COOLING/HEATING METHOD AND DEVICE BASED ON METAL-ORGANIC FRAMEWORKS AND INDUCED BY PRESSURE MODIFICATIONS

Abstract

A cooling/heating method including the application and removal of a pressurising gas on a hybrid organic-inorganic porous material (MOF) whereby a breathing transition is produced. In this transition, a change in volume in the structure of the compound occurs when its pores open/close, together with adsorption/desorption of a gas after applying and removing a pressurising gas on the compound; and breathing which occurs at temperatures close to ambient temperature (from ?20? C. to 60? C.) and at low pressures (from 10.sup.?5 bar up to 50 bar) and with great isothermal entropy changes (>100 J K.sup.?1 kg.sup.?1). A cooling/heating device comprising the hybrid materials defined above.

Claims

1. A cooling/heating method comprising: a) providing a porous organic-inorganic hybrid compound which is capable of undergoing a breathing transition consisting of a first-order phase transition in which a change in volume in the structure of the compound occurs when its pores open/close, together with adsorption/desorption of a gas after applying and removing a pressurising gas on the compound; b) inducing the breathing transition by means of a cycle of applying and removing pressure on the organic-inorganic hybrid material, in a pressure range ranging from 10.sup.?6 MPa up to 5 MPa; wherein: the application of pressure is generated by a pressurising gas that is selected from the group consisting of N.sub.2, CO.sub.2, CH.sub.4, air, and a mixture of any of the above in any percentage proportion by volume; the removal of pressure is carried out by means of releasing the pressurising gas through a depressurisation valve, by means of applying a vacuum through a vacuum pump, or through a depressurisation valve together with the application of a vacuum through a vacuum pump; the breathing transition generates a change in temperature and occurs at a temperature comprised between ?20? C. and 60? C.; the breathing transition generates an isothermal change in entropy equal to or greater than 100 J K.sup.?1 kg.sup.?1.

2. The cooling/heating method according to claim 1, which is for applications with a working temperature ranging from ?20? C. to 60? C.

3. The cooling/heating breathing method according to claim 1, wherein the organic-inorganic hybrid compound is selected from the group consisting of [Cu.sub.2(C.sub.6H.sub.4(COO).sub.2).sub.2(N.sub.2(C.sub.2H.sub.4).sub.3)], [Cu.sub.2(C.sub.6(CH.sub.3(CH.sub.2).sub.3O).sub.2H.sub.2(COO).sub.2).sub.2(N.sub.2(C.sub.2H.sub.4).sub.3)], [Zn(C.sub.6H.sub.4(COO).sub.2)(C.sub.6H.sub.4(C.sub.5H.sub.4N).sub.2)], [Zn(C.sub.6H.sub.4(COO).sub.2)(C.sub.6H.sub.2F.sub.2(C.sub.5H.sub.4N).sub.2)], [Zn.sub.2(C.sub.6S.sub.2(CH.sub.3).sub.2(COO).sub.2).sub.2((C.sub.5H.sub.4N).sub.2(CH).sub.2)], [Zn.sub.2(C.sub.6S.sub.2(CH.sub.3).sub.2(COO).sub.2).sub.2((C.sub.5H.sub.4N).sub.2(CH.sub.2).sub.2)], [Zn.sub.2(C.sub.6S.sub.2(CH.sub.3).sub.2(COO).sub.2).sub.2((C.sub.5H.sub.4N).sub.2C.sub.2)], [Zn.sub.2(C.sub.6S.sub.2(CH.sub.3).sub.2(COO).sub.2).sub.2((C.sub.5H.sub.4N).sub.2N.sub.2)], [Zn.sub.2(C.sub.20H.sub.1204).sub.2(C.sub.10H.sub.8N.sub.2)], [Zn.sub.2(C.sub.20H.sub.1204).sub.2(C.sub.10H.sub.8N.sub.2)].sub.n, [Cu(SiF.sub.6)(C.sub.6H.sub.4(Si(OC.sub.2H.sub.5).sub.3).sub.2)], [(Ni(C.sub.14H.sub.34N.sub.6)).sub.2((C.sub.6H.sub.3).sub.2(COO).sub.4], [Cu(C.sub.5H.sub.4N).sub.2(BF.sub.4).sub.2], [Co(CH.sub.4N).sub.2(NCS).sub.2].sub.n, [Zn.sub.2(C.sub.6H.sub.4(COO).sub.2).sub.2(C.sub.5H.sub.4N)], [(Me.sub.2NH.sub.2)].sub.n(C.sub.6H.sub.2(NH.sub.2).sub.2(COO).sub.2).sub.2], [Cd(C.sub.11H.sub.9N.sub.202).sub.2], [Zn(C.sub.6H.sub.4(COO).sub.2)(C.sub.2H.sub.2N.sub.3)].sub.n, [Zn.sub.2(C.sub.10H.sub.6(COO).sub.2).sub.2((C.sub.5H.sub.4N).sub.2C.sub.2)].sub.n, and M(OH.sub.m)[C.sub.6X.sub.4(COO).sub.2], wherein: n is an integer greater than 1; M is selected from the group consisting of any metal cation of the periodic table with oxidation state +3, any metal cation of the periodic table with oxidation state +2, and a mixture of any of the above in any atomic proportion; m takes any value comprised between 0 and 1 to compensate for the oxidation state of the M cations; and X is selected from the group consisting of H, Br, Cl, F, I, CH.sub.3, CF.sub.3, OCH.sub.3, COOH, NH.sub.2, NO.sub.2, NCO, NCS, SH, SO.sub.3H, and a mixture of any of the above at a molar ratio of 1:4, 2:4, and 3:4.

