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    • 专利摘要:
    The present invention relates to a multivariate metal-organic hybrid network consisting of two different metals (M1 and M2) with at least two different oxamidate ligands derived from at least two amino acids. The present invention also relates to the use of said network as a simultaneous or dual adsorbent of inorganic and organic contaminants, to a process for the simultaneous or dual removal of inorganic and organic contaminants in aqueous solutions and to a process for obtaining a hybrid network multivariate metal-organic. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2764348A1
    申请号:ES201831167
    申请日:2018-11-30
    公开日:2020-06-02
    发明作者:Conejero Marta Mon；Marin Emilio José Pardo；Soria Jesus Ferrando；Donatella Armentano
    申请人:Universitat de Valencia；Della Calabria, University of；Universita della Calabria；
    IPC主号:
    专利说明:

    [0003] SIMULTANEOUS ADSORBENT OF INORGANIC AND ORGANIC CONTAMINANTS
    [0005] Field of the Invention
    [0007] The present invention relates to the field of adsorption chemistry. In particular, the present invention relates to a multivariate metal-organic hybrid network consisting of two different metals and oxamidate ligands and to their use as a simultaneous adsorbent of inorganic and organic pollutants in aquatic ecosystems, as well as in water recycling plants from the industry (pharmaceutical, textile, food, leather, plastics, chrome, mining, printing, paper mills, pigments), agricultural and domestic use.
    [0009] Background of the Invention
    [0011] One of the most serious environmental problems facing modern societies is the contamination of aquatic systems. In fact, the magnitude of the problem is such that access to clean water streams is set in the United Nations (UN) sustainable development agenda as one of the main objectives. The pollutants present in the water are usually divided into inorganic and organic based on their chemical nature.
    [0013] Existing water recycling technologies (precipitation, coagulation / flocculation, membranes, biological processes, advanced oxidation processes and adsorption on activated carbons, zeolites, polymeric resins, bio-adsorbents and clays) are not efficient for both types of contaminants, Furthermore, they are not capable of eliminating them in a single stage when both are present.
    [0015] Multivariate metal-organic hybrid networks (in English Multivariate Metal-Organic Frameworks or MTV-MOF) are a subclass of crystalline porous metal-organic networks, consisting of more than one precursor (ligand and / or metal ions) of different nature. Investigations into MTV-MOFs, due to their difficulty, are still in an early stage and there are few groups that have managed to obtain families from them [Angew.
    [0016] Chem. Int. Ed. 2002 , 41, 133-135; Science 2010 , 327, 846-850; Science 2013 , 341, 882 885; J. Am. Chem. Soc. 2013 , 135, 17731-17734; Inorg. Chem. 2014 , 53, 5881-5883; J. Am. Chem. Soc. 2015 , 137, 2641-2650; J. Am. Chem. Soc. 2015 , 137, 3177-3180; J. Am. Chem. Soc. 2015 , 137, 13456-13459; J. Am. Chem. Soc. 2016 , 138, 13822-13825; J. Am. Chem. Soc. 2016 , 138, 8352-8355]. Very recently, the issue of adsorption of inorganic contaminants has been addressed separately [Coord. Chem. Rev., 2018 , 358, 92-107] and organic [J. Hazard. Mater. 2015 , 283, 329-339 and J. Mater. Chem. To 2015 , 3, 22484-22506] in MOFs. Even the present inventors have published a review article where a critical review of the state of the art is made in the adsorption of inorganic and organic contaminants present in water in MOFs [J. Mater. Chem. A 2018 , 6, 4912-4947]. Thus, for example, a study is known where anionic inorganic and organic contaminants are adsorbed in a cationic MOF [Nat. Commun.
    [0017] 2017 , 1354]. This study focuses primarily on understanding the adsorption of organic pollutants. The adsorption of ReO4 "and Cr2O72" (inorganic contaminants) is carried out to verify that the cationic nature of the MOF favors the adsorption of anionic species. Although the adsorption kinetics in this material is good, its reusability is quite poor. Furthermore, the use of formally charged MOFs in the network automatically makes it impossible to adsorb contaminants with the same charge, thereby limiting the range of applicability of these materials. All other cases of MOFs for adsorbing contaminants focus on studying the adsorption of a single type or a single class of contaminants, either inorganic or organic. None of these documents describe the removal of inorganic and organic contaminants simultaneously in a single step.
    [0019] The present inventors have found that by using multivariate metal-organic hybrid networks (MTV-MOF), as described herein, it is possible to obtain simultaneous adsorption of inorganic and organic contaminants. In particular, they have developed MTV-MOF with different oxamidate ligands derived from amino acids in particular for use to remove contaminants from aquatic ecosystems. To date, MTV-MOFs have only been applied in gas adsorption (CO2 and CH4) and catalysis.
