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WO2025114457A1 - Synthèse de réseaux organométalliques - Google Patents

Synthèse de réseaux organométalliques Download PDF

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Publication number
WO2025114457A1
WO2025114457A1 PCT/EP2024/083949 EP2024083949W WO2025114457A1 WO 2025114457 A1 WO2025114457 A1 WO 2025114457A1 EP 2024083949 W EP2024083949 W EP 2024083949W WO 2025114457 A1 WO2025114457 A1 WO 2025114457A1
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WIPO (PCT)
Prior art keywords
mof
metal
salt
zinc
magnesium
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English (en)
Inventor
Lok Yi Venus SO
Jack Turner
Selina AMBROSE
James Stephenson
Paul Kirkman
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PROMETHEAN PARTICLES Ltd
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PROMETHEAN PARTICLES Ltd
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Publication of WO2025114457A1 publication Critical patent/WO2025114457A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds

Definitions

  • the invention relates to metal-organic frameworks (MOFs) having a UTSA-16 structure and to a method of making said MOFs.
  • MOFs metal-organic frameworks
  • the invention relates to UTSA-16 (Mg, Zn) MOFs having good CO2 capture performance.
  • Metal-organic frameworks are porous crystalline materials with a modular synthetic chemistry. Due to high compositional tuneability, they are amenable to precise materials engineering allowing excellent performance in numerous commercially interesting applications. For example, certain MOFs have exhibited large CO2 uptake capacities, high CO2 selectivity and prolonged stability making them excellent CO2 capture sorbents.
  • the development of scalable and sustainable synthetic protocols is an essential step towards actual commercial applications of MOFs. This is because most intended MOF applications entail significant volumes of material (e.g., -3000 tonnes sorbent for a capture unit integrated with a 500 MW coal -based power facility). As such, the environmental impact and cost of manufacture substantially affect the overall economic viability of the process.
  • UTSA-16 is a highly promising MOF material for CO2 capture by adsorption due to the isotherm features, mechanism of adsorption, and stability. Almost all reported syntheses for this material are based on the protocol in Journal of the American Chemical Society, 2005, 127, 16352-16353, where only the vessel and solvent volume are adjusted to meet the required scale of synthesis. This reported solvothermal synthetic protocol requires specialized reactors, introducing additional capital costs for production, and precludes the use of common glass equipment, where the typical pressure rating is below 2 bar. Ongoing attempts to scale-up this material are hindered by failure to reduce the synthetic temperature below the boiling point of the solvent. In addition, the aforementioned protocol also necessitates extended crystallization time (up to 2 days).
  • the process disclosed in Gaikwad requires 14 washing steps using a wide range of solvents, has a reaction temperature of 90°C as a result of microwaves and is a batch process, so it is not a scalable method from a production perspective.
  • the invention provides a method of forming a metal-organic framework (MOF) having a UTSA-16 structure, the method comprising:
  • the invention provides a metal-organic framework (MOF) having a UTSA-16 structure obtainable by the method according to the first aspect of the invention.
  • MOF metal-organic framework
  • the metal organic-framework (MOF) having a UTSA-16 structure obtainable by method according to the first aspect of the invention may be a UTSA-16 magnesium-zinc (Mg, Zn) metal-organic framework (MOF) when the first fluid of the method comprises zinc salt and magnesium salt in a molar ratio of 1 : 1.
  • the invention provides a magnesium-zinc (Mg, Zn) metal-organic framework (MOF) having a UTSA-16 structure wherein the atomic % ratio of magnesium to zinc is Fat least 9.
  • the invention provides a magnesium-zinc (Mg, Zn) metal-organic framework (MOF) having a UTSA-16 structure comprising: from 0.1 to 1 atomic % of magnesium; and from 5 to 20 atomic % of zinc.
