the presence of acids or bases.
    [0032]
    [0033] Thus, the methods described to date are based on the extrinsic doping of the titanium MOF, the synthesis of the MOF being carried out and then the incorporation of the metals in a second stage, which does not allow an exact control over the distribution of metals in the MOF and, therefore, it is not possible to obtain a homogeneous distribution of the metals in the MOF. This fact has a very negative impact on the control of the physical / chemical properties of the final material, relevant for its subsequent application.
    [0034]
    [0035] Therefore, to date, there is no titanium heteromethalic MOF solid with homogeneous distribution of metals in the MOF that also has high surface area, crystallinity, good stability in aqueous medium and in extreme acid / base conditions and photocatalytic activity against to visible light and against UV radiation, which can be obtained on an industrial scale in an easy way and with simple, accessible and economical starting materials.
    [0036]
    [0037] There is also no titanium heteromethalic MOF solid in the state of the art, whose characteristics of photoactivity (visible light and UV radiation), electronic (band gap), or stability (in aqueous medium and in extreme acid / base conditions) can be controlled exactly and these can be pre-designed easily and with low cost.
    [0038]
    [0039] There is therefore a need for a methodology for the manufacture of an industrial scale heteromethalic MOF solid on an industrial scale, with high efficiency and low cost that allows the final properties of the titanium MOF solid to be pre-designed.
    [0040]
    [0041] For this, the present invention focuses on the structural unit of the MOF solid, a heteromethalic cluster of Ti (IV) -M (II), crystalline and porous. Proper selection of the starting materials in an intrinsic doping process allows, in a single step, to obtain a heteromethalic titanium MOF solid with homogeneous distribution of metals at the atomic level in the structure of the material, which has a high surface area, crystallinity , good chemical stability and photocatalytic activity against visible light and UV radiation, whose properties can be pre-designed at will according to the desired final application properties of the MOF solid.
    [0042]
    [0043] Description of the invention
    [0044]
    [0045] The present invention has been carried out taking into account the state of the art described above and the object of the present invention is, in a first aspect, to provide a crystalline and porous heteromethalic titanium MOF solid, with homogeneous distribution at the atomic level of metals in the MOF, whose photoactivity properties (against visible light and UV radiation), electronic (band gap) or stability (in aqueous medium and in extreme acid-base conditions), among others, can be modified easily and at low cost according to the desired properties in the final MOF.
    [0046]
    [0047] To solve the problem, the present invention provides, in a first aspect, a crystalline and porous heteromethal Ti (IV) MOF solid, characterized by the fact that it comprises a tricarboxylic ligand L as an organic part of MOF and TiIV with at least one divalent metal M m (1-5) as a structural unit and inorganic part of the MOF, where the TiIV and the at least one divalent metal M "(i -5) are homogeneously distributed at the atomic level in the structure of the MOF.
    [0048]
    [0049] In the context of the present invention, "structural unit" of the MOF means "active center (s)" of the MOF.
    [0050]
    [0051] In the context of the present invention, "titanium heterometallic MOF solid" means a solid of structured metal-organic material, whose structural unit or active centers of the MOF are formed by titanium and the divalent metal (s).
    [0052]
    [0053] In the context of the present invention, "homogeneous distribution at the atomic level" means that the atomic ratio between the different metals integrated in the solid is the same regardless of the area of the crystalline solid examined.
    [0054]
    [0055] In a preferable embodiment, the TiIV and the at least one divalent metal M "( i -5) are interconnected with the tricarboxylic ligand L forming a three-dimensional structure. In the present invention it is possible to assemble an architecture that combines high porosity with chemical stability and enhanced photocatalytic activity compared to that of titanium dioxide.
    [0056]
    [0057] That is, the authors of the present invention have found that the use of heteromethalic clusters of Ti (IV) as a structural unit of the MOF allows controlling the reactivity of the titanium in solution and adapting the synthesis of these MOFs to different procedures and combinations between metals , that is, between titanium and divalent metals, providing a homogeneous distribution thereof at the atomic level throughout the MOF.
    [0058]
    [0059] Thus, the scope of the present invention encompasses a system composed of said heteromethalic MOF solids of Ti (IV), whose relationship between titanium and divalent metals or metals can be modulated at will to optimize, among others, its structure, porosity, stability chemistry, electronic structure and photocatalytic activity with visible light, unlike titanium dioxide that is only active with UV radiation.
    [0060]
    [0061] This modification at the atomic level, that is, the introduction of two or more different metals in the structural unit of the MOF with different proportions between these metals in the structural unit, allows to better control the reactivity of the titanium in solution and adapt its synthesis to different procedures using high performance methodologies such as robotic chemistry. This control is not only limited to binary combinations, but also titanium can be combined with up to 5 different types of divalent metals in the same structural unit and inorganic part of the MOF solid.
    [0062]
    [0063] The heteromethalic MOF solid of Ti (IV) according to the first aspect of the invention may contain Ti (IV) and from 1 to 5 divalent metals M ", (MM (1-5)) and the ratio between Ti (IV) and M (II) is understood here considering that M (N) = IM (1-5) The TiIV: MM (1-5) ratio, unless otherwise specified, indicates moles of Ti (IV): moles of divalent metal (s) In the context of the invention, M (II) has the same meaning as MM, and Ti (IV) has the same meaning as TiIV.
    [0064]
    [0065] The combination of titanium with divalent metals by varying their identity and the relative proportion in the structure of the MOF at the atomic level allows to give a family of heteromethalic metal-organic materials of titanium with chemical stability, porosity, optical, electronic and catalytic properties in a very wide range. broad structures and formulations.
    [0066]
    [0067] In turn, the divalent metal MII can be selected from Mg2 +, Ca2 +, Sr2 +, Ba2 +, Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 + and Cd2 +.
    [0068]
    [0069] The crystalline and porous heteromethal Ti (IV) MOF solid exhibits photocatalytic activity against visible light and UV radiation.
    [0070]
    [0071] Advantageously, the variation in the TiIV: MM (1-5) ratio in the structural unit of the MOF allows the photocatalytic activity to be modulated with visible light and / or with UV radiation of the heteromethalic MOF solid of Ti (IV) of the invention.
    [0072]
    [0073] The crystalline and porous heteromethal Ti (IV) MOF solid has stability in aqueous medium and in extreme acid and basic conditions.
    [0074] Advantageously, the variation in the TiIV: MM (i -5) ratio in the structural unit of the MOF allows modulating stability in aqueous medium and in extreme acid / base conditions.
    [0075]
    [0076] In one embodiment, the Ti (IV) heteromethalic MOF solid exhibits chemical stability in a pH range between 1-13, 1-10 or 2-12.
    [0077]
    [0078] In a particular embodiment, the crystalline and porous heterometic Ti (IV) MOF solid has a surface area (BET) greater than 1,000 m2 / g.
    [0079]
    [0080] The crystalline and porous heteromethal Ti (IV) MOF solid has modular electronic properties.
    [0081]
    [0082] Advantageously, the variation in the TiIV: MM (1-5) ratio in the structural unit of the MOF allows to modulate electronic properties such as the band gap in the heteromethalic MOF solid of Ti (IV) of the invention.
    [0083]
    [0084] Preferably, the tricarboxylic ligand L is selected from an aryl-C6 tricarboxylic acid, an aryl-C3N3 tricarboxylic acid or a derivative thereof of the acid type (aryl-
    [0085]
    [0086] A tricarboxylic ligand L having one of the following structures is preferable:
    [0087] (A) tricarboxylic aryl-C6:
    [0088]
    [0089] Ri = -COOH
    [0090] R2 = -H, - (CH2V 5CH3, -NH2, -OH, -NO2, -COOH,
    [0091]
    [0092]
    [0093] (B) tricarboxylic aryl-C3N3:
    [0094]
    [0095]
    [0096]
    [0097] (C) (aryl-3-aryl-C6 tricarboxylic:
    [0098]
    [0099]
    [0100] where, Ri is selected from:
    [0101]
    [0102]
    [0103] and R2 is -H, - (CH2V 5CH3, -NH2, -OH, -NO2, -COOH or halogen.
