FR2985670A1 - Storing a gas, preferably hydrogen, comprises exposing an organometallic compound or a complex of metal hydride in a gas or a mixture of gases, and luminous irradiating of photostrictive compound - Google Patents

Storing a gas, preferably hydrogen, comprises exposing an organometallic compound or a complex of metal hydride in a gas or a mixture of gases, and luminous irradiating of photostrictive compound Download PDF

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FR2985670A1
FR2985670A1 FR1250310A FR1250310A FR2985670A1 FR 2985670 A1 FR2985670 A1 FR 2985670A1 FR 1250310 A FR1250310 A FR 1250310A FR 1250310 A FR1250310 A FR 1250310A FR 2985670 A1 FR2985670 A1 FR 2985670A1
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gas
bdc
compound
mof
metal hydride
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Bohdan Kundys
Michel Viret
Bernard Doudin
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Centre National de la Recherche Scientifique CNRS
Universite de Strasbourg
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Centre National de la Recherche Scientifique CNRS
Universite de Strasbourg
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015Organic compounds; Solutions thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031Intermetallic compounds; Metal alloys; Treatment thereof
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage
    • Y02E60/321Storage of liquefied, solidified, or compressed hydrogen in containers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage
    • Y02E60/324Reversible uptake of hydrogen by an appropriate medium
    • Y02E60/327Reversible uptake of hydrogen by an appropriate medium the medium being a metal or rare earth metal, an intermetallic compound or a metal alloy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage
    • Y02E60/324Reversible uptake of hydrogen by an appropriate medium
    • Y02E60/328Reversible uptake of hydrogen by an appropriate medium the medium being an organic compound or a solution thereof

Abstract

The present invention relates to an improved process for the storage of a gas and in particular hydrogen within a photostrictive compound, and more particularly to MOF organometallic compounds, which are crystalline organometallic compounds consisting of metal ions coordinated with molecules. organic, or complexes of metal hydrides, said compounds being subjected to a light irradiation step. The invention also relates to a photostrictive compound derived from the process of the invention in which a gas is stored. Finally, the present invention covers the use of photostrictive compounds according to the invention for the manufacture of fuel cells or photosensitive sensors, as well as their use for the distribution of drugs.

Description

The present invention relates to an improved method for storing gas comprising the use of photostrictive compounds, and more particularly organometallic compounds MOF, which are crystalline organometallic compounds consisting of metal ions coordinated with organic molecules, or complexes of metal hydrides, said compounds being subjected to a light irradiation step. The invention also relates to a photostrictive compound derived from the process of the invention in which a gas is stored. Finally, the present invention covers the use of photostrictive compounds according to the invention for the manufacture of fuel cells or photosensitive sensors, as well as their use for the distribution of drugs. Storing gas such as hydrogen is very important today for the production of clean energy, especially for self-propelled applications. At present, however, hydrogen storage is not economically efficient since it requires the use of modern physical methods that often consume energy. The problem of hydrogen storage is, and will probably continue for several decades, one of the most important technological and environmental issues, since hydrogen can, like oil, " advance a vehicle. There are now two ways of propelling a vehicle with hydrogen: internal combustion engines, whose efficiency is nevertheless limited by the Carnot cycle and whose efficiency is about 25%, 25 electrochemical engines based on a fuel cell (Journal of Physics IV, Colloque Cl, Supplement to Journal of Physics III, Volume 4, January 1994). The efficiency of these engines is not limited by the Carnot cycle, and their efficiency can reach 50 to 60%. The H2 loading of these systems however remains limited and must be controlled. The storage of hydrogen under normal temperature and pressure conditions is nevertheless problematic insofar as its volumetric storage density remains limited (AG Wong-Foy et al., J. Am. Chem. Soc., 2006, 128, 3494-3495).

