Porous liquids

Abstract

The invention relates to dispersions of porous solids in liquids selected from deep eutectic solvents, liquid oligomers, bulky liquids, liquid polymers, silicone oils, halogenated oils, paraffin oils or triglyceride oils, as well as to their methods of preparation. In embodiments of the invention, the porous solids are metal organic framework materials (MOFs), zeolites, covalent organic frameworks (COFs), porous inorganic materials, Mobil Compositions of Matter (MCMs) or a porous carbon. The invention also relates to the use of porous materials to form dispersions, and to assemblages of such dispersions with a gas or gases. The dispersions can exhibit high gas capacities and selectivities.

Claims

1. A dispersion comprising: a porous solid selected from a MOF, zeolite 5A, zeolite Rho, zeolite AgX, zeolite AgA, a covalent organic framework (COF), a Mobil Composition of Matter (MCM) and a porous carbon, dispersed in a liquid phase; wherein the liquid phase is selected from the group consisting of, liquid oligomers, liquid polymers, halogenated oils, silicone oil 20 cst, silicone oil 50 cst, silicone oil 350 cst, silicone oil 1000 cst, silicone oil AP 100, silicone oil AR 20, and combinations thereof; and wherein the dispersion comprises 0.1-50 wt % of the porous solid.

2. The dispersion as claimed in claim 1, wherein the porous solid is a MOF, the MOF comprising a metal ion co-ordinated to an organic ligand selected from oxalate, carboxylates, imidazoles, sulfonates, phosponates, peptides, carboranes, polyoxymetalates, heterocycles, and derivatives thereof; and mixtures thereof; or to an inorganic anion selected from SiF.sub.6, TiF.sub.6 and mixtures thereof.

3. The dispersion as claimed in claim 1, wherein the MOF is selected from HKUST-1, ZIF-8, Al(fumarate)(OH), SIFSIX-3-Zn, SIFSIX-3-Cu, UiO-66-NH2, UiO-66, Zr(fumarate), ZIF-67, MOF-5, IRMOF-3, UiO-67, CAU-10, SIFSIX-3-Ni, MIL-53, MIL-101, NOTT-100, PCN-14, SIFSIX-3-Co, ZIF-90, ZIF-7, BIT-101, MOF-74, MOF-177, CuBTTri, IRMOF-3, MOF-5CH.sub.3, PCN-222, and UiO-66-CH.sub.3.

4. The dispersion as claimed in claim 1, wherein the liquid phase is selected from silicone oil AP 100 and silicone oil AR 20.

5. The dispersion as claimed in claim 1, wherein the liquid phase is a halogenated oil, optionally a fluorinated, brominated or chlorinated oil.

Description

FIGURES

(1) FIG. 1 is a schematic diagram showing apparatus for gas uptake measurement;

(2) FIG. 2 shows SEM images of the synthesized MOFs; namely FIG. 2(a) ZIF-8, FIG. 2(b) HKUST-1, FIG. 2(c) Al(fumarate)(OH), FIG. 2(d) SIFSIX-3-Zn;

(3) FIG. 3 shows PXRD traces of the dispersions of Examples 5 to 8; wherein FIG. 3(a) shows (i) ZIF-8 in silicone oil, (ii) ZIF-8, and (iii) silicone oil; FIG. 3(b) shows (i) HKUST-1 in silicone oil, (ii) HKUST-1 and (iii) silicone oil; FIG. 3(c) shows (i) Al(fumarate)(OH) in silicone oil, (ii) Al(fumarate)(OH) and (iii) silicone oil; and FIG. 3(d) shows (i) SIFSIX-3-Zn in silicone oil, (ii) SIFSIX-3-Zn and (iii) silicone oil;

(4) FIG. 4 shows IR spectra for the dispersions of Examples 5 to 8; namely FIG. 4(a) shows (i) ZIF-8 in 50 cst silicone oil, (ii) 50 cst silicone oil and (iii) ZIF-8; FIG. 4(b) shows (i) HKUST-1 in 50 cst silicone oil, (ii) 50 cst silicone oil and (iii) HKUST-1;

(5) FIG. 4(c) shows (i) Al(fumarate)(OH) in 50 cst silicone oil, (ii) 50 cst silicone oil and (iii) A(fumarate)(OH): and FIG. 4(d) shows (i) SIFSIX-3-Zn in 50 cst silicone oil, (ii) 50 cst silicone oil and (iii) SIFSIX-3-Zn;

(6) FIG. 5 is a reversibility test and shows CO.sub.2 uptake for dispersions of Examples 6 and 7 following regeneration;

(7) FIG. 6 is a regeneration study of HKUST-1 in silicone oil and shows CO.sub.2 uptake for dispersions of Examples 6 following multiple regeneration cycles;

(8) FIG. 7 shows further regeneration studies, depicting CO.sub.2 update for various dispersions after one, two and three cycles; and

(9) FIG. 8 shows experimental and theoretical_CO.sub.2 uptake for dispersions of Examples 37-40.

(10) FIG. 9 shows a Parr reactor used in the high pressure gas update studies.

EXAMPLES

(11) The following examples are intended to be illustrative only.

Experimental Methodology

(12) Materials

(13) All materials were obtained from Sigma Aldrich UK in >98% purity or Molekula in >96% purity and were used as obtained without further purification. PXRD measurements were carried out on a PAN analytical X'Pert Pro X-ray diffractometer. Copper was used as the X-ray source with a wavelength of 1.5405 Å. Diffractograms were typically obtained from 550° with a step size of 0.0167°. CO.sub.2 uptake test was carried out on BINDER oven with EDWARDS pressure monitor. Gas uptake measurement was carried out at 25° C. and c.a. 0.8 bar.

(14) Equipment

(15) FIG. 1 is a schematic diagram showing apparatus for gas uptake measurements performed by a pressure drop method. The apparatus is held within a temperature controlled oven (TB) and the whole system is attached to a vacuum line. The liquid sample was held in the sample cell (EC) with a stirring bar and the gas reservoir (B) was filled with a known amount of CO.sub.2 and remains closed before measurement. The system was then isolated from vacuum and the CO.sub.2 was released from the gas reservoir. The pressure in the system was monitored by a manometer (M) attached to a PC (PC).

