WO2008094007A1 - Complexes polymère-hydrure métallique contenant un groupe aromatique utilisés comme matériaux de stockage d'hydrogène, et procédé de préparation de ces complexes - Google Patents

Complexes polymère-hydrure métallique contenant un groupe aromatique utilisés comme matériaux de stockage d'hydrogène, et procédé de préparation de ces complexes Download PDF

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WO2008094007A1
WO2008094007A1 PCT/KR2008/000611 KR2008000611W WO2008094007A1 WO 2008094007 A1 WO2008094007 A1 WO 2008094007A1 KR 2008000611 W KR2008000611 W KR 2008000611W WO 2008094007 A1 WO2008094007 A1 WO 2008094007A1
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polymer
transition metal
chemical formula
integer
independently selected
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PCT/KR2008/000611
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Jisoon Ihm
Hoonkyung Lee
Hyo Jin Jeon
Jong Sik Kim
Dong Ok Kim
Hee Bock Yoon
Jeasung Park
Seong-Geun Oh
Chul Oh
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Seoul National University Industry Foundation
Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University)
Hanwha Chemical Corporation
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Priority claimed from KR1020080009017A external-priority patent/KR20080072543A/ko
Application filed by Seoul National University Industry Foundation, Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University), Hanwha Chemical Corporation filed Critical Seoul National University Industry Foundation
Publication of WO2008094007A1 publication Critical patent/WO2008094007A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible 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
    • C01B3/001—Reversible 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
    • C01B3/0015—Organic compounds; Solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible 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
    • C01B3/001—Reversible 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
    • C01B3/0026—Reversible 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 of one single metal or a rare earth metal; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/12—Hydrides
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a hydrogen storage material, and a process for preparing the same. More specifically, it relates to a hydrogen storage material which can adsorb or desorb hydrogen under mild condition (for example, for storage at 25 ° C, 30 atm; for release at 100°C under 2 atm) as compared to conventional storage materials, and dramatically increase the storage amount, and a process for preparing the same.
  • the invention relates to a polymer-transition metal hydride complex as hydrogen storage materials which provides a large capacity of hydrogen storage in a safe and reversible manner, and a process for preparing the same.
  • LiBH 4 lithium borohydride
  • Second one is to utilize metal-organic framework.
  • N. L. Rosi et al. the achievement of research and development by N. L. Rosi et al. is disclosed in [Science 300, 1127, (2003)].
  • this process gives insufficient maximum hydrogen storage capacity, and involves several disadvantages as in the case of metal hydrides.
  • Fig. 1 (c) when Sc atoms are attached on fluorene, it is expected that a large number of hydrogen molecules are to be adsorbed thereon, as was reported by Y. Zhao [Physical Review Letters, 94, 155504, (2005)].
  • Fig. 1 (d) when Ti atoms are attached on carbon nanotubes, it is also expected that a large number of hydrogen molecules are to be well adsorbed thereon, as reported by T. Yildirim and S.
  • Fourth one is to utilize polymer metal complex r epr esen ted by [X (CF3SO 3 ) 2L 2 ] n (X is bivalent transition metal and L is an organic ligand) , as is disclosed in Japanese Patent Laid-Open No. 2005-232033.
  • Seventh one is to store hydrogen by employing hydrogenation-dehydrogenation using a transition metal catalyst on an expanded ⁇ -conjugated substrate, as described in USP 71015330 and Korean Patent Laid-Open No. 2006-0022651.
  • An aromatic compound such as coronene is mixed with a transition metal compound such as titanium dihydride (TiH 2 ) , and the mixture is subjected to milling under high temperature (200°C) and high pressure (82bar) to carry out hydrogenation, and then milling under high temperature (150°C) and low pressure (1 bar) to carry out dehydrogenation, so that hydrogen bond is chemically formed and broken.
  • a transition metal compound such as titanium dihydride (TiH 2 )
  • the hydrogen storage material according to the present invention is suggested to overcome the disadvantages and restrictions of conventional hydrogen storage materials as described above.
