(19)
(11)EP 3 056 273 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
06.03.2019 Bulletin 2019/10

(21)Application number: 14851906.9

(22)Date of filing:  08.10.2014
(51)Int. Cl.: 
B01J 31/18  (2006.01)
C01B 3/26  (2006.01)
B01J 31/22  (2006.01)
H01M 8/06  (2016.01)
(86)International application number:
PCT/JP2014/076953
(87)International publication number:
WO 2015/053317 (16.04.2015 Gazette  2015/15)

(54)

CATALYST USED FOR DEHYDROGENATION OF FORMIC ACID, METHOD FOR DEHYDROGENATING FORMIC ACID, AND METHOD FOR PRODUCING HYDROGEN

KATALYSATOR ZUR DEHYDRIERUNG VON AMEISENSÄURE, VERFAHREN ZUR DEHYDRIERUNG VON AMEISENSÄURE UND VERFAHREN ZUR HERSTELLUNG VON WASSERSTOFF

CATALYSEUR UTILISÉ POUR LA DÉSHYDROGÉNATION D'ACIDE FORMIQUE, PROCÉDÉ DE DÉSHYDROGÉNATION D'ACIDE FORMIQUE, ET PROCÉDÉ DE PRODUCTION D'HYDROGÈNE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 11.10.2013 JP 2013213576

(43)Date of publication of application:
17.08.2016 Bulletin 2016/33

(60)Divisional application:
19151992.5

(73)Proprietor: National Institute of Advanced Industrial Science and Technology
Tokyo 100-8921 (JP)

(72)Inventors:
  • HIMEDA Yuichiro
    Tsukuba-shi Ibaraki 305-8565 (JP)
  • WANG Wan-Hui
    Tsukuba-shi Ibaraki 305-8565 (JP)
  • MANAKA Yuichi
    Tsukuba-shi Ibaraki 305-8565 (JP)
  • AMAMOTO Yuki
    Tsukuba-shi Ibaraki 305-8565 (JP)

(74)Representative: Graf von Stosch, Andreas et al
Graf von Stosch Patentanwaltsgesellschaft mbH Prinzregentenstraße 22
80538 München
80538 München (DE)


(56)References cited: : 
EP-A1- 2 543 675
WO-A2-2013/040013
JP-A- 2013 193 983
WO-A1-2013/111860
JP-A- 2013 193 983
US-A1- 2013 220 825
  