(16) Preparation of MOFs

(17) All MOFs were synthesized as described in the literature and known in the art. Generally, the starting metal salt and corresponding ligand are mixed in methanol and stirred overnight. The resulting precipitate is washed with methanol three times and collected by centrifugation. The resultant MOF is dried under air. Specific syntheses are described below:

Example 1: Synthesis of ZIF-8

(18) Solution synthesis: Zn(NO.sub.3).sub.2.6H.sub.2O (1.00 g, 3.36 mmol) was dissolved in 20 mL methanol (MeOH) in a conical flask. 2-methylimidazole (1.10 g, 13.44 mmol) was dissolved in a separated 20 mL methanol and mixed with former solution. The mixture is then stirring overnight at room temperature under air. The obtained solid was washed with 20 mL MeOH 3 times. Activation conditions: 200° C. for 3 hours in the oven. Ball mill synthesis: Zn.sub.5(CO.sub.3).sub.2(OH).sub.6 (0.175 g, 0.32 mmol) and 2-methylimidazole (0.393 g, 4.79 mmol) were added to a 25 mL ball mill jar with 13.6 ball bearing, followed by addition of 50 uL MeOH. The mixture was then milled for 30 min at 20 Hz. The obtained solid was washed with 10 mL EtOH 3 times. Activation conditions: 150° C. for 3 hours in the oven.

Example 2: Synthesis of HKUST-1

(19) Solution synthesis: Cu(NOs).sub.2.2.5H.sub.2O (0.5 g, 2.15 mmol) was dissolved in 10 mL methanol in a conical flask. Benzene-1,3,5-tricarboxylic acid (0.91 g, 4.30 mmol) was dissolved in a separated 10 mL methanol and mixed with former solution. The mixture was then stirring overnight at room temperature under air. The obtained solid was washed with 10 mL MeOH 3 times. Activation conditions: 200° C. for 5 hours in the oven. Ball mill synthesis: Cu(OH).sub.2 (0.21 g, 2.15 mmol) and benzene-1,3,5-tricarboxylic acid (0.29 g, 1.37 mmol) were added to a 25 mL ball mill jar with 13.6 ball bearing, followed by addition of 0.5 mL MeOH. The mixture was then milled for 15 min at 25 Hz. The obtained solid was washed with 20 mL EtOH 3 times. Activation conditions: 200° C. for 3 hours in the oven.

Example 3: Synthesis of Al(fumarate)(OH)

(20) A.sub.2(SO.sub.4).sub.3.18H.sub.2O (1.225 g, 3.58 mmol) was dissolved in 15 mL deionised water in a conical flask. Fumaric acid (415 mg, 3.57 mmol) and NaOH (286.4 mg, 7.16 mmol) were dissolved in a separate 15 mL quantity of deionised water and mixed with the former solution. The mixture was then heated at 60° C. for 3 hours and cooled to room temperature. The off-white precipitate was collected by centrifugation and washed with 15 mL deionised water twice, followed by 15 mL MeOH twice, the obtained solid was dried under air. Activation conditions: 200° C. for 3 hours in the oven.

Example 4: Synthesis of SIFSIX-3-Zn

(21) ZnSiF.sub.6 (100 mg, 0.48 mmol) was dissolved in 3 mL methanol in a vial. Pyrazine (77.2 mg. 0.96 mmol) was dissolved in a separate 2 mL quantity of methanol and mixed with the former solution. The mixture was stirred overnight at room temperature under air. A pale yellow precipitate was collected by centrifugation, washed with 5 mL MeOH twice, dried under vacuum and stored under N.sub.2. Activation conditions: 55° C. for 3 hours under vacuum.

Example 4a: Synthesis of SIFSIX-3-Cu

(22) CuSiF.sub.6 (98.7 mg, 0.48 mmol) was dissolved in 3 mL methanol in a vial. Pyrazine (77.2 mg, 0.96 mmol) was dissolved in a separate 2 mL quantity of methanol and mixed with the former solution. The mixture was stirred overnight at room temperature under air. A pale yellow precipitate was collected by centrifugation, washed with 5 mL MeOH twice, dried under vacuum and stored under N.sub.2. Activation conditions: 55° C. for 3 hours under vacuum.

Example 4b: Synthesis of UiO-66

(23) ZrCl.sub.4 (1.29 g, 5.54 mmol) was dissolved in 30 mL DMF in a conical flask. Terephthalic acid (0.9 g, 7.76 mmol) was dissolved in a separate 30 mL quantity of DMF and mixed with the former solution. The mixture was transferred to an autoclave and heated at 120° C. overnight before being allowed to cool to room temperature. The off-white precipitate was collected by centrifugation, washed with 20 mL DMF twice, followed by 20 mL MeOH, and the obtained solid was dried overnight in air. Activation condition: 200° C. for 2 hours under vacuum.

Example 4c: Synthesis of UiO-66-NH.SUB.2

(24) ZrCl.sub.4 (200 mg, 0.86 mmol) was dissolved in a mixture of 5 mL DMF and 0.1 mL H.sub.2O in a conical flask. 2-amino-terephthalic acid (155.5 mg. 0.86 mmol) was dissolved in a separate 5 mL quantity of DMF and mixed with the former solution. The mixture was transferred to an autoclave and heated at 120° C. overnight before being allowed to cool to room temperature. The pale yellow precipitate was collected by centrifugation, washed with 10 mL DMF twice, followed by 10 mL MeOH, and the obtained solid was dried overnight in air. Activation condition: 200° C. for 2 hours under vacuum.

Example 4d: Synthesis of ZIF-67

(25) CO(NO).sub.2.6H.sub.2O (1.50 g, 5.15 mmol) was dissolved in 50 mL deionised water in a conical flask. 2-methylimidazole (1.69 g, 20.58 mmol) and triethylamine (2 mL) were dissolved in a separate 50 mL quantity of deionised water and mixed with the former solution. The mixture was stirred overnight at room temperature under air. The obtained solid was washed with 20 mL deionised water 3 times. Activation condition: 150° C. for 3 hours in the oven.

Example 4e: Synthesis of ZIF-90

(26) Zn(NO.sub.3).sub.2.6H.sub.2O (0.51 g, 1.72 mmol) was dissolved in 10 mL DMF in a conical flask. 2-imidazolecarboxaldehyde (0.79 g, 8.27 mmol) and dihexylamine (1.2 mL) were dissolved in a separate 10 mL quantity of DMF and mixed with the former solution. The mixture was stirred overnight at room temperature under air. The obtained solid was washed with 20 mL DMF twice and methanol twice. Activation condition: 150° C. for 2 hours in the oven.

Example 4f: Synthesis of Zr(Fumarate)

(27) ZrCl.sub.4 (2.33 g, 9.99 mmol) was dissolved in 25 mL deionised water in a conical flask. Fumaric acid (1.16 g, 9.99 mmol) was dissolved in acetic acid (25 mL) and mixed with the former solution. The mixture was heated to 95° C. for 1 hour under air. The obtained solid was washed with 50 mL deionised water 3 times. Activation condition: 200° C. for 2 hours in the oven.