    [0021] Regarding MOFs constructed with a single derivative of natural amino acids functionalized with oxamidate ligands, two MOFs constructed with oxamidate ligands derived from L-methionine have been described for the removal of solutions. aqueous mercury salts (Hg2 + and CH3Hg +) [Angew. Chem. Int. Ed. 2016 , 55, 11167 11172; J. Mater. Chem. A 2017 , 5, 20120-20125]. In addition, an MOF formed with oxamidate ligands derived from L-serine which efficiently adsorbs drugs from acetonitrile solutions has also been described [Mater. Horiz. 2018 , DOI: 10.1039 / C8MH00302E]. These MOFs provide a solution to the adsorption of certain pollutants (inorganic or organic) for which current water treatment methods are not efficient.
    [0023] However, the described materials do not allow the adsorption of inorganic and organic contaminants simultaneously in a single stage of aqueous solutions. This is because their goodness as adsorbents of inorganic or organic pollutants is based on the presence of a single type of functional groups in their pores, which are only capable of establishing specific supramolecular interactions with a single type of pollutants.
    [0025] Therefore, the MTV-MOFs described in the present invention and due to their main technical characteristic, which are that they consist of two different oxamidate ligands derived from at least two different amino acids, allowing the presence of two or more types of functional groups. Different in their pores, they show, for the first time, the adsorption of inorganic and organic pollutants simultaneously in a single stage. This is a considerable advance with respect to the state of the art and would entail a considerable reduction in the economic and time costs of treatment protocols, particularly contaminated water. Furthermore, these materials are environmentally friendly materials, they are relatively cheap and their production would be easily scalable to kilograms, which is not very common in MTV-MOFs. Lastly, they are easily regenerable, maintaining their adsorption efficiency of inorganic and organic contaminants after several cycles of adsorption and desorption of the contaminants.
    [0027] Brief description of the drawings
    [0029] Figure 1 shows a general diagram of the structure of MTV-MOF, in which the homogeneous and alternating distribution of the two oxamidate ligands derived from two different amino acids is observed. The basic oxamidate-metal ligand units are enlarged for better visualization.
    [0030] Figure 2 schematically shows the structure of the MTV-MOF after adsorption of inorganic and organic contaminants.
    [0032] Summary description of the invention
    [0034] In a first aspect, the present invention relates to a multivariate metal-organic hybrid network consisting of two different metals (M1 and M2) with at least two different oxamidate ligands derived from at least two amino acids.
    [0036] In a second aspect, the present invention relates to the use of a multivariate metal-organic hybrid network according to the first aspect of the invention as a simultaneous or dual adsorbent of inorganic and organic contaminants.
    [0038] In a third aspect, the present invention also relates to a process for the simultaneous or dual removal of inorganic and organic contaminants in aqueous solutions comprising contacting the multivariate metal-organic hybrid network according to the first aspect of the invention with a solution aqueous containing inorganic and organic contaminants.
    [0040] In a fourth aspect, the present invention additionally relates to a process for obtaining a multivariate metal-organic hybrid network according to the first aspect of the invention.
    [0042] Detailed description of the invention
    [0044] The present invention relates in a first aspect to a multivariate metal-organic hybrid network consisting of two different metals (M1 and M2) with at least two different oxamidate ligands derived from at least two amino acids.
    [0046] In a preferred embodiment, said amino acids are found alternately in network channels (MTV-MOF). By "alternately" it is meant that the amino acids are organized homogeneously along the pore and it is not observed that each of the constituent amino acids of the MTV-MOF occupies a certain pore.
    [0047] In another preferred embodiment, said amino acids are found within the pore of the MTV-MOF pointing towards the center of the channels.
    [0049] In another preferred embodiment, the first metal is copper and the second metal is selected from calcium, strontium and barium, more preferably calcium.
    [0051] In another preferred embodiment, said two amino acids are naturally occurring amino acids, preferably selected from the group consisting of L-methionine, L-serine, L-threonine, L-histidine and L-methylcysteine.
    [0053] The MTV-MOFs used in the present invention have been shown to have the following advantageous properties:
    [0054] - They are robust enough to endure in aqueous solutions without decomposing for months. Furthermore, they allow residues of two different amino acids with a homogeneous distribution to be stored inside their pores. In this way, they are capable of adsorbing inorganic and organic contaminants in a single stage and reducing their concentration to limits permissible by the WHO, avoiding tedious decontamination protocols applied in sequence.
    [0055] - They are crystalline and resistant enough to allow the X-ray determination of the structure of these MTV-MOFs and the adsorbed contaminants, and thus be able to unambiguously characterize the interactions that are established between them and that are responsible for their efficiency. decontaminant.
    [0056] - They allow to be recovered and reused repeatedly, substantially maintaining their decontamination activity and efficiency.
    [0058] In a second aspect, the present invention relates to the use of a multivariate metal-organic hybrid network, according to any embodiment of the first aspect of the invention, as a simultaneous or dual adsorbent of inorganic and organic contaminants.
    [0060] In a preferred embodiment, said inorganic and organic contaminants are found in aquatic ecosystems.