  • the object of the invention is to prepare polymer-transition metal hydride complex which is a safe and reversible hydrogen storage material with high capacity of hydrogen storage, while suggesting optimal reaction conditions for good yield and stable productivity.
  • another object of the present invention is to suggest a process for preparing said polymer-transition metal hydride complex and a precursor thereof, the polymer-transition metal halide complex.
  • Another object of the present invention is to provide hydrogen storage material comprising said polymer- transition metal hydride complex, and a hydrogen storage device comprising said hydrogen storage material.
  • the present invention is contrived to solve the above- mentioned problems, and pertains to a polymer-transition metal hydride complex wherein the aromatic ring of a homopolymer or a copolymer of a monomer comprising an aromatic ring has been bonded to transition metal hydride, and a process for preparing the same.
  • the invention relates to a polymer-transition metal hydride complex which is prepared by applying various hydrogen source to a polymer-transition metal compound prepared by chemical reaction of a polymer selected from homopolymers and copolymers of a monomer comprising an aromatic ring with a transition metal compound.
  • the invention relates to a hydrogen storage material comprising said polymer-transition metal hydride complex and a hydrogen storage device comprising said hydrogen storage material .
  • the polymer-transition metal hydride complex according to the present invention is a substance wherein a transition metal hydride is bonded to the aromatic ring of homopolymer or copolymer of a monomer comprising aromatic ring. More specifically, it is a polymer-transition metal hydride complex wherein transition metal hydride is bonded to the aromatic ring (Ar) of the homopolymer or copolymer having one or more repeated unit(s) selected from the structures represented by Chemical Formula (1) .
  • Ar is selected from C 6 -C 2 O aromatic rings
  • J is selected from -O-, -NH-, -S- and -PH-;
  • Y is selected from halogen atoms, -NO 2 , -NO, -NH 2 , -R 1 / -OR 2 ,
  • R 1 through R 3 are independently selected from Ci ⁇ C 30 linear or branched alkyl groups, and C 6 ⁇ C 2 o aromatic rings, Xi is a halogen atom, and k is an integer from 0 to 10; and a is an integer from 0 to 4.
  • the polymer-transition metal hydride complex according to the invention is recognized to have a structure r epr esen ted by Chemical Formula (2).
  • Ar x and Ar 2 are independently selected from C 6 ⁇ C 2 o aromatic rings;
  • Ji and J 2 are independently selected from -0-, -NH-, -S- and -PH-;
  • Yi and Y 2 are substituents which are not contained in the polymer chain but having been chemically bonded to the aromatic ring, and independently selected from halogen atoms, -NO 2 , -NO, - NH 2 , -Ri, -OR 2 , -(CO)R 3 , -SO 2 NH 2 , SO 2 X 1 , -SO 2 Na, - (CH 2 ) k SH and -CN, wherein R 1 through R 3 in Yi and Y 2 are independently selected from Ci ⁇ C 30 linear or branched alkyl group, and C 6 ⁇ C 2 o aromatic rings, Xi is a halogen atom, and k is an integer from 0 to 10; M is one or more transition metal (s) selected from transition metals having the valence of at least 2; p and q represent an integer from 0 to 4; r is an integer from 1 to 2, i represents an integer (valence of M - 1), and m and n are integers
  • Ar x and Ar 2 in Chemical Formula (2) are independently selected from phenylene, naphthylene and anthrylene, and M is recognized to be bonded on the plane of aromatic ring Ari.
  • M is one or more metal(s) selected from transition metals having the valence of at least 2, with being single metal element or different metal elements in one compound.
  • the valence of M preferably ranges from 2 to 7, so that i is an integer from 1 to 6.
  • M comprises one or more transition metal (s) such as Ti, V, Sc (which are known to be able to adsorb high volume of hydrogen via Kubas binding) .
  • i is more preferably from 2 to 4, and most preferably 3.