  • Mg, Zn magnesium-zinc
  • MOF metal-organic framework
  • the invention provides a method of capturing CO2 comprising the step of exposing a material comprising a metal organic-framework (MOF) to an environment containing CO2, wherein the metal organic-framework (MOF) is obtainable by a method according to the first aspect of the invention or the metal organic-framework (MOF) is according to the third or fourth aspect of the invention.
  • a metal organic-framework MOF
  • Figure 1 shows a schematic diagram of a method according to the present invention.
  • Figure 2 shows an example of a reactor that may be used in the method according to the present invention.
  • Figure 3 shows X-ray diffraction (XRD) patterns of bimetallic UTSA-16-type MOFs obtained according to the method of the present invention and their calculated BET surface area and the CO2 uptake measured by thermogravimetric analysis (TGA).
  • XRD X-ray diffraction
  • Figure 4 shows N2 adsorption isotherm graphs of the UTSA-16 metal-organic frameworks (MOFs) of example 3.
  • Figure 5 shows the CO2 uptake from a 15% CO2 gas stream, quantified using TGA, of the UTSA-16-type (Mg, Zn) MOF of example 3.
  • the invention is based on the finding that metal-organic frameworks (MOFs) having a UTSA-16 structure can be synthesised at room temperature in continuous flow.
  • MOFs metal-organic frameworks
  • the method of making UTSA-16 MOFs of the present invention is significantly faster under milder reaction conditions than known methods of making MOFs, provides instantaneous and homogeneous mixing and has millisecond reaction times and excellent scale-up reproducibility. The method is consistent and thorough, leading to a satisfactory yield of UTSA-16 MOF.
  • the method of the present invention can be used to produce UTSA-16 MOFs having good CO2 capture performance and surface area.
  • UTSA-16 (Mg, Zn) MOFs unexpectedly show high surface area and CO2 uptakes.
  • the invention provides a method of forming a metal-organic framework (MOF) having a UTSA-16 structure, the method comprising:
  • the mixing reactor may be a reactor suitable for mixing two fluids. Typically, it will be suitable for forming metal-organic framework (MOF) particles having a UTSA-16 structure.
  • the mixing reactor may be a counter current mixing reactor. In the method of the present invention the mixing reactor may be a counter current mixing reactor for continuously mixing two fluids.
  • the second inlet of the mixing reactor may be diametrically opposed to the first inlet.
  • the mixing reactor may comprise a body having a first inlet, a second inlet and an outlet.
  • the first inlet may be at a first end of the body and the second inlet may be at a second end of the body.
  • the mixing reactor may comprise a body having the first inlet, the second inlet, the outlet, an inner passage through the body from the first inlet to the second inlet and an outer passage closer to a surface of the body than the inner passage.
  • the inner passage and outer passage as described here may meet at a junction where the first and second fluids are mixed.
  • the mixing reactor may comprise a body having a first inlet, a second inlet and an outlet, in which there is an inner passage through the body from the first inlet at a first end of the body to the second inlet at a second end of the body, the inner passage may further have a side wall along a length of the body, and an outer passage closer to a surface of the body than the inner passage, the outer passage running from the outlet at the second end of the body along the length of the body and meeting the inner passage at a junction at the first end, the outer passage joining the inner passage through the side wall at the junction.
  • the inner and outer passages may be symmetrical about the centreline of the inner passage.
  • the body may be made of a metal material or a chemically resistant polymer.
  • the metal material may be a metal, such as stainless steel, or alloys such as Hastelloy, Inconel, Monel or Nimonic.
  • the first fluid may be pumped into the body through the first inlet at the first end of the body.
  • the second fluid may be pumped into the inner passage of the body through the second inlet at the second end of the body.
  • the first fluid may be flowed up into the body through the first inlet.
  • the second fluid may be flowed down into the inner passage of the body through the second inlet.
  • the invention provides a method of forming (Mg, Zn) MOF, (Mn, Zn) MOF, (Fe, Zn) MOF, (Cu, Zn) MOF or (Co, Zn) MOF having a UTSA-16 structure.