Example 4g: Synthesis of MIL-53(Al)

(28) A(NO.sub.3).H.sub.2O (1.00 g, 2.67 mmol) was dissolved in 10 mL deionised water in a conical flask. Terephthalic acid (0.996 g, 5.99 mmol) was dissolved in 25 mL DMF and mixed with the former solution. The mixture was transferred to autoclave and heated to 150° C. for 3 days. The obtained solid was washed with 10 mL DMF and 10 deionised water 3 times. Activation condition: 200° C. for 2 hours in the oven.

Example 4h: Synthesis of CAU-10-H

(29) Aluminium sulfate hydrate (Al2(SO4)3.18H2O) (5.05 g, 7.5 mmol) was dissolved in 25 mL of H2O, and isophthalic acid (1.32 g, 7.9 mmol) dissolved in 7 mL of DMF. The two solutions were combined in a round bottom flask. The combined mixture was heated under reflux at 105° C. for 117 hrs. After cooling down the precipitate was filtered, redispersed for washing in 200 mL of H.sub.2O by stirring. The dispersion was filtered again and dried for 2 days at 100° C. Activation condition: 120° C. for 5 days under vacuum.

Example 4i: Synthesis of ZIF-7

(30) A solid mixture of zinc nitrate hexahydrate (0.8 g, 2.69 mmol) and of benzimidazole (0.24 g, 2.03 mmol) was dissolved in 75 mL of dimethylformamide (DMF). The solution was poured into a Teflon autoclave and put into oven at 130° C. for 48 hours. The product was then filtered. To remove the DMF from the pores of ZIF-7, the product underwent a solvent exchange with methanol for 48 hours at room temperature. The solid was then washed with methanol and dried at room temperature. Activation conditions: 150° C. for 2 hours in the oven.

Example 4j: Synthesis of Silver Zeolite AgX or AgA

(31) silver nitrate (8.49 g, 50 mmol) was dissolved in 100 mL distilled water to make a 0.5 M solution. Then 1 g of zeolite 5A/zeolite 13X was added into the silver nitrate solution and allowed to stir for 5 hours at 353K. Afterwards, the solid was washed thoroughly with distilled water (3×30 mL) and dried at room temperature. Activation conditions: 200° C. for 2 hours in the oven.

Example 4k: Synthesis of PAF-1

Tetrakis(4-bromophenyl)methane synthesis

(32) To a three-necked round-bottom flask containing bromine (6.4 mL, 19.9 g), tetraphenylmethane (2.0 g, 6.24 mmol) was added stepwise in small portions under vigorous stirring at room temperature (25° C.). After the addition was completed, the resulting solution was stirred for 60 min and then cooled to 0° C. At 0° C., ethanol (25 mL) was added slowly, and the reaction mixture was allowed to warm to room temperature overnight. Then, the precipitate was filtered and subsequently washed with saturated aqueous sodium hydrogensulfite solution (25 mL) and water (100 mL). After drying at 80° C. for 24 h under vacuum, tetrakis(4-bromophenyl) methane was recrystallized in EtOH/CH.sub.2Cl.sub.2 to afford a yellow solid.

PAF-1 Synthesis

(33) Tetrakis(4-bromophenyl)methane (509 mg, 0.8 mmol) was added to a solution of 2,2-bipyridyl (565 mg. 3.65 mmol), bis(1,5cyclooctadiene)nickel(0) (1.0 g, 3.65 mmol), and 1,5-cyclooctadiene (0.45 mL, 3.65 mmol) in anhydrous DMF/THF (60 mL/90 mL), and the mixture was stirred overnight at room temperature under nitrogen atmosphere. After the reaction, 6 M HCl (60 mL) was added slowly, and the resulting mixture was stirred for 12 h. The precipitate was collected by filtration, then washed with methanol and water, and dried at 150° C. for 24 h under vacuum (80 mbar) to produce PAF-1 as a white powder.

(34) Activation conditions: 200° C. for 3 hours.

(35) Characterisation of MOFs

(36) The physical characteristics of the selected MOFs of Examples 1 to 4 are shown in Table 3 below.

(37) TABLE-US-00003 TABLE 3 Physical characteristics of synthesized MOFs Average Morphology particle Size Density Aperture Colour HKUST-1 Irregular 500 nm 0.88 6.9 Å, Light blue g/cm.sup.3 4.1 Å ZIF-8 Hexagonal 400 nm 0.95 3.4 Å Off white g/cm.sup.3 Al(fumarate)(OH) Flake N/A N/A N/A Off white SIFSIX-3-Zn Rectangular 20 um 1.4  3.8 Å Pale yellow g/cm.sup.3

(38) The MOFs were also imaged using Scanning Electron Microscopy (SEM) and SEM images of the MOFs of Examples 1 to 4 are shown in FIG. 2.

Synthesis of Dispersions

Example 5: ZIF-8 in Silicone Oil (50 Cst)

(39) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) with stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial. The dispersion was characterized by powder X-Ray Diffraction (PXRD) and Infrared Spectroscopy (IR) and the data are shown in FIGS. 3(a) and 4(a).

Example 6: HKUST-1 in Silicone Oil (50Cst)

(40) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial. The dispersion was characterized by powder X-Ray Diffraction (PXRD) and Infrared Spectroscopy (IR) and the data are shown in FIGS. 3(b) and 4(b).

Example 7: Al(Fumarate)OH) in Silicone Oil (50Cst)

(41) A(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated A(fumarate)(OH) powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial. The dispersion was characterized by powder X-Ray Diffraction (PXRD) and Infrared Spectroscopy (IR) and the spectra are shown in FIGS. 3(c) and 4(c).

Example 8: SIFSIX-3-Zn in Silicone Oil (50Cst)

(42) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial. The dispersion was characterized by powder X-Ray Diffraction (PXRD) and Infrared Spectroscopy (IR) and the data are shown in FIGS. 3(d) and 4(d).

Example 9: ZIF-8 in Silicone Oil (350Cst)

(43) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 10: HKUST-1 in Silicone Oil (350Cst)

(44) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 11: Al(Fumarate)OH) in Silicone Oil (350Cst)

(45) A(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated Al(fumarate)(OH) powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 12: SIFSIX-3-Zn in Silicone Oil (350Cst)

(46) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 13: ZIF-8 in Silicone Oil (1000Cst)

(47) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 14: HKUST-1 in Silicone Oil (1000Cst)

(48) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 15: Al(Fumarate)(OH) in Silicone Oil (1000Cst)

(49) A(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated Al(fumarate)(OH) powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 16: SIFSIX-3-Zn in Silicone Oil (1000Cst)

(50) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 17: ZIF-8 in Fomblin Y Oil (60Cst)

(51) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL Fomblin Y oil (density: 1.88 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 18: HKUST-1 in Fomblin Y Oil (60Cst)

(52) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL Fomblin Y oil (density: 1.88 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 19: Al(Fumarate)OH) in Fomblin Y Oil (60Cst)