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  • JONATHAN H. BARNARD ET AL: "Long-range metal-ligand bifunctional catalysis: cyclometallated iridium catalysts for the mild and rapid dehydrogenation of formic acid", CHEMICAL SCIENCE, vol. 4, no. 3, 19 December 2012 (2012-12-19), pages 1234-1244, XP055333463, United Kingdom ISSN: 2041-6520, DOI: 10.1039/c2sc21923a
  • KEVEN MULLER ET AL: "Structure-Reactivity Relationships in the Hydrogenation of Carbon Dioxide with Ruthenium Complexes Bearing Pyridinylazolato Ligands", CHEMISTRY - A EUROPEAN JOURNAL, vol. 19, no. 24, 10 June 2013 (2013-06-10) , pages 7825-7834, XP055333465, ISSN: 0947-6539, DOI: 10.1002/chem.201204199
  • PRASAD K T ET AL: "Mono and dinuclear half-sandwich platinum group metal complexes bearing pyrazolyl-pyrimidine ligands: Syntheses and structural studies", JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 695, no. 4, 15 February 2010 (2010-02-15), pages 495-504, XP026877705, ISSN: 0022-328X [retrieved on 2009-11-26]
  • M. LAURA SORIANO ET AL: "Synthesis and characterization of Ru(arene) complexes of bispyrazolylazines: Catalytic hydrogen transfer of ketones", INORGANICA CHIMICA ACTA, vol. 362, no. 12, 23 April 2009 (2009-04-23), pages 4486-4492, XP055382331, NL ISSN: 0020-1693, DOI: 10.1016/j.ica.2009.04.011
  • GUPTA G ET AL: "Ruthenium half-sandwich complexes with tautomerized pyrazolyl-pyridazine ligands: Synthesis, spectroscopic and molecular structural studies", JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 694, no. 16, 15 July 2009 (2009-07-15), pages 2618-2627, XP026172288, ISSN: 0022-328X, DOI: 10.1016/J.JORGANCHEM.2009.03.043 [retrieved on 2009-04-05]
  • RAYMOND ZIESSEL ET AL: "Synthesis and molecular structure of new families of iridium( III)-Cp* and rhodium( III)-Cp* complexes derived", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 441, 1 January 1992 (1992-01-01), pages 143-154, XP055333481,
  • GUPTA G ET AL: "Study of new mononuclear platinum group metal complexes containing eta<5> and eta<6> - Carbocyclic ligands and nitrogen based derivatives and formation of helices due to N?H...Cl interactions", JOURNAL OF MOLECULAR STRUCTURE, ELSEVIER, AMSTERDAM, NL, vol. 979, no. 1-3, 27 August 2010 (2010-08-27), pages 205-213, XP027190462, ISSN: 0022-2860 [retrieved on 2010-06-25]
  • Venkateswara Rao Anna ET AL: "Study of half-sandwich mono and dinuclear complexes of platinum group metals containing pyrazolyl pyridine analogues: Synthesis and spectral characterization", Journal of Chemical Sciences, vol. 124, no. 3 1 May 2012 (2012-05-01), 1 May 2012 (2012-05-01), pages 565-575, XP055382567, India DOI: 10.1007/s12039-012-0249-x Retrieved from the Internet: URL:https://rd.springer.com/article/10.100 7%2Fs12039-012-0249-x
  • SHAVALEEV NAIL M ET AL: "Steric hindrance at metal centre quenches green phosphorescence of cationic iridium(III) complexes with 1-(2-pyridyl)-pyrazoles", INORGANICA CHIMICA ACTA, ELSEVIER BV, NL, vol. 404, 14 March 2013 (2013-03-14), pages 210-214, XP028568476, ISSN: 0020-1693, DOI: 10.1016/J.ICA.2013.03.002
  • FELIPE GOMEZ-DE LA TORRE ET AL: "Synthesis and Characterization of Palladium(II) Complexes with New Polydentate Nitrogen Ligands. Dynamic Behavior Involving Pd?N Bond Rupture. X-ray Molecular Structure of [{Pd(? 3 -C 4 H 7 )} 2 (Me-BPzTO)](4-MeC 6 H 4 SO 3 ) [Me-BPzTO = 4,6-Bis(4-methylpyrazol-1-yl)-1,3,5-triazi n-2-olate]", INORGANIC CHEMISTRY, vol. 37, no. 26, 1 December 1998 (1998-12-01), pages 6606-6614, XP055382598, EASTON, US ISSN: 0020-1669, DOI: 10.1021/ic980307n
  • YUICHI MANAKA ET AL: "Efficient H 2 generation from formic acid using azole complexes in water", CATALYSIS SCIENCE & TECHNOLOGY, vol. 4, no. 1, 23 October 2013 (2013-10-23), pages 34-37, XP055333485, United Kingdom ISSN: 2044-4753, DOI: 10.1039/C3CY00830D
  • WAN-HUI WANG ET AL: "Highly Robust Hydrogen Generation by Bioinspired Ir Complexes for Dehydrogenation of Formic Acid in Water: Experimental and Theoretical Mechanistic Investigations at Different pH", ACS CATALYSIS, vol. 5, no. 9, 30 July 2015 (2015-07-30), pages 5496-5504, XP055382404, US ISSN: 2155-5435, DOI: 10.1021/acscatal.5b01090
  • BARNARD, J. H. ET AL.: 'Long-range metal-ligand bifunctional catalysis: cyclometallated iridium catalysts for the mild and rapid dehydrogenation of formic acid' CHEMICAL SCIENCE vol. 4, no. 3, 2013, pages 1234 - 1244, XP055333463
  • MULLER, K. ET AL.: 'Structure-Reactivity Relationships in the Hydrogenation of Carbon Dioxide with Ruthenium Complexes Bearing Pyridinylazolato Ligands' CHEM. EUR. J. vol. 19, no. 24, 15 April 2013, pages 7825 - 7834, XP055333465 DOI: 10.1002/CHEM.201204199
  • ZIESSEL, R. ET AL.: 'Synthesis and molecular structure of new families of iridium(III)-Cp* and rhodium(III)-Cp* complexes derived from 1,2-dicyanoethene-1,2-dithiolate, 2,2'- biimidazole or 2,2'-bithiazole. Single crystal structures of [(eta5-Me5C5)Ir(biimH2)Cl]Cl and ([(eta5-Me5C5)Rh(dcdt' J. ORGANOMET. CHEM. vol. 441, no. 1, 01 December 1992, pages 143 - 154, XP055333481
  • PRASAD, K. T. ET AL.: 'Mono and dinuclear half- sandwich platinum group metal complexes bearing pyrazolyl-pyrimidine ligands: Syntheses and structural studies' J. ORGANOMET. CHEM. vol. 695, no. 4, 26 November 2009, pages 495 - 504, XP026877705
  • HIMEDA, Y.: 'Highly efficient hydrogen evolution by decomposition of formic acid using an iridium catalyst with 4,4'-dihydroxy-2,2'- bipyridine' GREEN CHEM. vol. 11, no. 12, 06 October 2009, pages 2018 - 2022, XP055237675
  • FUKUZUMI, S. ET AL.: 'Hydrogen storage and evolution catalysed by metal hydride complexes' DALTON TRANS. vol. 42, no. 1, pages 18 - 28, XP055333483
  • MANAKA, Y. ET AL.: 'Efficient H2 generation from formic acid using azole complexes in water' CATAL. SCI. TECHNOL. vol. 4, no. 1, 23 October 2013, pages 34 - 37, XP055333485
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Technical Field



