METAL-ORGANIC FRAMEWORK-BASED COOLING / HEATING METHOD AND DEVICE BOTH INDUCED BY PRESSURE CHANGE - Patent application

Abstract

The present invention relates to a cooling / heating method involving the application and removal of pressurized gas to a hybrid organic-inorganic porous material (MOF) that causes a breathing transition. In this transition, a volume change occurs in the structure of the compound when the pores of the compound open / close with the adsorption / desorption of gas after the application and removal of pressurized gas to the compound, and the transition occurs at temperatures close to ambient temperature (-20°C to 60°C) and low pressure (10 -5 bar to up to 50 bar), large isothermal entropy changes (>100 JK -1 kg -1 The present invention also relates to a cooling / heating device comprising the above hybrid material.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims priority to Spanish Patent Application No. P202130753, filed August 2, 2021.

[0002] [Technical field] The present invention relates to a cooling / heating method based on the use of porous organic-inorganic hybrid compounds belonging to a family of compounds called Metal-Organic Frameworks, or MOFs, which exhibit a first-order phase transition that results in the opening / closing of the pores of the material in combination with the adsorption / desorption of gases that are highly sensitive to pressure changes of the pressurized gas (this effect is known as the breathing transition, gate opening transition or pore opening transition of MOFs). The present invention also relates to The present invention relates to a device comprising said MOF with the above-mentioned breathing transition and a means for applying / removing pressure by pressurized gas and a vacuum pump, as well as to the use of the "MOF compound" for cooling and heating applications. [Background technology]

[0003] According to a recent report from the International Energy Agency, approximately 20% of the world's electricity consumption is provided to cooling technologies, such as refrigerators, freezers, and heating, ventilation, and air conditioning (HVAC) equipment. Moreover, the demand in this sector is expected to increase significantly in the coming decades. In parallel, the current COVID-19 pandemic has highlighted the critical importance of cooling. This global disaster has forced buildings to improve their ventilation to avoid airborne infections indoors, without neglecting the maintenance of thermal comfort for the people who may be inside. Accordingly, one of the most pressing challenges remains the cooling of the COVID-19 vaccine, which represents a significant barrier limiting the global distribution and access to said vaccine.

[0004] Today, most cooling technologies are based on compression / expansion cycles of volatile refrigerant gases that were first used more than 180 years ago. Although these technologies are long-established, they continue to operate below their theoretical maximum thermodynamic efficiency (average efficiency is only 60%). In turn, cooling systems are responsible for 7% of global greenhouse gas emissions, with 5% due to indirect emissions originating from the inefficient energy consumption of these technologies and 2% due to direct emissions of refrigerant gases, mainly fluorinated hydrocarbons (F-gases), which have a global warming potential (GWP) several thousand times higher than CO2. Therefore, the Kigali Agreement and the F-gas Regulation (EU Regulation No. 517 / 2014) require that 80% of these fluorinated refrigerants be phased out by 2030.

[0005] In this critical situation, the main alternatives to F-gases are non-fluorinated hydrocarbons, ammonia or CO2, which have low GWP. However, these alternatives also pose new risks for the environment and users. For example, most hydrocarbons are flammable and ammonia is highly toxic and corrosive.

[0006] As for CO2, it is a chemically stable, non-toxic, non-flammable, widely available and cheap gas. It should also be noted that, although CO2 is undoubtedly the best known greenhouse gas, in cooling applications it is extracted from the air. It therefore does not contribute to global warming, but rather the opposite: its use in cooling contributes to the reduction of CO2 in the atmosphere.

[0007] Moreover, CO2 is one of the refrigerant gases with a lower GWP. Therefore, CO2 cooling systems can result in net zero carbon emissions. In this sense, Europe is leading the way in the use of CO2 cooling systems, with around 14% of all food establishments adopting this type of system.

[0008] However, most CO2 cooling systems require operating pressures of between 45 and 70 bar at ambient temperatures, and between 100 and 150 bar at temperatures above 30 °C. These pressures are much higher than those used by other refrigerant gases, which usually operate at only a few tens of bar (10 to 20 bar).

[0009] On the other hand, a more environmentally friendly alternative are solid materials that exhibit solid-state phase transitions that are also induced by compression / expansion. These solid materials, known as barocaloric compounds, exhibit large thermal changes (isothermal change in entropy, ΔS, or adiabatic change in temperature, ΔT) associated with a first-order transition and can be used for both cooling and heating, similar to refrigerant gases (see Non-Patent Document 1). A first-order transition is defined as a phase transition in which a change in volume occurs between a first and a second phase.

[0010] Several of these valocaloric compounds exhibit heat changes, ΔS>100 JK, comparable to those observed for commercial refrigerant gases. -1 kg -1 (see Non-Patent Document 2). For this reason, barocaloric compounds have recently been postulated by the Henry Royce Institute as a promising tool for achieving the goal of zero carbon emissions by 2050 (see Non-Patent Document 3). However, this report also highlights the need to dramatically reduce the operating pressure of barocaloric materials to below 300 bar, since most of them require pressures between 1000 and 2500 bar (see Non-Patent Document 1).

[0011] Barocaloric materials have also been described that can operate at pressures between 1 and 70 bar, which represents a significant reduction in the working pressure of these materials (see non-patent literature 4; non-patent literature 5). These low working pressures are due to the fact that the materials used, which are non-porous organic-inorganic hybrid compounds, are highly compressible due to the organic components present in their structure, making them highly flexible. However, the thermal changes (ΔS<40 J K) of these materials are very low. -1 kg-1 ) and operating temperature range (T(act)>57°C) are relatively small compared to refrigerant gases, limiting the number of practical applications.