(53) A(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated A(fumarate)(OH) powder was added to 1.3 mL Fomblin Y oil (density: 1.88 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 20: SIFSIX-3-Zn in Fomblin Y Oil (60Cst)

(54) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL Fomblin Y oil (density: 1.88 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 21: ZIF-8 in Olive Oil (84 Cst)

(55) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL olive oil (density: 0.91 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 22: HKUST-1 in Olive Oil (84 Cst)

(56) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL olive oil (density: 0.91 gmL.sup.1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 23: Al(Fumarate)(OH) in Olive Oil (84 Cst)

(57) A(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated A(fumarate)(OH) powder was added to 1.3 mL olive oil (density: 0.91 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 24: SIFSIX-3-Zn in Olive Oil (84 Cst)

(58) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL olive oil (density: 0.91 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 25: ZIF-8 in Sesame Oil (65 Cst)

(59) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL sesame oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 26: HKUST-1 in Sesame Oil (65 Cst)

(60) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL sesame oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 27: Al(Fumarate)OH) in Sesame Oil (65 Cst)

(61) A(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated Al(fumarate)(OH) powder was added to 1.3 mL sesame oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 28: SIFSIX-3-Zn in Sesame Oil (65 Cst)

(62) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL sesame oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 29: ZIF-8 in Paraffin Oil (110-230 Cst)

(63) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL paraffin oil (density: 0.827-0.890 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 30: HKUST-1 in Paraffin Oil (110-230 Cst)

(64) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL paraffin oil (density: 0.827-0.890gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 31: Al(Fumarate)(OH) in Paraffin Oil (110-230 Cst)

(65) A(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated A(fumarate)(OH) powder was added to 1.3 mL paraffin oil (density: 0.827-0.890 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 32: SIFSIX-3-Zn in Paraffin Oil (110-230 Cst)

(66) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL paraffin oil (density: 0.827-0.890 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 33: ZIF-8 in Castor Oil (964 Cst)

(67) ZIF-8 MOF was prepared as described in Example 1, and activated by heating at 200° C. for 2 hours. 200 mg of the activated ZIF-8 powder was added to 1.3 mL castor oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 34: HKUST-1 in Castor Oil (964 Cst)

(68) HKUST-1 MOF was prepared as described in Example 2, and activated by heating at 200° C. for 3 hours. 180 mg of the activated HKUST-1 powder was added to 1.3 mL castor oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 35: A(Fumarate)OH) in Castor Oil (964 Cst)

(69) Al(fumarate)(OH) MOF was prepared as described in Example 3 and activated by heating at 200° C. for 2 hours. 180 mg of the activated A(fumarate)(OH) powder was added to 1.3 mL castor oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 36: SIFSIX-3-Zn in Castor Oil (964 Cst)

(70) SIFSIX-3-Zn MOF was prepared as described in Example 4 and activated by vacuum at 55° C. for 3 hours. 180 mg of the activated SIFSIX-3-Zn powder was added to 1.3 mL castor oil (density: 0.92 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 37: Porous SiO.SUB.2 .in Paraffin Oil

(71) 180 mg of the porous SiO.sub.2 was added to 1.3 mL paraffin oil (density: 0.827-0.890 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 38: PAF-1 in Silicone Oil (50 Cst)

(72) 62 mg of PAF-1 was added to 2.2 mL silicone oil (density: 0.98 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 38: PAF-1 in Paraffin Oil

(73) 62 mg of PAF-1 was added to 2.2 mL paraffin oil (density: 0.827-0.890 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Example 38: PAF-1 In Polyethylene glycol (Genosorb)

(74) 180 mg of PAF-1 was added to 1.3 mL polyethylene glycol (density: 0.93 gmL.sup.−1) under stirring at 600 rpm with a magnetic stirrer in a 10 mL glass vial.

Comparative Example 1: HKUST-1 in PEG-200

Comparative Example 2: ZIF-8 in PEG-200

Comparative Example 3: ZIF-8 in 15-Crown-5

Comparative Example 4: HKUST-1 in Oleic Acid

Comparative Example 5: ZIF-8 in Oleic Acid

(75) Characterisation of Dispersions

(76) Following synthesis, all dispersions were characterized by Powder X-Ray Diffraction (PXRD) and Infrared Spectroscopy (IR). Each of the PXRD spectra showed MOF patterns which were identical to those of the original MOF, confirming that the structure of the MOF component of the dispersion remained intact after mixing in the dispersion. The PXRD patterns and IR spectra of the dispersions of examples 5 to 8 are shown in FIGS. 3 (PXRD) and 4 (IR).

(77) Stability Studies

(78) The stability of the dispersions of the invention is important for their industrial applicability. The stability of the dispersions can be optimised by, for instance, reducing the size of the porous particles, increasing the viscosity of the liquid component, matching the densities of the porous solid particles and the liquid component, as well as by enhancing interaction between the solid particles and the liquid medium. The stability of MOFs in various liquid phases was determined and the results are shown in Tables 4a and 4b.

(79) TABLE-US-00004 TABLE 4a Summary of dispersion stability Liquid MOF medium HKUST-1 ZIF-8 Al(fum)(OH) SIFSIX-3-Zn SIFSIX-3-Cu Silicone oil X √ √ X X (20 cst) Silicone oil X √ √ X X (50 cst) Silicone oil √ √ √ √ √ (350 cst) Silicone oil √ √ √ √ √ (1000 cst) Silicone based oil AR 20 √ √ √ X √ Fomblin Y oil 60 cst X X X √ X Krytox Y oil 60 cst √ √ √ √ √ Paraffin oil √ √ √ X √ Olive Oil √ √ √ √ √ Castor Oil √ √ √ √ √ Sesame Oil √ √ √ √ √ Corn oil √ √ √ √ √ Soy bean oil √ √ √ √ √ Sunflower oil √ √ √ √ √ Safflower oil √ √ √ √ √ X: requires stirring to maintain homogeneous dispersion. √: without stirring, dispersion remains stable for at least one day.

(80) TABLE-US-00005 TABLE 4b Summary of dispersion stability Liquid medium Silicone oil (50 cst) Olive oil Krytox oil 177 cst MOFs UiO-66 X √ — UiO-66-NH2 X √ — ZIF-67 √ √ — Zr-fumarate X √ — ZIF-90 √ √ — Zeolites √ — Zeolite 3A X √ — Zeolite 5A X √ — Zeolite 13X X √ — Activated carbon X √ √ X: requires stirring to maintain homogeneous dispersion. √: without stirring, dispersion remains stable for at least one day.

(81) From the above tables it can be seen that some of the dispersions are stable for at least one day. Other dispersions require stirring in order to maintain a homogeneous dispersion.