[0001] The present invention relates to a catalyst used for dehydrogenation of formic acid, a method for dehydrogenating formic acid using the catalyst, and a method for producing hydrogen.

Background Art



[0002] Hydrogen (H2) has been produced in an amount of about five hundred billion Nm3 all over the world. The hydrogen has attracted much attention as future clean energy as well as has been applied for a variety of uses such as refinement of oil or production of ammonia. For example, a fuel cell is capable of efficiently supplying electricity when the hydrogen is supplied externally thereto. However, the hydrogen is highly reactive gas, so that it is difficult to be transported and stored. Therefore, there has been a need for a safe and inexpensive transportation and storage technology in order to stably supply the hydrogen. In the field of the fuel cell, there has been a problem that a poisoning substance is by-produced on a surface of an electrode catalyst by the action of carbon monoxide. Thus, there has been a need to supply high purity hydrogen generally containing 10 ppm or less of carbon monoxide.

[0003] As a hydrogen storage method, at present, a method for storing hydrogen as high pressure gas in a gas cylinder is commonly used. However, in this method, there are problems of safety upon transportation of the high pressure gas, and hydrogen brittleness of container materials. A method for storing hydrogen gas in the form of liquid hydrogen under an extremely low temperature is also used. However, there are problems that much energy is consumed in a liquefaction process and that the liquid hydrogen is lost in a percentage of 3% per day to 6% per day due to vaporization.

[0004] In order to solve the above described problems with regard to hydrogen transportation and storage technologies, there has been considered a method for storing hydrogen as liquid fuel (e.g., methanol and formic acid) which is obtained by hydrogenating carbon dioxide. For example, formic acid (HCOOH) has recently been attracted the attention as a hydrogen storage material since the formic acid, which is in the liquid form at normal temperature and has a relatively low toxicity, can be reversibly converted to hydrogen (H2) and carbon dioxide (CO2). However, there has been a problem that a dehydrogenation reaction of the formic acid using a conventionally known catalyst generally requires a high temperature of 200°C or higher, and generates carbon monoxide as a by-product. Therefore, there has been a need to develop a catalyst which allows high quality hydrogen to be produced from the formic acid under a mild condition.