[0012] On the other hand, porous hybrid materials of the "MOF" type have also been widely studied for cooling purposes, but with a different strategy of taking advantage of their remarkable adsorption properties. These porous hybrids induce the cooling effect using the change in enthalpy induced by the change in environmental temperature, which causes the evaporation of water molecules inserted in the cavities (see Non-Patent Document 6; Patent Document 1; or Patent Document 2). This mechanism is similar to the adsorption cooling observed in zeolites and is different from the barocaloric effect, where a first-order phase transition induced by a change in pressure occurs. However, the main drawback of these adsorption cooling methods is the need to use water as the adsorption / desorption material, which means a negative impact on the water footprint associated with these technologies, since water leaks into the atmosphere when it evaporates in an open system. Furthermore, these systems cannot operate at temperatures near and / or below 0°C, since water is in a solid state and cannot be adsorbed / desorbed. Thus, they cannot be used in low-temperature freezers or refrigerators, and are usually used in air conditioning systems. Similarly, they do not operate under pressure changes, but rather under environmental temperature changes, resulting in a dependency on an external heat source.

[0013] Considering all this, it is clear that there is still a great deal of room for improvement to provide new solid-state materials that can exhibit large thermal changes for cooling and heating applications at temperatures close to ambient (including freezers, refrigerators and HVAC equipment in general) and at small operating pressures. In this sense, large thermal changes (ΔS>100 J K -1 kg -1It is desirable to find new materials that exhibit a thermal conductivity (defined as 0.25° C.) and can operate at temperatures close to ambient (including temperatures close to and / or below 0° C.) and pressures below 70 bar, conditions not previously met by solid materials. Furthermore, it is also desirable that these materials do not consume or require the use of water, or be produced in closed systems that cannot escape into the atmosphere, a limited and essential resource for other more important areas of life. [Prior art documents] [Patent documents]

[0014] [Patent Document 1] WO2014 / 028574 A2 [Patent Document 2] WO2018 / 118377 A1 [Non-patent literature]

[0015] [Non-Patent Document 1] P.Lloveras et al.,MRS Energy Sustain.2021,8,3-15 [Non-Patent Document 2] P.Lloveras et al.Nat.Commun.2019,10,1-7 [Non-Patent Document 3] X.Moya,et al.Materials for the Energy Transition Roadmap,Henry Royce Inst.2020 [Non-Patent Document 4] JMBermudez-Garcia et al.,Nat.Commun.,2017,8,15715 [Non-Patent Document 5] JMBermudez-Garcia et al.J.Mater.Chem.C,2018,6(37),9867-9874 [Non-Patent Document 6] MFDe Lange et al.Chem.Rev.2015,115(22),12205-1225 Summary of the Invention

[0016] The inventors of the present invention have discovered that hybrid organic-inorganic compounds belonging to a family called metal-organic frameworks or MOFs that exhibit breathing transitions can be used for cooling / heating applications in domestic, commercial and industrial refrigeration systems (including freezers, refrigerators and HVAC equipment in general) at near ambient temperatures, particularly at temperatures between -20°C and 60°C.

[0017] Thus, MOFs are a subclass of organic-inorganic hybrid materials that are defined as porous because they have high porosity and specific surface area (see S.R. Batten et al., CrystEngComm, 2012, 14, 3001-3004). These materials are different from all barocaloric organic-inorganic hybrid materials reported in the scientific literature or patents, since all the described barocaloric hybrid materials are non-porous materials (see G. Kieslich et al., Chem.Sci., 2014, 5, 4712, and J. Garcia-Ben et al., Coord.Chem.Rev., 2022, 454, 214337).

[0018] The advantage of the MOFs of the present invention over previously described barocaloric hybrid materials is that their high porosity allows them to have breathing transitions, which combine a first-order phase transition in which the pores of the material open / close, along with the adsorption / desorption of gas due to the high porosity of the material, which is highly sensitive to changes in the pressure of the pressurized gas.

[0019] These MOFs with breathing transitions useful for cooling / heating applications in the systems and conditions described above have ΔS>100 J K -1 kg -1 Larger isothermal entropy, operating temperature range of -20℃~60℃, and 10 -5Crowbar (10 -6 It must demonstrate a change in operating pressure from 100 bar (40 MPa) to 50 bar (5 MPa).

[0020] A first-order phase transition is any transition that occurs when there is a change in entropy and volume and, furthermore, the first derivative of the Gibbs potential shows a discontinuity. The material of the present invention exhibits a first-order phase transition, which means that the opening / closing of the pores of the material occurs in combination with the adsorption / desorption of gas that is highly sensitive to pressure changes of the pressurized gas (an effect known as the breathing transition, gate opening transition or pore opening transition of MOFs). The terms breathing transition are used interchangeably with gate opening transition and pore opening transition.