  • the present invention provides hydrogen storage material comprising the polymer-transition metal hydride complex r epr esen ted by Chemical Formula (2) or a mixture thereof. With hydrogen (H 2 ) being adsorbed, the hydrogen storage material can be r epr esen ted by Chemical Formula (3) : [Chemical Formula 3]
  • M Ari, Ar 2 , Ji, J2, Yi, Y2, Pr Qr r, i, m and n are defined as in Chemical Formula (2), and d is an integer from 1 to 10.
  • the present invention provides a hydrogen storage device which comprises said polymer-transition metal hydride complex or a mixture thereof as a hydrogen storage material .
  • r epr esen tative polymers to specify polymer- transition metal hydride complex selected were polyaniline (PANI) and poly (2, 6- dimethyl-1, 4-phenylene oxide (dimethyl-PPO) which 1) have excellent stability under circumstances in laboratories, 2) can be produced in a large scale, and 3) may have relatively large capacity of hydrogen storage with less chemical formula weight of the monomer.
  • PANI polyaniline
  • dimethyl-PPO dimethyl-1, 4-phenylene oxide
  • the transition metal bonded on the plane of the aromatic ring in the polymer-transition metal hydride titanium (Ti) , scandium (Sc) and vanadium (V) , which can adsorb hydrogen via Kubas binding were selected.
  • titanium (Ti) is most desirable as the transition metal to specify the present invention, since it 1) can adsorb hydrogen molecules more stably, 2) has large amount of deposits, and 3) has no toxicity.
  • polyaniline-transition metal complex prepared by applying polyaniline (PANI) as the polymer is shown in Fig. 2.
  • PANI polyaniline
  • Two transition metals form strong chemical bonds on the plane of the aromatic ring for individual monomers of polyaniline polymer, to provide a stable structure.
  • the weight percentage of stored hydrogen (6H 2 ) with respect to the weight of each polymer [ (C 6 H 2 (CH 3 ) 2 O- 2TiH 1 ) n ⁇ (C 6 H 2 (CH 3 ) 2 ⁇ '2TiHi) n ] is about 5.2 to 5.9%, which is very close to the standard value (6%) of minimum hydrogen storage amount suggested by DOE of the United States.
  • the present invention provides a polymer-transition metal halide complex which is r epr esen ted by Chemical Formula (4), as a precursor for preparing the polymer-transition metal hydride complex.
  • the present invention provides a process for preparing a polymer-transition metal halide complex wherein a polymer compound comprising an aromatic ring represented by Chemical Formula (5) is reacted with alkali metal to activate the aromatic ring, and a metal halide of Chemical Formula (6) is reacted with the activated aromatic ring to obtain a polymer-transition metal halide complex of Chemical Formula (4).
  • Chemical Formula 4 [Chemical Formula 4]
  • Ar, Ari and Ar2 are independently selected from C 6 -C 2 O aromatic rings;
  • J, Ji and J 2 are independently selected from -O-, -NH-, -S- and -PH-;
  • Y, Yi and Y 2 are independently selected from halogen atoms, -NO 2 , -NO, -NH 2 , -R 1 , -OR 2 , -(CO)R 3 , -SO 2 NH 2 , SO 2 Xi, -SO 2 Na, - (CH 2 ) k SH and -CN, wherein R 1 through R 3 in Y, Y 1 and Y 2 are independently selected from Ci-C 30 linear or branched alkyl groups, and C 6 ⁇ C 2 o aromatic rings, Xi is a halogen atom, and k is an integer from 0 to 10; M is one or more transition metal (s) selected from transition metals having the valence of at least 2;
  • X is selected from halogen atoms; a, p and q represent an integer from 0 to 4; r is an integer from 1 to 2, i r epr esen ts an integer (valence of M - 1), and m and n are integers satisfying 10 ⁇ m+n ⁇ 100000 and 0.1 ⁇ m/ (m+n) ⁇ 1. ]
  • n means the number of monomers with which the transition metal halide is bonded
  • the binding ratio (m/ (m+n) ) of the transition metal halide can be adjusted as desired, and the ratio for a hydrogen storage material preferably is at least 10%.