    [0062] In another preferred embodiment, said inorganic contaminants are at least one of salts of heavy metal ions, oxoanions / cations of metals and nonmetals, and inorganic anions without oxygen. More preferably, said inorganic contaminants are at least one of mercury salts, lead salts, cadmium salts, oxoanions / cations of arsenic, oxoanions / cations of phosphorus, oxoanions / cations of selenium, oxoanions / cations of chromium, perchlorate anion, sulfate anion, nitrate anion and fluoride anion.
    [0064] In another preferred embodiment, said organic contaminants are at least one of drugs, personal hygiene products, food additives, artificial sweeteners, agricultural products, industrial products, organic colorants. More preferably, said organic pollutants are at least one of antibiotics, anti-inflammatories, makeup products, herbicides, pesticides, fertilizers, sweeteners, organoarsenic compounds, aromatic and aliphatic compounds selected from bisphenol A, phthalates, naphthol and hydrocarbons, organic dyes selected from methylene blue, bright green, pyronine Y, auramine O, rhodamine R6G, sweat I and methyl orange.
    [0066] In a third aspect, the present invention relates to a process for the simultaneous removal of inorganic and organic contaminants in aqueous solutions comprising contacting the multivariate metal-organic hybrid network, according to any of the embodiments of the first aspect of the invention, with an aqueous solution containing inorganic and organic contaminants.
    [0068] In a preferred embodiment, said contact of the multivariate metal-organic hybrid network with an aqueous solution can be carried out with the multivariate metal-organic hybrid network in the form of microcrystalline powders or in the form of pellets, which are obtained following a process previously described [Angew. Chem. Int. Ed. 2016 , 55, 11167-11172].
    [0070] In another preferred embodiment, said procedure is carried out at a temperature between 10 and 30 ° C, preferably between 20 and 25 ° C.
    [0072] In yet another preferred embodiment, said procedure is carried out between 5 min and 24 hours, preferably between 5 minutes and 60 minutes.
    [0074] In yet another preferred embodiment, said inorganic contaminants are at least one of salts of heavy metal ions, oxoanions / cations of metals and nonmetals, and inorganic anions without oxygen. More preferably, said inorganic contaminants are at least one of mercury salts, lead salts, cadmium salts, oxoanions / cations of arsenic, oxoanions / cations of phosphorus, oxoanions / cations of selenium, oxoanions / cations of chromium, perchlorate anion, sulfate anion, nitrate anion and fluoride anion.
    [0076] In yet another preferred embodiment, said organic contaminants are at least one of drugs, personal hygiene products, food additives, artificial sweeteners, agricultural products, industrial products, organic dyes. More preferably, said organic pollutants are at least one of antibiotics, anti-inflammatories, makeup products, herbicides, pesticides, fertilizers, sweeteners, organoarsenic compounds, aromatic and aliphatic compounds selected from bisphenol A, phthalates, naphthol and hydrocarbons, organic dyes selected from methylene blue, bright green, pyronine Y, auramine O, rhodamine R6G, sweat I and methyl orange.
    [0078] In a fourth aspect, the present invention refers to a process for obtaining a multivariate metal-organic hybrid network, according to any of the embodiments of the first aspect of the invention, comprising the steps of:
    [0079] (i) obtain at least two dinuclear complexes with oxamidate ligands derived from at least two different amino acids as precursor subunits of the formula:
    [0080] (A) 2 {M l2 [(Lx)] (OH) 2}. nl-hO (Lx = 1, 2, ...)
    [0081] in which
    [0082] A = (alkyl) 4N, where alkyl is selected from methyl, ethyl and butyl
    [0083] M1 = metal 1
    [0084] Lx = (S, S) -amino acid with oxamidate ligand
    [0085] n = 4 or 5
    [0087] (ii) slowly add a solution of a metal 2 salt (M2), in which M2 is different from M1, in stoichiometric amounts to equimolar mixtures of two precursor subunits obtained in step (i);
    [0088] (iii) stir at room temperature for at least 24 hours;
    [0089] (iv) separating the multivariate metal-organic hybrid network obtained in step (iii) after stirring.
    [0091] In the case where M1 is Cu, the procedure for obtaining a multivariate metal-organic hybrid network comprises the steps of:
    [0092] (i) obtain at least two dinuclear complexes with oxamidate ligands derived from at least two different amino acids as precursor subunits of the formula:
    [0093] (A) 2 {M12 [(Lx)] (OH) 2}. nH2O (x = 1, 2)
    [0094] in which
    [0095] A = (alkyl) 4N, where alkyl is selected from methyl, ethyl and butyl
    [0096] M1 = Cu
    [0097] L = (S, S) -amino acid with oxamidate ligand
    [0098] n = 4 or 5
    [0100] (ii) slowly add a solution of a Ca2 +, Sr2 + or Ba2 + (M2) salt in stoichiometric amounts to equimolar mixtures of two precursor subunits obtained in step (i);
    [0101] (iii) stir at room temperature for at least 24 hours;
    [0102] (iv) separate the multivariate metal-organic hybrid network, with the formula {M2M16 (L1) 1.5 (L2) 1.5 (OH) 2 (H2O)}. mH2O, obtained in step (iii) after stirring.