  • the first and second fluids may be liquids, including solutions, dispersions or suspensions.
  • the metal salt solution may be a bimetallic salt solution.
  • the first fluid comprises a metal salt solution.
  • the metal salt solution may comprise, for example, a solution of metal nitrates, metal sulphates, metal acetates, metal acetylacetonates, metal halides, metal carbonates or combination thereof.
  • the metal salt solution may comprise a copper salt, cobalt salt, iron salt, magnesium salt, manganese salt, zinc salt, or combinations thereof.
  • the metal salt solution may comprise zinc salt.
  • the zinc salt may be zinc acetate dihydrate.
  • the metal salt solution may comprise magnesium acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate, iron acetate, copper acetate monohydrate, zinc acetate dihydrate or combinations thereof.
  • the metal salt solution may be a bimetallic salt solution comprising a first metal salt and a second metal salt.
  • the metal salt solution of the first fluid may comprise a first metal salt selected from magnesium salt, manganese salt, iron salt, copper salt or cobalt salt and a second metal salt being zinc salt.
  • the metal salt solution may comprise a mixture of a first metal salt selected from magnesium acetate tetrahydrate, cobalt acetate tetrahydrate, manganese acetate, iron acetate or copper acetate monohydrate and a second metal salt being zinc acetate dihydrate.
  • the first fluid may further comprise water, methanol, ethanol or combinations thereof.
  • the first fluid may further comprise water and ethanol.
  • the first fluid may comprise a magnesium salt, a zinc salt, water and ethanol.
  • the first fluid may comprise magnesium acetate tetrahydrate, zinc acetate dihydrate, water and ethanol.
  • the first fluid may comprise a cobalt salt, a zinc salt, water and ethanol.
  • the first fluid may comprise cobalt acetate tetrahydrate, zinc acetate dihydrate, water and ethanol.
  • the metal salt solution may comprise a first metal salt selected from magnesium salt, manganese salt, iron salt, copper salt or cobalt salt, and a second metal salt being zinc salt, wherein the molar ratio of first metal salt to second metal salt is 1 : 1 or 2:7.
  • the metal salt solution may comprise magnesium salt and zinc salt in a molar ratio 1 : 1 or cobalt salt and zinc salt in a molar ratio 1 : 1.
  • the metal salt solution may comprise magnesium acetate tetrahydrate and zinc acetate dihydrate in a molar ratio 1 : 1 or cobalt acetate tetrahydrate and zinc acetate dihydrate in a molar ratio 1 : 1.
  • the metal salt solution of the present invention may comprise a first metal salt selected from manganese salt, iron salt, or copper salt, and a second metal salt being a zinc salt, wherein the molar ratio of first metal salt to second metal salt is 2:7.
  • the metal salt solution of the present invention may comprise a first metal salt selected from manganese acetate, iron acetate or copper acetate monohydrate, and a second metal salt being zinc acetate dihydrate, wherein the molar ratio of first metal salt to second metal salt is 2:7.
  • the second fluid comprises a ligand solution.
  • the ligand solution may comprise a ligand and a basic solution.
  • the ligand may be terephthalic acid, citric acid, fumaric acid, isophthalic acid, dihydroxyisophthalic acid, trimesic acid, 2-methylimidazole, 2-aminoterephthalic acid, 2,5- dihydroxyterephthalic acid or 2,5- pyrazole-2,5-dicarboxylic acid.
  • the second fluid may further comprise potassium hydroxide, sodium hydroxide, triethylamine, ammonium hydroxide, pyridine, water or combinations thereof.
  • the second fluid may comprise citric acid, potassium hydroxide and water.
  • the metal-organic framework (MOF) dispersion may be particle-bearing suspension or dispersion.
  • the metal-organic framework (MOF) dispersion may comprise MOF particles in solution, dispersion or suspension.