    [0104] (D) (aril-
    [0105]
    [0106]
    [0107] where, Ri is selected from:
    [0108]
    [0109]
    [0110] and R2 is -H, - (CH2) or -5CH3, -NH2, -OH, -NO2, -COOH or halogen.
    [0111] Even more preferable is the 1,3,5-benzene-tricarboxylic acid ligand, also called trimesic acid or trimesate ligand.
    [0112]
    [0113] The molecular structure of the Ti (IV) heteromethalic MOF solid according to the first aspect of the invention includes polar solvent molecules, which may be water molecules due to the effect of ambient humidity or as a consequence of the method of production.
    [0114]
    [0115] In one embodiment, the crystalline and porous heterometic Ti (IV) MOF solid has a molecular structure represented by the general formula (MUV-10):
    [0116] [ YOU IV3 MM 3 (O) 3 l_ 4 ] S
    [0117] where
    [0118] MII (1-5), each independently, is a cation Mg2 +, Ca2 +, Sr2 +, Ba2 +, Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 + or Cd2 +;
    [0119] L is a tricarboxylic ligand; Y
    [0120] S is a molecule of N, N-dimethylformamide, N, N-diethylformamide, N, N’-dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, or a water molecule.
    [0121]
    [0122] In one embodiment of the molecular structure of the general formula (MUV-10), the TiIV: MM (1_5) ratio may be between 50:50 and 99: 1.
    [0123]
    [0124] In a different embodiment, the crystalline and porous crystalline and porous Ti (IV) MOF solid has a molecular structure represented by the general formula (MUV-101):
    [0125] [CüM (3-2z) Tl IVz (L) 2 ] -S
    [0126] where
    [0127] z is a rational number between 0 and 1.5;
    [0128] L is a tricarboxylic ligand; Y
    [0129] S is a molecule of N, N’-dimethylformamide, N, N’-diethylformamide, N, N’-dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, or a water molecule.
    [0130]
    [0131] In one embodiment of the molecular structure of the general formula (MUV-101), the TiIV: Cu "ratio may be between 99: 1 and 15:85.
    [0132]
    [0133] In yet another different embodiment, the crystalline and porous heterometic Ti (IV) MOF solid has a molecular structure represented by the general formula (MUV-102): [T i ' V w) M IIw O (L) 2 X (3.w) ] S
    [0134] where
    [0135] w is a rational number between 0 and 3, with the proviso that when w is 0, an X is O2- and the rest, independently, an anion F-, Cl- or OH-;
    [0136] Mii (1-5), each independently, is a cation Mg2 +, Ca2 +, Sr2 +, Ba2 +, Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 + or Cd2 +;
    [0137] L is a tricarboxylic ligand; Y
    [0138] S is a molecule of N, N’-dimethylformamide, N, N’-diethylformamide, N, N’-dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, or a water molecule.
    [0139]
    [0140] In one embodiment of the molecular structure of the general formula (MUV-102), the TiIV: MII (1-5) ratio may be between 99: 1 and 33:67.
    [0141]
    [0142] Surprisingly, the authors of the present invention have found that all solid heteromethalic MOFs of Ti (IV) according to the first aspect of the present invention have photocatalytic activity with visible light and at least one of the following conditions:
    [0143] - chemical stability in aqueous medium;
    [0144] - chemical stability in a pH range between 1-13, 1-10 or 2-12;
    [0145] - porosity with a surface area (BET) greater than 1,000 m2 / g;
    [0146] - photocatalytic activity with UV radiation.
    [0147]
    [0148] In the present invention, the sizes of the micrometer particles that make up the MOF crystalline solids obtained are between 1-500 pm.
    [0149]
    [0150] In addition, the crystalline and porous heteromethal Ti (IV) MOF solids have thermal stability between -50 and 500 ° C and good gas adsorption properties such as N2 and CO2.
    [0151]
    [0152] These and other intrinsic characteristics of the new solid heteromethalic MOFs of Ti (IV) make them especially useful in the generation of solar fuels, photoactivated degradation processes, CO2 photoreduction, heterogeneous catalysis and as porous semiconductors with variable electronic properties, among others.
    [0153]
    [0154] In a second aspect, the present invention provides a method of obtaining the heteromethalic MOF solids of Ti (IV) that are based on an intrinsic doping in a single stage of synthesis and with simple and low-cost precursors, which allows modifying at will, among other properties, their photocatalytic activity against visible light and UV radiation
    [0155]
    [0156] Advantageously, the metal precursors used are simple and low-cost compounds, and the process for obtaining the heteromethalic MOF solid of Ti (IV) is designed to allow them to be combined in a single stage with high yields, with exact control over the distribution of the metals, that is, titanium and the divalent metals or metals, at the atomic level in the MOF obtained, and with the desired ratio between both metals for extreme control over the electronic, catalytic and photoactive properties of the MOF obtained.
    [0157]
    [0158] Surprisingly, the authors of the invention have found how to introduce metals, Ti (IV) and M (II) (1-5), as the active center of the MOF so that they are distributed homogeneously at the atomic level along the MOF.
    [0159]
    [0160] Thus, in a second aspect, the invention provides a method for obtaining the heteromethalic MOF solid of Ti (IV) defined in the first aspect of the invention, the process of which is characterized by the fact that it is carried out in a one-synthesis pot comprising the stages of:
    [0161] (i) mix in a polar solvent, S:
    [0162] - a precursor of Ti (IV),
    [0163] - at least one salt of a divalent metal of formula MX2 or MY,
    [0164] where
    [0165] M is Mg2 +, Ca2 +, Sr2 +, Ba2 +, Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 + or Cd2 +;
    [0166] X is F-, Cl-, Br-, I-, NO3-, ClO4-, BF4-, SCN-, OH-, CH3COO- or C5H7O2-,
    [0167] And it is SO42- and CO32-,
    [0168] - a tricarboxylic ligand L,
    [0169] where the stoichiometric ratio between the at least one divalent metal salt and the ligand is between 1: 1 and 1: 6, preferably about 1: 3,
    [0170] - and, optionally, an inorganic acid in a molar ratio between 5 and 500 equivalents g / mol of MX2 or MY salt;
    [0171] and then,
    [0172] (ii) heating the reaction mixture to give the TiF-MII solid MOF (1-5).
    [0173] Advantageously, the process described here allows intrinsic doping in a single stage or one-pot synthesis in an easy way and with direct control of the precursor ratios of Ti (IV) and metal salt (s) divalent (es) ) in the MOF obtained, where the proportion of titanium in the MOF is less than or equal to 50% and that of the divalent metal (s) the rest up to 100%.
    [0174]
    [0175] Unexpectedly, the combination of Ti (IV) precursors and certain divalent metal salts with the selection of a tricarboxylic ligand allows the formation of a crystalline solid of trigonal prismatic geometry with new intrinsic characteristics in the MOF obtained.
    [0176]
    [0177] All the procedures described herein provide a heteromethalic Ti (IV) MOF solid with homogeneous distribution of the metals -Ti (IV) and M (N) (1-5} - at the atomic level throughout the MOF structure.
    [0178]
    [0179] Advantageously, the processes described herein allow to obtain a crystalline and porous heteromethal Ti (IV) MOF solid, at gram scale with efficiencies greater than 80%.