    [0104] Preferably, the salt of M2 when M2 is Ca2 + is CaCh.
    [0106] Preferably, the salt of M2 when M2 is Sr2 + is Sr (NO3) 2.
    [0108] Preferably, the salt of M2 when M2 is Ba2 + is BaCh.
    [0110] In a preferred embodiment, the amino acids of L1 and L2 are selected from L-methionine, L-serine, L-threonine, L-histidine and L-methylcysteine.
    [0112] Step (i) is known and can be consulted in J. Am. Chem. Soc. 2016 , 138, 7864-7867; J. Am. Chem. Soc. 2017 , 139, 8098-8101; Mater. Horiz. 2018
    [0114] In the following, a series of examples will be provided that are intended to illustrate the invention and in no way limit the scope thereof, which is established by the appended claims.
    [0116] EXAMPLES
    [0118] Example 1: MTV-MOF synthesis procedure with the amino acids L-methionine and L-serine. [Ca2 [{Cu6 [(S, S) -methox] 3 (OH) 2 (H2O)} {Cu6 [(S, S) -serimox] 3 (OH) 2 (H2O)}]].
    [0119] H2O ( 1 ) was prepared in powder form after adding dropwise with stirring to an equimolar aqueous solution (100 ml H2O, 6 mmol of each precursor) of (Me4N) 2 {Cu2 [(S, S) -methox] (OH) 2}. 4 H2O ( J. Am. Chem. Soc. 2016 , 138, 7864-7867) and (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2} ■ 5 H2O ( Mater. Horiz. 2018 , DOI: 10.1039 / C8MH00302E), another aqueous solution of CaCÍ2 (0.44 g, 4 mmol ). After 24 h stirring at room temperature, the sample was filtered off. Blue prisms suitable for single crystal X-ray diffraction are obtained by slow diffusion into H-tubes of aqueous solutions of (Me4N) 2 {Cu2 [(S, S) -methox] (OH) 2} ■ 4 H2O (0, 13 g, 0.18 mmol) and (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2} ■ 5 H2O (0.12 g, 0.18 mmol) on the one hand and CaCl2 ( 0.01 g, 0.06 mmol) on the other. Anal .: calc (%) for C60Ca2Cu 12H110S6N12O63 (3042.7): C, 23.69; H, 3.64; N, 5.52. Found: C, 23.68; H, 3.63; N, 5.55. IR (KBr): u = 1612 cm-1 (C = O).
    [0121] Example 2: Procedure 1 for the adsorption of the inorganic contaminant HgCl 2 and the bright green organic dye. 50 mg of polycrystalline powder / 1 pellets were immersed in an aqueous / mineral water solution (10 ml) 10 ppm HgCh and 10 ppm bright green for one week with stirring at room temperature. To follow the adsorption process, aliquots of 200 pl were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440, 10080 min). The Hg2 + concentration was estimated by ICP-MS analysis, while the organic dye concentration by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3 ": 140 mg L-1; SO42": 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; SiO2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0123] Example 3: Procedure 1 for the adsorption of the inorganic contaminant HgCh and the organic dye methylene blue. 50 mg of polycrystalline powder / pellets of 1 were immersed in an aqueous / mineral water solution (10 ml), 10 ppm of HgCL and 10 ppm of methylene blue for one week with stirring at room temperature. To follow the adsorption process, aliquots of 200 pL were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440, 10080 min). The Hg2 + concentration was estimated by ICP-MS analysis, while the organic dye concentration by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3-: 140 mg L-1; SO42-: 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; SiO2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0124] Example 4: Procedure 1 for the adsorption of the inorganic contaminant HgCl 2 and the organic organic dye of acridine. 50 mg of polycrystalline powder / 1 pellets were immersed in an aqueous / mineral water solution (10 ml) 10 ppm HgCh and 10 ppm acridine orange for one week with stirring at room temperature. To follow the adsorption process, 200 ml aliquots were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440, 10080 min). The Hg2 + concentration was estimated by ICP-MS analysis, while the organic dye concentration by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3 ": 140 mg L-1; SO42": 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; SiO2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0126] Example 5: Procedure of 1 for the adsorption of the inorganic contaminant HgCh and the organic colorant pyronine Y. 50 mg of polycrystalline powder / pellets of 1 were immersed in an aqueous / mineral water solution (10 ml) 10 ppm of HgCh and 10 ppm of Pyronine Y for one week under stirring at room temperature. To follow the adsorption process, 200 ml aliquots were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440, 10080 min). The Hg2 + concentration was estimated by ICP-MS analysis, while the organic dye concentration by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3-: 140 mg L-1; SO42-: 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; SiO2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0128] Example 6: Procedure 1 for the adsorption of the inorganic contaminant Pb (NO 3) 2 and the bright green organic dye. 50 mg of polycrystalline powder / pellets 1 were immersed in an aqueous / mineral water solution (10 ml) 10 ppm Pb (NO3) 2 and 10 ppm bright green for one week with stirring at room temperature. To follow the adsorption process, 200 ml aliquots were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440, 10080 min). The concentration of Pb2 + was estimated by means of ICP-MS analysis, while that of the organic dye by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3-: 140 mg L-1; SO42-: 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; YES 2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0130] Example 7: Procedure 1 for the adsorption of the inorganic contaminant Pb (NO 3 ) 2 and the organic dye methylene blue. 50 mg polycrystalline powder / pellets
    [0131] of 1 were immersed in an aqueous / mineral water solution (10 ml) 10 ppm Pb (NO3) 2
    [0132] and 10 ppm of methylene blue for one week with stirring at room temperature.