[0005] Recently, many reports have been made with regard to a dehydrogenation reaction of formic acid using a metal complex catalyst (PTLs 1 and 2 and NPLs 1 to 8). In these reactions, although hydrogen is produced through dehydrogenation of formic acid, carbon monoxide is hardly by-produced. However, most of them need organic solvents or amine additives. On the other hand, a reaction in water free of organic additives is problematic in low catalytic activity and durability (PTLs 3 to 7, NPLs 9 to 12). Besides the above reports, the present inventors have been found catalysts which are extremely highly active in the dehydrogenation reaction of formic acid in water free of organic additives. However, these catalysts are problematic in durability because they are easily decomposed in a high-concentration formic acid solution or under a high temperature reaction condition (PTLs 8 to 14, NPLs 13 to 21).

Citation List


Patent Literature



[0006] 

PTL 1: International Publication No. WO2008/047312

PTL 2: International Publication No. WO2012/070620

PTL 3: Japanese Patent (JP-B) No. 4572393

PTL 4: JP-B No. 4875576

PTL 5: International Publication No. WO2011/108730

PTL 6: Japanese Patent Application Laid-Open (JP-A) No. 2010-083730

PTL 7: JP-A No. 2010-208927

PTL 8: JP-B No.3968431

PTL 9: JP-B No.4009728

PTL 10: JP-B No.4822253

PTL 11: JP-B No.5030175

PTL 12: International Publication No. WO2013/040013

PTL 13: International Publication No. WO2013/111860

PTL 14: JP-A No. 2013-193983


Non-Patent Literature



[0007] 

NPL 1: Schaub, T.; Paciello, R. A. Angew. Chem.-Int. Edit. 2011, 50, 7278.

NPL 2: Boddien, A.; Gartner, F.; Federsel, C.; Sponholz, P.; Mellmann, D.; Jackstell, R.; Junge, H.; Beller, M. Angew. Chem.-Int. Edit. 2011, 50, 6411.

NPL 3: Tanaka, R.; Ymashita, M.; Chung, L. W.; Morokuma, K.; Nozaki, K. Organometallics 2011, 30, 6742.

NPL 4: Boddien, A.; Mellmann, D.; Gaertner, F.; Jackstell, R.; Junge, H.; Dyson, P. J.; Laurenczy, G.; Ludwig, R.; Beller, M. Science 2011, 333, 1733.

NPL 5: Loges, B.; Boddien, A.; Junge, H.; Beller, M. Angew. Chem.-Int. Edit. 2008, 47, 3962.

NPL 6: Zell, T.; Butschke, B.; Ben-David, Y.; Milstein, D. Chem.-Eur. J. 2013, 19, 8068.

NPL 7: Barnard, J. H.; Wang, C.; Berry, N. G.; Xiao, J. Chem. Science 2013, 4, 1234

NPL 8: Sponholz, P.; Mellmann, D.; Junge, H.; Beller, M. ChemSusChem 2013, 6, 1172.

NPL 9: Fellay, C.; Dyson, P. J.; Laurenczy, G. Angew. Chem.-Int. Edit. 2008, 47, 3966.

NPL 10: Papp, G.; Csorba, J.; Laurenczy, G.; Joo, F. Angew. Chem.-Int. Edit. 2011, 50, 10433.

NPL 11: Fukuzumi, S.; Kobayashi, T.; Suenobu, T. J. Am. Chem. Soc. 2010, 132, 1496.

NPL 12: Maenaka, Y.; Suenobu, T.; Fukuzumi, S. Energy Environ. Sci. 2012, 5, 7360.

NPL 13: Himeda, Y.; Onozawa-Komatsuzaki, N.; Sugihara, H.; Arakawa, H.; Kasuga, K. J. Mol. Catal. A-Chem. 2003, 195, 95

NPL 14: Himeda, Y.; Onozawa-Komatsuzaki, N.; Sugihara, H.; Arakawa, H.; Kasuga, K. Organometallics 2004, 23, 1480.

NPL 15: Himeda, Y. Eur. J. Inorg. Chem. 2007, 3927.

NPL 16: Himeda, Y.; Onozawa-Komatsuzaki, N.; Sugihara, H.; Kasuga, K. Organometallics 2007, 26, 702.

NPL 17: Himeda, Y.; Miyazawa, S.; Onozawa-Komatsuzaki, N.; Hirose, T.; Kasuga, K., Dalton Transactions, 2009, (32), 6286-6288.

NPL 18: Himeda, Y. Green Chem. 2009, 11, 2018.