    [0180]
    [0181] In a preferable embodiment of the process of the invention, intrinsic doping is carried out by "direct reaction".
    [0182]
    [0183] In a different embodiment of the process of the invention, intrinsic doping is carried out by "post-synthetic transformation." The general post-synthetic methodology for preparing heteromethalic MOFs involves the metallic exchange by chemical treatment of a preformed material in the presence of the metal. which has to be incorporated into the same structure by metallic exchange. On the contrary, in this embodiment, the material called MUV-10 can be used as starting material to generate new heteromethalic MOFs by transforming this precursor into other MOFs with structure, porosities and different physical properties.
    [0184]
    [0185] Advantageously, post-synthetic transformation provides in the same way that intrinsic doping by direct reaction a heteromethalic MOF solid of Ti (IV) with homogeneous atomic distribution of metals, titanium and divalent metal (s), throughout MOF structure. This is achieved because the Ti (IV) precursor chosen for use in the post-synthetic transformation is a heteromethalic Ti (IV) MOF solid as defined in the first aspect of the present invention.
    [0186] In the context of the invention, the polar solvent may be constituted by a single solvent or a mixture of polar solvents.
    [0187]
    [0188] The polar solvent can be selected from N, N'-dimethylformamide (DMF), N, N'-diethylformamide (DEF), N, N'-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), methanol, ethanol, isopropanol, n-propanol, water and mixtures thereof.
    [0189]
    [0190] The preferred polar solvent is N, N’-dimethylformamide (DMF) or a mixture of N, N’-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP), preferably at a 1: 1 ratio.
    [0191]
    [0192] In the context of the invention, inorganic acid can be selected from hydrochloric acid, formic acid, acetic acid, propanoic acid, benzoic acid and derivatives thereof.
    [0193]
    [0194] The Ti (IV) precursor may be selected from an organometallic Ti (IV) precursor such as a Ti (IV) alkoxide, preferably Ti (IV) isopropoxide, Ti (IV) methoxide, Ti (IV) ethoxide , Ti (IV) n-proproxide, Ti (IV) n-butoxide, Triethanolamine-Ti (IV) isopropoxide, Ti (IV) fe / f-butoxide, Ti (IV) oxo di-acetylacetonate; the Ti (IV) precursor can also be a titanium compound such as Ti (IV) tetrachloride, bis (cyclopentadienyl) -Ti (IV) dichloride, cyclopentadienyl-Ti (IV) trichloride or Ti (IV oxosulfate) ) or the like; or an air-stable Ti (IV) polynuclear compound such as a hexanuclear Ti (IV) complex.
    [0195]
    [0196] In one embodiment, the Ti (IV) precursor is the Ti (IV) heteromethalic MOF solid itself according to the first aspect of the invention, preferably the Ti (IV) heteromethalic MOF solid of formula MUV-10.
    [0197]
    [0198] In one embodiment, the tricarboxylic ligand L may be selected from an aryl-C6 tricarboxylic acid, an aryl-C3N3 tricarboxylic acid or a derivative thereof of the acidic (aryl-C'6) 3-aryl-C6 type or (aryl-C '6) 3-aryl-C3N3 tricarboxylic. Preferably, the tricarboxylic ligand L is trimesic acid.
    [0199]
    [0200] In one embodiment of the process of the invention, the Ti (IV) heteromethalic MOF solid that is prepared has the formula (MUV-10) [T iIV3MM3 (O) 3L4] S, and comprises in a onepof synthesis and by direct reaction the following stages:
    [0201] (i) mix in the polar solvent, S: the precursor of Ti (IV), at least one salt of a divalent metal of formula MX2 or MY, the tricarboxylic ligand L and inorganic acid, and then,
    [0202] (ii) heating the reaction mixture at a temperature greater than 80 ° C for a period equal to or greater than 24 hours, and then cooling to give the MOF solid of formula (MUV-10).
    [0203] In one embodiment, the TiIV and the at least one divalent metal MM (1_5) are in a TiIV: M "(1-5) ratio between 50:50 and 99: 1.
    [0204]
    [0205] In another different embodiment of the process of the invention, the MOF solid that is prepared has the formula (MUV-101) [CuM (3-2z) Ti IVz (L) 2 ] S, and comprises in a one-pot synthesis and by Direct reaction the following stages:
    [0206] (i) mixing in the polar solvent, S: the Ti (IV) precursor, at least one salt of a divalent metal of the formula CuX2 or CuY and the tricarboxylic ligand L,
    [0207] and then,
    [0208] (ii) heating the reaction mixture to a temperature greater than 100 ° C and then cooling to give the MOF solid of formula (MUV-101).
    [0209] In one embodiment, TiIV and Cu "are in a TiIV: Cu" (1-5) ratio between 99: 1 and 15:85.
    [0210]
    [0211] In another different embodiment of the process of the invention, the MOF solid that is prepared has the formula (MUV-102) [Ti IV (3-w) M IIw O (L) 2 X (3-w) ] S, and comprises in a one-pot synthesis and by direct reaction the following stages:
    [0212] (i) mixing in the polar solvent, S: the Ti (IV) precursor, at least one salt of a divalent metal of formula MX2 or MY, the tricarboxylic ligand L and the inorganic acid, and then,
    [0213] (ii) heating the reaction mixture at a temperature greater than 80 ° C for a period equal to or greater than 48 hours, and then cooling to give the MOF solid of formula (MUV-102).
    [0214] In one embodiment, the TiIV and the at least one divalent metal MM (1-5) are in a TiIV: M "(1-5) ratio between 99: 1 and 33:67.
    [0215]
    [0216] In another different embodiment of the process of the invention, the MOF solid that is prepared has the formula (MUV-101) [Cu II (3-2z) Ti IVz (L) 2 ] S, and comprises in a one-pot synthesis and by post-synthetic transformation the following stages:
    [0217] (i) mixing in the polar solvent, S: a Ti (IV) precursor, at least one salt of a divalent metal of formula CuX2 or CuY and the tricarboxylic ligand L,
    [0218] wherein the Ti (IV) precursor is a heteromethal Ti (IV) MOF solid as defined in the first aspect of the present invention, preferably the Ti (IV) heteromethal MOF solid of formula MUV-10,
    [0219] and then,
    [0220] (ii) heating the reaction mixture to a temperature below 100 ° C and then cooling to give the MOF solid of formula (MUV-101).
    [0221] In one embodiment, TiIV and CuII are in a TiIV: CuII ratio between 99: 1 and 15:85.
    [0222]
    [0223] In yet another different embodiment of the process of the invention, the MOF solid that is prepared has the formula (MUV-102) [TiIV (3-w) MMwO (L) 2X (3-w)] S, and comprises in a synthesis one-pot and by post-synthetic transformation the following stages:
    [0224] (i) mixing in the polar solvent, S: a Ti (IV) precursor, at least one salt of a divalent metal of formula MX2 or MY and the tricarboxylic ligand L,
    [0225] wherein the Ti (IV) precursor is a heteromethal Ti (IV) MOF solid as defined in the first aspect of the present invention, preferably the Ti (IV) heteromethal MOF solid of formula MUV-10,
    [0226] and then,
    [0227] (ii) heating the reaction mixture to a temperature below 100 ° C and then cooling to give the MOF solid of formula (MUV-102).
    [0228] In one embodiment, TiIV and at least one divalent metal MN (1-5) are in a TiIV: MM (1-5) ratio between 99: 1 and 33:67.
    [0229]
    [0230] In a preferred embodiment of these processes, the proportion of Ti (IV) precursor with respect to the divalent metal salt (s) of formula MX2 or MY to be added to the initial mixture (i ) may vary between 99: 1 and 50:50 depending on the MOF material synthesized. This proportion is understood as considering moles of Ti (IV) in the precursor used with respect to moles of divalent metal (s) in the salt or salts of divalent metals used.