    [0133] To follow the adsorption process, aliquots of 200 pL were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440,
    [0134] 10080 min). Pb2 + concentration was estimated by ICP-MS analysis, while
    [0135] than that of the organic dye by UV-vis spectroscopy. Composition / dry residue
    [0136] mineral water: 140 mg L-1; HCO3-: 140 mg L-1; SO42-: 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg
    [0137] L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; SiO2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0139] Example 8: Procedure 1 for the adsorption of the inorganic contaminant Pb (NO 3 ) 2 and the acridine orange organic dye. 50 mg of polycrystalline powder / 1 pellets were immersed in an aqueous / mineral water solution (10 ml)
    [0140] 10 ppm Pb (NO3) 2 and 10 ppm acridine orange for one week with stirring
    [0141] at room temperature. To follow the adsorption process, aliquots were taken
    [0142] 200 pL at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180,
    [0143] 240, 300, 360, 720, 1440, 10080 min). Pb2 + concentration was estimated by
    [0144] ICP-MS analysis, while that of the organic dye by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3-: 140 mg L-1; SO42-: 15 mg
    [0145] L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; S O 3.7 mg L-1.
    [0146] By suspension in a solution of methanol and another of dimethyl sulfide for 24
    [0147] h Compound 1 could be regenerated and reused without observing a decrease in
    [0148] its decontamination efficiency.
    [0150] Example 9: Procedure of 1 for the adsorption of the inorganic contaminant Pb (NO 3 ) 2 and the organic dye pyronine Y. 50 mg of polycrystalline powder / pellets of 1
    [0151] were immersed in an aqueous / mineral water solution (10 ml) 10 ppm Pb (NO3) 2 and
    [0152] 10 ppm pyronine Y for one week under stirring at room temperature. To follow the adsorption process, aliquots of 200 pL were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440, 10080 min). The concentration of Pb2 + was estimated by means of ICP-MS analysis, while that of the organic dye by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3 ": 140 mg L-1; SO42": 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; SiO2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0154] Example 10: Procedure of 1 for the adsorption of the inorganic contaminants HgCl 2 Pb (NO 3) 2 and the organic dyes bright green, methylene blue, acridine orange and pyronine Y. 50 mg of polycrystalline powder / pellets of 1 were immersed in an aqueous / mineral water solution (10 ml) 10 ppm of each of the following contaminants HgCh, Pb (NO3) 2, bright green, methylene blue, acridine orange and pyronine Y for one week under stirring at room temperature. To follow the adsorption process, aliquots of 200 pL were taken at different time intervals (0, 1, 5, 10, 15, 30, 45, 60, 75, 90, 120, 180, 240, 300, 360, 720 , 1440, 10080 min). The concentration of Hg2 + and Pb2 + was estimated by ICP-MS analysis, while that of organic dyes by UV-vis spectroscopy. Composition / dry residue mineral water: 140 mg L-1; HCO3-: 140 mg L-1; SO42-: 15 mg L-1; Cl-: 4.8 mg L-1; Ca2 +: 46 mg L-1; Mg2 +: 5.6 mg L-1; Na +: 2.3 mg L-1; SiO2: 3.7 mg L-1. By suspension in a solution of methanol and another of dimethyl sulfide for 24 h, compound 1 could be regenerated and reused without observing a decrease in its decontamination efficiency.
    [0156] Example 11: Synthesis procedure of other MTV-MOFs with other binary combinations of the amino acids L-methionine, L-serine, L-threonine, L-histidine and L-methylcysteine. Following an identical procedure to that described for obtaining 1 (example 1), multivariate hybrid materials have been synthesized with the following combinations: methionine-threonine ( 2 ), methionine-methylcysteine ( 3 ), methylcysteine-serine ( 4 ), histidine- serine ( 5 ) and serine-threonine ( 6 ). MTV-MOFs 2 , 3 , 4 , 5 and 6 have been shown to be efficient for adsorption of inorganic and organic contaminants in a single stage (examples 2-10).