[0021] Accordingly, a first aspect of the present invention is a cooling / heating method comprising the steps of: a) providing an organic-inorganic hybrid compound capable of undergoing a breathing transition consisting of a first-order phase transition in which a volume change of the structure of the compound occurs when its pores open / close, together with the adsorption / desorption of gas after the application and removal of pressurized gas to the compound; b)10 -6 and inducing a breathing transition by cycling the application and removal of pressure to the organic-inorganic hybrid material at a pressure range of from 0.5 MPa to 5 MPa; The application of pressure is caused by a pressurized gas selected from the group consisting of N2, CO2, CH4, air, and mixtures of any of the above in any percentage by volume, the removal of pressure is performed by releasing the pressurized gas through a pressure reducing valve, by applying a vacuum through a vacuum pump, or through a pressure reducing valve together with the application of a vacuum through a vacuum pump, the respiratory transition causes a temperature change and occurs at a temperature comprised between -20°C and 60°C, and the respiratory transition occurs at a temperature comprised between 100 J K -1 kg -1 The present invention relates to a method for producing the above isothermal change in entropy.

[0022] In certain embodiments, the hybrid organic-inorganic compound used in the cooling / heating method has a temperature of 250 J K -1 kg -1An isothermal change occurs with entropy above this level. In an even more preferred embodiment, the hybrid organic-inorganic compound used in the cooling / heating method is 400 J K -1 kg -1 An isothermal change occurs with entropy above this level. In certain embodiments, the hybrid organic-inorganic compound used in the cooling / heating method has a thermal conductivity of 100 to 400 J K -1 kg -1 An isothermal change occurs with entropy of In another particular embodiment, the hybrid organic-inorganic compound used in the cooling / heating method is in the range of 100 to 250 J K -1 kg -1 An isothermal change occurs with entropy of In a preferred embodiment, the hybrid organic-inorganic compound used in the cooling / heating method has a thermal conductivity of 250-400 J K -1 kg -1 An isothermal change occurs with entropy of

[0023] The organic-inorganic hybrid compounds of the present invention, also called MOFs, are composed of two main components: metal ions or groups of metal ions and organic ligands that act as bridges between the metal centers and give rise to potential voids (pores) in the structure with diameters of 50 nm or less. The pore size can be measured, for example, by X-ray diffraction. Thus, for example, a Bruker Kappa diffractometer equipped with an APEX II CCD detector and monochromatic MoKα radiation (λ=0.71073 Å) can be used, and the sample (in single crystal form) can be mounted on a MiTeGen MicroMount™ using Paratone® (Chevron Corporation) and cooled to 100 K. Data collection, integration and reduction can be performed with the APEX2 V2015.9-0 software package (Bruker AXS, 2015). The structure can be solved by direct methods using the SHELXT 2014 program and refined by least-squares methods in SHELXL2014 / 7.

[0024] In a particular embodiment, the pore size is between 2 and 50 nm. In another particular embodiment, the pore size is between 10 and 25 nm. In another particular embodiment, the pore size is between 2 and 25 nm. In another particular embodiment, the pore size is 2 nm or less.

[0025] In certain embodiments, the hybrid compound comprises: [Cu2(C6H4(COO)2)2(N2(C2H4)3)], [Cu2(C6(CH3(CH2)3O)2H2(COO)2)2(N2(C2H4)3)], [ Zn(C6H4(COO)2)(C6H4(C5H4N)2)], [Zn(C6H4(COO)2)(C6H2F2(C5H4N)2)], [Zn2(C6S2(CH 3)2(COO)2)2((C5H4N)2(CH)2)], [Zn2(C6S2(CH3)2(COO)2)2((C5H4N)2(CH2)2)], [Zn2( C6S2(CH3)2(COO)2)2((C5H4N)2C2)], [Zn2(C6S2(CH3)2(COO)2)2((C5H4N)2N2)], [Zn2(C 20 H 12 O4)2(C 10 H8N2)], [Zn2(C 20 H 12 O4)2(C 10 H8N2)] n , [Cu(SiF6)(C6H4(Si(OC2H5)3)2)], [(Ni(C 14 H 34 N6))2((C6H3)2(COO)4], [Cu(C5H4N)2(BF4)2], [Co(C5H4N)2(NCS)2] n , [Zn2(C6H4(COO)2)2(C5H4N)], [(Me2NH2)In(C6H2(NH2)2(COO)2)2], [Cd(C 11 H9N2O2)2], [Zn(C6H4(COO)2)(C2H2N3)] n , [Zn2(C 10 H6(COO)2)2((C5H4N)2C2)] n , and M(OH m )[C6X4(COO)2]; where n is an integer greater than 1 indicating that the molecular formula belongs to a polymer, M is selected from the group consisting of any metal cation of the periodic table in the oxidation state +3, any metal cation of the periodic table in the oxidation state +2, and mixtures of any of the above metal cations in any atomic ratio, and m can take any value from 0 to 1 to compensate for the oxidation state of the cation of M; X is selected from the group consisting of H, Br, Cl, F, I, CH3, CF3, OCH3, COOH, NH2, NO2, NCO, NCS, SH, SO3H, and mixtures of any of the above in ratios of 1:4, 2:4, and 3:4;