    [0231]
    [0232] Advantageously, the Ti (IV) heteromethalic MOF solid can be prepared on a gram scale with high efficiency from simple precursors. In addition, it has the advantage that the solid can be isolated in the form of crystals of well-defined morphology in all cases regardless of the incorporated metals and / or the specific procedure employed.
    [0233]
    [0234] An additional advantage of the different formulations described herein (multiple combinations of divalent metals with tetravalent titanium) is that they have both photocatalytic activity with ultraviolet radiation as with visible light.
    [0235]
    [0236] In conclusion, the properties of the new solid MOFs of Ti (IV) -M (II) can be modulated at will. The MOFs solids of Ti (IV) -M (N) (1-5) according to the invention can be prepared as large-scale crystals and have excellent chemical stability. Heteromethalic clusters in their structures represent a versatile platform that allows you to manipulate your electronic structure and photoactivity simply by the appropriate choice of divalent metal, compared to other much more complex strategies used that involve the functionalization of the linker element (the ligand).
    [0237]
    [0238] A relevant advantage of the present invention is the possibility of incorporating variable percentages of TiIV: MM in the various materials described without sacrificing in any case their homogeneous distribution throughout the material. The synthesis procedures described here ensure the formation of a single material with a homogeneous distribution of metals, that is, titanium and at least one divalent metal, at the atomic level, which allows physical properties to be controlled more precisely (electronic structure ) and catalytic material as well as its chemical stability.
    [0239]
    [0240] This and other properties intrinsic to the crystalline and porous heteromethalic MOF solids of Ti (IV), make them relevant for use, in accordance with a third aspect of the invention, in the generation of solar fuels, photoactivated degradation, CO2 photoreduction , water treatment by degradation of organic pollutants or heavy metal capture, heterogeneous catalysis, as a component or part of an electronic component and / or as porous or photoactive coatings in ceramic products, paints, plastics and gelcoat for the control of pollutants in the atmosphere inside.
    [0241]
    [0242] Therefore, with the Ti (IV) heteromethalic MOF solid, according to the first aspect of the invention, as well as with the method of obtaining it, in accordance with the second aspect of the invention, the aforementioned drawbacks are resolved, also presenting other advantages that will be described below in the detailed description of the invention.
    [0243]
    [0244] Brief description of the figures
    [0245]
    [0246] To better understand how much has been exposed, some drawings are attached in which, schematically and only by way of non-limiting example, a practical case is represented of realization.
    [0247]
    [0248] Figure 1 shows (a) scanning electron miscroscopy (SEM) images and (b) optical microscope images of MUV-10 family crystals obtained in accordance with Example 1 and using different titanium (IV) precursors, in particular, from left to right: titanium (IV) [Ti (OiPr) 4] isopropoxide, bis-cyclopentadienylthitanium (IV) dichloride [Cp2TiCl2], and titanium (IV) [Ti6] hexanuclear complex, and in (c) X-ray powder diffractograms of the materials obtained with the different precursors, demonstrating the formation of the same phase of the material throughout the MUV-10 family.
    [0249]
    [0250] Figure 2 shows the homogeneous distribution of calcium and titanium metals obtained with the electron microscope along the entire surface of the MUV-10 (Ca) material prepared according to Example 1.
    [0251]
    [0252] Figure 3 shows (a) X-ray powder diffractograms of MUV-10 (Ca) after immersing in aqueous solutions at different pH values (from bottom to top: pH = 2 - pH = 12) and (b) isotherms of adsorption of N2 at 77 K before and after immersion in aqueous solutions with different pH values (from bottom to top: obtained, pH = 2, pH = 7, pH = 12).
    [0253]
    [0254] Figure 4 shows (a) SEM images of the MUV-101 Family (Ti-Cu) obtained according to Example 2 or 3, (b) X-ray powder diffraction representative of the MUV-101 Family, demonstrating the formation of HKUST type structures after the incorporation of copper, (c) Comparison of the porosity of different MUV-101 materials with a Ti: Cu ratio in its structure 15:85.
    [0255]
    [0256] Figure 5 shows the refinement by the LeBail method of the powder X-ray diffractogram of a material of the MUV-102 family (Ti-Fe) obtained according to Example 4 or 5, which demonstrates the formation of zeolitic type structures mnt. The inside box shows the representative morphology of the crystals of these materials.
    [0257]
    [0258] Figure 6 shows the adsorption Isotherm of N2 to 77 K of the MUV-102 (Ti-Fe) material obtained according to Example 4 or 5.
    [0259]
    [0260] Figure 7 shows different powder X-ray diffractograms after immersion in aqueous solutions at different pHs (from bottom to top: pH = 1, 2, 4, 6, 7, 8, 10 and 13) of MUV-102 materials (Ti-Fe) obtained according to Example 4 or 5, which demonstrates its chemical stability against acids and bases.
    [0261]
    [0262] Figure 8 shows the homogeneous distribution of iron and titanium metals acquired with the electron microscope along the entire surface of MUV-102 (Ti-Fe) prepared according to Example 4 or 5.
    [0263]
    [0264] Detailed description of the invention
    [0265]
    [0266] In the following, preferred embodiments for carrying out the present invention are described.
    [0267]
    [0268] The problem that the present invention intends to solve is that of providing new crystalline and porous materials based on Ti (IV) making use of Ti-M heteromethalic clusters as species of controlled reactivity to allow the formation of multiple metal-organic architectures by combination of clusters Ti (IV) -M (II) (M = Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd) and ligands based on low-cost polyaroaromatic carboxylic acids .
    [0269]
    [0270] To date, this type of material has not been able to be generated efficiently due to the intrinsic limitations to the synthesis of titanium MOFs set forth in the background section of the invention. This problem has been addressed by the inventors through the use of another metal precursor M (II), in addition to that of Ti (IV), under conditions determined in the synthesis of these materials. This allows to generate TiIV-MM heteromethalic MOFs of high chemical stability that allows combining both types of metals in the structure in variable proportions to generate multiple combinations and architectures of variable porosity.
    [0271]
    [0272] TiF-MM MOF solids (1-5) can be obtained on a large scale, easily and with control over both crystal size and morphology. MOF solids of TiIV-MII (1-5) with variable formulations can be generated by direct control of the proportion of Ti and the rest of metals in the material. The control is not limited only to binary combinations, titanium can be combined with up to 5 different types of metals in the same material. Unlike the extrinsic doping methodologies described to date - synthesis of the material and subsequent incorporation of other metals in a second stage - the procedures described here allow you to combine Ti with divalent metals in a single stage, with exact control over their distribution in the MOF and the desired ratio for precise control over the electronic, catalytic and photoactive properties of the final MOF.
    [0273] In a preferred embodiment, the TiF-MM (i-5) MOF solids family is prepared with the general formula (MUV-10): [TiIV3MII3 (O) 3L4] S
    [0274]
    [0275] MUV-10 family
    [0276] These materials have a sodalite structure in which the TiIV-M "heteromethalic units" are joined by trimesic acid to form a three-dimensional neutral network with two types of pores, one of octahedral geometry and one of dodecahedral geometry.