The hydrogen is in gaseous form and has a density of 0.09 kg / m3. Under these conditions, the mass of hydrogen necessary to give a vehicle a range of at least 300 km is 3 kg, ie a volume of hydrogen of approximately 45 m3 (45,000 liters). Under these conditions, the tank must have the dimensions of a cube of 3.5 m side, which means that with a tank to standard dimensions the vehicle could only travel 600 m. In addition, liquid hydrogen requires cryogenic storage and bubbles around 20 ° K. The liquefaction of hydrogen therefore requires well insulated reservoirs, as well as considerable energy to maintain its temperature.

Compressed hydrogen is the most studied alternative. Hydrogen has a good energy density (energy per unit volume). However, compared to other hydrocarbons, this energy density remains poor. A hydrogen reservoir will therefore typically be heavier than a hydrocarbon reservoir to store the same amount of energy, other factors being equal. In addition, the compression step is very energy intensive: the energy required for the compression of hydrogen from ambient pressure to a pressure of 20 MPa is of the order of 7% of the energy contained in the hydrogen. . Due to their original structural properties, "Metal-Organic Frameworks" (MOF), which are crystalline organometallic compounds consisting of metal ions coordinated with organic molecules (clusters) to form uni-, bi- or three-dimensional structures, possibly porous, have emerged as ideal candidates for storing hydrogen (LJ Murray et al., Chem Soc Rev., 2009, 38, 1294-1314). Hydrogen adsorption within MOFs is dominated by physisorption and van der Waals forces, so the storage density of these compounds is highly dependent on the volume of their crystal lattice. In addition, and despite a high molecular weight, these compounds have high gravimetric densities (energy per unit mass) and volumetric densities. They also have an exceptionally high surface area / volume ratio and a chemically transformable structure (whose molecular topology, geometry and electronic structure can be modified in response to an electronic configuration change due to a chemical reaction or substitution of a new chemical element). MOF organometallic compounds generally have pores of about 10 Å in their three dimensional arrangement, in which hydrogen can be accommodated and attached by weak van der Waals bonds. By way of example, the gravimetric density of ZnO 4 (1,4-benzenedicarboxylate) at 100 bar is 10% by weight (S. S. Kaye et al., J. Am Chem Soc., 2007, 129, 14176). This value is similar to the density of liquid hydrogen. However, these systems must be operated at a low temperature (about 77 ° K), which limits the density of hydrogen that can be stored in these compounds. In addition to their use for storing hydrogen (LJ Murray et al., Soc.Rev., 2009, 38, 1294-1314), MOF organometallic compounds can be used as luminescent materials (MD Allendorf et al. Rev. Chem., 2009, 38, 1330-1352) or as magnetoelectric (multiferroic) materials (R. Ramesh, Nature, Vol 46, 29 October 2009). The storage properties of MOF organometallic compounds are comparable to those of metal hydride complexes already widely studied, all of which are considered promising candidates for the storage of hydrogen (IP Jain et al., Journal of Alloys). compounds, 2010, 503, 303). However, for hydrides, it is the opposite problem that arises since the operating temperature (above 400 ° K) appears much too high. The identification of parameters capable of improving the storage density properties, while operating under normal conditions of temperature and pressure, and without the thermal cycles necessary for the recovery of the stored hydrogen to alter the compounds used, remains one of the major challenges in the field of gas storage, including hydrogen. To date, only chemical substitution methods, or methods requiring significant changes in temperature and pressure have been used to improve gas storage. It therefore seems desirable today to be able to control the volume of the crystal lattice of the materials that are candidates for gas absorption, without variation of temperature and pressure (absence of thermodynamic cycle). The inventors have now developed a process which improves the ability of certain materials to absorb and store gases under the effect of light. The present invention indeed proposes to modify the pore size of an organometallic compound MOF or a metal hydride complex via a light excitation.