[0026] Also forming part of the invention is a cooling / heating method comprising the steps of: a) [Cu2(C6H4(COO)2)2(N2(C2H4)3)], [Cu2(C6(CH3(CH2)3O)2H2(COO)2)2(N2(C2H4)3)], [ Zn(C6H4(COO)2)(C6H4(C5H4N)2)], [Zn(C6H4(COO)2)(C6H2F2(C5H4N)2)], [Zn2(C6S2(CH 3)2(COO)2)2((C5H4N)2(CH)2)], [Zn2(C6S2(CH3)2(COO)2)2((C5H4N)2(CH2)2)], [Zn2( C6S2(CH3)2(COO)2)2((C5H4N)2C2)], [Zn2(C6S2(CH3)2(COO)2)2((C5H4N)2N2)], [Zn2(C 20 H 12 O4)2(C 10 H8N2)], [Zn2(C 20 H 12 O4)2(C 10 H8N2)] n , [Cu(SiF6)(C6H4(Si(OC2H5)3)2)], [(Ni(C 14 H 34 N6))2((C6H3)2(COO)4], [Cu(C5H4N)2(BF4)2], [Co(C5H4N)2(NCS)2] n , [Zn2(C6H4(COO)2)2(C5H4N)], [(Me2NH2)In(C6H2(NH2)2(COO)2)2], [Cd(C 11H9N2O2)2], [Zn(C6H4(COO)2)(C2H2N3)] n , [Zn2(C 10 H6(COO)2)2((C5H4N)2C2)] n , and M(OH m )[C6X4(COO)2] where n is an integer greater than 1, M is selected from the group consisting of any metal cation of the periodic table in oxidation state +3, any metal cation of the periodic table in oxidation state +2, and mixtures of any of the above metal cations in any atomic ratio, m takes any value between 0 and 1 to complement the oxidation state of the cation of M, and X is selected from the group consisting of H, Br, Cl, F, I, CH3, CF3, OCH3, COOH, NH2, NO2, NCO, NCS, SH, SO3H, and mixtures of any of the above in molar ratios of 1:4, 2:4, and 3:4; b) Organic-inorganic hybrid materials -6 Cycles of applying and removing pressure ranging from 100MPa to 5MPa were applied to cause the opening and closing of the pores of the compound along with the adsorption and desorption of the pressurized gas. Temperature changes between -20℃ and 60℃ and 100JK were also performed. -1 kg -1 causing an isothermal change in entropy above The method wherein the application of pressure is caused by a pressurized gas selected from the group consisting of N2, CO2, CH4, air, and mixtures of any of the above in any percentage by volume, and the removal of pressure is achieved by releasing the pressurized gas through a pressure reducing valve, by applying a vacuum through a vacuum pump, or through a pressure reducing valve in conjunction with the application of vacuum through a vacuum pump. Note that the fact that n is an integer greater than 1 indicates that it is a polymer.

[0027] In certain embodiments of the method defined in any of the above aspects, the hybrid compound has the molecular formula M(OH m )[C6X4(COO)2], where M is V 3+ , Al3+ , Cr 3+ , Fe 3+ , In 3+ , Ga 3+ , Sc 3+ , Fe 2+ , Co 2+ , Ni 2+ and Mn 2+ and mixtures of any of the aforementioned metal cations, and X is selected from the group consisting of the functional groups H, Br, Cl, F, I, CH3, CF3, OCH3, COOH, NH2, NO2, NCO, NCS, SH and SO3H, and mixtures of any of the aforementioned functional groups.

[0028] In a preferred embodiment, the organic-inorganic hybrid compound is Al(OH)[C6H4(COO)2]. In another preferred embodiment, the organic-inorganic hybrid compound is [Zn2(C6H4(COO)2)2(C5H4N)]. In another preferred embodiment, the organic-inorganic hybrid compound is Al 0.5 Cr 0.5 (OH)[C6H3NH2(COO)2]. In another preferred embodiment, the organic-inorganic hybrid compound is Cr(OH)[C6H4(CO2)2]. In another preferred embodiment, the organic-inorganic hybrid compound is Cr 0.5 Fe 0.5 (OH)[C6H4(CO2)2].

[0029] In a particular embodiment, the cooling / heating method is carried out in the device by pressurizing and depressurizing a pressurized gas through the organic-inorganic hybrid compound defined above, in a manner that generally comprises the following steps: a) increasing the pressure and temperature of the hybrid material by using pressurized gas; b) maintaining the pressure achieved in the previous step for a given period during which the hybrid material releases heat and its temperature decreases; c) reducing the pressure by removing the pressurized gas so that the temperature of the hybrid material is further reduced; and d) maintaining the pressure achieved in the previous step for a period during which the hybrid material absorbs heat and its temperature increases.

[0030] Generally, the time for which the applied pressure is maintained is 0.05 to 60 seconds. Preferably, the time for which the applied pressure is maintained is 1 to 10 seconds. More preferably, the time for which the applied pressure is maintained is approximately 1 second.

[0031] Generally, the time for which the removed pressure is maintained is 0.05 to 60 seconds. Preferably, the time for which the removed pressure is maintained is 1 to 10 seconds. More preferably, the time for which the removed pressure is maintained is approximately 1 second.

[0032] As used herein, the term "approximately / about" refers to the value indicated in the corresponding unit ±5%.

[0033] In certain embodiments, the heat absorption of the material is used to effect a cooling process, whereby heat generated by the material is removed.

[0034] In another particular embodiment, the generation of heat in the material is used to effect the heating process, and not the absorption of heat in the material.

[0035] In another particular embodiment, the absorption of heat in a material is used to effect a cooling process and the generated heat is used to effect a heating process.

[0036] In another particular embodiment, the cooling / heating method is a method in which excess heat is generated by applying pressure and maintaining a pressurized gas at a constant pressure for a period of time, and the heat is transferred to a heat sink, either by direct contact of the hybrid material with the heat sink or by using a heat transfer fluid; Removal of the pressurized gas results in cooling of the hybrid compound and absorption of heat from the chamber or space intended to be cooled, either by direct contact of the hybrid material with the chamber or by use of a heat transfer fluid.