    [0277] Such MOF solids of TiIV-MII (1-5) are prepared by direct reaction of Ti (IV) organometallic precursors, generally with Ti (IV) alkoxides (e.g., Ti (IV) isopropoxide, Ti methoxide (IV), Ti (IV) ethoxide, Ti (IV) n -propoxide, Ti (IV) n-butoxide, Triethanolamine-Ti (IV) isopropoxide, Ti (IV) tert-butoxide, oxo di- Ti (IV) acetylacetonate, among others), or other commercial Ti (IV) precursors (Ti (IV) tetrachloride, bis (cyclopentadienyl) -Ti (IV) dichloride, cyclopentadienyl-Ti (IV) trichloride or oxosulfate of Ti (IV)), as well as other non-commercial Ti (IV) polynuclear compounds that are stable to air, such as the hexanuclear complexes of Ti (IV); and simple salts MX2 (X = F, Cl, Br, I, NO3 ', ClO4', BF4 ', SCN-, OH-, acetate or acetylacetonate) or MY (Y = SO42', CO32 ') of divalent metals (MM = Mg, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd), so as to maintain net neutrality, with trimesic acid in stoichiometric ratio 1: 3 in polar solvents with a boiling point greater than 80 ° C such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, water.
    [0278] To this solution is added an inorganic acid that acts as a modulator of crystalline growth in varying proportions, typically between 5 and 500 equivalents g / mol, depending on the inorganic acid used, and is kept under stirring until the reagents are completely dissolved.
    [0279] This reaction mixture is heated at a temperature greater than 80 ° C for a period equal to or greater than 24 hours.
    [0280] After this time, the mixture is cooled to room temperature and the solid obtained is separated by centrifugation, washed thoroughly with organic solvents to remove the unreacted material and allowed to dry under vacuum overnight. The procedure is suitable for any of the metal precursors described above and can be scaled to produce grams of material in reactors up to 1 liter in volume.
    [0281] The resulting MOF solid is isolated in the form of crystals with well-defined morphologies that they can be controlled both by temperature, reaction time and by the proportion of inorganic acid added. This size can vary from hundreds of nanometers to 250 pm, while the morphology of the crystals can vary from cubic to octahedral, through different intermediate morphologies between the two named (Figure 1).
    [0282] The crystalline structure of the MOF solid of TiIV-MM (1-5) as well as the homogeneous distribution of the metals along the crystal is always the same, regardless of the morphology and size of the crystals (Figure 2).
    [0283] These MOF solids of TiIV-MII (1-5) can be prepared with any type of tricarboxylic ligand, that is, aryl-C6 tricarboxylic acid ligands (for example, trimesic acid (1,3,5-benzene-tricarboxylic acid) ) or aryl-C3N3 tricarboxylic acid type (for example, 2,4,6-triazine-tricarboxylic acid), as well as derivatives thereof of the (aryl-C'6) 3-aryl-C6 or (aryl-) type C'6) 3-aryl-C3N3 tricarboxylic.
    [0284] The incorporation of different metals in the structure allows modulating the absorption of radiation to make these systems active against visible light and as a consequence the improvement of their photocatalytic activity.
    [0285] Chemical stability experiments were performed to check the resilience of these materials against aqueous solutions at different pH values. It was found that all the materials studied were stable in water between the pH values between 2 and 12, without observing any signs of degradation in their structure or in their adsorption properties of N2 to 77 K with surface areas close to 1000 m2 / g (Figure 3).
    [0286] The mixture of TiIV-MM MOF solids (1-5) with a solution of a divalent metal salt under the appropriate reaction conditions also allows the post-synthetic transformation of the MUV-10 family structure into other structures (MUV Family -101, MUV-102) with controlled Ti: M ratios, as described in the examples below.
    [0287]
    [0288] In another embodiment, the TiF-MII (1-5) MOF solids family is prepared with the general formula (MUV-101): [Cu "(3-2z) TiIVz (L) 2] S
    [0289]
    [0290] MUV-101 family
    [0291] These materials have the same structure as the compound known as HKUST-1, with formula Cu3 (btc) 2, where btc refers to trimesic acid. The main difference lies in the introduction of variable percentages of Ti (IV) replacing the Cu (II) dimethyl units present in the material originally described.
    [0292] The preparation of materials of the MUV-101 family is carried out by direct reaction of Ti (IV) organometallic precursors, such as those described above for the MUV-10 family, with trimesic acid in the presence of a simple Cu salt (II) (CuF2, CuCL, CuBr2, CuI2, Cu (OAc) 2 CuSO4, Cu (NO3) 2, CuCO3) in polar solvents such as N, N'-dimethylformamide, N, N'-diethylformamide, N, N ' -dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, water and at temperatures above 100 ° C.
    [0293] After completion of the reaction, the resulting solid is separated by centrifugation and washed thoroughly with organic solvents and dried under vacuum.
    [0294] The family of resulting materials that we call MUV-101, are isolated in the form of crystals with cubic morphology, surface areas between 1000-2000 m2 / g and Ti: Cu ratios varying between 99: 1 and 15:85 depending on the Ti ratio: Cu initially employed (Figure 4).
    [0295] These systems have stability in water in the presence of acid and base in pH ranges between 1 and 10.
    [0296] The preparation of this MOF solid of TiIV-MM (1-5) can also be carried out using preformed MUV-10 family materials based on Ti (IV) and M (II) as precursors. These are subjected to a post-synthetic transformation procedure, not described to date, in the presence of simple salts of Cu "(CuF2, CuCL, CuBr2, CuL, Cu (OAc) 2 CuSO4, Cu (NO3) 2, CuCO3) using different polar solvents such as N, N'-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, water, at temperatures below 100 ° C.
    [0297] Once the reaction is over, the new material is isolated by centrifugation, washing with the solvent and drying under vacuum.
    [0298] The family of MUV-101 materials synthesized by this route are also isolated in the form of crystals with cubic morphology surface areas between 1000-2000 m2 / g and Ti: Cu ratios varying between 99: 1 and 15:85 depending on the time and the reaction temperature
    [0299]
    [0300] In another embodiment, the TiIV-MM (1-5) MOF solids family is prepared with the general formula (MUV-102): [TiIV (3-w) MIIwO (L) 2X (3-w)] S
    [0301]
    [0302] MUV-102 family
    [0303] The materials have the same zeolite type structure of mtn topology described above for the MIL-100 family of MOFs. In contrast to these, the materials of the invention incorporate TiIV-M "heteromethalic clusters" replacing the homometallic M (III) (M = Cr, Al, Fe) described.
    [0304] The MOF solids of this family have the general formula included above. Heteromethalic clusters are connected by trimesate ligands to form a porous three-dimensional network with two pore sizes of 2.4 and 2.9 nm in diameter. Like the MUV-10 family, these materials can be prepared by direct reaction of the organ-metallic precursors of Ti (IV) and simple MX2 or MY salts of divalent metals with trimesic acid in polar solvents with a boiling point greater than 80 ° C such as N, N'-dimethylformamide, N, N'-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, water.
    [0305] To this solution is added an inorganic acid that acts as a modulator of crystalline growth in varying proportions, typically between 5 and 500 equivalents g / mol, depending on the inorganic acid used, and is kept under stirring until the reagents are completely dissolved.
    [0306] This reaction mixture is heated at a temperature greater than 80 ° C for a period equal to or greater than 48 hours. After this time, the mixture is cooled to room temperature and the solid obtained is separated by centrifugation, washed thoroughly with organic solvents to remove the unreacted material and allowed to dry under vacuum overnight.
    [0307] The procedure is suitable for any of the metal precursors described above and can be scaled to produce grams of material in reactors up to 1 liter in volume.
    [0308] The family of resulting materials that we call MUV-102, are isolated in the form of crystals with octahedral morphology, ratios Ti: M "variables between 99: 1 and 33:67 depending on the Ti: M ratio used (Figure 5), with surface areas close to 2000 m2.g-1 in all cases (Figure 6). Figure 7 shows the results of representative stability for one of the materials in the family that confirms its structural stability in aqueous solutions in pH ranges between 1 and 10, as does the MUV-101 family.