(82) As listed, some porous liquid mixtures can form stable dispersion for at least 1 day, but few of them require stirring in order to maintain the homogeneous dispersion.

(83) Gas Uptake Studies

(84) Gas uptake studies were carried out using a volumetric technique based on an isochoric method. The measurements were carried out at around 0.8 bar and 298 k.

(85) All pure porous solids have been measured to compare with known literature values (Table 5a). Also, pure liquid media have been measured for calculation of prediction gas uptake. All porous liquids were measured with 12.5 wt % porous solid content, unless specified.

(86) TABLE-US-00006 TABLE 5a CO.sub.2 uptake of pure porous solids Experimental Literature (mg/g (mmol/g)) (mg/g (mmol/g)) MOFs HKUST-1 170.76 (3.88) 197.61 (4.49) ZIF-8  36.97 (0.84)  43.13 (0.98) Al(fum)(OH)  95.59 (2.17)  91.98 (2.09) SIFSIX-3-Zn 118.83 (2.70) 112.23 (2.55) SIFSIX-3-Cu 109.14 (2.48) — UiO-66  79.22 (1.80)  55.89 (1.27) UiO-66-NH2  90.66 (2.06) 102.10 (2.32) ZIF-67  42.25 (0.96)  41.37 (0.94) Zr-fumarate  79.22 (1.80)  80.10 (1.82) ZIF-90 104.30 (2.37) — MIL-53(Al)   98.6 (2.24) 110.03 (2.50) CAU-10-H  98.60 (2.24) 110.20 (2.30) Zeolites Zeolite 3A 134.23 (3.05)* — Zeolite 5A  47.97 (1.09)* — Zeolite 13X  69.54 (1.58)* — Zeolite RhO  115.7 (2.63) 154.04 (3.50) Activated carbon G-60 126.31 (2.87) — *No activation treatment.
CO.sub.2 Uptake

(87) CO.sub.2 uptake was measured for each of the dispersions of Examples 5 to 36 above, and for the dispersions prepared in accordance with comparative examples 1 to 3. Theoretical uptake, based on known uptake for the MOF and liquid phase components were calculated, and the measured and theoretical values are shown in Table 5b below. All solid content in porous liquids are measured at 12.5 wt % loading, unless specified.

(88) TABLE-US-00007 TABLE 5b CO.sub.2 uptake of elected compositions of porous liquids (mg/g (mmol/g)) Silicone oil Silicone oil Silicone oil Fluorinated (50 cst) (350 cst) (1000 cst) oil (60 cst)** 5.04 (0.12) 3.87 (0.09) 3.27 (0.07) 3.16 (0.07) Exp. Cal. Exp. Cal. Exp. Cal. Exp. Cal. HKUST-1 23.76 25.96 24.77 24.89 21.28 24.36  6.21 14.72 (0.54) (0.59) (0.56) (0.57) (0.48) (0.55) (0.14) (0.33) ZIF-8  9.68  9.24  8.61  8.41  7.76  7.89  6.40  5.48 (0.22) (0.21) (0.20) (0.19) (0.18) (0.18) (0.15) (0.12) Al(fum)(OH) 15.84 16.28 16.86 15.43 16.87 14.91 11.57  9.63 (0.36) (0.37) (0.38) (0.35) (0.38) (0.39) (0.26) (0.22) SIFSIX-3-Zn 19.81 21.12 18.17 18.35 16.51 17.83  8.58 11.25 (0.45) (0.48) (0.41) (0.42) (0.38) (0.41) (0.19) (0.26) Paraffin oil Olive oil Castor oil Sesame oil 3.67 (0.08) 3.86 (0.09) 3.64 (0.08) 3.80 (0.09) Exp. Cal. Exp. Cal. Exp. Cal. Exp. Cal. HKUST-1  3.05 24.87 21.13 24.65 21.28 25.34 20.04 25.25 (0.07) (0.57) (0.48) (0.56) (0.48) (0.58) (0.46) (0.57) ZIF-8  8.23  7.88  9.24  7.48  9.55  7.96  8.84  7.87 (0.19) (0.18) (0.21) (0.17) (0.22) (0.18) (0.20) (0.18) Al(fum)(OH) 13.73 15.26 15.40 15.40 14.21 15.34 15.81 15.25 (0.32) (0.35) (0.35) (0.35) (0.33) (0.35) (0.36) (0.35) SIFSIX-3-Zn 14.89 18.32 15.84 18.48 15.53 18.40 15.12 18.31 (0.34) (0.42) (0.36) (0.42) (0.35) (0.42) (0.34) (0.42) **6.5 wt % loading

(89) Additionally, 2 wt % of porous solid loading have been tested and also show good agreement of experimental values and theoretical values (Table 5c)

(90) TABLE-US-00008 TABLE 5c CO.sub.2 uptake of 25 wt % porous solid loading Experimental Theoretical ZIF-8 in sesame oil 10.98 11.71 HKUST-1 in silicone oil 42.50 44.12 Zn-SIFSIX-3 in paraffin oil 27.12 26.62 Al (fum) (OH) in olive oil 28.33 26.19

(91) TABLE-US-00009 TABLE 5d CO.sub.2 uptake table for a broader range of example compositions (mg/g (mmol/g)). silicone oil 50 cst Olive oil 4.84 (0.11) 3.08 (0.07) Exp. Theo. Exp. Theo. MOFs SIFSIX-3-Cu 14.96 (0.34) 18.04 (0.41) 17.60 (0.40) 16.28 (0.37) UiO-66 11.44 (0.26) 14.52 (0.33) 11.44 (0.26) 13.20 (0.30) UiO-66-NH2 15.40 (0.35) 15.84 (0.36) 15.40 (0.35) 14.52 (0.33) ZIF-67 10.56 (0.24)  9.68 (0.22)  8.36 (0.19)  7.92 (0.18) Zr-fumarate 16.72 (0.38) 14.52 (0.33) 10.56 (0.24) 12.63 (0.29) ZIF-90 15.84 (0.36) 17.60 (0.40) 14.52 (0.33) 15.84 (0.36) MIL-53(Al) 31.24 (0.71) 28.16 (0.64) — — CAU-10-H 16.96 (0.39) 16.74 (0.38) 13.96 (0.32) 14.99 (0.34) Zeolites Zeolite 3A 20.25 (0.46) 20.68 (0.47) 20.68 (0.47) 21.12 (0.48) Zeolite 5A  9.68 (0.22)  9.68 (0.22)  9.68 (0.22)  9.24 (0.21) Zeolite 13X 13.64 (0.31) 13.20 (0.30) 13.64 (0.31) 13.20 (0.30) Zeolite Rho 20.23 (0.46) 18.92 (0.43) 20.25 (0.46) 17.16 (0.39) Act. Carbon Activated carbon 15.40 (0.35) 20.24 (0.46) 15.84 (0.36) 18.48 (0.42) G-60