4. The cooling/heating method according to claim 3, wherein the organic-inorganic hybrid material is the compound Al(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2].

5. The cooling/heating method according to claim 3, wherein the organic-inorganic hybrid material is the compound Cr.sub.0.5Fe.sub.0.5(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2].

6. The cooling/heating method according to claim 3, wherein the organic-inorganic hybrid material is the compound Cr(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2].

7. The cooling/heating method according to claim 3, wherein the organic-inorganic hybrid material is the compound Al.sub.0.5Cr.sub.0.5(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2].

8. The cooling/heating method according to claim 3, wherein the organic-inorganic hybrid material is the compound [Zn.sub.2(C.sub.6H.sub.4(COO).sub.2).sub.2(C.sub.5H.sub.4N)].

9. The cooling/heating method according to claim 1, wherein said method is cyclical and continuous, and wherein each cycle further comprises: a) applying and maintaining the pressurising gas for a given time period, during which the hybrid material releases heat which is conducted to the outside; b) removing the pressurising gas for a given time period, during which the hybrid material cools down and the cooling/heating cycle is completed.

10. The cooling/heating method according to claim 9, wherein: by applying pressure and maintaining the pressurising gas at a constant pressure for a time period, excess heat is generated and is transferred to a heat sink by direct contact of the hybrid material with said heat sink, or alternatively, using a heat transfer fluid; and by removing the pressurising gas, the cooling of said hybrid compound occurs, and the absorption of heat from a chamber or space that is intended to be cooled by direct contact of the hybrid material with this chamber, or alternatively by using a heat transfer fluid, occurs.

11. The cooling/heating method according to claim 10, wherein the heat transfer fluid is selected from the pressurising gas itself, air, water, and alcohols.

12. Method for cooling/heating for applications with a working temperature ranging from ?20? C. to 60? C., which comprises using a porous organic-inorganic hybrid material which is capable of undergoing a breathing transition consisting of a first-order phase transition in which a change in volume in the structure of the compound occurs when its pores open/close, together with adsorption/desorption of a gas after applying and removing a pressurising gas on the compound, as defined in claim 1, wherein for said applications the material is part of a device.

13. A device with cooling/heating capacity induced by pressure variation by a pressurising gas, application of a vacuum, or by pressure variation by a pressurising gas together with the application of a vacuum, comprising: a) a porous organic-inorganic hybrid material which is capable of undergoing a breathing transition consisting of a first-order phase transition in which a change in volume in the structure of the compound occurs when its pores open/close, together with adsorption/desorption of a gas after applying and removing a pressurising gas on the compound, as defined in claim 1; and b) means for applying/removing the pressurising gas on said hybrid material for a given time period.