  • the mixing reactor will mix the first and second fluids, so that both fluids mix together and MOF particles are formed.
  • the initial mixing location may be where the two fluids firstly meet, for example at the junction.
  • the mixing reactor may be operated with at least 50 mL/min flow rate measured at the outlet, such as at least 100 mL/min, or at least 140 mL/min, or at least 200 mL/min, or at least 1 L/min, or at least 5 L/min, or at least 10 L/min flow rate measured at the outlet.
  • the mixing reactor may be operated with from 50 mL/min to 10 L/m flow rate measured at the outlet, such from 50 mL/min to 8 L/m, or from 50 mL/min to 7 L/m, or from 50 mL/min to 6 L/m, or from 50 mL/min to 5 L/m, or from 50 mL/min to 4 L/m, or from 50 mL/min to 2 L/m, or from 100 mL/min to 10 L/m, or from 100 mL/min to 8 L/m, or from 100 mL/min to 7 L/m, or from 100 mL/min to 6 L/m, or from 100 mL/min to 5 L/m, or from 100 mL/min to 4 L/m, or from 100 mL/min to 3.5 L/m, or from 100 mL/min to 1 L/m, or from 500 mL/min to 10 L/m, or from 500 mL/min to 8 L/m, or from 500
  • the method may comprise heating or cooling the mixed fluid as it passes through the outer passage of the body as describe herein.
  • the mixing reactor may further comprise a heater coupled to the surface, such as a band heater. This will heat the outer passage rather than the inner passage or the first inlet.
  • the body may be made of heat-conductive material, such as a metal material, such as stainless steel, typically stainless steel, or alloys such as Hastelloy, Inconel, Monel or Nimonic.
  • the mixing reactor may be operated at ambient temperature or a temperature between 2 °C and 200 °C, such as between 2 °C and 150 °C, or between 2 °C and 100 °C, or between 2 °C and 50 °C, or between 5 °C and 150 °C, or between 5 °C and 100 °C, or between 5 °C and 70 °C, or between 5 °C and 50 °C, or between 5 °C and 40 °C, or between 10 °C and 200 °C, or between 10 °C and 100 °C, or between 10 °C and 70 °C, or between 10°C and 60 °C, or between 10 °C and 50 °C, or between 10 °C and 40 °C, or between 20 °C and 30 °C, or between 20 °C and 70 °C, or between 20°C and 60 °C, or between 20 °C and 50 °C, or between 20 °C and 40 °C, or between 20
  • the method described herein may also be carried out without heating the reactor or without preheating the first and/or second fluids. In one embodiment the method of the present invention does not require heating.
  • the method described herein may be carried out at ambient or room temperature, for example between 20 °C and 28 °C. In one embodiment, the first and/or second fluids are not heated before entering the reactor.
  • the mixing reactor may be operated from 0.5 bar to 240 bar, or from 1 bar to 240 bar, or from 0.5 bar to 200 bar, or from 0.5 bar to 150 bar, or from 0.5 bar to 100 bar, or from 0.5 bar to 150 bar, or from 1 bar to 200 bar, or from 1 bar to 150 bar, or from 1 bar to 10 bar.
  • the mixing reactor may be operated at 1 bar.
  • the method of the present invention may be used to form bimetallic UTSA-16 metalorganic frameworks (MOFs) comprising zinc and a metal (X) selected from magnesium (Mg), manganese (Mn), iron (Fe), copper (Cu) or cobalt (Co).
  • MOFs metalorganic frameworks
  • X selected from magnesium (Mg), manganese (Mn), iron (Fe), copper (Cu) or cobalt (Co).
  • the UTSA-16 MOFs obtained by the process of the present invention may be UTSA-16 (Mg, Zn) MOF, when the first fluid comprises zinc salt and magnesium salt in a molar ratio of 1 : 1, or the UTSA-16 MOFs obtained by the process of the present invention may be UTSA-16 (Co, Zn) MOF, when the first fluid comprises zinc salt and cobalt salt in a molar ratio of 1: 1.