  • the polymer compound of Chemical formula (5) is selected from homopolymers or copolymers having one or more repeated unit(s) selected from the structures represented by Chemical Formula (1).
  • Ar is selected from phenylene, naphthylene and anthrylene. More specifically, Ar is phenylene.
  • the molecule may be an oligomer or a polymer with high molecular weight. Specific compounds include, but are not limited to, poly (2, 6-dimethyl-l, 4- phenylene oxide) [dimethyl-PPO] , poly (1, 4-phenylene oxide) [PPO], polyaniline [PANI], and polymer substances consisting of one or more derivative (s) thereof or copolymer (s) thereof.
  • reaction Formula (1) In the process for preparing the polymer-metal halide complex according to the invention, the reaction can be expressed by two steps as shown in Reaction Formula (1), for instance, if Ar is phenylene and alkali metal is sodium.
  • Reaction Formula 1 Y, J, X, a, i, m and n are defined as before. [Reaction Formula 1]
  • a polymer compound (Chemical Formula 5) comprising an aromatic ring is dissolved in solvent, and then subjected to activation to induce ionization of the aromatic ring, by means of alkali metal such as Na, K as a strong base.
  • alkali metal such as Na, K as a strong base.
  • an excess amount of alkali metal is used to maximize the activity of alkali metal as an electron donor, or the external shape of alkali metal is processed in powder or slices.
  • the external shape of alkali metal is not restricted to those shapes.
  • the temperature of the first step ranges from -100 to 0 ° C, preferably from -78 to -20 ° C. If the reaction temperature is lower than -100 ° C, the activation rate of Na is insufficient to proceed with sufficient ionization of the polymer compound
  • reaction temperature is higher than 0 ° C, it is difficult to adjust the activity of alkali metal so that various types of byproducts are produced.
  • the duration of the reaction under reflux in step (1) is from 1 to 5 hours, preferably from 2 to 4 hours, more preferably from 2 to 3 hours. If the reaction time is less than 1 hour, it is difficult to proceed with sufficient ionization of Compound
  • reaction time needs not to be restricted to the above-mentioned range, since the reaction time can be appropriately adjusted depending upon the reaction temperature.
  • metal halide of Chemical Formula (6) is dissolved in solvent, and the solution of compound of Chemical Formula (5) obtained from the first reaction step is incorporated to solution of compound of Chemical Formula (6) to carry out the reaction to prepare the polymer-transition metal halide complex of Chemical Formula (4).
  • Progress of side-reactions such as cross-linking can be inhibited by controlling the injection rate of the polymer substance of Chemical Formula (5) .
  • the metal halide of Chemical Formula (6) sensitively reacts upon contacting with air and moisture to be converted to its metal oxide form (stable form), so that all procedures of synthesis and purification are preferably carried out under nitrogen atmosphere, and the organic solvent is preferably used after appropriate purification.
  • the reaction of the second step in Reaction Formula (1) is carried out within a temperature range from 60 to 120 ° C, preferably from 80 to 100°C. If the reaction temperature is lower than 60 °C, hydrohalide (HX) gas may be present inside the reactor to inhibit completion of the reaction. If the reaction temperature is higher than 100 ° C, the aromatic ring of Compound (5) is decomposed.
  • HX hydrohalide
  • reaction time is from 3 to 24 hours, preferably from 10 to 20 hours. If the reaction time is less than 3 hours, the reaction may be incompleted. If it is more than 24 hours, decomposition of the product may occur.
  • HX hydrohalide
  • the reaction mixture is purified by using a suitable solvent for removing the unreacted reactants and byproducts, and the organic solvent for purification is then removed by means of a rotary evaporator or distillation under reduced pressure. Drying in vacuo for at least 1 hour, preferably at least 5 hours gives the polymer- transition metal halide complex.