    [0309] These materials can also be prepared by post-synthetic transformation of the MUV-10 family in a manner analogous to the MUV-101 family described above. In this procedure, heteromethalic MOFs of the TiIV-MM-based family are suspended in a solution of a single MX2 or MY salt of divalent metals in polar solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N- dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, water, at temperatures below 100 ° C.
    [0310] Once the reaction is finished, the material is separated by centrifugation and washed thoroughly with the organic solvent used, to remove unreacted remains.
    [0311] Again, the resulting MOF-MUV-102 solids are isolated as octahedral morphology particles and with variable TiIV-MM ratios between 99: 1 and 33:67, depending on the time and the reaction temperature, as well as the concentration of the dissolution of the metal used. Unlike the post-synthetic metal exchange methodologies described above, this post-synthetic transformation ensures a homogeneous distribution of metals throughout the entire crystal (Figure 8).
    [0312]
    [0313] As described in the descriptive part of the invention, the systems integrated by solid heteromethal Ti (IV) MOFs of the invention have the following advantages:
    [0314]
    [0315] - Use of heteromethal clusters of Ti (IV) as the structural unit of the MOF.
    [0316] - Heteromethal Ti (IV) MOFs solids with variable formulations by direct control of the proportion of Ti (IV) and other divalent metals that form the structural unit of the MOF.
    [0317] - Up to 5 different types of metals in addition to titanium with homogeneous distribution at the atomic level in the same MOF.
    [0318] - Exact control over the distribution of metals in the MOF and the desired proportion of TiIV-MM for severe control over the electronic, catalytic and photoactive properties of the final MOF material.
    [0319] - Control of the morphology and particle size of the heteromethal Ti (IV) MOF solid, essential for the adequate dispersion of MOFs in organic solvents and processed in the manufacture of functional coatings.
    [0320] - One-pot synthesis procedures by direct reaction with multiple metal precursors and / or by post-synthetic transformation from a heteromethalic titanium MOF solid defined in the invention. In both cases, the synthesis procedure is easily scalable to reactor sizes of at least one liter in volume.
    [0321] - Intrinsic doping in a single stage and using cheaper precursors to obtain heteromethalic titanium MOFs.
    [0322] - Improvement of photocatalytic activity with visible light.
    [0323] - High chemical stability. The heteromethalic MOF solids of Ti (IV) remain intact when immersed in water, even in the presence of acid or base (pH range 2 12) without this treatment affecting its crystalline structure, or its properties.
    [0324]
    [0325] Example plos
    [0326] Example 1: Synthesis of MUV-10 (Ca)
    [0327] 125 mg of trimesic acid (595 pmol) is dissolved in a mixture of 12 mL of N, N-dimethylformamide (DMF) and 3.5 mL of acetic acid. To this solution is added 36 pL of Ti (IV) [Ti (Oi) Pr) 4] isopropoxide (120 pmol) and 26 mg of calcium chloride (120 pmol) under an inert atmosphere and in the absence of moisture. The mixture is stirred until the reagents are completely dissolved and heated in an oven at 120 ° C for 48 hours. After this time, the solid obtained is separated by centrifugation, washed with two portions of DMF and methanol and allowed to dry in vacuo.
    [0328]
    [0329] The same methodology as above was repeated, except that in this case bis-cyclopentadienylthitanium (IV) dichloride [Cp2TiCh] was added instead of the titanium (IV) isopropoxide.
    [0330]
    [0331] The same previous methodology was repeated, except that in this case the hexanuclear titanium (IV) [Ti6] complex was added instead of bis-cyclopentadienylthitanium (IV) dichloride.
    [0332]
    [0333] The different morphologies, homogeneous distribution of metals, crystallinity and chemical stability of the MUV-10 family of materials are shown in Figures 1, 2 and 3.
    [0334]
    [0335] Example 2: Synthesis of MUV-101 Ti-Cu by direct reaction
    [0336]
    [0337] 125 mg of trimesic acid (595 pmol) is dissolved in a mixture of 12 mL of N, N-dimethylformamide (DMF) and 3 mL of acetic acid. To this solution is added 17 pL Ti (IV) isopropoxide (54 pmol) and 41 mg Cu (II) chloride (306 pmol). The mixture is stirred until the reagents are completely dissolved and heated in an oven at 120 ° C for 48 hours. After this time, the solid obtained is separated by centrifugation, washed with two portions of DMF and methanol and allowed to dry in vacuo.
    [0338]
    [0339] Example 3: Synthesis of MUV-101 Ti-Cu by Post-Synthetic Transformation (PST) of MUV-10
    [0340]
    [0341] 100 mg of MUV-10 (Ca) is suspended in 10 mL of a 0.005 M solution of Cu (II) chloride in a DMF: 1: 1 MPN mixture. The mixture is placed in a preheated oven at 65 ° C for a maximum period of 15 days. After this time, the solid obtained is separated by centrifugation, washed with two portions of DMF and methanol and allowed to dry in vacuo.
    [0342]
    [0343] The morphology, crystallinity and porosity of the MUV-101 family of materials is shown in Figure 4.
    [0344] Example 4: Synthesis of MUV-102 Ti-Fe by direct reaction
    [0345]
    [0346] 125 mg of trimesic acid (595 pmol) is dissolved in a mixture of 12 mL of W, W-dimethylformamide (DMF) and 3 mL of acetic acid. To this solution is added 36 pL of Ti (IV) isopropoxide (120 pmol) and 48 mg of Fe (II) chloride (240 pmol) in a dry box or absence of oxygen. The mixture is stirred until the reagents are completely dissolved and heated in an oven at 120 ° C for 48 hours. After this time, the solid obtained is separated by centrifugation, washed with two portions of DMF and methanol and allowed to dry in vacuo.
    [0347]
    [0348] Example 5: Synthesis of MUV-102 Ti-Fe by Post-Synthetic Transformation (PST) of MUV-10
    [0349]
    [0350] 100 mg of MUV-10 (Ca) is suspended in 10 mL of a 0.005 M solution of Fe (II) chloride in a DMF: NMP 1: 1 mixture in the absence of oxygen. The mixture is placed in a preheated oven at 65 ° C for a maximum period of 10 days. After this time, the solid obtained is separated by centrifugation, washed with two portions of DMF and methanol and allowed to dry in vacuo.
    [0351]
    [0352] The morphology, crystallinity, chemical stability and homogeneous distribution of metals of the MUV-102 family of materials are shown in Figures 5, 6, 7 and 8.
    [0353]
    [0354] Study of the properties of the solid MUV-10
    [0355]
    [0356] The distribution of the pore size obtained from adsorption isotherms of N2 confirmed a homogeneous pore diameter of 10.3A, which is in accordance with the theoretical value of 12.0A calculated from the structure.
    [0357]
    [0358] The hydrolytic stability of the material between pH 2 and 12 was analyzed. According to the refraction of the diffraction pattern and the adsorption measures of N2, the immersion of the solid MUV-10 (Ca) in concentrated solutions of HCl and NaOH (aq) for 24 hours it did not affect its crystallinity or its surface area.