  • the method described here may be a method of forming a magnesium-zinc (Mg, Zn) metal-organic framework (MOF) having a UTSA-16 structure, the method comprising:
  • the mixing reactor used in the method of obtaining the UTSA-16 (Mg, Zn) MOF is as described herein, so for example, the reactor may have the second inlet diametrically opposed to the first inlet.
  • the mixing reactor may be operated at ambient temperature as described herein.
  • the mixing reactor may be operated at ambient temperature, for example between 20 °C and 28 °C.
  • the first fluid may comprise a magnesium salt to zinc salt molar ratio of 1 : 1.
  • the first fluid may comprise magnesium acetate tetrahydrate, zinc acetate dihydrate, water and ethanol, as described herein.
  • the second fluid may comprise citric acid, potassium hydroxide and water.
  • the first fluid may comprise from 0.0 IM to 0.4M magnesium acetate tetrahydrate (Mg(OAc)2.4H2O), such as from 0.03M to 0.4M, or 0.05M to 0.4M, or from 0.07M to 0.4M, or from 0.01M to 0.3M, or from 0.01M to 0.2M, or from 0.03M to 0.3M, or 0.05M to 0.3M, or from 0.07M to 0.3M, or from 0.03M to 0.2M, or 0.05M to 0.2M, or from 0.07M to 0.2M, or from 0.08M to 0.4M magnesium acetate tetrahydrate (Mg(OAc)2.4H2O).
  • Mg(OAc)2.4H2O magnesium acetate tetrahydrate
  • the first fluid may comprise from 0.0 IM to 0.4M zinc acetate dihydrate (Zn(OAc)2.2H2O), such as from 0.03M to 0.4M, or 0.05M to 0.4M, or from 0.07M to 0.4M, or from 0.01M to 0.3M, or from 0.01M to 0.2M, or from 0.03M to 0.3M, or 0.05M to 0.3M, or from 0.07M to 0.3M, or from 0.03M to 0.2M, or 0.05M to 0.2M, or from 0.07M to 0.2M, or from 0.08M to 0.4M zinc acetate dihydrate (Zn(OAc) 2 .2H 2 O).
  • Zn(OAc)2.2H2O zinc acetate dihydrate
  • the first fluid may comprise from 0.0 IM to 0.4M magnesium acetate tetrahydrate (Mg(OAc)2.4H2O) and from 0.0 IM to 0.4M zinc acetate dihydrate (Zn(OAc)2.2H2O), wherein the molar ratio of magnesium acetate tetrahydrate to zinc acetate dihydrate is 1 : 1.
  • the second fluid may comprise between 0.05M and IM of citric acid, such as between 0.05M and 0.8M , or between 0.05M and 0.7M , or between 0.05 M and 0.6 M, or between 0.05M and 0.55M, or between 0.08M and 0.8M, or between 0.08M and 0.7M, or between 0.08M and 0.6M, or between 0. IM and 0.8M, or between 0. IM and 0.6M, or between 0. IM and 0.55M, or between 0. 13M and 0.8M, or between 0.13M and 0.55M, or between 0.1333M and 0.5332M, or between 0.05M and IM of citric acid, such as between 0.05M and 0.8M , or between 0.05M and 0.7M , or between 0.05 M and 0.6 M, or between 0.05M and 0.55M, or between 0.08M and 0.8M, or between 0.08M and 0.7M, or between 0.08M and 0.6M, or between 0. IM and 0.8M, or between 0. IM and
  • the second fluid may comprise between 0.1M and 2M of potassium hydroxide (KOH), such as between 0.1M and 1.8M, or between 0.1M and 0.16M, or between 0.1M and 1.5M, or between 0.2M and 2M, or between 0.2M and 1.8M, or between 0.2M and 1.6M, or between 0.2M and 1.5M, or between 0.3M and 2M, or between 0.3M and 1 ,8M, or between 0.3M and 1.6M, or between 0.3M and 1.5M, or between 0.35M and 2M, or between 0.35M and 1.8M, or between 0.35M and 0.16M, or between 0.35M and 1.5M, or between 0.4M and 2M, or between 0.4M and 1.8M, or between 0.4M and 1.5M of potassium hydroxide (KOH).