  • one or more solvent (s) selected from l-methyl-2-pyrrolidinone, tetrahydrofuran, trichlorobenzene, benzene, toluene, chloroform, chlorobenzene, phenyl ether, pyridine, nitrobenzene, dimethylformamide, dimethyl sulfoxide and benzophenone may be used as the reaction solvent.
  • the present invention also provides a process for preparing a polymer-transition metal hydride complex r epr esen ted by Reaction Formula (2), wherein the polymer-transition metal hydride complex of Chemical Formula (2) is prepared via substitution of the leaving group (L) of the polymer-transition metal complex of Chemical Formula (7) by hydrogen (H) in the presence of hydrogen source.
  • M Ari, Ar 2 , Ji, J 2 , Yi, Y2, P, q, r, i, m and n are defined as in Chemical Formula (2), and L r epr esen ts any leaving group which can be substituted by hydrogen (H) , and the type of leaving group is not restricted.
  • L include halogen atom (X) , -OR4, -NHR 5 , -SO 4 and -NO 3 , and R 4 and R 5 are independently selected from Ci ⁇ Cio linear or branched alkyl groups.
  • the number b is defined by the value (valence of M - I)/ (valence of L).
  • the valence of L means the number of bonding (s) with metal; the valence of L of halogen atom (X) , -OR 4 , -NHR 5 or -NO 3 is 1, while that of SO 4 2" is 2.
  • X halogen atom
  • -OR 4 , -NHR 5 or -NO 3
  • SO 4 2 SO 4 2
  • b is an integer from 1 to 6 when the valence of L is 1, while b is a value of 0.5, 1, 1.5, 2, 2.5 or 3 when the valence is 2.
  • the compound of Chemical Formula (7) can be prepared by chemical reaction of a metal compound selected from metal alkoxides, metal alkylamido compounds, metal nitrates, metal sulfates and metal halides with a polymer comprising an aromatic ring.
  • L is a halogen atom (X) .
  • the polymer-transition metal complex of Chemical Formula (7) may be expressed by the polymer-transition metal halide complex of Chemical Formula (4).
  • a reaction of hydrodehalogenation using a hydrogen source and a catalyst at the same time, or a radical hydrodehalogenation using a radical reductant and a radical initiator at the same time can be referred as examples.
  • the synthetic process is not restricted to those referred, but any conventional synthetic processes for substituting a halogen atom (X) by hydrogen (H) can be employed.
  • the hydrodehalogenation reaction which employs a hydrogen source and a catalyst at the same time, uses H2 gas as the hydrogen source, and one or more hydrogen donor (s) selected from the group consisting of phosphites such as sodium hypophosphate (NaH 2 PO 2 ) , sodium phosphite (NaH 2 PO 3 ) , sodium phosphate (NaH 2 PO 4 ) or sodium perphosphate (NaHPOs) ; metal hydrides such as lithium borohydride (LiBH 4 ) , lithium aluminum hydride (LiAlH 4 ), sodium borohydride (NaBH 4 ), sodium aluminum hydride (NaAlH 4 ), magnesium borohydride (Mg (BH 4 ) 2 ), magnesium aluminum hydride (Mg (AlH 4 ) 2), calcium borohydride (Ca(BH 4 J 2 )A calcium aluminum hydride (Ca (AlH 4 ) 2 ) , lithium hydride (LiH),
  • the polymer-transition metal hydride complex can be prepared in high yield by carrying out hydrodehalogenation in liquid phase in the presence of a neutralizer selected from one or more hydroxide compounds such as NaOH and KOH, and a noble metal catalyst for 1 ⁇ 12 hours.
  • a neutralizer selected from one or more hydroxide compounds such as NaOH and KOH, and a noble metal catalyst for 1 ⁇ 12 hours.