[0037] In another particular embodiment, the cooling / heating method is one in which the heat transfer fluid is selected from the pressurized gas itself, air, water, and alcohol.

[0038] As an example, in the first step of the method, the pressure is increased by using pressurized gas on the organic-inorganic hybrid compound, for example Al(OH)[C6H4(COO)2], thereby heating the material. In the second step, the applied pressurized gas remains at a constant pressure for a certain period of time so that the excess heat generated is transferred to a heat sink. This excess heat generated can be directed to the heat sink by direct contact of the hybrid material with the heat sink or by using a heat transfer fluid (e.g., the pressurized gas itself, air, water, alcohol, etc.). In the third step, once the organic-inorganic hybrid compound releases the excess heat generated, the pressurized gas is removed, thereby cooling the hybrid compound. In the fourth step, by maintaining the removed pressurized gas for a certain period of time, the hybrid organic-inorganic compound (cooled in the previous step) absorbs heat from the chamber (or space) intended to be cooled, for example, inside a refrigerator. The heat is absorbed by direct contact of the hybrid material with this chamber or by using a heat transfer fluid (e.g., the pressurized gas itself, air, water, alcohol, etc.). This four-step process is repeated cyclically for a specific, predetermined period of time, where the pressurized gas acts to automatically increase and decrease pressure in an infinite cycle.

[0039] In certain embodiments, the pressurized gas is selected from the group consisting of N2, CO2, CH4, and air, and mixtures of any of the above in any percentage by volume. In a preferred embodiment, the pressurized gas is air. In an even more preferred embodiment, the pressurized gas is N2. In an even more preferred embodiment, the pressurized gas is CO2.

[0040] In a preferred embodiment, the pressurized gas increases the pressure from 1 bar (0.1 MPa) to 50 bar (5 MPa). In an even more preferred embodiment, the pressurized gas increases the pressure from 1 bar (0.1 MPa) to 40 bar (4 MPa). In an even more preferred embodiment, the pressurized gas increases the pressure from 1 bar (0.1 MPa) to 30 bar (3 MPa). In an even more preferred embodiment, the pressurized gas increases the pressure from 1 bar (0.1 MPa) to 20 bar (2 MPa). In an even more preferred embodiment, the pressurized gas increases the pressure from 1 bar (0.1 MPa) to 10 bar (1 MPa). In an even more preferred embodiment, the pressurized gas increases the pressure from 1 bar (0.1 MPa) to 5 bar (0.5 MPa).

[0041] In a preferred embodiment, the vacuum pump provides a pressure of 1 bar (0.1 MPa) to 10 -6 Crowbar (10 -7 In an even more preferred embodiment, the vacuum pump reduces the pressure to between 1 bar (0.1 MPa) and 10 -5 Crowbar (10 -6 In an even more preferred embodiment, the vacuum pump reduces the pressure to between 1 bar (0.1 MPa) and 10 -4 Crowbar (10 -5 In an even more preferred embodiment, the vacuum pump reduces the pressure to between 1 bar (0.1 MPa) and 10 -3 Crowbar (10 -4 In an even more preferred embodiment, the vacuum pump reduces the pressure to between 1 bar (0.1 MPa) and 10 -2 Crowbar (10 -3 In an even more preferred embodiment, the vacuum pump reduces the pressure to between 1 bar (0.1 MPa) and 10 -1 Crowbar (10 -2 The pressure is reduced to MPa.

[0042] In a preferred embodiment, the pressure application and removal cycles are 10 -5 Crowbar (10 -6 In an even more preferred embodiment, the pressure application and removal cycles are in the range of 10 -4 Crowbar (10 -5 In an even more preferred embodiment, the pressure application and removal cycles are in the range of 10 bar (4 MPa) to 40 bar (4 MPa). -3 Crowbar (10 -4 In an even more preferred embodiment, the pressure application and removal cycles are in the range of 10 bar (3 MPa) to 30 bar (3 MPa). -3 Crowbar (10 -4 In an even more preferred embodiment, the pressure application and removal cycles are in the range of 10 bar (2 MPa) to 20 bar (2 MPa). -2 Crowbar (10 -3 In an even more preferred embodiment, the cycles of applying and removing pressure are in the range of 10 -1 Crowbar (10 -2 In an even more preferred embodiment, the cycle of applying and removing pressure is in the range of 1 bar (0.1 MPa) to 10 bar (1 MPa).

[0043] In certain embodiments, the hybrid organic-inorganic compounds used in the cooling / heating methods of the present invention allow operation at an operating temperature range of -20°C to 60°C. Preferably, the operating temperature range is -10°C to 40°C. More preferably, the operating temperature range is -5 to 30°C.

[0044] In certain embodiments of the cooling / heating method, the organic-inorganic hybrid compound comprises: Al(OH)[C6H4(CO2)2]. In another particular embodiment of the cooling / heating method, the organic-inorganic hybrid compound comprises: [Zn2(C6H4(COO)2)2(C5H4N)]. In another particular embodiment of the cooling / heating method, the organic-inorganic hybrid compound comprises: Al 0.5 Cr 0.5 (OH)[C6H3NH2(COO)2]. In another particular embodiment of the cooling / heating method, the organic-inorganic hybrid compound comprises: Cr 0.5 Fe 0.5 (OH)[C6H4(CO2)2]. In another particular embodiment of the cooling / heating method, the hybrid organic-inorganic compound comprises: The compound Cr(OH)[C6H4(CO2)2]. In another preferred embodiment of the cooling / heating method, the organic-inorganic hybrid compound comprises: Compound Cr 0.5 Fe 0.5 (OH)[C6H4(CO2)2].