  • KOH potassium hydroxide
  • the first fluid may comprise a ratio of ethanol to water of 20:80, or 30:70, or 40:60, or 50:50.
  • the method of the present invention may be carried out at ambient temperature.
  • the method of the present invention may be carried out at 25 °C.
  • the method of the present invention may further comprise separating the metal-organic framework (MOF) particles (e.g. the UTSA-16 (Mg, Zn) MOF particles) from the solution.
  • the method may further comprise separating the MOF particles from the solution by centrifugation.
  • MOF metal-organic framework
  • the method of the present invention may further comprise separating the metal-organic framework (MOF) particles (e.g. the UTSA-16 (Mg, Zn) MOF particles) from the supernatant and washing and drying the UTSA-16 MOF particles.
  • MOF metal-organic framework
  • the method may further comprise pelletizing the UTSA-16 metal-organic framework (MOF) particles (e.g. the UTSA-16 (Mg, Zn) MOF particles) using a binder.
  • MOF metal-organic framework
  • the invention provides a metal-organic-framework (MOF) having a UTSA-16 structure, obtainable by the method as described herein.
  • MOF metal-organic-framework
  • the metal-organic framework (MOF) having a UTSA-16 structure obtainable by the method described herein may be a bimetallic metal organic framework, wherein the metal salt solution of the first fluid may comprise a first metal salt and a second metal salt, and the first metal salt may be selected from copper salt, cobalt salt, iron salt, magnesium salt or manganese salt and the second meal is zinc salt.
  • the mixing reactor, conditions, and first and second fluids may be as described herein.
  • the invention further provides a magnesium-zinc (Mg, Zn) metal organic framework (MOF) having a UTSA-16 structure, obtainable by a process comprising:
  • the mixing reactor, conditions and first and second fluids may be as described herein.
  • the invention provides a magnesium-zinc (Mg, Zn) metal organic framework (MOF) having a UTSA-16 structure comprising an atomic % ratio of magnesium to zinc is l :least 9.
  • Mg, Zn magnesium-zinc
  • MOF metal organic framework
  • the magnesiunrzinc atomic % ratio is l :at least 9.
  • the atomic % ratio of magnesium to zinc may be from 1 :9 to 1 : 30, or from 1 : 11 to 1 :30, or from 1 : 13 to 1 :30, or from 1 : 15 to 1 :30, or from 1 :9 to 1 : 25, or from 1 : 11 to 1:25, or from 1 : 13 to 1 :25, or from 1 : 15 to 1 :25, or from 1 :9 to 1 :20, or from 1 : 1 1 to 1 :20, or from 1 : 13 to 1 :20, or from 1 : 15 to 1 :20, or from 1 :9 to 1 : 18, or from 1 : 1 1 to 1 : 18, or from 1 : 13 to 1 : 18, or from 1 : 15 to 1 : 18.
  • the invention provides a magnesium-zinc (Mg, Zn) metal organic framework (MOF) having a UTSA-16 structure comprising: from 0.1 to 1 atomic % of magnesium; and from 5 to 20 atomic % of zinc.
  • Mg, Zn magnesium-zinc
  • MOF metal organic framework
  • Magnesium (Mg) is present in the UTSA-16 (Mg, Zn) MOF in an atomic % from 0.1 to 1.