    [0157] With the amino acids L-methionine and L-threonine . [Ca2 [{Cu6 [(S, S) -methox] 3 (OH) 2 (H2O)} {Cu6 [(S, S) -threomox] 3 (OH) 2 (H2O)}]] ■ 22 H2O ( 2 ) was prepared as a powder after adding dropwise with stirring to an equimolar aqueous solution (100 ml H2O, 6 mmol of each precursor) of (Me4N) 2 {Cu2 [(S, S) -methox] (OH) 2 } ■ 4 H2O ( J. Am. Chem. Soc. 2016 , 138, 7864-7867) and (Me4N) 2 {Cu2 [(S, S) -threomox] (OH) 2} ■ 4 H2O, another aqueous solution of CaCh (0.44 g, 4 mmol). After 24 h stirring at room temperature, the sample was filtered off. Blue prisms suitable for single crystal X-ray diffraction are obtained by slow diffusion into H-tubes of aqueous solutions of (Me4N) 2 {Cu2 [(S, S) -methox] (OH) 2} ■ 4 H2O (0, 13 g, 0.18 mmol) and (Me4N) 2 {Cu2 [(S, S) -threomox] (OH) 2} ■ 4 H2O (0.12 g, 0.18 mmol) on the one hand and CaCh ( 0.01 g, 0.06 mmol) by other ^ AnaL: calc (%) for C66Ca2Cu12H128S6N ^ O 72 (3276.9): C, 24.19; H, 3.94; N, 5.13 ^ Found: C, 24.28; H, 3.93; N, 5.15 ^ IR (KBr): u = 1610 cm-1 (C = O)
    [0159] With the amino acids L-methionine and L-methylcysteine . [Ca2 [{Cu6 [(S, S) -methox] 3 (OH) 2 (H2O)} {Cu6 [(S, S) -mecysmox] 3 (OH) 2 (H2O)}]] ■ 20H2O ( 3 ) It was prepared as a powder after adding dropwise with stirring to an equimolar aqueous solution (100 ml H2O, 6 mmol of each precursor) of (Me4N) 2 {Cu2 [(S, S) -methox] (OH) 2} ■ 4 H2O ( J. Am. Chem. Soc. 2016 , 138, 7864-7867) and (Me4N) 2 {Cu2 [(S, S) -mecysmox] (OH) 2} ■ 6 H2O, another aqueous solution of CaCl2 (0.44 g, 4 mmol) After 24 h stirring at room temperature, the sample was filtered off. Blue prisms suitable for single crystal X-ray diffraction are obtained by slow diffusion into H-tubes of aqueous solutions of ( Me4N) 2 {Cu2 [(S, S) -methox] (OH) 2} ■ 6 H2O (0.13 g, 0.18 mmol) and (Me4N) 2 {Cu2 [(S, S) -mecysmox] ( OH) 2} ■ 6 H2O (0.13 g, 0.18 mmol) on the one hand and CaCh (0.01 g, 0.06 mmol) on the other ^ AnaL: calc (%) for C66Ca2Cu12H132S12N12O66 (3377.3 ): C, 23.47; H, 3.94; N, 4.98 ^ Found: C, 23.40; H, 3.90; N, 4.95 ^ IR (KBr): u = 1614 cm-1 (C = O)
    [0161] With the amino acids L-methylcysteine and L-serine . [Ca2 [{Cu6 [(S, S) -mecysmox] 3 (OH) 2 (H2O)} {Cu6 [(S, S) -serimox] 3 (OH) 2 (H2O)}]] ■ 24 H2O ( 4 ) was prepared as a powder after adding dropwise with stirring to an equimolar aqueous solution (100 ml H2O, 6 mmol of each precursor) of (Me4N) 2 {Cu2 [(S, S) -mecysmox] (OH) 2 } ■ 6 H2O and (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2} ■ 5 H2O ( Mater. Horiz. 2018 , DOI: 10 ^ 1039 / C8MH00302E), another aqueous solution of CaCh ( 0.44 g, 4 mmol) After 24 h stirring at room temperature, the sample was filtered off. Blue prisms suitable for single crystal X-ray diffraction are obtained by slow diffusion into H-tubes of aqueous solutions of (Me4N ) 2 {Cu2 [(S, S) -mecysmox] (OH) 2} ■ 6 H2O (0.13 g, 0.18 mmol) and (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2} ■ 5 H2O (0.12 g, 0.18 mmol) on one side and of CaCl2 (0.01 g, 0.06 mmol) by another. Anal .: calc (%) for C54Ca2Cu12H116S6N12O76 (3184.6): C, 20.37; H, 3.67; N, 5.28. Found: C, 20.40; H, 3.60; N, 5.27. IR (KBr): u = 1608 cm-1 (C = O).
