Porous material for storing of molecules and its use
11298676 · 2022-04-12
Assignee
Inventors
Cpc classification
C07F9/65685
CHEMISTRY; METALLURGY
B01J20/3085
PERFORMING OPERATIONS; TRANSPORTING
C01B3/0015
CHEMISTRY; METALLURGY
F17C11/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01J20/226
PERFORMING OPERATIONS; TRANSPORTING
Y02C20/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J20/28061
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28064
PERFORMING OPERATIONS; TRANSPORTING
International classification
C08G83/00
CHEMISTRY; METALLURGY
C01B3/00
CHEMISTRY; METALLURGY
B01J20/30
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention concerns new types of porous coordination polymers (MOF) and a method for their preparation. MOFs have been prepared through synthesis of salts of trivalent cations M.sup.3+, the source of which are aluminium, chromium, iron or yttrium salts, it is advantageous if of chlorides, nitrates or sulphates, with linkers carrying two or more phosphinic groups under presence of solvent. Linkers are phenylene-1,4-bis(R phosphinic acid) (PBPA) and biphenylene-4,4′-bis(R phosphinic acid) (BBPA). For the prepared MOFs, the structure has been tested using x-ray powder diffraction, specific surface and porousness which have been characterised through adsorption isotherm of nitrogen and further the stability of prepared MOFs has been determined using thermogravimetric analysis. All the prepared MOFs have been stable around 400° C. and have contained mesopores or micropores where hydrogen or CO.sub.2, for example, can be stored.
Claims
1. A porous material for storing of molecules distinguished by the fact that it has porosity of 220 m.sup.2/g to 1200 m.sup.2/g and that consists of a coordination polymer net formed of coordination polymer of bis to tetra phosphinic acid and of trivalent metal cation in ratio 3:1 of bound phosphinic groups to metal cation with polymer chemical structure with monomer unit of general formula: ##STR00008## where R.sup.1 is hydrogen, alkyl or aryl and possibly alkyl or aryl carrying a functional group or it substitutes the second bond of phosphorus to spacer, M is a trivalent metal cation and spacer is aryl frame of bis- or tris-phosphinic acid or aryl frame of residuum of tetrakis-phosphinic acid with two free phosphine groups.
2. The porous material for storing of molecules according to claim 1 distinguished by the fact that the metal is iron, chrome, aluminium or yttrium.
3. The porous material for storing of molecules according to claim 1 distinguished by the fact that the aryl frame of residuum of bis-phosphinic acid has this structure: ##STR00009## where R.sup.2 and R.sup.3 is hydrogen, alkyl, aryl or functional group and possibly alkyl or aryl carrying a functional group.
4. The porous material for storing of molecules according to claim 1 distinguished by the fact that the bis-phosphine acid has this structure: ##STR00010##
5. The porous material for storing of molecules according to claim 1 distinguished by the fact that the tris-phosphine acid has this structure: ##STR00011##
6. The porous material for storing of molecules according to claim 1 distinguished by the fact that the tetrakis-phosphine acid has this structure: ##STR00012##
7. A method of preparation of the porous material for storing of molecules according to claim 1 distinguished by the fact that the chloride, nitrate or sulphate of metal cation is mixed with bis, tri or tetra-phosphine acid, in molar ratio of metal to phosphine groups 1:2 to 1:8, solvent is added and the mixture is kept at temperature 25° C. to 250° C. for, at least, 24 hours without stirring, and after cooling the resulting mixture is separated.
8. The method of preparation of porous material for storing of molecules according to claim 5, distinguished by the fact that the range of molar ratio of metal to phosphine group of bis, tri or tetra phosphinic acid is 1:4.
9. The method of preparation of porous material for storing of molecules according to claim 5, distinguished by the fact that the chloride of metal cation is chloride of aluminium or of chromium or of yttrium or of iron or its hydride.
10. The method of preparation of porous material for storing of molecules according to claim 5, distinguished by the fact that the solvent is water, N,N-dialkyl formamide, formamide, acetone, hexane, acetonitrile, toluene, dimethylsulphoxide, N-methyl-2-pyrrolidone, tetrahydrofuran, monohydric alcohol, organic acid or mixtures of these solvents.
11. The method of preparation of porous material for storing of molecules according to claim 5, distinguished by the fact that the solvent is ethanol.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) In figures R=alkyl or aryl group, e.g. Me, i-Pr, Ph.
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DETAILED DESCRIPTION OF THE INVENTION
Examples of Invention Completion
Example 1
(54) Preparation of Porous Fe-MOF with PBPA(Me)
(55) The initial suspension containing 18.8 mg of phenylene-1,4-bis(methylphosphinic acid)—PBPA(Me) with the amount of substance of 0.08 mmol, 10.8 mg FeCl.sub.3.6H.sub.2O with the amount of substance of 0.04 mmol and 5 ml of anhydrous EtOH was heated in an autoclave with capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 24 hours without stirring.