(92) TABLE-US-00010 TABLE 5d CO.sub.2 uptake summary table for a range of further example compositions (mg/g (mmol/g)) Silicone oil Silicone oil Silicone oil Silicone oil Silicone based Fomblin Y oil Krytox oil 177 20 cst 50 cst 350 cst 1000 cst oil AR 20 60** cst cst** 3.52 (0.08) 4.84 (0.11) 3.96 (0.09) 3.08 (0.07) 3.08 (0.07) 3.08 (0.07) 3.96 (0.09) Exp. Lit. Exp. Theo. Exp. Theo. Exp. Theo. Exp. Theo. Exp. Theo. Exp. Theo. Exp The. MOFs ZIF-8  36.97 43.12  8.80  7.92  9.68  9.24  8.80  7.92  7.92  7.92  9.68  7.92  6.60  5.28  6.16  6.16 (0.84) (0.98) (0.20) (0.18) (0.22) (0.21) (0.20) (0.18) (0.18) (0.18) (0.22) (0.18) (0.15) (0.12) (0.14) (0.14) Zeolites Zeolite 134.23 — 22.89 19.80 20.24 20.68 24.65 20.25 22.45 19.80 19.36 19.81 12.76 12.32 13.20 12.32 3A (3.05) (0.52) (0.45) (0.46) (0.47) (0.56) (0.46) (0.51) (0.45) (0.44) (0.45) (0.29) (0.28) (0.30) (0.28) **6.5 wt % porous solid loading

(93) TABLE-US-00011 TABLE 5d ctd CO.sub.2 uptake summary table for a range of further example compositions (mg/g (mmol/g)) Paraffin oil Olive oil Castor oil Sesame oil Sunflower oil Safflower oil Soy Bean oil Corn oil 3.52 (0.08) 3.08 (0.07) 3.52 (0.08) 3.52 (0.08) 3.52 (0.08) 3.96 (0.09) 3.08 (0.07) 3.52 (0.08) Exp. Lit. Exp Theo. Exp Theo. Exp. Theo. Exp. Theo. Exp. Theo Exp. Theo. Exp Theo. Exp. Theo. MOFs ZIF-8  36.97 43.12  8.36  7.92  9.24  7.48  9.68  7.92  8.80  7.92  7.92  7.48  7.92  7.48  7.92  7.92  8.80  7.92 (0.84) (0.98) (0.19) (0.18) (0.21) (0.17) (0.22) (0.18) (0.20) (0.18) (0.18) (0.17) (0.18) (0.17) (0.18) (0.18) (0.20) (0.18) Zeolites Zeolite 134.23 20.24 20.24 20.68 21.12 20.68 20.68 20.25 21.12 20.25 20.68 20.25 20.25 20.25 20.25 20.25 20.25 3A (3.05) (0.46) (0.46) (0.47) (0.48) (0.47) (0.47) (0.46) (0.48) (0.46) (0.47) (0.46) (0.46) (0.46) (0.46) (0.46) (0.46)

(94) TABLE-US-00012 TABLE 5e CO.sub.2 uptake for PAF-1 (mg/g (mmol/g)) 3 wt % PAF-1 3 wt % 3 wt % 3 wt % 3 wt % in silicone PAF-1 in PAF-1 in PAF-1 in PAF-1 in oil 50 cst paraffin oil Olive oil Sesame oil Castor oil Exp Cal Exp Cal Exp Cal Exp Cal Exp Cal 8.96 8.82 8.23 8.29 8.96 8.58 9.19 8.53 7.96 8.25 (0.20) (0.20) (0.19) (0.19) (0.20) (0.19) (0.21) (0.19) (0.18) (0.19) 3 wt % 3 wt % PAF-1 in 3 wt % PAF-1 in 3 wt % 12.5 wt % Safflower PAF-1 in Sunflower PAF-1 in PAF-1 in oil Soybean oil oil Corn oil Genosorb Exp Cal Exp Cal Exp Cal Exp Cal Exp Cal 8.33 8.36 8.56 8.39 8.29 8.36 8.24 8.19 31.91 32.34 (0.19) (0.19) (0.19) (0.19) (0.19) (0.19) (0.19) (0.19) (0.73) (0.73)

(95) TABLE-US-00013 TABLE 5f CO.sub.2 uptake for other compositions (mg/g (mmol/g)) 12.5 wt % 12.5 wt % 12.5 wt % 25 wt % ZIF-8 in ZIF-8 in ZIF-8 in ZIF-8 in 6.5 wt % Polyethylene Polyethylene Polyethylene Polyethylene activated glycol bis(2-ethyl- dimethyl bis(2-ethyl- carbon in dibenzoate hexanoate) ether acrylate hexanoate) Krytox oil Exp Cal Exp Cal Exp Cal Exp Cal Exp Cal 6.57 7.05 11.3 11.52 7.41 8.98 14.84 16.49 8.52 10.23 (0.15) (0.16) (0.26) (0.26) (0.16) (0.20) (0.34) (0.37) (0.19) (0.23)

(96) These results show that all of the dispersions show significantly higher levels of CO.sub.2 uptake when compared with the uptake of the liquid phase alone, and in many cases up to 5 times higher than that of the pure oil. The measured values also show good correlation to the predicted, or calculated values, allowing for the precise design of the so-called porous liquids or dispersions. When the uptake of the comparative examples were measured, however, the uptake of the dispersions showed significant deviations from the predicted/calculated uptake values for the MOFs and the liquids, and in many cases lower uptake than the pure liquids alone.

(97) CH.sub.4 and N.sub.2 Uptake

(98) Gas selectivity is essential for industrial applications such as CO.sub.2 capture from power plants or natural gas reserves. Accordingly, the CH.sub.4 and N.sub.2 uptake of the dispersions were also investigated, and the results are shown in Tables 6, 7, 7a, 7b, 7c and 7d.