    [0163] With the amino acids L-histidine and L-serine . [Ca2 [{Cu6 [(S, S) -hismox] 3 (OH) 2 (H2O)} {Cu6 [(S, S) -serimox] 3 (OH) 2 (H2O)}]] - 18 H2O ( 5 ) was prepared as a powder after adding dropwise with stirring to an equimolar aqueous solution (100 ml H2O, 6 mmol of each precursor) of (Bu4N) 2 {Cu2 [(S, S) -hismox] (OH) 2 } - 4 H2O ( J. Am. Chem. Soc. 2017 , 139, 8098-8101) and (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2} -5 H2O ( Mater. Horiz. 2018 , DOI: 10.1039 / C8MH00302E), another aqueous solution of CaCh (0.44 g, 4 mmol). After 24 h stirring at room temperature, the sample was filtered off. Blue prisms suitable for single crystal X-ray diffraction are obtained by slow diffusion into H-tubes of aqueous solutions of (Bu4N) 2 {Cu2 [(S, S) -hismox] (OH) 2} - 4 H2O (0, 19 g, 0.18 mmol) and (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2} - 5 H2O (0.12 g, 0.18 mmol) on the one hand and CaCh ( 0.01 g, 0.06 mmol) on the other. Anal .: calc (%) for C60Ca2Cu12H104N24O66 (3060.3): C, 23.55; H, 3.43; N, 10.99. Found: C, 23.49; H, 3.40; N, 11.03. IR (KBr): u = 1602 cm-1 (C = O).
    [0165] With the amino acids L-serine and L-threonine . [Ca2 [{Cu6 [(S, S) -serimox] 3 (OH) 2 (H2O)} {Cu6 [(S, S) -threomox] 3 (OH) 2 (H2O)}]] - 26 H2O ( 6 ) was prepared as a powder after adding dropwise with stirring to an equimolar aqueous solution (100 ml H2O, 6 mmol of each precursor) of (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2 } - 5 H2O ( Mater '. Horiz. 2018 , DOI: 10.1039 / C8MH00302E) and (Me4N) 2 {Cu2 [(S, S) -threomox] (OH) 2} -4 H2O, another aqueous solution of CaCl2 (0 , 44 g, 4 mmol). After 24 h stirring at room temperature, the sample was filtered off. Blue prisms suitable for single crystal X-ray diffraction are obtained by slow diffusion into H-tubes of aqueous solutions of (Me4N) 2 {Cu2 [(S, S) -serimox] (OH) 2} -5 H2O (0, 12 g, 0.18 mmol) and (Me4N) 2 {Cu2 [(S, S) -threomox] (OH) 2} -4 H2O (0.12 g, 0.18 mmol) on the one hand and CaCh ( 0.01 g, 0.06 mmol) on the other. Anal .: calc (%) for C54Ca2Cu12HmN12O82 (3084.2): C, 21.03; H, 3.66; N, 5.45. Found: C, 21.08; H, 3.63; N, 5.38. IR (KBr): u = 1614 cm-1 (C = O).
    权利要求:
    Claims (24)
    [1]
    1. Multivariate metal-organic hybrid network consisting of two different metals (M1 and M2) with at least two different oxamidate ligands derived from at least two amino acids.
    [2]
    2. Multivariate metal-organic hybrid network, according to claim 1, in which the first metal (M1) is copper and the second metal (M2) is selected from calcium, strontium and barium.
    [3]
    3. A multivariate metal-organic hybrid network, according to claim 1 or 2, in which said two amino acids are natural amino acids.
    [4]
    4. A multivariate metal-organic hybrid network according to any of claims 1 to 3, wherein said amino acids are selected from the group consisting of L-methionine, L-serine, L-threonine, L-histidine and L-methylcysteine.
    [5]
    5. Use of a multivariate metal-organic hybrid network, according to any of the preceding claims, as a simultaneous adsorbent of inorganic and organic contaminants.
    [6]
    6. Use of a multivariate metal-organic hybrid network, according to claim 5, in which said inorganic and organic pollutants are found in aquatic ecosystems.
    [7]
    7. Use of a multivariate metal-organic hybrid network according to claim 5 or 6, wherein said inorganic contaminants are at least one of heavy metal ion salts, oxoanions / cations of metals and nonmetals and inorganic anions without oxygen.
    [8]
    8. Use of a multivariate metal-organic hybrid network, according to claim 7, wherein said inorganic contaminants are at least one of mercury salts, lead salts, cadmium salts, oxoanions / cations of arsenic, oxoanions / cations of phosphorus, selenium oxoanions / cations, chromium oxoanions / cations, perchlorate anion, sulfate anion, nitrate anion and fluoride anion.
    [9]
    9. Use of a multivariate metal-organic hybrid network, according to any of the Claims 5 to 8, wherein said organic pollutants are at least one of drugs, personal hygiene products, food additives, artificial sweeteners, agricultural products, industrial products, organic dyes.
    [10]
    10. Use of a multivariate metal-organic hybrid network, according to claim 9, in which said organic contaminants are at least one of antibiotics, anti-inflammatories, makeup products, herbicides, pesticides, fertilizers, sweeteners, organoarsenic compounds, aromatic compounds and aliphatics selected from bisphenol A, phthalates, naphthol and hydrocarbons, organic dyes selected from methylene blue, bright green, pyronine Y, auramine O, rhodamine R6G, sweat I and methyl orange.