  • the amount of hydrogen supply during the reaction is maximized in the reaction mixture by supplying H 2 gas and the hydrogen donor at the same time. It is more preferable to simultaneously select one or more hydrogen donor (s) from 1) ⁇ -hydrogen containing 2- hydroxy alkane having the property that it is relatively easy to be handled at ambient temperature and ready to be released by methyl group (which serves as a leaving group adjacent to ⁇ - carbon) , and 2) metal hydrides generating a large amount of hydrogen via hydrolysis under the action of noble metal catalyst under strongly basic condition.
  • 2-hydroxy alkane 2-propanol or 2-butanol is more preferably used.
  • metal hydride one or more substance (s) selected from lithium borohydride (LiBH 4 ), sodium borohydride (NaBH 4 ) and magnesium borohydride (Mg (BH 4 ) 2) is (are) more preferably used, with sodium borohydride being most preferable .
  • the hydrodehalogenation comprises following steps: a) mixing a polymer-transition metal halide complex; one or more compound(s) selected from lithium borohydride (LiBH 4 ), sodium borohydride (NaBH 4 ) and magnesium borohydride (Mg (BH 4 ) 2) as metal hydride; and 2-propanol or 2-butanol as 2-hydroxy alkane, under nitrogen atmosphere to prepare a reaction mixture; and b) incorporating a noble metal catalyst to the reaction mixture and heating the resultant mixture under reflux with hydrogen gas supply.
  • a noble metal catalyst one or more metal (s) selected from Pt, Pd, Ru and Rh can be used.
  • Palladium (Pd) having high activity in hydrodehalogenation, or platinum (Pt) having high activity in hydrolysis of sodium borohydride can be more preferably used.
  • the noble metal catalyst is preferably applied as a heterogeneous catalyst, which is in a solid catalyst form supported on a carrier.
  • the carrier can be selected from carbon substance such as graphite, silica, alumina and titania.
  • the amount of the noble metal catalyst supported is from 1 to 20% by weight, preferably from 1 to 10% by weight, more preferably from 1 to 5% by weight on the basis of total weight of the carrier and the noble metal catalyst. If the amount is less than 1% by weight, active sites are insufficient to fail to proceed with the reaction. If the amount is more than 20% by weight, problem of high cost occurs due to the use of precious noble metal catalyst.
  • step b) it is preferable to add hydroxide compound in order to inhibit unstable generation of hydrogen from the metal hydride, and as a neutralizer for HX produced during the reaction.
  • the hydroxide compounds include NaOH, KOH, or the like.
  • the preparation condition was established on the basis of the production parameters such as the individual contents of the polymer-transition metal halide complex as the reactant, the hydrogen donor, the neutralizer, the noble metal catalyst in the reaction mixture, and pressure of H 2 gas applied, for the purpose of steady production of the polymer- transition metal hydride complex as hydrogen storage material.
  • the content of the polymer-transition metal halide complex in the reaction mixture is from 0.0001 to IM, preferably from 0.001 to 0.5M, more preferably from 0.01 to 0.1M. If the content in the reaction vessel is less than 0.0001M, production of the product may be insufficient, while if it is more than IM, the byproducts cannot be thoroughly washed during the washing stage of the product after the reaction.
  • the content of the metal hydride in the reaction mixture is from 0.0001 to 3OM, preferably from 0.001 to 15M, more preferably from 0.01 to 3M. If the content in the reaction vessel is less than 0.0001M, thorough proceeding of hydrodechlorination may be difficult, while if it is more than 3OM, the by-products cannot be thoroughly washed during the washing stage of the product after the reaction.
  • the content of 2-hydroxy alkane in the reaction mixture is from 0.0001 to 3OM, preferably from 0.001 to 1OM, more preferably from 0.01 to 3M. If the content in the reaction vessel is less than 0.0001M, thorough proceeding of hydrodechlorination may be difficult, while if it is more than 3OM, the by-products can not be thoroughly washed during the washing stage of the product after the reaction.
  • the content of the hydroxide compound in the reaction mixture is from 0.0001 to 18M, preferably from 0.001 to 6M, more preferably from 0.01 to 1.8M. If the content in the reaction vessel is less than 0.0001M, neutralization of HCl by-product does not properly occur so that poisoning of the catalyst becomes severe to cause difficulties in completion of hydrohalogenation.