(56) After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed first with water (3×30 ml) and acetone (3×30 ml) and it was dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit iron (III) phenylene-1,4-bis(methylphosphinate) with weight of 10 mg was acquired. MOF was characterised using the adsorption isotherm of nitrogen, and from it its specific surface (using t-plot method) and porosity (using HK-plot method) were determined, and the specific surface was 712 m.sup.2/g and the diameter of pores was 0.8 nm.
(57) Stability of Fe-MOF with PBPA(Me) was characterised with boiling of 20 mg of Fe-MOF with PBPA(Me) in 10 ml of H.sub.2O for 24 hours. Then the specific surface was measured, it was 582 m.sup.2/g.
Example 2
(58) Preparation of Porous Al-MOF with PBPA(Me)
(59) The initial suspension containing 18.8 mg of phenylene-1,4-bis(methylphosphinic acid)—PBPA(Me) with the amount of substance of 0.08 mmol, 9.7 mg AlCl.sub.3.6H.sub.2O with amount of substance of 0.04 mmol and 5 ml of anhydrous ethanol was heated in an autoclave with capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 24 hours without stirring.
(60) After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed first with water (3×30 ml) and acetone (3×30 ml) and it was dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit aluminium phenylene-1,4-bis(methylphosphinate) with weight of 10 mg was acquired. MOF was characterised using the adsorption isotherm of nitrogen, and from it its specific surface (using t-plot method) and porosity (HK-plot) were determined, and the specific surface was 921 m.sup.2/g and the diameter of pores was 0.9 nm. Stability of Al-MOF with PBPA(Me) was characterised with boiling of 20 mg Al-MOF with PBPA(Me) in 10 ml of H.sub.2O in water for 24 hours. Then the specific surface was measured, it was 1038 m.sup.2/g.
Example 3
(61) Preparation of Porous Y-MOF with PBPA(Me)
(62) The initial suspension containing 18.8 mg of phenylene-1,4-bis(methylphosphinic acid)—PBPA(Me) with the amount of substance of 0.08 mmol, 7.8 mg YCl.sub.3 with the amount of substance of 0.04 mmol and 5 ml of anhydrous ethanol was heated in an autoclave with the capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 96 hours without stirring.
(63) After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed first with water (3×30 ml) and acetone (3×30 ml) and dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit phenylene-1,4-bis(methylphosphinate) with weight of 10 mg was acquired. MOF was characterised using the adsorption isotherm of nitrogen, and from it its specific surface (using t-plot method) and porosity (HK-plot) were determined, and the specific surface was 711 m.sup.2/g. MOF had wide distribution of pores and the diameter of pores was over 0.5 nm.
Example 4
(64) Preparation of Porous Cr-MOF with PBPA(Me)
(65) The initial suspension containing 18.8 mg of phenylene-1,4-bis(methylphosphinic acid)—PBPA(Me) with the amount of substance of 0.08 mmol, 10.6 mg CrCl.sub.3.6H.sub.2O with the amount of substance of 0.04 mmol and 6 ml of water was heated in an autoclave with capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 48 hours without stirring.
(66) After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed first with water (3×30 ml) and acetone (3×30 ml) and dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit chromium (III) phenylene-1,4-bis(methylphosphinate) with weight of 10 mg was acquired.
(67) MOF was characterised using the adsorption isotherm of nitrogen, and from it its specific surface (using t-plot method) and porosity (using HK-plot method) were determined, and the specific surface was 811 m.sup.2/g and the diameter of pores was 0.8 nm.
Example 5
(68) Preparation of Porous Al-MOF with PBPA(pH)
(69) The initial suspension containing 14.3 mg of phenylene-1,4-bis(phenylphosphinic acid)—PBPA(Ph) with the amount of substance of 0.04 mmol, 4.8 mg AlCl.sub.3.6H.sub.2O with the amount of substance of 0.02 mmol and 5 ml of anhydrous ethanol was heated in an autoclave with the capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 24 hours without stirring.
(70) After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed first with water (3×30 ml) and acetone (3×30 ml) and it was dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit aluminium phenylene-1,4-bis(phenylphosphinate) with weight of 10 mg was acquired. MOF was characterised using the adsorption isotherm of nitrogen, and from it its specific surface (using t-plot method) and the diameter of pores (using HK-plot method) were determined, and the specific surface was 224 m.sup.2/g and the diameter of pores was in range 0.4-0.6 nm.
Example 6
(71) Preparation of Porous Fe-MOF with BBPA(Me)
(72) The initial suspension containing 24.8 mg of biphenylene-4,4′-bis(methylphosphinic acid) BBPA(Me) with the amount of substance of 0.08 mmol, 10.8 mg FeCl.sub.3.6H.sub.2O with the amount of substance of 0.04 mmol and 10 ml of N,N-dimethylformamide was heated at 120° C. for 72 hours without stirring.