NPL 19: Himeda, Y.; Miyazawa, S.; Hirose, T. ChemSusChem 2011, 4, 487.

NPL 20: Hull, Jonathan F.; Himeda, Yuichiro; Wang, Wan-Hui; Hashiguchi, Brian; Periana, Roy; Szalda, David J.; Muckerman, James T.; Fujita, Etsuko, Nature Chemistry 2012, 4, 383-388.

NPL 21: Wang, Wan-Hui; Hull, Jonathan F.; Muckerman, James T.; Fujita, Etsuko; Takuji, Hirose; Himeda, Yuichiro, Chemistry - A European Journal 2012, 18, 9397-9404.


Summary of Invention


Technical Problem



[0008] The present invention has an object to provide a catalyst allowing hydrogen to be produced through dehydrogenation of formic acid in a highly efficient, highly energy-efficient, highly selectively, and highly durable manner even in a high-concentration aqueous formic acid solution under a high temperature reaction condition.

[0009] The present invention also has an object to provide a method for producing hydrogen through dehydrogenation of formic acid using the catalyst in a highly efficient and inexpensive manner with simple operation, and a method for high-pressure hydrogen free of carbon monoxide so as to stably and continuously supply hydrogen in an amount required for hydrogen consumption devices (e.g., fuel cells).

Solution to Problem



[0010] The present inventors conducted extensive studies to solve the above-described problems and consequently have found that a metal complex as defined in claim 1 is useful for a dehydrogenation reaction of formic acid, to thereby complete the present invention.

[0011] The catalyst used for a dehydrogenation reaction of at least one of formic acid and a formic acid salt has a structure represented by any selected from the group consisting of
the following Formulae (13) to (19) and (21):











[0012] The invention also relates to a method for producing hydrogen, the method including:
allowing a solution containing at least one of formic acid and a formic acid salt to react in the presence of the catalyst defined above, to thereby dehydrogenate the at least one of formic acid and a formic acid salt.

Advantageous Effects of Invention



[0013] Use of a complex according to the present invention, an isomer or a salt of the complex as a catalyst enables to provide a high-pressure hydrogen gas free of carbon monoxide through dehydrogenation of formic acid or a formic acid salt in a highly efficient, highly energy-efficient, highly selectively, and highly durable manner. Use of a method for dehydrogenating according to the present invention allows hydrogen to be regenerated easily from formic acid or a formic acid salt which is liquid fuel suitable for transportation and storage.

[0014] A complex catalyst according to the present invention has extremely higher durability than those of the complex catalysts described in PTLs 12 to 14, and has excellent catalytic performance allowing the catalyst to stably maintain high catalytic performance for a long period of time in a high-concentration formic acid solution under a high temperature reaction condition.

Brief Description of Drawings



[0015] 

FIG. 1 is a graph illustrating a time-dependent change in an amount of a gas released through dehydrogenation of formic acid by a dehydrogenation reaction of the formic acid using an 8 M aqueous formic acid solution with the complex catalyst (18).

FIG. 2 is a graph illustrating a pH-dependent change in reaction velocity of a dehydrogenation reaction of formic acid with the complex catalyst (18).

FIG. 3 is a graph illustrating a time-dependent change in volume and pressure of a gas released from an 8 M aqueous formic acid solution (50 mL) with the mononuclear catalyst (18) in a sealed glass autoclave with a back pressure valve pressure of 2 MPa at a reaction temperature of 80°C.

FIG. 4 is a graph illustrating a time-dependent change in ratios of carbon dioxide and a hydrogen gas released from an 8 M aqueous formic acid solution (50 mL) with the mononuclear catalyst (18) in a sealed glass autoclave with a back pressure valve pressure of 2 MPa at a reaction temperature of 80°C.


Description of Embodiments



[0016] As used herein, the phrase "at least one of formic acid and a formic acid salt" refers to the formic acid alone, the formic acid salt alone, a mixture of the formic acid with the formic acid salt, or a mixture of the formic acid or the formic acid salt with an acid or a base.