Surprisingly, the inventors have demonstrated the photostrictive properties of MOF organometallic compounds and metal hydride complexes, and thereby the possibility of increasing the gas insertion capacity within these compounds. In addition, the process of the invention is carried out at room temperature, without a thermal cycle, which makes it possible to limit the energy losses and to increase the longevity of the storage material, while being less expensive and faster than the processes already described in the prior art. Thus, the first object of the present invention is a method for storing a gas or gas mixture or for recovering a gas or gas mixture stored within a photostrictive compound. comprising at least the following steps: (i) exposing an organometallic compound MOF or a metal hydride complex to a gas, and more particularly hydrogen, and (ii) irradiating this organometallic compound with light MOF. If light is used as a source of external deformation, the forces of deformation creation may be microscopic within the materials. In MOF organometallic compounds, the deformations are due to the fact that organic molecules are sensitive to light. MOF organometallic compounds or metal hydride complexes of the invention are said to be "photostrictive"; they can be "ferroelectric" or "non-ferroelectric". For the purposes of the invention, the term "photostriction" means the ability of certain materials to change dimensions when illuminated by light. The term "ferroelectric" (or "non-ferroelectric") means that the compounds possess (or do not possess) an electrical polarization in the spontaneous state, this polarization being reversible by the application of an external electric field. Advantageously, the photostrictive compound of the invention is an organometallic compound MOF comprising at least one metal ion selected Na +, Li +, K +, Mn2 +, Cd2 +, Fe2 +, Cu2 +, Ca2 +, Mg2 +, Zn2 +, A124, Al3 +. The most preferred MOF organometallic compounds are chosen from compounds of the following formulas: (CnH2n + INH3) 2MC14, in which M = Mn2 +, Cd2 +, Fe2 +, Cu2 +, and n is between 1 and 12, Zrt4O (BDC) 3 wherein BDC = 1,4-benzenedicarboxylate, or Zn40 (adc) wherein adc = 9,10-anthracenedicarboxylate, -Zn40 (BTB) 2 wherein BTB3- = 1,3,5-benzenetribenzoate, Zn40 (NDC) 3 in which NDC = 2,6-naphthalene dicarboxylate, Zn2 (NDC) 2 (diPyNI) in which NDC = 2,6-dicarboxylate and diPyNI = 5 N, N-di- (4-pyridyl) -1,4,5,8 -naphthalenetetracarboxydiimide, - Mu3 [(Mn4Cl) 3 (BTT) 8] in which H3BTT = benzene-1,3,5-tris (1H-tetrazole), [(C3H2B0) 6 (C9F112) Cu3BTC2, wherein BTC = 1, 3,5-benzenetricarboxylate, Al (OH) (BDC) wherein BDC = 1,4-benzenedicarboxylate, Cr3OF (BDC) 3 wherein BDC = 1,4-benzenedicarboxylate, M40 (O2CR) 6 wherein M = Be or Co, and R = CH3 or CF3, Be40 (BDC) 3 wherein BDC = 1,4-benzenedicarboxylate, Co40 (BDC) wherein BDC = 1,4-benzene nedicarboxylate, 15 Mg40 (BDC) 3 in which BDC = 1,4-benzenedicarboxylate, Mg40 (02CR) 6 in which BDC = 1,4-benzenedicarboxylate, and R CH3 or CF3, - Mg3 (NDC) 3, Cd4 (TCPM) 2, wherein TCPM4 = tetrakis (4-carboxyphenyl) methane, CuRCu4C1) (t-tpm) 212, wherein ttpm4 = tetrakis (4-tetrazolylphenyl) methane, (C5H5) V (CO) 3 (H2), Mo ( CO) 5 (H2), - (MV) BiI3Cl2 wherein MV2 + = methylviologen, (H2bp4do) (Hbp4do) 4 (Bi4Bri8) 3, 2H2O, wherein bp4do = 4,4'-bipyridine-N, N'-dioxide , (Hbp4do) 2 (Sb2Br8), Sc (A1 (1 -,) Mgx) in which x varies from 0 to 0.8, X4 (OH) 8 [C1008H2] in which X = Na, Li, K, Mn, Cd, Fe Cu, Ca, Mg, Zn and Al, or among porous carbons activated by polythiophene with KOH, carbon-palladium composites and Mg-based composites and nanoparticles.