14. The device according to claim 13, wherein the porous organic-inorganic hybrid material with breathing transition is in the form of a powder within a reservoir contained in the cooling/heating device.

15. The device according to claim 13, wherein the porous organic-inorganic hybrid material with breathing transition is in the form of a coating on the pressurising gas conduction pipes.

16. The device according to claim 13, which is an electronic apparatus, wherein the organic-inorganic hybrid material is in the form of a thin film.

17. The device according to claim 13, wherein the porous organic-inorganic hybrid material with breathing transition is in the form of micrometric particles, submicrometric particles, or a mixture thereof, embedded in a fabric.

18. The device according to claim 13, further comprising: c) a heat sink that is responsible for dissipating heat to the outside; d) optionally a heat exchange fluid; and e) a chamber or space that needs to be cooled.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0074] FIG. 1: Crystal structures of the compound Al(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2] obtained by single-crystal X-ray diffraction. Note: the structure on the left corresponds to the open-pore polymorph when the material is depressurised while the structure on the right corresponds to the closed-pore polymorph when the material is pressurised by CO.sub.2 gaseous.

[0075] FIG. 2: calorimetric curves as a function of pressure at different isothermal conditions of the compound Al(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2].

[0076] FIG. 3: Thermal properties ((a) isothermal change in entropy, ?S, and (b) working temperature range, T.sub.span, versus working pressure, p, at which the previous parameters are observed) of the materials MOF (1)=Al(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2], MOF (2)=Al.sub.0.5Cr.sub.0.5(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2] and MOF (3)=[Zn.sub.2(C.sub.6H.sub.4(COO).sub.2).sub.2(C.sub.5H.sub.4N)] compared to those properties of some of the best commercial gaseous refrigerants and barocaloric solid materials. Note: the different shaded areas correspond to the areas where the different materials show their thermal properties: GASES=refrigerant gases; BARO=barocaloric solid materials, MOFs=Metal-Organic Frameworks with breathing transitions.

EXAMPLES

Example 1: Determination of Thermal Properties (Isothermal Change in Entropy, Working Pressure Range and Working Temperature Range)

[0077] The thermal properties of the materials described here were studied by differential scanning calorimetry. In this way, around 4 mg of sample of the different materials were analysed in a TA Instruments Q2000 calorimeter equipped with a pressure cell. The samples were maintained in different isothermal conditions at different temperatures while they were subjected to pressurisation and depressurisation ramps by means of a pressurising gas (CO.sub.2) at a speed of ?1 bar min.sup.?1, and under CO.sub.2 atmosphere. These pressurisation and depressurisation cycles were carried out at a minimum pressure of 1 bar and a maximum of 50 bar. FIG. 2 shows the calorimetric curves obtained for the example Al(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2]. FIG. 3 shows the thermal properties (isothermal change in entropy, ?S, working temperature range, T.sub.span, and working pressure, p, at which the previous parameters are observed) of the material Al(OH)Al(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2], Al.sub.0.5Cr.sub.0.5(OH)[C.sub.6H.sub.4(CO.sub.2).sub.2] and [Zn.sub.2(C.sub.6H.sub.4(COO).sub.2).sub.2(C.sub.5H.sub.4N)] compared to those properties of some of the best commercial gaseous refrigerants and barocaloric solid materials. The isothermal change in entropy is obtained by integrating the calorimetric curves obtained and dividing the value obtained by the isothermal temperature at which the measurement was taken. The working temperature range is defined as the range between the maximum and minimum temperature values where the value of the isothermal change in entropy is different from 0 J K.sup.?1 kg.sup.?1. The working pressure range is defined as the range between the maximum and minimum pressure values where the value of the isothermal change in entropy is different from 0 J K.sup.?1 kg.sup.?1.

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Patent Literature

[0090] WO2014028574A2 [0091] WO2018118377A1