(73) After the resulting suspension cooled, it was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed with ethanol (3×30 ml) and then acetone (3×30 ml) and dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit iron (III) biphenylene-4,4′-bis(methylphosphinate) with weight of 15 mg was acquired. For the resulting MOF the adsorption isotherm of nitrogen was measured and specific surface (with BET method) and porosity (with NLDFT method for cylindric silicate pores calculated using program Belmaster™) were calculated, and the specific surface was 978 m.sup.2/g, the total volume of pores was 1.57 cm.sup.3/g and the diameter of pores was 2.4 nm.
Example 7
(74) Preparation of Porous Fe-MOF with BBPA(pH)
(75) The initial suspension containing 34.8 mg of biphenylene-4,4′-bis(phenylphosphinic acid)—BBPA(Ph) with the amount of substance of 0.08 mmol, 10.8 mg FeCl.sub.3.6H.sub.2O with the amount of substance of 0.04 mmol and 10 ml of anhydrous ethanol was heated in an autoclave with capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 24 hours without stirring.
(76) After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed with EtOH (3×30 ml) and then with acetone (3×30 ml) and dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit iron (III) biphenylene-4,4′-bis(phenylphosphinate) with weight of 25 mg was acquired.
(77) For the resulting MOF the adsorption isotherm of nitrogen was measured and specific surface (with BET method) and porosity (with NLDFT method for cylindric silicate pores calculated using program Belmaster™) were calculated, and the specific surface was 1172 m.sup.2/g, the total volume of pores was 2.40 cm.sup.3/g and the diameter of pores was 2.2 nm.
Example 8
(78) Preparation of Porous Fe-MOF with PBPA (Me) in the Form of Nanoparticles
(79) The initial suspension containing 4.7 mg of phenylene-1,4-bis(methylphosphinic acid)—PBPA(Me) with the amount of substance of 0.02 mmol, 5.4 mg FeCl.sub.3.6H.sub.2O with the amount of substance of 0.02 mmol and 10 ml of formamide was heated at 100° C. for 24 hours without stirring.
(80) After the resulting suspension cooled, it was centrifuged at 10000 rpm for 10 minutes and the product deposit was separated through decantation. The product was washed first with water (3×10 ml) and then with anhydrous EtOH (2×10 ml) and the resulting nanoparticles were kept in the form of colloidal solution in anhydrous EtOH. Coordination polymer of porous MOF with monomer unit iron (III) phenylene-1,4-bis(methylphosphinate) with weight of 3 mg was acquired.
Example 9
(81) Preparation of Porous Fe-MOF with BBPA(CH.sub.2═CH.sub.2pH)
(82) 19.5 mg of biphenylene-4,4′-bis(4-vinylphenylphosphinic acid)—BBPA(CH.sub.2═CH.sub.2Ph) with the amount of substance of 0.04 mmol and 5.4 mg of FeCl.sub.1.6H.sub.2O with the amount of substance of 0.02 mmol was suspended in 10 ml of formic acid. The resulting mixture was stirred in a vial at temperature 30° C. for 48 hours.
(83) After stirring was finished, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed with EtOH (3×30 ml) and then acetone (3×30 ml) and dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit iron (III) biphenylene-4,4′-bis(4-vinylphenylphosphinate) with weight of 10 mg was acquired.
(84) For the resulting MOF the adsorption isotherm of nitrogen was measured and specific surface (with BET method) and porosity (with NLDFT method for cylindric silicate pores calculated using program Belmaster™) were calculated, and the specific surface was 569 m.sup.2/g, the total volume of pores was 0.88 cm.sup.3/g (NLDFT) and the diameter of pores was 1.9 nm.
Example 10
(85) Preparation of Porous Fe-MOF with TPBTPA(Me)
(86) The initial suspension containing 14.0 mg of 1,3,5-triphenylbenzene-4′,4″,4′″-tris(methylphosphinic acid)—TPBTPA(Me) with the amount of substance of 0.026 mmol, 4.0 mg of FeCl.sub.3.6H.sub.2O with the amount of substance of 0.015 mmol and 10 ml of anhydrous ethanol was heated in an autoclave with capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 24 hours without stirring. After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed with ethanol (3×30 ml) and then with acetone (3×30 ml) and it was dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit iron (III) 1,3,5-triphenylbenzene-4′,4″,4′″-tris(methylphosphinate) with weight of 7 mg was acquired.
(87) MOF was characterised using the adsorption isotherm of nitrogen, and from it its specific surface (using t-plot method and porosity (HK-plot) were determined, and the specific surface was 869 m.sup.2/g and the diameter of pores was 0.9 nm.