(99) TABLE-US-00014 TABLE 6 N.sub.2 uptake Measured N.sub.2 Calculated N.sub.2 Uptake of N.sub.2 in Liquid uptake (mg/g uptake (mg/g pure liquid (mg/g Example MOF phase (mmol/g)) (mmol/g)) (mmol/g)) Ex. 6 HKUST-1 Silicone oil 2.10 (0.07) 3.43 (0.12) 0.81 (0.03) (50 cst) Ex. 7 Al(fum)(OH) Silicone oil 1.42 (0.05) 1.63 (0.06) 0.81 (0.03) (50 cst) Ex. 22 HKUST-1 Olive oil 3.68 (0.13) 5.59 (0.18) 2.65 (0.09) Ex. 23 Al(fum)(OH) Olive oil 2.82 (0.11) 3.18 (0.11) 2.65 (0.09)

(100) TABLE-US-00015 TABLE 7 CH.sub.4 uptake Measured CH.sub.4 Calculated CH.sub.4 Uptake of CH.sub.4 Liquid uptake (mg/g uptake (mg/g in pure liquid Example MOF phase (mmol/g)) (mmol/g)) (mg/g (mmol/g)) Ex. 6 HKUST-1 Silicone oil 2.80 (0.17) 3.08 (0.19) 1.31 (0.07) (50 cst) Ex. 7 Al(fum)(OH) Silicone oil 3.43 (0.21) 3.58 (0.22) 1.31 (0.07) (50 cst) Ex. 22 HKUST-1 Olive oil 2.25 (0.14)  3.1 (0.20) 1.33 (0.08) Ex. 23 Al(fum)(OH) Olive oil 3.21 (0.20) 3.72 (0.23) 1.33 (0.08)

(101) TABLE-US-00016 TABLE 7a CH.sub.4 uptake ctd (units: mg/g (mmol/g)) Silicone oil 50 cst 1.31 (0.07) Olive oil 1.33 (0.08) Exp. Exp. Theo. Exp. Theo. MOFs HKUST-1 15.40 (0.96) 2.80 (0.17) 3.08 (0.19) 2.24 (0.14) 3.19 (0.20) ZIF-8  4.49 (0.28) 1.44 (0.09) 1.76 (0.11) 1.28 (0.08) 1.76 (0.11) Al(fum)(OH) 19.41 (1.21) 3.43 (0.21) 3.58 (0.22) 3.21 (0.20) 3.72 (0.23) SIFSIX-3-Zn 15.56 (0.97) 2.72 (0.17) 2.89 (0.18) 2.89 (0.18) 2.89 (0.18) UiO-66  4.97 (0.31) 1.60 (0.10) 1.60 (0.10) 1.28 (0.08) 1.76 (0.11) UiO-66-NH2 12.67 (0.79) 2.08 (0.13) 2.57 (0.16) 2.73 (0.17) 2.57 (0.16) Zeolites Zeolite 13X  5.13 (0.32) 1.44 (0.09) 1.60 (0.10) 1.28 (0.08) 1.76 (0.11)

(102) TABLE-US-00017 TABLE 7b N.sub.2 uptake (units: mg/g (mmol/g)) Silicone oil 50 cst 0.81 (0.03) Olive oil 2.65 (0.09) Exp. Exp. Theo. Exp. Theo. MOFs HKUST-1 12.59 (0.45) 2.10 (0.07) 3.43 (0.12) 3.68 (0.13) 5.59 (0.18) ZIF-8  5.84 (0.21) 1.67 (0.06) 1.70 (0.06) 1.86 (0.07) 1.96 (0.07) Al(fum)(OH)  6.64 (0.24) 1.42 (0.05) 1.63 (0.06) 2.82 (0.11) 3.18 (0.11) SIFSIX-3-Zn  8.68 (0.31) 2.01 (0.07) 2.15 (0.08) 2.35 (0.08) 3.39 (0.12) SIFSIX-3-Cu 10.31 (0.37) 2.10 (0.07) 2.13 (0.08) 2.35 (0.08) 2.38 (0.08) UiO-66  4.20 (0.15) 1.15 (0.04) 2.26 (0.06) 1.12 (0.04) 1.12 (0.04)

(103) TABLE-US-00018 TABLE 7c C.sub.2H.sub.4 uptake (units: mg/g (mmol/g)) Paraffin oil Silicone oil Sesame oil 1.60 (0.06) 2.81 (0.10) 1.96 (0.07) Exp. Lit. Exp. Theo. Exp. Theo. Exp. Theo. HKUST- 171.11 — 8.98 22.72 20.76 22.98 23.84 23.28 1 (6.10) (0.32) (0.81) (0.74) (0.85) (0.85) (0.83) ZIF-8  57.22 38.99 8.78  8.42  9.26  9.54  7.85  8.98 (2.04) (1.39) (0.31) (0.30) (0.33) (0.34) (0.28) (0.32) ZIF-7  50.49 58.91 4.77  7.85  9.82  8.70  7.57  8.13 (1.80) (2.10) (0.17) (0.28) (0.35) (0.31) (0.27) (0.29) Zeolite  26.65 — 5.05  4.77  4.49  5.61  4.49  5.05 13X (0.95) (0.16) (0.17) (0.16) (0.20) (0.16) (0.18) Zeolite  44.04 68.16 8.42  7.01  7.29  7.85 10.38  7.29 5A (1.57) (2.43) (0.30) (0.25) (0.25) (0.28) (0.37) (0.26) Zeolite  83.59 63.39 7.85 11.77  9.26 12.90  8.13 12.34 AgX (2.98) (2.26) (0.28) (0.42) (0.33) (0.46) (0.29) (0.44) Zeolite  53.58 58.91 9.82  8.13 12.62  9.26  8.42  8.42 AgA (1.91) (2.10) (0.35) (0.29) (0.45) (0.33) 0.30) (0.30)

(104) TABLE-US-00019 TABLE 7d C.sub.2H.sub.6 uptake (units: mg/g (mmol/g)) Paraffin oil Silicone oil Sesame oil 3.91 (0.13) 6.01 (0.20) 4.51 (0.15) Exp. Lit. Exp. Theo. Exp. Theo. Exp. Theo. HKUST-1 125.99 —  6.01 19.25 16.84 21.05 20.45 19.55 (4.19) (0.20) (0.64) (0.56) (0.67) (0.68) (0.65) ZIF-8  65.55 75.18 12.33 11.73 12.93 13.23  8.12 12.03 (2.18) (2.50) (0.41) (0.39) (0.43) (0.44) (0.27) (0.40) ZIF-7  69.46 67.66 13.54 12.33  9.05 13.83 13.53 12.63 (2.31) (2.25) (0.45) (0.41) (0.31) (0.46) (0.45) (0.42) Zeolite  51.72 — 10.53  9.92  9.02 11.73 11.73 10.22 13X (1.72) (0.35) (0.33) (0.30) (0.39) (0.39) (0.34) Zeolite  32.48 51.72  9.62  7.52  9.02  9.32  9.92  7.82 5A (1.08) (1.72) (0.32) (0.25) (0.3) (0.31) (0.33) (0.26) Zeolite  9.53 43.60  7.82 10.83 12.03 12.63 11.12 11.43 AgX (1.98) (1.45) (0.26) (0.36) (0.40) (0.42) (0.3) (0.38) Zeolite  3.91  2.71  2.51  3.91  4.21  5.71  6.32  4.21 AgA (0.13) (0.09) (0.08) (0.13) (0.14) (0.19) (0.21) (0.14)
Selectivity (IAST)

(105) As noted above, gas selectivity is extremely useful in industrial processes. Selectivity can be evaluated by the Ideal Absorbed Solution Theory (IAST) from pure gas adsorption as shown by Equation (1):

(106) $\begin{array}{cc}S=\frac{q_i/p_i}{q_i/p_j}& \mathrm{Equation}\left(1\right)\end{array}$

(107) In Equation 1, q.sub.i and q.sub.j represent the adsorption capacity of pure gas component; while p.sub.i and p.sub.j represent the partial pressure of the pure gas component.