    [11]
    11. Procedure for the simultaneous removal of inorganic and organic contaminants in aqueous solutions, comprising contacting the multivariate metal-organic hybrid network, according to any of claims 1 to 4, with an aqueous solution containing inorganic and organic contaminants.
    [12]
    12. - Elimination process, according to claim 11, in which said contact can be carried out with the multivariate metal-organic hybrid network in the form of microcrystalline powders or in the form of pellets.
    [13]
    13. - Elimination procedure, according to claim 11 or 12, wherein said procedure is carried out at a temperature between 10 and 30 ° C.
    [14]
    14. - Elimination procedure, according to any of claims 11 to 13, wherein said procedure is carried out between 5 min and 24 hours.
    [15]
    15. - Elimination process, according to any of claims 11 to 14, in which said inorganic contaminants are at least one of salts of heavy metal ions, oxoanions / cations of metals and nonmetals and inorganic anions without oxygen.
    [16]
    16. Elimination process according to claim 15, wherein said inorganic contaminants are at least one of mercury salts, lead salts, cadmium salts, oxoanions / cations of arsenic, oxoanions / cations of phosphorus, oxoanions / cations of selenium and oxoanions / cations of chromium, perchlorate anion, sulfate anion, nitrate anion and fluoride anion.
    [17]
    17. Elimination method according to any of claims 11 to 16, wherein said organic contaminants are at least one of drugs, personal hygiene products, food additives, artificial sweeteners, agricultural products, industrial products, organic dyes.
    [18]
    18. Elimination process according to claim 17, wherein said organic contaminants are at least one of antibiotics, anti-inflammatories, makeup products, herbicides, pesticides, fertilizers, sweeteners, organoarsenic compounds, aromatic and aliphatic compounds selected from bisphenol A , phthalates, naphthol and hydrocarbons, organic dyes selected from methylene blue, bright green, pyronine Y, auramine O, rhodamine R6G, sweat I and methyl orange.
    [19]
    19. Procedure for obtaining a multivariate metal-organic hybrid network, according to claim 1, comprising the steps of:
    (i) obtain at least two dinuclear complexes with oxamidate ligands derived from at least two different amino acids as precursor subunits of the formula:
    (A) 2 {M12 [(Lx)] (OH) 2}. nl-hO (Lx = 1, 2, ...)
    in which
    A = (alkyl) 4N, where alkyl is selected from methyl, ethyl and butyl
    M1 = metal 1
    Lx = (S, S) -amino acid with oxamidate ligand
    n = 4 or 5
    (ii) slowly add a solution of a metal 2 salt (M2), in which M2 is different from M1, in stoichiometric amounts to equimolar mixtures of two precursor subunits obtained in step (i);
    (iii) stir at room temperature for at least 24 hours;
    (iv) separating the multivariate metal-organic hybrid network obtained in step (iii) after stirring.
    [20]
    20. Procedure for obtaining a multivariate metal-organic hybrid network, according to any of claims 2 to 4, comprising the steps of:
    (i) obtain at least two dinuclear complexes with oxamidate ligands derived from at least two different amino acids as precursor subunits of the formula:
    (A) 2 {M12 [(Lx)] (OH) 2}. nH2O (x = 1, 2)
    in which
    A = (alkyl) 4N, where alkyl is selected from methyl, ethyl and butyl
    M1 = Cu
    L = (S, S) -amino acid with oxamidate ligand
    n = 4 or 5
    (ii) slowly add a solution of a Ca2 +, Sr2 + or Ba2 + (M2) salt in stoichiometric amounts to equimolar mixtures of two precursor subunits obtained in step (i);
    (iii) stir at room temperature for at least 24 hours;
    (iv) separate the multivariate metal-organic hybrid network, with the formula {M2M16 (L1) 1.5 (L2) 1.5 (OH) 2 (H2O)}. mH2O, obtained in step (iii) after stirring.
    [21]
    21. The process according to claim 19 or 20, wherein the salt of M2 when M2 is Ca2 + is CaCl2.
    [22]
    22. The process according to claim 19 or 20, wherein the salt of M2 when M2 is Sr2 + is Sr (NO3) 2.
    [23]
    23. The process according to claim 19 or 20, wherein the salt of M2 when M2 is Ba2 + is BaCl2.
    [24]
    24. The method according to any of claims 19 to 23, wherein the amino acids of L1 and L2 are selected from L-methionine, L-serine, L-threonine, L-histidine and L-methylcysteine.
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    ES2764348B2|2020-11-13|
    WO2020109638A1|2020-06-04|
    引用文献:
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    WO2021250639A1|2020-06-12|2021-12-16|Universita' Della Calabria|Polymeric membrane based on porous metal-organic frameworks for the decontamination of polluted waters|
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