Even more advantageously, the MOF organometallic compound of the invention belongs to the family of compounds of formula (C 1 H 2n 1 -N INF 13) 2MC 14, in which M = Mn 2 +, Cd 2 ', Fe 2 +, Cu 2 +, and n is between These compounds consisting of octahedra and organic amonium cations crystallize in the stratified perovskite structure (JP Steadmen et al., Inorg Chem., Acta 1970, 4, 367, K. Knorr et al., Solid State Commun. 1974, 15, 1879, R. Kind et al., Phys Rev B., 1979, 19, 3743, G. Chapuis et al., Phys Status Solidi, 1975, A 31, 449). The metal hydride complexes are chemical compounds comprising a transition metal bonded to a hydrogen atom. The hydrides are said to be metallic when the main bond between the hydrogen and the metallic element is of metallic type. In metal hydrides, hydrogen is stored in atomic form (H) and not in molecular form (H2). There may be mentioned in particular the following metal hydride complexes: M '(A1H4) 2, M'3A1H6, M'NH2, M'2NH, M' (NH2) 2, M'4BN3H10, M'BH4, M '(BH4) ) 2, M '(BH4) 3, M' (NH2) 2, wherein M '= Na, Li +, K +, Ca2 +, Mg2 +, and Mg2FeH6, Mg2FeH6 being the most preferred metal hydride complex. The irradiation step (ii) of the process of the invention is preferably carried out at a wavelength corresponding to the maximum optical absorption of the organometallic compound MOF or of the metal hydride complex. Preferably, step (ii) is carried out at a wavelength of between 300 and 1000 nm, preferably between 300 and 530 nm or between 700 and 1000 nm. The duration of irradiation step (ii) may be equal to the cycle time required to increase the pressure; it is advantageously between 1 and 60 seconds. According to a particularly advantageous embodiment, the angle of incidence of the beam of the light can also be used as a control parameter. The angle between the irradiation light applied in step (ii) and the axis (100) is preferably between 0 and 45 °, the maximum deformation having been observed when the polarization of the light is parallel. to the axis (100). In addition, the deformation observed along the axis (110) is maximum when the angle between the polarization vector of the light and the axis (110) is between 45 and 75 °.

The method of the invention may be suitable: either for storing a gas or a gas mixture within the MOF organometallic compound or the metal hydride complex, or for recovering a gas or a mixture of gases that would be stored in an organometallic MOF compound or a metal hydride complex, since in the dark, the volume of the irradiated photostrictive compound decreases, thereby allowing the controlled release of the stored gas. The method of the invention may therefore also comprise an additional step of recovering the gas stored within the MOF organometallic compound or the metal hydride complex, either by reducing the pressure, preferably to ambient pressure, or by increasing the temperature, preferably up to 400 ° K. Another subject of the invention relates to an organometallic compound MOF or a metal hydride complex in which a gas or a mixture of gases is stored which can be obtained by a process as defined above, said compound consisting of pores having a diameter less than 3 nm, and preferably having a diameter of between 3 and 20 Å. The invention also relates to the use of an organometallic compound MOF or a metal hydride complex, obtainable by a process as defined above, for the manufacture of fuel cells or photosensitive sensors. these compounds can also be used for dispensing drugs in the human or animal body (Nature Materials, Vol.9, February 2010). In addition to the foregoing, the invention further comprises other provisions which will emerge from the additional description which follows, which relates to examples highlighting the improvement of the storage properties of organometallic materials MOF or metal hydrides. after light irradiation, as well as in the appended figures in which: - Figure 1 represents a crystalline structure of (C2H5NH3) 2CuC14 subjected to polarized light irradiation, - Figure 2 represents the phototransition of a crystalline structure of (C2H5NH3) 2CuC14 as a function of time and under different lighting conditions: (a) Photostriction as a function of the angle of rotation of the light polarization, (b) Measurements made in the dark with a red laser (5 mW, 632.8 nm) and a green laser (5 mW, 532 nm), Figure 3 shows the hydrogen absorption in a crystalline structure of (C2H5NH3) 2 CuC14 as a function of pressure, at a temperature of at 5 300 ° K with alternating light. EXAMPLE: An MOF organometallic compound of formula (C2H5NH3) 2 CuCh4 in the form of a crystal 2 mm in length as shown in FIG. 1 was subjected in the dark to different light irradiations with a HeNe laser: a laser red: laser power: 5 mW, wavelength: 632.8 nm, and - a green laser: laser power: 5 mW, wavelength: 532 nm. The crystal photostriction was measured using a dilatometer having a capacity similar to that described in B. Kundys et al, Rev. Sci. Instrum., 2004, 75, 2192. The distance between the laser and the sample is 12 cm. The crystal was irradiated in the crystalline axis (axis a in Figure 1), and the changes in length (110) were measured. The sample was first illuminated at a wavelength of 632.8 nm (red laser) at a power of 5 mW. The deformation produced by the light leads to an increase in the dimensions of the sample of the order of 80 * 10-6 for the red laser and 120 * 10-6 for the green laser. The measured response time is less than 30 seconds, which is much faster than for some polymeric materials (H. Finkelmann et al., Phys Rev. Lett., 87, 015501, 2001). The amplitude of the effect does not depend on the irradiation time, which indicates that the thermal expansion effect due to the light power is negligible. To confirm this, the photostriction of the sample was measured after irradiation at an angle of 60 ° to the axis (100). As can be seen in FIG. 2, the irradiation of the sample produces a photoelastic effect evidenced by a change in the length of the sample measured along the axis (110). The magnitude of the effect also depends on the direction of irradiation relative to the crystalline axis of the sample (Figure 2 (a): red laser). The polarization of the light was also rotated during irradiation of the sample, still at an angle of 60 ° to the axis a (Figure 1). It is observed that the effect is maximal when the component in the plane of polarization of the light is parallel to the direction of the detection of the deformation and minimum when the plane of polarization of the light is perpendicular to this direction (Figure 2 (b )). The sample was then illuminated at a wavelength of 532 nm (green laser) at the same power (5 mW). There is a significant increase in the photo-elastic effect.