Example 11
(88) Preparation of Porous Fe-MOF with TPMTPA(Me)
(89) The initial suspension containing 11.7 mg of tetraphenylmethane-4′,4″,4′″,4″″-tetrakis(methylphosphinic acid)—TPMTPA(Me) with the amount of substance of 0.02 mmol, 5.4 mg of FeCl.sub.3.6H.sub.2O with the amount of substance of 0.02 mmol and 10 ml of H.sub.2O was heated in an autoclave with capacity of 50 ml with teflon inlet under autogenous pressure at 250° C. for 24 hours without stirring. After the autoclave cooled, the resulting suspension was centrifuged at 10000 rpm for 5 minutes and the product deposit was separated through decantation. The product was washed with ethanol (3×30 ml) and then with acetone (3×30 ml) and it was dried in air at laboratory temperature. Coordination polymer of porous MOF with monomer unit iron (III) tetraphenylmethane-4′,4″,4′″,4″″-tetrakis(methylphosphinic acid) with weight of 5 mg was acquired.
(90) MOF was characterised using the powder x-ray diffraction and its structure was found using electron diffraction tomography.
Example 12
(91) Comparison of Porosity of Prepared MOFs
(92) Fe-MOF with BBPA(Me) produced according to Example 5 was compared with Fe-MOF with BBPA(Ph) that was prepared according to Example 6. The size of pores of Fe-MOF with BBPA(Ph) was 0.2 nm less when compared with Fe-MOF with BBPA(Me). This shows that if the substituent at the R.sup.1 position is phenyl, this will shrink size of pores when compared with substitution with methyl.
(93) Fe-MOF with PBPA(Me) produced according to Example 1 was compared with Al-MOF with PBPA(Me) that was prepared according to Example 2, with Y-MOF with PBPA(Me) produced according to Example 3 and with Cr-MOF with PBPA(Me) produced according to Example 4. The applied method of measurement could not determine porousness of Y-MOF with PBPA(Me), according to the resulting graph the porousness was over 0.5 nm. Fe-MOF with PBPA(Me), Al-MOF with PBPA(Me) and Cr-MOF with PBPA(Me) had pores of comparable size 0.8-0.9 nm which falls within the experimental error of the applied method and it indicates independence of size of pores on used metal.
(94) Last but not least, Al-MOF with PBPA(Ph) prepared according to Example 4 was compared with Al-MOF with PBPA(Me) prepared according to Example 2. The size of pores of Al-MOF with PBPA(Ph) was 1 nm less than the size of pores in the structure of Al-MOF with PBPA(Me). Likely the size of pores of Al-MOF with PBPA(Ph) was almost equal to size of nitrogen atoms and thus the measurement was at the limits of the applied method. However, we can expect that the size of pores of Al-MOF with PBPA(Ph) is less than in MOF with a lesser substituent and this is methyl in the structure of Al-MOF with PBPA(Me).
Example 13
(95) Analysis of Absorption of N2, H2 and CO2 in MOFs Samples
(96) MOF—adsorbent
(97) N.sub.2, H.sub.2 and CO.sub.2—adsorbate
(98) We weighted a cuvette, poured a sample of prepared MOF inside, then the sample was evacuated at least 24 hours by 80° C. to remove residua of solvents and of air moisture. We weighted the cuvette again after the evacuation had finished, to determine the weight of the MOF specimen—adsorbent. Subsequently we filled it with known amount of adsorbate N.sub.2, H.sub.2 or CO.sub.2, we measured the pressure in the cuvette corresponding to the amount of adsorbed adsorbate after the pressure in the cuvette was in equilibrium and we added more adsorbate up to pressure 0.95 bar. In case of sorption of N.sub.2 we also measured desorption i.e. small quantity of gas-adsorbate was pumped out and we waited till the pressure stabilised down to 0.3 bar where we finished the experiment. We did the measurement with a device Belsorp max II (company MicrotracBel). Before the measurement we evacuated the samples at temperature 80° C. for 24 hours, at least, in order to remove residua of solvents and of air moisture. Then we evacuated the samples and gradually added adsorbate while monitoring pressure increase so that each point in the graph would correspond to the equilibrium conditions for that pressure. We measured up to 0.95 bar. Then we measured gas desorption for N.sub.2 in a similar way, only the pressure was decreased down to 0.3 bar.
(99) We measured adsorbate H.sub.2 and N.sub.2 at 77K (fluid nitrogen) and CO.sub.2 at 25° C.
APPLICABILITY IN INDUSTRY
(100) MOFs with the above properties can be used for applications oriented particularly on storing of gases, separation of gases, as drug carriers, for preparation of membranes, of heterogeneous catalysts, sorbents, lithium batteries, of proton conductors and they can be used in analytical chemistry as sensors, above all, of gases, ions or biologically active substances.