  • the content of the noble metal catalyst in the reaction mixture is from 0.01 to 50 mol%, preferably from 1 to 50 mol% on the basis of the amount of the polymer-transition metal halide complex. If the content of the noble metal catalyst is less than 0.01mol%, thorough proceeding of the reaction may be difficult, while if it is more than 50mol%, better effect can be hardly obtained but provides disadvantages in terms of cost.
  • the pressure of hydrogen gas supply in step b) is from 1 to 30 bar, preferably from 1 to 20 bar, more preferably from 1 to 10 bar. If the pressure is less than 1 bar, the reaction rate may be lowered, while if it is more than 30 bar, decomposition of the reactant may occur.
  • the duration of reaction under reflux in step b) is from 1 to 48 hours, preferably from 1 to 24 hours, more preferably from 1 to 12 hours. If the reaction time is less than 1 hour, the reaction may not be completed, while if it is more than 48 hours, decomposition of the reactant may occur.
  • radical hydrodehalogenation employs radical reductant as the hydrogen source.
  • radical reductant s
  • One or more radical reductant (s) can be selected from TMS 3 CH, Bu 3 SnH, Ph 3 SnH and Me 3 SnH.
  • radical initiator such as AIBN and VAZO (1, 1-azobis (cyclohexane carbonitrile) ) is employed along with the radical reductant.
  • radical hydrodehalogenation a halide is radicalized and then substituted by hydride by means of reductant to provide polymer-transition metal hydride complex.
  • the radical hydrodehalogenation likewise said hydrodehalogenation, is carried out under nitrogen atmosphere, and it is preferable to use solvent, if any, that was purified in an appropriate manner, in order to prevent side reaction of producing metal oxide.
  • Solvent such as tetrahydrofuran, toluene, benzene, dichloromethane and chloroform can be used.
  • the present invention provides a process for preparing a polymer-transition metal hydride complex which comprises the steps of
  • a reaction of hydrodehalogenation using a hydrogen source and a catalyst at the same time, or a radical hydrodehalogenation using a radical reductant and a radical initiator at the same time can be referred as an example.
  • the synthetic process is not restricted to those referred, but any conventional synthetic processes for substituting a halogen atom (X) by hydrogen (H) can be employed.
  • Fig. l(a), 1 (b) , l(c) and 1 (d) show chemical structures of three types of hydrogen storage materials according to the conventional techniques.
  • Fig. 2 shows chemical structure of a novel hydrogen storage material having titanium atom bonded to polyaniline according to one embodiment of the present invention.
  • Fig. 3 shows the chemical structure wherein hydrogen molecules are bonded as much as possible to the novel hydrogen storage material having titanium atom bonded to an polyaniline according to one embodiment of the present invention.
  • Fig. 4 schematically shows hydrodehalogenation reaction.
  • polyaniline titanium hydride was prepared from polyaniline titanium chloride.
  • a 100 ml three-necked round-bottomed flask was charged with polyaniline titanium chloride (0.072 g, 0.18 itunol, based on the monomer) thus prepared under nitrogen atmosphere.
  • Sodium borohydride (3 g) and 2-propanol (50 ml) were added thereto, and the resultant mixture was stirred at 65 ° C for 12 hours.
  • poly (2, 6- dimethyl-1, 4-phenylene oxide) titanium hydride was prepared from poly (2, 6-dimethyl-l, 4-phenylene oxide) titanium chloride.
  • the polymer-transition metal hydride complex according to the invention as hydrogen storage material can store and use under a condition approximate to ambient temperature and ambient pressure via Kubas binding between transition metal and hydrogen.
  • the complex can bind multiple transition metals per molecule since it utilize alkali metal as a strong base to activate the aromatic ring during the course of the preparation and use the activated aromatic ring as a reactive group, so that high weight percentage of stored hydrogen per total material, and weight of hydrogen per unit volume are expected.