    [0359]
    [0360] In addition to their chemical stability, ultraviolet (UV) light photoactivity of the MOFs of the invention was also studied. For this, the electronic structure of MUV-10 (Ca) was computed computationally using the theory of functional density (DFT). According to its state density diagram, this TiIV-Ca MOF "is a semiconductor with a band 3.1 eV gap, consistent with the estimated optical band gap from diffuse reflectance spectroscopy. As in other prior art MOFs, the conduction band (CB) is dominated by the 3d orbitals of the Ti, while the valence band (VB) is mainly populated by the 2p orbitals of the carbon atoms and oxygen in the aromatic ligand. To test the photoactivity of MUV-10 (Ca), the suspended solid was irradiated in tetrahydrofuran (THF) deoxygenated with UV-B radiation (A = 280-315 nm). This produced a change in color, from white to dark brown, in less than 2 hours. This change remained stable over time and was reversed immediately after exposure of the solid to air. The electron paramagnetic resonance spectrum (EPR) of MUV-10 (Ca) before and after irradiation confirmed the presence of two signals exclusively for the irradiated sample. A wide signal at 0.35 T with parameters g adjusted to gn = 1,975 and gI = 1,946, characteristic of the Ti (III) species, and a narrower and better defined one to the lower fields with a g = 2.00 that can attributed to the formation of photoexcited radicals of the trimesate ligand. This fact confirmed that the photoreduction of titanium in the MOF occurs through the generation of an excited state of the ligand that transfers the charge to the Ti (IV) centers in the metal clusters of the MOF by a ligand-charge transfer mechanism. metal.
    [0361]
    [0362] Visible light photoactivity of the heteromethalic MOFs of the invention that incorporated metals with d electrons into their valence layer was also tested to improve their photoactivity with visible light. For this, a solid MUV-10 (Mn) was prepared by direct reaction following the same methodology as for solid MUV-10 (Ca), detailed in the examples. According to the theoretical calculations (equivalent to those detailed above for the same material with Ca), the incorporation of Mn into the material significantly reduces the band gap (2.6 eV) as a result of the introduction of electrons d into the conduction band. Next, the activity of the solid MUV-10 (Mn) was demonstrated with visible light. For this, the activity of the MOF solid was studied as a photocatalyst for the generation of H2. A suspension of the solid was irradiated in an H2O: CH3OH mixture with a xenon lamp (300 W), confirming that the MUV-10 (Mn) phase produces 6500 pmol / g- of H2, more than double the amount generated by the MUV-10 (Ca) material, after 24 hours of irradiation, without altering the structure or porosity of the solid. This fact confirms the possibility of modifying the electronic structure and photoactivity of the solid by appropriate choice of the metals incorporated into its structure.
    [0363]
    [0364] Although reference has been made to a specific embodiment of the invention, it is apparent to one skilled in the art that the solvent type or the titanium (IV) precursor, for example, among others, they are susceptible to variations and modifications, and that all the mentioned details can be substituted by other technically equivalent ones, without departing from the scope of protection defined by the appended claims.
    权利要求:
    Claims (32)
    [1]
    1. Heteromethal Ti (IV), crystalline and porous MOF solid, characterized in that it comprises a tricarboxylic ligand L as an organic part of MOF and TiIV with at least one divalent metal Mm (1-5) as a structural unit and part inorganic MOF, where TiIV and at least one divalent metal Mm (1-5) are homogeneously distributed at the atomic level in the MOF.
    [2]
    2. Ti (IV) heteromethalic MOF solid according to claim 1, wherein the TiIV and the at least one MII divalent metal (1-5) are interconnected with the tricarboxylic ligand L forming a three-dimensional structure.
    [3]
    3. Ti (IV) heteromethalic MOF solid according to any one of the preceding claims, wherein:
    - the tricarboxylic ligand L is selected from an aryl-C6 tricarboxylic acid, an aryl-C3N3 tricarboxylic acid or a derivative thereof of the acid type (aryl-
    [4]
    4. Ti (IV) heteromethalic MOF solid according to any one of the preceding claims, wherein the tricarboxylic ligand L is one of the following (A, B, C, D):
    (A) tricarboxylic aryl-C6:
    R1 = -COOH
    R2 = -H, - (CH2V 5CH3, -NH2, -OH, -NO2, -COOH,

    [5]
    5. Ti (IV) heteromethalic MOF solid according to claim 4, wherein the tricarboxylic ligand L is 1,3,5-benzene-tricarboxylic acid.
    [6]
    6. Ti (IV) heteromethalic MOF solid according to any one of claims 1-5, wherein the MOF solid has the general formula (MUV-10):
    [ YOU IV3 MM 3 (O) 3 l_ 4 ] S
    where
    Mii (1-5), each independently, is a cation Mg2 +, Ca2 +, Sr2 +, Ba2 +, Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 + or Cd2 +;
    L is a tricarboxylic ligand; Y
    S is a molecule of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, or a water molecule.
    [7]
    7. Ti (IV) heteromethalic MOF solid according to claim 6, wherein the TiIV and the at least one Mii divalent metal (1-5) are in a TiIV: MM (1_5) ratio between 50:50 and 99: 1 .
    [8]
    8. Ti (IV) heteromethalic MOF solid according to any one of claims 1-5, wherein the MOF solid has the general formula (MUV-101):
    [Cü II (3-2z) Tl IVz (L) 2 ] -S
    where
    z is a rational number between 0 and 1.5;
    L is a tricarboxylic ligand; Y
    S is a molecule of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, or a water molecule.
    [9]
    9. Ti (IV) heteromethalic MOF solid according to claim 8, wherein the TiIV and the Cu1 are in a TiIV: CuI1 ratio between 99: 1 and 15:85.
    [10]
    10. Ti (IV) heteromethalic MOF solid according to any one of claims 1-5, wherein the MOF solid has the general formula (MUV-102):
    [T i IV (3-w) MM w O (L) 2 X (3-w) ] S
    where
    w is a rational number between 0 and 3, with the proviso that when w is 0, an X is O2- and the rest, independently, an anion F-, Cl- or OH-;
    Mii (1-5), each independently, is a cation Mg2 +, Ca2 +, Sr2 +, Ba2 +, Ti2 +, V2 +, Cr2 +, Mn2 +, Fe2 +, Co2 +, Ni2 +, Cu2 +, Zn2 + or Cd2 +; 9
    L is a tricarboxylic ligand; Y
    S is a molecule of N, N-dimethylformamide, N, N-diethylformamide, N, N dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol, n-propanol, or a water molecule.
    [11]
    11. Ti (IV) heteromethalic MOF solid according to claim 10, wherein the TiIV and the
    at least one divalent metal MM (1-5) is in a TiIV: MII (1-5) ratio between 99: 1 and
    33:67
    [12]
    12. Ti (IV) heteromethalic MOF solid according to any one of the preceding claims (1-11), which has photocatalytic activity with visible light and at least one of the following conditions:
    - chemical stability in aqueous medium;
    - chemical stability in a pH range between 1-13, 1-10 or 2-12;
    - porosity with a surface area (BET) greater than 1,000 m2 / g;
    - photocatalytic activity with UV radiation.
    [13]
    13. Method of synthesis of a heteromethalic MOF solid of Ti (IV), crystalline and
    porous according to any one of claims 1-12, characterized in that
    that, through a one-pot synthesis, the procedure comprises:
    (i) mix in a polar solvent, S:
    - a precursor of Ti (IV),
    - at least one salt of a divalent metal of formula MX2 or MY,
    where

    [14]
    14. Synthesis process according to claim 13, wherein the inorganic acid is selected from hydrochloric acid, formic acid, acetic acid, propanoic acid, benzoic acid and derivatives thereof.
    [15]
    15. Synthesis process according to claim 13, wherein the polar, S, is selected from N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methanol, ethanol, isopropanol , n-propanol, water and mixtures thereof.
    [16]
    16. Synthesis method according to claim 13, wherein the Ti (IV) precursor and the at least one salt of a divalent metal of formula MX2 or MY are added to the mixture in a ratio between 99: 1 and 50:50 .