The hydrogen uptake in the (C2H5NH3) 2CuCl4 sample was measured at 300 ° K as a function of pressure on a standard AutoSorb-iQ instrument. The results are shown in Figure 3. As can be seen, the irradiation leads to an increase in volume, and therefore to an increase in the storage capacity of the compound (C2H5NH3) 2CuC14.15

Claims (15)

  1. REVENDICATIONS1. Process for storing a gas, characterized in that it comprises at least the following steps: (i) exposing an organometallic compound MOF or a metal hydride complex to a gas or a mixture of gas, and (ii) the light irradiation of this photostrictive compound.
  2. 2. Process according to claim 1, in which the compound of step (i) is an organometallic compound MOF comprising at least one metal ion selected from Na +, Li +, K +, Mn2 +, cd2 +, Fe2 +, cu2 +, ca2 +, mg2 +, zn2 +. , m2 +, A13 +.
  3. 3. Process according to claim 1 or claim 2, in which the compound of step (i) is an organometallic compound MOF chosen from compounds of the following formulas: (CnH2n + 1 NH3) 2MC14, in which M = Mn2 +, Cd2 +, Fe2 +, C1.12 +, and n is between 1 and 12, - Zn40 (BDC) 3 in which BDC = 1,4-benzenedicarboxylate, or Zn40 (adc) in which adc = 9,10-anthracenedicarboxylate, - Zn40 ( BTB) 2 in which BTB3 "= 1,3,5-benzenetribenzoate, Zn40 (NDC) 3 wherein NDC = 2,6-naphthalene dicarboxylate, - Zn2 (NDC) 2 (diPyNI) wherein NDC = 2,6-dicarboxylate and diPyN1 = N, N-di- (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide, - Mn3 [(Mn4Cl) 3 (BTT) 812 wherein H3BTT = benzene-1,3,5-tris ( 1H-Tetrazole), RC3112B0) 6. (C91-112) 1], Cu3BTC2, wherein BTC = 1,3,5-benzenetricarboxylate, Al (OH) (BDC) wherein BDC = 1,4-benzenedicarboxylate, Cr3OF ( BDC) 3 wherein BDC = 1,4-benzenedicarboxylate, 1 440 (02CR) 6 wherein M = Be or Co, and R = CH3 or CF3, Be40 (BDC) 3 da wherein BDC = 1,4-benzenedicarboxylate, Co40 (BDC) wherein BDC = 1,4-benzenedicarboxylate, Mg40 (BDC) 3 wherein BDC = 1,4-benzenedicarboxylate, Mg40 (O2CR) 6 wherein BDC = 1, 4-benzenedicarboxylate, and R = CH3 or CF3, Mg3 (NDC) 3, Cd4 (TCPM) 2, wherein TCPM4 = tetrakis (4-carboxyphenyl) methane, CuRCu4C1) (ttpm) 2] 2, wherein ttpm4 = tetrakis ( 4-tetrazolylphenyl) methane, (C5H5) V (CO) 3 (H2), Mo (CO) 5 (H2), (MV) BiI3Cl2 wherein MV2 + = methylviologen, (H2bp4do) (Hbp4do) 4 (Bi4Bri8) 3, 2H2O wherein bp4do = 4,4'-bipyridine-N, N'-dioxide, (Hbp4do) 2 (Sb2Br8), Sc (A1 (1)) Mgx) in which x varies from 0 to 0.8, X4 (OH) 8 [C1008H2] wherein X = Na, Li, K, Mn, Cd, Fe, Cu, Ca, Mg, Zn and Al.