[0045] Yet another aspect of the present invention relates to the use of the hybrid organic-inorganic material as a cooling / heating material for cooling / heating devices in near ambient temperature applications (including freezers, refrigerators and HVAC equipment in general), particularly in applications having operating temperatures in the range of -20°C to 60°C.

[0046] The particular preferred embodiments of the cooling / heating methods described above are also particular preferred embodiments of this embodiment of the invention.

[0047] These materials can be incorporated into cooling / heating devices that can be used in a variety of sectors, including air conditioning and heat pump cooling / heating sectors, general HVAC equipment, domestic cooling, industrial cooling, commercial cooling, refrigerators, freezers, electronics, automotive, and personal protective equipment.

[0048] Thus, another aspect of the invention includes a cooling / heating device, the cooling capacity of which is generated by a pressure change from pressurized gas, by application of a vacuum, or by a pressure change from pressurized gas with application of a vacuum, the device comprising: (1) a hybrid organic-inorganic compound having a respiratory transition as defined above, and (2) A means for cyclically applying and removing pressure to the organic-inorganic hybrid compound for a given period of time using pressurized gas, vacuum, or pressure fluctuations from pressurized gas accompanied by the application of a vacuum.

[0049] The particular preferred values ​​of the pressures exerted by the pressurized gas and vacuum defined above for the cooling / heating methods are also particular / preferred values ​​of the medium of the device.

[0050] In another particular embodiment, the device of the present invention comprises: (3) A heat sink, which serves to dissipate heat to the outside; (4) Heat exchange fluid, if necessary; and (5) The chamber or space that needs to be cooled.

[0051] The heat sink may be, for example, a fan, a radiator, etc. The heat exchange fluid is optional and, if present, may be selected from the pressurized gas itself, air, water, alcohol, oil, etc. As an example, in the case of a refrigerator, the chamber or space that needs to be cooled is a chamber within said refrigerator. As another example, in the case of a smartphone, the space that needs to be cooled is the interior of the phone. As another example, in the case of an air conditioner or heat pump, the reservoir is the interior of a building or room whose temperature is to be controlled.

[0052] Furthermore, in cooling / heating devices, organic-inorganic hybrid compounds with breathing transitions can be used in powder form in a reservoir housed in the cooling / heating device, or as a coating in a pressurized gas conducting pipe, or as a thin film (thin layer) in an electronic device, embedded in fabrics, e.g. clothing, footwear and personal protective equipment (PPE), in the form of micrometer particles with a diameter of 1000 μm or less, submicrometer particles with a size of 1 μm or less, or a mixture thereof. The size of the particles can be determined, for example, by transmission electron microscopy. Thus, for example, a JEOL 1010 model transmission electron microscope operating at 100 kV can be used, and the sample (in the form of a powder suspended in isopropanol) is placed on a copper grid and introduced onto the sample holder of the microscope.

[0053] Thus, in a particular embodiment of the cooling / heating device, the organic-inorganic hybrid compound having a breathing transition is in the form of a coating on a pressurized gas conducting pipe.

[0054] In another particular embodiment of the cooling / heating device, the organic-inorganic hybrid compound having a respiratory transition is in the form of a powder within a reservoir contained in the cooling / heating device.

[0055] A particular embodiment of the present invention is a compound having the formula: Al(OH)[C6H4(CO2)2] (i.e., the formula: M(OH) m [C6X4(CO2)2], wherein M is for Al 3+ The compound includes an organic-inorganic hybrid compound having a respiratory transition of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 120, 121, 122, 133, 134, 140, 141, 142, 143, 14

[0056] As an example, single crystal X-ray diffraction at ambient temperature has shown that the compound Al(OH)[C6H4(CO2)2] has an open crystal structure with orthorhombic symmetry and the following cell parameters: a=19.513(2)Å, b=7.612(1)Å, c=6.576(1)Å It indicates that it has.

[0057] Throughout the specification and claims, the word "comprise" and its variations are not intended to exclude other technical features, additions, components or steps. Moreover, the word "comprise" includes the case of "consists of". Other objects, advantages and features of the present invention will be inferred to those skilled in the art from both the description and practical use of the present invention. The following examples and figures are provided by way of illustration and are not intended to limit the present invention. Moreover, the present invention covers all possible combinations of the specific preferred embodiments shown herein. [Brief description of the drawings]

[0058] [Figure 1] Schematic showing the crystal structure of the compound Al(OH)[C6H4(CO2)2] obtained by single crystal X-ray diffraction. Note: The structure on the left corresponds to the open-pore polymorph when the material is decompressed, and the structure on the right corresponds to the closed-pore polymorph when the material is pressurized with CO2 gas. [Diagram 2] Graph showing the calorimetric curves of the compound Al(OH)[C6H4(CO2)2] as a function of pressure at different isothermal conditions. [Diagram 3]Thermal properties of materials MOF(1) = Al(OH)[CH(CO)], MOF(2) = AlCr(OH)[CH(CO)] and MOF(3) = [Zn(CH(COO))(CHN)] compared to some properties of the best commercial gaseous refrigerants and barocaloric solid materials ((a) isothermal change in entropy ΔS, and (b) operating temperature range T [span] versus operating pressure p, where previous parameters are observed). Note: Different shaded regions correspond to areas where different materials show their thermal properties: GASES = refrigerant gases; BARO = barocaloric solid materials, MOFs = metal-organic frameworks with breathing transitions). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0059] The following describes the embodiment. EXAMPLES

[0060] Example 1: Determination of thermal properties (entropy, isothermal change in working pressure range and working temperature range).