    [17]
    17. Synthesis method according to claim 13 or 16, wherein the Ti (IV) precursor is selected from an organometallic Ti (IV) precursor such as a Ti (IV) alkoxide, preferably, Ti (IV) isopropoxide , Ti (IV) methoxide, Ti (IV) ethoxide, Ti (IV) n-propoxide, Ti (IV) n-butoxide, Triethanolamine-Ti (IV) isopropoxide, Ti / t-butoxide (IV) , Ti (IV) oxo di-acetylacetonate; a Ti (IV) precursor such as Ti (IV) tetrachloride, bis (cyclopentadienyl) -Ti (IV) dichloride, cyclopentadienyl-Ti (IV) trichloride or Ti (IV) oxosulfate or the like; an air-stable Ti (IV) polynuclear compound such as a Ti (IV) hexanuclear complex, or a heteromethal Ti (IV) MOF solid, preferably the Ti (IV) heteromethalic MOF solid of formula (MUV-10) .
    [18]
    18. Synthesis process according to claim 13, wherein the tricarboxylic ligand L is selected from an aryl-C6 tricarboxylic acid, an aryl-C3N3 tricarboxylic acid or a derivative thereof of the acidic (aryl-C'6) 3-aryl type -C6 or (aryl-C'6) 3-aryl-C3N3 tricarboxylic acid.
    [19]
    19. Method according to any one of claims 13 to 18 for obtaining the MOF solid of formula (MUV-10) [TiIV3MM3 (O) 3L4] S, defined in claims 6-7, comprising in a one-pot synthesis and by direct reaction the following stages:
    (i) mixing in the polar solvent, S: the Ti (IV) precursor, at least one salt of a divalent metal of formula MX2 or MY, the tricarboxylic ligand L and inorganic acid, and then,
    (ii) heating the reaction mixture at a temperature greater than 80 ° C for a period equal to or greater than 24 hours, and then cooling to give the MOF solid of formula (MUV-10).
    [20]
    20. Method according to claim 19, wherein the TiIV and the at least one divalent metal MII (1-5) are in a TiIV: MM (1-5) ratio between 50:50 and 99: 1.
    [21]
    21. Method according to any one of claims 13 to 18 for obtaining the MOF solid of formula (MUV-101) [CuII (3-2z) TiIVz (L) 2] S, defined in claims 8-9, comprising in a one-pot synthesis and by direct reaction the following stages:
    (i) mixing in the polar solvent, S: the Ti (IV) precursor, at least one salt of a divalent metal of the formula CuX2 or CuY and the tricarboxylic ligand L,
    and then,
    (ii) heating the reaction mixture to a temperature greater than 100 ° C and then cooling to give the MOF solid of formula (MUV-101).
    [22]
    22. Method according to any one of claims 13 to 18 for obtaining the MOF solid of formula (MUV-101) [CuM (3-2z) TiIVz (L) 2] S, defined in claims 8-9, comprising in a one-pot synthesis and by post-synthetic transformation the following stages:
    (i) mixing in the polar solvent, S: a Ti (IV) precursor, at least one salt of a divalent metal of formula CuX2 or CuY and the tricarboxylic ligand L,
    wherein the Ti (IV) precursor is a heteromethal Ti (IV) MOF solid according to any one of claims 1 to 12, preferably the Ti (IV) heteromethal MOF solid of formula (MUV-10),
    and then,
    (ii) heating the reaction mixture to a temperature below 100 ° C and then cooling to give the MOF solid of formula (MUV-101).
    [23]
    23. Method according to claim 21 or 22, wherein the TiIV and the at least one divalent metal MII (1-5) are in a TiIV: MM (1-5) ratio between 99: 1 and 15:85.
    [24]
    24. Method according to any one of claims 13 to 18 for obtaining the MOF solid of formula (MUV-102) [TiIV (3-w) MIIwO (L) 2X (3-w)] S, defined in claims 10 -11, which comprises in a one-pot synthesis and by direct reaction the following steps:
    (i) mixing in the polar solvent, S: the Ti (IV) precursor, at least one salt of a divalent metal of formula MX2 or MY, the tricarboxylic ligand L and inorganic acid, and then,
    (ii) heating the reaction mixture at a temperature greater than 80 ° C for a period equal to or greater than 48 hours, and then cooling to give the MOF solid of formula (MUV-102).
    [25]
    25. Method according to any one of claims 13 to 18 for obtaining the MOF solid of formula (MUV-102) [TiIV (3-w) MIIwO (L) 2X (3-w)] S, defined in claims 10 -11, which comprises in a one-pot synthesis and by post-synthetic transformation the following stages:
    (i) mixing in the polar solvent, S: a Ti (IV) precursor, at least one salt of a divalent metal of formula MX2 or MY and the tricarboxylic ligand L,
    wherein the Ti (IV) precursor is a heteromethal Ti (IV) MOF solid according to any one of claims 1 to 12, preferably the Ti (IV) heteromethal MOF solid of formula (MUV-10),
    and then,
    (ii) heating the reaction mixture to a temperature below 100 ° C and then cooling to give the MOF solid of formula (MUV-102).
    [26]
    26. Method according to claim 24 or 25, wherein the TiIV and the at least one divalent metal MII (1-5) are in a TiIV: MM (1-5) ratio between 99: 1 and 33:67
    [27]
    27. Use of a crystalline and porous heteromethal Ti (IV) MOF solid according to any one of claims 1 to 12 for solar fuel generation.
    [28]
    28. Use of a crystalline and porous heteromethal Ti (IV) MOF solid according to any one of claims 1 to 12 for photoactivated degradation.
    [29]
    29. Use of a crystalline and porous heteromethal Ti (IV) MOF solid according to any one of claims 1 to 12 for CO2 photoreduction.
    [30]
    30. Use of a crystalline and porous heteromethal Ti (IV) MOF solid according to any one of claims 1 to 12 for heterogeneous catalysis.
    [31]
    31. Use of a crystalline and porous heterometic Ti (IV) MOF solid according to any one of claims 1 to 12 as a component or part of an electronic component.
    [32]
    32. Use of a crystalline and porous heterometic Ti (IV) MOF solid according to any one of claims 1 to 12 as a porous or photoactive coating for the control of contaminants.
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    同族专利:
    公开号 | 公开日
    CA3101959A1|2019-11-28|
    ES2732803B2|2020-07-13|
    US20210261577A1|2021-08-26|
    WO2019224413A1|2019-11-28|
    EP3805239A1|2021-04-14|
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    US20100226991A1|2007-10-01|2010-09-09|Centre National De La Recherche Scientifique - Cnrs-|Solid inorganic/organic hybrid with modified surface|
    EP3001495A2|2014-08-29|2016-03-30|Samsung Electronics Co., Ltd.|Composite, method of preparing the composite, electrolyte comprising the composite, and lithium secondary battery comprising the electrolyte|
    CN106299344A|2016-11-04|2017-01-04|中南大学|A kind of sodium-ion battery nickel titanate negative material and preparation method thereof|ES2844934A1|2020-01-22|2021-07-23|Univ Valencia|Solid MOF of titanium-iron, procedure for its obtaining and its use for the degradation of compounds |FR2942229B1|2009-02-18|2011-02-25|Univ Paris Curie|TITANIUM-BASED POLYCARBOXYLATE INORGANIC-ORGANIC HYBRID SOLID MATERIAL, PROCESS FOR PREPARING THE SAME AND USES THEREOF|
    EP3254755B1|2016-06-10|2021-04-14|Centre National de la Recherche Scientifique CNRS|High degree of condensation titanium-based inorganic-organic hybrid solid material, method for preparing same and uses thereof|CN111330619B|2020-03-12|2021-03-16|中国科学院上海硅酸盐研究所|Ru/WNO catalyst for wide pH value and high-efficiency hydrogen evolution and preparation method thereof|
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