  • the atomic % of magnesium in the (Mg, Zn) MOF may be from 0.1 to 0.9, such as from 0.1 to 0.8, or from 0.1 to 0.7, or from 0.1 to 0.6, or from 0.1 to 0.5, or from 0.2 to 1, or from 0.2 to 0.9, or from 0.2 to 0.8, or from 0.2 to 0.7, or from 0.2 to 0.6, or from 0.3 to 1, or from 0.3 to 0.9, or from 0.3 to 0.8, or from 0.3 to 0.7, or from 0.3 to 0.6, or from 0.4 to 1, or from 0.4 to 0.9, or from 0.4 to 0.8, or from 0.4 to 0.7, or from 0.4 to 0.6.
  • Zinc (Zn) is present in the UTSA-16 (Mg, Zn) MOF in an atomic % from 5 to 20.
  • the atomic % of zinc in the (Mg, Zn) MOF may be from 5 to 18, such as from 5 to 16, or from 5 to 14, or from 5 to 12, or from 5 to 10, or from 5 to 9, or from 6 to 18, or from 6 to 16, or from 6 to 14, or from 6 to 12, or from 6 to 10, or from 6 to 9, or from 7 to 18, or from 7 to 16, or from 7 to 14, or from 7 to 12, or from 7 to 10, or from 7 to 9, or from 8 to 18, or from 8 to 16, or from 8 to 14, or from 8 to 12, or from 8 to 10, or from 8 to 9.
  • MOFs described herein may be formed under milder conditions (such as 25 °C and 1 bar).
  • the MOFs described herein or made by the method according to the invention may have a Brunauer-Emmett-Teller (BET) surface area from 300 to 1500 m 2 /g, such as from 300 to 1500 m 2 /g, or from 300 to 1000 m 2 /g, or from 300 to 800 m 2 /g, or from 300 to 700 m 2 /g, or from 400 to 1500 m 2 /g, or from 400 to 1000 m 2 /g, or from 400 to 800 m 2 /g, or from 400 to 700 m 2 /g, or from 450 to 1500 m 2 /g, or from 450 to 1000 m 2 /g, or from 450 to 800 m 2 /g, or from 450 to 700 m 2 /g, or from 500 to 1500 m 2 /g, or from 500 to 1000 m 2 /g, or from 500 to 800 m 2 /g, or from 500 to 700 m 2 /g, or from 500 to 700 m 2 /
  • N2 adsorption isotherms were recorded using a Tristar II instrument (Micromeritics, USA) at 77 K, and at partial pressures between 0.00 and 0.90. Prior to measurement, approximately 60-100 mg of MOF materials were degassed under vacuum overnight at 150 °C using a VacPrep 061 (Micromeritics, USA), before being allowed cool to room temperature for analysis. Following measurement of N2 isotherms, surface areas were calculated using the BET method, through the analysis procedure contained within the instrument software (Microactive).
  • the MOFs described herein, including the UTSA-16 (Mg, Zn) MOFs, may be useful in CO2 capture.
  • the ability of the sorbent to capture CO2 can be demonstrated by measuring adsorption by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the MOFs of the current invention may have a CO2 uptake (from a 15% CO2 gas stream) greater than 0.5 mmol/g, such as greater than 0.8mmol/g, or greater than 1 mmol/g, or greater than 1.2 mmol/g, or greater than 1.5 mmol/g, or greater than 1.8 mmol/g, or greater than 2 mmol/g.
  • the MOFs of the present invention may have a 15% CO2 uptake from 0.5 to 3 mmol/g, or from 0.5 to 2.7 mmol/g, or from 0.5 to 2.5 mmol/g, or from 0.8 to 3 mmol/g, or from 1 to 3 mmol/g, or from 1 to 2.5 mmol/g, or from 1.2 to 3 mmol/g, or from 1.2 to 2.5 mmol/g, or from 1.5 to 3 mmol/g, or from 1.5 to 2.5 mmol/g.
  • the MOFs described herein may be shaped into pellets using a binder.
  • the binder may be polyvinyl butyral (PVB).
  • the MOF of the present invention may be useful in capturing CO2.