[0061] The thermal properties of the materials described herein were studied by differential scanning calorimetry. Thus, samples of about 4 mg of the different materials were analyzed in a TA Instruments Q2000 calorimeter equipped with a pressure cell. The samples were subjected to pressurization and decompression gradients with pressurized gas (CO2) under a CO2 atmosphere at a rate of about 1 bar / min while being maintained in different isothermal conditions at different temperatures. These pressurization and decompression cycles were performed at a minimum pressure of 1 bar and a maximum pressure of 50 bar. Figure 2 shows the calorimetric curves obtained for the Al(OH)[C6H4(CO2)2] case. Figure 3 shows the calorimetric curves obtained for the materials Al(OH)Al(OH)[C6H4(CO2)2], Al, in comparison with some properties of the best commercial gaseous refrigerants and barocaloric solid materials. 0.5 Cr 0.5The thermal properties (isothermal change in entropy ΔS, operating temperature range T(span), operating pressure p versus the isothermal change in entropy ΔS, where the previous parameters are observed) of (OH)[C6H4(CO2)2] and [Zn2(C6H4(COO)2)2(C5H4N)] are shown. The isothermal change in entropy is obtained by integrating the calorimetric curve and dividing the value obtained by the isothermal temperature at which the measurement was performed. The operating temperature range is the range where the value of the isothermal change in entropy is 0 JK. -1 kg -1 The working pressure range is defined as the range between the maximum and minimum temperature values ​​different from the values ​​of 0 JK for the isothermal change of entropy. -1 kg -1 is defined as the range between a maximum pressure value and a minimum pressure value different from each other.

[0062] [List of references] "Non-Patent Literature" - Regulation EU No 517 / 2014 - P. Lloveras, J.-L. Tamarit, MRS Energy Sustain. 2021, 8, 3-15 - P. Lloveras, A. Aznar, M. Barrio, P. Negrier, C. Popescu, A. Planes, L. Manosa, E. Stern-Taulats, A. Avramenko, ND Mathur, X. Moya, JL Tamarit, Nat. Commun. 2019, 10, 1-7 - X. Moya, IM Ilevbare, Materials for the Energy Transition Roadmap: Caloric Energy Conversion Materials. Henry Royce Inst. 2020 - JM Bermudez-Garcia et al., Nat. Commun., 2017, 8, 15715 - JM Bermudez-Garcia et al. J. Mater. Chem. C, 2018, 6 (37), 9867-9874 - MF De Lange et al. Chem. Rev. 2015, 115 (22), 12205-1225 - SR Batten et al., CrystEngComm, 2012, 14, 3001-3004 - G. Kieslich et al., Chem. Sci., 2014, 5, 4712 - J. Garcia-Ben et al., Coord.Chem.Rev., 2022, 454, 214337 - M. Alhamami et al., 2014, 7, 3198-3250 - A. Boutin et al., J. Phys. Chem. C, 2010, 53, 22237-22244 "Patent Documents" WO2014 / 028574 A2 WO2018 / 118377 A1 [Explanation of symbols]

[0063] In FIG. 3(a), GASES = refrigerant gases BARO = Barocaloric solid material MOFs = Metal-Organic Frameworks with Breathing Transitions

Claims

1. A cooling / heating method comprising: a) providing a porous organic-inorganic hybrid compound capable of undergoing a breathing transition consisting of a first-order phase transition where a volume change in the structure of the compound occurs with the adsorption / desorption of gas after applying and removing a pressurized gas, and the pores of the compound open / close; b) 10 －６ inducing the respiratory transition by a cycle of applying and removing pressure to the organic-inorganic hybrid material at a pressure in the range of 10 MPa to 5 MPa; including The application of pressure is caused by N ２ , CO ２ , CH ４ , air, and a pressurized gas selected from the group consisting of any mixture of the four in any percentage by volume ratio removing the pressure by discharging the pressurized gas through a pressure reducing valve, or by applying a vacuum through a vacuum pump, or by applying a vacuum through a vacuum pump and also through a pressure reducing valve; wherein the breathing transition causes a temperature change and occurs at a temperature within the range of -20°C to 60°C; wherein the respiratory transfer results in an isothermal change in entropy of 100 JK －１ kg －１ or more, and the cooling / heating method is characterized by this.

2. The cooling / heating method according to claim 1, which is for use with an operating temperature in the range of -20°C to 60°C.