(108) This method is commonly used in porous solid materials (i.e. MOFs) to predict their gas selectivity behaviour. However, given that porous liquids are novel materials this method needs to be validated in relation to these new materials. Therefore, at this stage, a simpler and more straightforward method is applied for estimating gas selectivity. Selectivity is estimated by ratio (A.sub.mmol/g/B.sub.mmol/g) in order to compare it with the existing material (Genosorb 1753).

(109) Values for CO.sub.2 selectivity over N.sub.2 (CO.sub.2/N.sub.2) and over CH.sub.4 (CO.sub.2/CH.sub.4) were calculated for the dispersions of Examples 6, 7, 22 and 23, and the results are shown in Table 8 below:

(110) TABLE-US-00020 TABLE 8 CO.sub.2 selectivity over N.sub.2 (CO.sub.2/N.sub.2) and over CH.sub.4 (CO.sub.2/CH.sub.4) CO.sub.2/N.sub.2 CO.sub.2/CH.sub.4 Silicone oil Silicone oil 50 cst Olive oil 50 cst Olive oil 3.67 0.77 1.57 0.88 Exp. Theo. Exp. Theo. Exp. Theo. Exp. Theo. MOFs HKUST-1 7.75 4.91 3.66 2.93 3.19 3.25 3.40 2.93 ZIF-8 3.67 3.67 3.00 2/45 2.41 2.22 2.62 1.62 Al(fum)(OH) 7.12 6.43 3.46 3.07 1.69 1.69 1.74 1.50 SIFSIX-3-Zn 6.26 6.21 4.25 4.91 2.42 2.61 1.98 2.30 SIFSIX-3-Cu 4.86 5.13 5.00 5.12 — — — — UiO-66 6.38 5.55 6.85 7.49 2.62 3.23 3.21 2.72 UiO-66-NH2 — — — — 2.73 2.25 2.09 2.09 Zeolites Zeolite 13X — — — — 3.50 2.98 3.86 2.76

(111) In addition, the separation of ethylene (C.sub.2H4) and ethane (C.sub.2He) is an important industrial process. As shown in Table 8a below, the porous liquids of the invention also have selectivity on ethylene over ethane.

(112) TABLE-US-00021 TABLE 12 Selectivity of porous liquids by ratio: (C.sub.2H.sub.4/C.sub.2H.sub.6). Paraffin oil Silicone oil Sesame oil 0.43 0.50 0.50 Exp. Theo. Exp. Theo. Exp. Theo. Exp. Theo. MOFs HKUST-1  1.45 — 1.63 1.27 1.32 1.22 1.25 1.27 ZIF-8  0.94  0.56 0.77 0.78 0.77 0.77 1.03 0.80 ZIF-7  0.78  0.93 0.37 0.68 1.15 0.68 0.58 0.69 Zeolites Zeolite 13X  0.55 — 0.45 0.51 0.52 0.53 0.40 0.53 Zeolite 5A  1.46  1.41 0.94 0.98 0.84 0.92 1.12 0.99 Zeolite AgX  1.51  1.56 1.08 1.16 0.82 1.09 0.80 1.16 Zeolite AgA 15.33 23.17 4.49 2.19 3.27 1.74 1.44 2.11
High Pressure Measurement (1-5 Bar, 25° C.-75° C.)

(113) High pressure gas uptake studies have been carried out using a Parr reactor (see FIG. 9) based on mass flow as developed at Queen's University, Belfast by Prof. David Rooney. All the measurements are carried out from 1 to 5 bar at 298K, 323K and 348K. Examples using Al(fum)(OH) are shown below (Table 13). Importantly, the measured CO.sub.2 uptake of porous liquids under high pressure is comparable to the predicted values. This demonstrates the potential of the use of these materials in the gas separation industry (e.g. pressure swing adsorption (PSA) processes).

(114) TABLE-US-00022 TABLE 13 High Pressure gas uptake measurement (1-5 bar; 298, 323, 348K) Al(fum)(OH) Silicone oil (50 cst) literature value 298K 323K 348K 298K 323K 348K 1 bar  4.58  3.74  3.28  92.42  66.02  41.81 2 bar  8.90  7.27  6.32 136.43  96.82  66.02 3 bar 13.59 11.03  9.93 158.44 118.83  88.02 4 bar 18.50 15.05 13.62 176.04 140.83 107.83 5 bar 24.03 19.33 17.75 184.84 154.04 121.03 12.5 wt % Al(fum)(OH) in SC50 298K 323K 348K Exp. Cal. Exp. Cal. Exp. Cal. 1 bar 17.09 17.32 11.74 11.53  6.68  8.10 2 bar 24.83 25.14 17.21 18.46 11.60 13.78 3 bar 30.79 31.43 22.29 24.51 15.63 19.69 4 bar 36.34 38.12 26.96 30.77 19.74 25.40 5 bar 42.72 45.95 31.59 36.17 23.87 30.66
Reversibility/Regeneration Studies

(115) Material regeneration is a highly desirable characteristic of materials for use in industrial processes such as separation. The dispersions of Examples 6 and 7 were regenerated by applying vacuum (8.5×10.sup.−2 bar) for 30 minutes, and their uptake of CO.sub.2 measured after the first and second cycles. The results of these studies are shown in FIG. 5. From these, it can be seen that the dispersions of Examples 6 and 7 showed at least 75% CO.sub.2 uptake capacity after two cycles of regeneration. However, the same studies on a conventional amine-based solution (12.5 wt. % MEA in H.sub.2O) showed almost no regeneration.

(116) Further regeneration studies were performed with 13 wt % HKUST-1 in silicone oil, by applying vacuum (up to 8.5×10.sup.−2 bar) to remove captured CO.sub.2. The results, shown in FIG. 6, show that CO.sub.2 uptake capacity can be maintained for at least 5 cycles.

(117) Additional regeneration tests were performed with (i) 13 wt % ZIF-8 in sesame oil, (ii) 13 wt % HKUST-1 in silicone oil, (iii) Al(fum)(OH) in olive oil and (iv) Zn-SIFSIX-3 in paraffin oil, by applying vacuum (up to 8.5×10.sup.−2 bar) to remove captured CO.sub.2. The results are shown in FIG. 7, and demonstrate that CO.sub.2 uptake capacity can be maintained for at least 3 cycles for a variety of porous liquids.