  • a method of capturing CO2 comprising the step of exposing a material comprising a MOF as described herein to an environment containing CO2.
  • UTSA-16 metal organic frameworks (MOFs) were synthesised using a counter-current reactor (1) as shown in the schematic diagram of Figure 1.
  • the first fluid (2) comprising the metal salt solution was prepared dissolving magnesium acetate tetrahydrate (5.471 g, 25 mmol) and zinc acetate dihydrate (5.599 g, 25 mmol) in 50 m of water, followed by addition of 200 m of ethanol.
  • the second fluid (3) comprising a ligand solution was prepared mixing citric acid (6.466 g, 33.3 mmol) and potassium hydroxide (6.233 g, 100 mmol) dissolved in 250 mb water.
  • the first fluid (2) was placed in the upflow feed (4) and the second fluid (3) in the downflow feed (5) (see Figure 1).
  • the fluids were pumped into the reactor (1) and the reaction product, namely the metal organic framework (MOF) dispersion (6) collected at the outlet feed.
  • the reaction was run with a flow rate of 140 mL/min at each flow using ambient conditions (25 °C and 1 bar).
  • the reaction product was collected from the outflow feed using a suitable collection vessel.
  • the product was centrifuged at 2500 rpm to remove the supernatant.
  • the isolated solid reaction product was redispersed/washed with methanol and centrifuged a second time. The solution was removed and the centrifuged solids oven dried at 100°C for 1 hour to remove the excess solvent.
  • Figures 2 show an example of a counter current mixing reactor (1) that may be used in the method of the present invention. It comprises a body (7) having a first inlet (8), a second inlet (9) and an outlet (10). There is an inner passage (11) through the body (7) from the second inlet (9) at a second end (13) of the body (7) towards the first inlet (8) at a first end (12) of the body (7), the inner passage (11) having a side wall (14) along a length of the body (7), and an outer passage (15) closer to a surface (16) of the body (7) than the inner passage (11), the outer passage (15) running from the outlet (10) at the second end (13) of the body (7) along the length of the body (7) and meeting the inner passage (11) at a junction (17) at the first end (12), the outer passage (15) joining the inner passage (11) through the side wall (14) at the junction (17).
  • the mixing reactor (1) has been used with the following reactants to produce UTSA-16 (Mg, Zn) MOF:
  • metal salt solution citric acid: KOH ratio (wherein the metal salt solution is the result of dissolving the Mg(OAc) 2 .4H 2 O and Zn(OAc) 2 .2H 2 O in the water and ethanol)
  • the reaction was run at ambient conditions (25 °C and 1 bar).
  • MOFs were synthesised using the above method but replacing magnesium acetate by cobalt acetate tetrahydrate, manganese acetate, iron acetate or copper acetate monohydrate.
  • UTSA-16 (Co, Zn) MOF was synthesised using 1 : 1 molar ratio of cobalt acetate tetrahydrate to Zn(OAc) 2 .2H 2 O.
  • UTSA-16 (X, Zn; Fe, Mn and Cu) MOFs the ratio of manganese acetate, iron acetate or copper acetate monohydrate to Zn(OAc) 2 .2H 2 O was 2:7.
  • Table 1 shows weight percentages of element and atomic percentages obtained from SEM analysis of UTSA-16 (Mg, Zn) MOF with a reactant metal salt molar ratio of 1 : 1.

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Abstract

L'invention concerne un procédé de formation d'un réseau organométallique (MOF) ayant une structure UTSA-16, le procédé consistant à : (i) prendre un réacteur de mélange comprenant une première entrée, une seconde entrée et une sortie ; (ii) distribuer un premier fluide à la première entrée, le premier fluide comprenant une solution de sels métalliques ; (iii) distribuer un second fluide à la seconde entrée, le second fluide comprenant une solution de ligand ; et (iv) extraire une solution de réseau organométallique (MOF) de la sortie.
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