3. wherein the organic-inorganic hybrid compound is selected from the group consisting of [Cu ２ (C ６ H ４ (COO) ２ ) ２ (N ２ (C ２ H ４ ) ３ )], [Cu ２ [C ６ [CH ３ [CH ２ ) ３ O) ２ H ２ (COO) ２ ) ２ (N ２ (C ２ H ４ ) ３ )], [Zn(C ６ H ４ (COO) ２ )(C ６ H ４ (C ５ H ４ (CN)) ２ )], [Zn(C ６ H ４ (COO) ２ )(C ６ H ２ F ２ (C ５ H ４ (CN)) ２ ) [Zn ２ (C ６ S ２ (CH ３ ) ２ (COO) ２ ) ２ ((C ５ H ４ N) ２ (CH) ２ )] [Zn ２ (C ６ S ２ (CH ３ ) ２ (COO) ２ ) ２ ((C ５ H ４ N) ２ (CH ２ ) ２ )], [Zn ２ (C ６ S ２ (CH ３ ) ２ (COO) ２ ) ２ ((C ５ H ４ N) ２ C ２ )] [Zn ２ (C ６ S ２ (CH ３ ) ２ (COO) ２ ) ２ ((C ５ H ４ N) ２ N ２ )] [Zn ２ (C ２０ H １２ O ４ ) ２ (C １０ H ８ N ２ )], [Zn ２ (C ２０ H １２ O ４ ) ２ (C １０ H ８ N ２ )] ｎ , [Cu(SiF ６ )(C ６ H ４ (Si(OC ２ H ５ )) ３ )) ２ ) [[(Ni(C １４ H ３４ N ６ )) ２ ((C ６ H ３ )) ２ ((COO)) ４ , [Cu(C ５ H ４ N) ２ (BF ４ ) ２ , [Co(C ５ H ４ N) ２ (NCS) ２ ｎ ,​ [Zn ２ (C ６ H ４ (COO) ２ ) ２ (C ５ H ４ N)]、 [(Me ２ NH ２ )In(C ６ H ２ (NH ２ ) ２ (COO) ２ ) ２ , [Cd(C １１ H ９ N ２ O ２ ) ２ , [Zn(C ６ H ４ (COO) ２ )(C ２ H ２ N ３ )] ｎ , [Zn ２ (C １０ H ６ (COO) ２ ) ２ ((C ５ H ４ N) ２ C ２ )] ｎ and M(OH ｍ )[C ６ X ４ (COO) ２ ​ where n is an integer greater than 1; M is selected from the group consisting of any metal cation of the periodic table in an oxidation state of +3, any metal cation of the periodic table in an oxidation state of +2, and any mixture of the above metal cations in any atomic ratio; m takes any value included in the range of 0 to 1 to compensate for the oxidation state of the cation of M;

4. X is H, Br, Cl, F, I, CH ３ , CF ３ , OCH ３ , COOH, NH ２ , NO ２ , NCO, NCS, SH, SO ３ H, and a mixture of any of the fifteen in a molar ratio of 1:4, 2:4, and 3:4, the cooling / heating method according to claim 1, selected from the group consisting of any mixtures of the fifteen substances.

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

6. The organic-inorganic hybrid material is the compound Cr ０．５ Fe ０．５ (OH)[C ６ H ４ (CO ２ ) ２ , and the cooling / heating method according to claim 3.

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

8. The organic-inorganic hybrid material is the compound Al ０．５ Cr ０．５ (OH)[C ６ H ４ (CO ２ ) ２ , and the cooling / heating method according to claim 1.

9. The cooling / heating method according to claim 1, The organic-inorganic hybrid material is a compound [Zn ２ (C ６ H ４ (COO) ２ ) ２ (C ５ H ４ N)], and the cooling / heating method according to claim 3 wherein the method is periodic and continuous, and each cycle includes a) applying and maintaining the pressurized gas for a given period during which heat conducted from the hybrid material to the outside is released; b) removing the pressurized gas for a given period during which the hybrid material is cooled and the cooling / heating cycle is completed.

10. By applying pressure and maintaining the pressurized gas at a constant pressure for a certain period, excess heat is generated, and the heat is transferred to a heat sink either by direct contact of the hybrid material with the heat sink or by using a heat transfer fluid. Removing the pressurized gas causes cooling of the hybrid compound. Absorption of heat from a chamber or space intended to be cooled occurs either by direct contact of the hybrid material with the chamber or by using a heat transfer fluid. The cooling / heating method according to claim 9.

11. ​ ​ The cooling / heating method according to claim 9, wherein the heat transfer fluid is selected from the pressurized gas itself, air, water, and alcohol.

12. Use of a porous organic-inorganic hybrid material for cooling / heating in applications having an operating temperature in the range of -20 °C to 60 °C, wherein the porous organic-inorganic hybrid material is capable of undergoing a breathing transition consisting of a first-order phase transition where a volume change in the structure of the compound occurs when the pores open / close along with the adsorption / desorption of gas after applying and removing the pressurized gas to / from the compound, as described in claim 1, characterized in that, for the said application, the material forms part of a device.

13. A device having a cooling / heating capacity induced by pressure fluctuations with a pressurized gas, application of a vacuum, or pressure fluctuations with a pressurized gas involving application of a vacuum, a) a porous organic-inorganic hybrid material capable of undergoing a breathing transition consisting of a first-order phase transition where a volume change in the structure of the compound occurs when the pores open / close along with the adsorption / desorption of gas after applying and removing the pressurized gas to / from the compound, as described in claim 1, b) means for applying / removing the pressurized gas to / from the hybrid material over a given period, characterized by comprising the above.

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

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

16. The device according to claim 13, wherein the device is an electronic device and 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 having a breathing transition is in the form of micrometer particles, sub-micrometer particles, or a mixture thereof embedded in a fabric.

18. c) a heat sink serving to dissipate heat externally, d) optionally, a heat exchange fluid, e) a chamber or space to be cooled, The device according to claim 13, further comprising the above.

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