  • the process for preparing the polymer-transition metal hydride according to the present invention provides an advantage of preparing the object substance, polymer-transition metal hydride, under stable production condition in a good yield.

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Abstract

L'invention se rapporte à un matériau de stockage d'hydrogène et à un procédé de préparation de ce matériau. Elle concerne un matériau comprenant un complexe polymère-hydrure de métal de transition qui permet un stockage sûr et réversible de l'hydrogène dans une capacité élevée, et un procédé de préparation de ce matériau. Plus spécifiquement, l'invention porte sur un complexe polymère-hydrure de métal de transition dans lequel un hydrure de métal de transition est lié au noyau aromatique d'un homopolymère ou d'un copolymère formés à partir d'un monomère comprenant un noyau aromatique, ainsi que sur un procédé pour préparer ce complexe, un matériau de stockage d'hydrogène et un dispositif de stockage d'hydrogène comprenant ce matériau. Le métal de transition peut être le titane (Ti), le vanadium (V) ou le scandium (Sc), qui sont capables de se lier à l'hydrogène par une liaison de Kubas.
PCT/KR2008/000611 2007-02-01 2008-02-01 Complexes polymère-hydrure métallique contenant un groupe aromatique utilisés comme matériaux de stockage d'hydrogène, et procédé de préparation de ces complexes WO2008094007A1 (fr)

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KR10-2007-0010618 2007-02-01
KR20070010618 2007-02-01
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KR1020080009017A KR20080072543A (ko) 2007-02-01 2008-01-29 수소 저장 물질로서 방향족 고리를 포함하는고분자-전이금속 하이드라이드 복합체 및 이의 제조방법

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US9376316B2 (en) 2011-12-15 2016-06-28 USW Commercial Services Ltd. Metal hydrides and their use in hydrogen storage applications
US9739423B2 (en) 2014-06-13 2017-08-22 University Of South Wales Commercial Services Ltd. Synthesis and hydrogen storage properties of novel metal hydrides
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US9376316B2 (en) 2011-12-15 2016-06-28 USW Commercial Services Ltd. Metal hydrides and their use in hydrogen storage applications
US10974961B2 (en) 2011-12-15 2021-04-13 USW Commercial Services, Ltd. Metal hydrides and their use in hydrogen storage applications
US11851327B2 (en) 2011-12-15 2023-12-26 USW Commercial Services Ltd. Metal hydrides and their use in hydrogen storage applications
EP2899156A4 (fr) * 2012-09-18 2016-05-25 Wuhan Kaidi Eng Tech Res Inst Matériau de stockage d'hydrogène polymère macromoléculaire à haute capacité et son procédé de préparation
US9960441B2 (en) 2013-06-14 2018-05-01 University Of South Wales Commercial Services Ltd. Synthesis and hydrogen storage properties of novel manganese hydrides
US10622655B2 (en) 2013-06-14 2020-04-14 Usw Commercial Services Ltd Synthesis and hydrogen storage properties of novel manganese hydrides
US9739423B2 (en) 2014-06-13 2017-08-22 University Of South Wales Commercial Services Ltd. Synthesis and hydrogen storage properties of novel metal hydrides
US10465852B2 (en) 2014-06-13 2019-11-05 USW Commercial Services Ltd. Synthesis and hydrogen storage properties of novel metal hydrides
US11421826B2 (en) 2014-06-13 2022-08-23 USW Commercial Services, Ltd. Synthesis and hydrogen storage properties of novel metal hydrides
CN108083986A (zh) * 2016-11-22 2018-05-29 中国科学院大连化学物理研究所 有机-无机杂化材料及其制备和在储氢中的应用
CN108083986B (zh) * 2016-11-22 2020-08-04 中国科学院大连化学物理研究所 有机-无机杂化材料及其制备和在储氢中的应用
CN117654484A (zh) * 2023-12-07 2024-03-08 烟台大学 一种金属掺杂二氧化钛纳米管及其制备方法和应用

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