  4. 4. The method of claim 1 wherein the compound of step (i) is a metal hydride complex selected from: M'A1H4, M '(A1H4) 2, M'3A1H6, M'NH2, M'2NH , M '(NH2) 2, Ne4BN3Fl10, M'BH4, M' (BH4) 2, M '(BH4) 3, M' (NH2) 2, wherein M '= Na, Li +, K +, Ca2 +, Mg2 +, and - Mg2FeH6.
  5. 5. Method according to one of claims 1 to 4 wherein the gas is hydrogen.
  6. 6. Method according to one of claims 1 to 5 wherein the step (ii) of irradiation is carried out at a wavelength corresponding to the maximum optical absorption of the organometallic compound MOF or the metal hydride complex.
  7. 7. The method of claim 6 wherein the step (ii) of irradiation is carried out at a wavelength of between 300 and 1000 nm, and preferably between 300 and 530 nm or between 700 and 1000 nm.
  8. 8. Method according to one of claims 1 to 7 wherein the step (ii) of irradiation is carried out for a period of between 1 and 60 seconds.
  9. 9. Method according to one of claims 1 to 8 wherein the angle between the irradiation light applied in step (ii) and the axis (100) is between 0 and 45 °,
  10. 10. Process according to one of claims 1 to 9 for the storage of a gas or a mixture of gases within the MOF organometallic compound or the metal hydride complex.
  11. 11. The method of claim 10 characterized in that it comprises an additional step of recovering the gas or gas mixture stored in the organometallic compound MOF or the metal hydride complex, either by reducing the pressure or by temperature increase.
  12. 12. Method according to one of claims 1 to 9 for the controlled release of a gas or a mixture of gases that would be stored in the organometallic compound MOF or the metal hydride complex characterized in that it comprises an additional step of placing the irradiated compound in the dark.
  13. 13. Photostrictive compound in which is stored a gas or a mixture of gases, obtainable by a process as defined according to one of claims 1 to 12, characterized in that it consists of pores having a diameter. less than 3 nm, and preferably having a diameter of between 3 and 20 Å.
  14. 14. Use of an organometallic compound MOF or a metal hydride complex as defined in claim 13 for the manufacture of fuel cells or photosensitive sensors.
  15. MOF organometallic compound or metal hydride complex as defined in claim 13 for use in dispensing drugs in the human or animal body.
FR1250310A 2012-01-12 2012-01-12 Storing a gas, preferably hydrogen, comprises exposing an organometallic compound or a complex of metal hydride in a gas or a mixture of gases, and luminous irradiating of photostrictive compound Withdrawn FR2985670A1 (en)

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Citations (6)

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