[0017] In the present invention, a dehydrogenation reaction of at least one of formic acid and a formic acid salt represented by the following scheme allows hydrogen and carbon dioxide to be highly efficiently produced. Upon the reaction, there is a possibility that carbon monoxide and water are by-produced through a decarbonylation reaction of formic acid. However, use of a catalyst for dehydrogenation of formic acid according to the present invention allows only the dehydrogenation reaction of formic acid to proceed in a highly selective and highly efficient manner, to thereby produce a hydrogen gas free of carbon monoxide.

        HCOOH → H2 + CO2



[0018] In the complex catalyst represented by any of the Formulae (13) to (19) or (21), a counter ion thereof is not particularly limited. Examples of anions serving as the counter ion include a hexafluorophosphate ion (PF6-), a tetrafluoroborate ion (BF4-), a hydroxide ion (OH-), an acetate ion, a carbonate ion, a phosphate ion, a sulfate ion, a nitrate ion, a halide ion (e.g., a fluoride ion (F-), a chloride ion (Cl-), a bromide ion (Br-), and an iodide ion (I-)), a hypohalite ion (e.g., a hypofluorite ion, a hypochlorite ion, a hypobromite ion, and a hypoiodite ion), a halite ion (e.g., a fluorite ion, a chlorite ion, a bromite ion, and an iodite ion), a halate ion (e.g., a fluorate ion, a chlorate ion, a bromate ion, and an iodate ion), a perhalate ion (e.g., a perfluorate ion, a perchlorate ion, a perbromate ion, and a periodate ion), a trifluoromethanesulfonate ion (OSO2CF3-), and a tetrakis(pentafluorophenyl)borate ion [B(C6F5)4-]. Examples of cations serving as the counter ion include, but are not limited to, various metal ions, such as a lithium ion, a magnesium ion, a sodium ion, a potassium ion, a calcium ion, a barium ion, a strontium ion, an yttrium ion, a scandium ion, and a lanthanoid ion; and a hydrogen ion. One type of these counter ions may be used alone, or two or more types may be used in combination. However, the above description is intended to only exemplify possible mechanisms, and the present invention is not limited thereto.

[0019] The catalyst according to the present invention is a catalyst containing, as an effective ingredient, a complex represented by any of the General Formulae (13) to (19) or (21), as salts thereof, and used for a method for dehydrogenating at least one of formic acid and a formic acid salt (or a method for producing hydrogen) or a method for producing hydrogen. For example, one compound or a plurality of compounds serving as the effective ingredient may be used as-is as the complex catalyst according to the present invention, or a mixture of the above-described isomers may be used as the complex catalyst. Other ingredients may be appropriately added (preferably in an amount of less than 10% by mass).

[0020] In the complex catalyst according to the present invention, the ligand significantly improves efficiency of the dehydrogenation reaction of formic acid. For example, a bipyridine complex which contains a bidentate ligand including a 6-membered ring skeleton similar to the complex catalyst represented by the General Formulae (13) to (19) or (21) exhibits only extremely low catalytic performance in the dehydrogenation reaction of formic acid (see, Comparative Example 1). From the above results, it has been found that it is necessary for one or more of aromatic rings constituting the ligand to include an aromatic heterocyclic 5-membered ring skeleton having 2 or more nitrogen atoms in order to accelerate the dehydrogenation reaction of formic acid.

[0021] A method for dehydrogenating formic acid (or a method for producing hydrogen) according to the present invention includes at least one step selected from the group consisting of a step of stirring a solution containing at least one of formic acid and a formic acid salt with a catalyst containing, as the effective ingredient, the complex catalyst, tautomers or stereoisomers thereof, or salts thereof according to the present invention, and a step of heating the solution. Specifically, for example, the complex catalyst according to the present invention is added to solution containing at least one of formic acid and a formic acid salt, and then stirred, optionally with heating. In the case of heating, a temperature is not particularly limited, but is, for example, 0°C to 300°C, preferably 20°C to 120°C, more preferably 60°C to 100°C. A method for collecting hydrogen released is not particularly limited. For example, known methods such as a downward displacement of water method or an upward displacement method may be appropriately used.

[0022] In the method for dehydrogenating formic acid (or a method for producing hydrogen) according to the present invention, the formic acid or the formic acid salt can also be dehydrogenated under pressure by using a sealable reaction container. A gas pressure in the reaction container is not particularly limited, but is, for example, 0 MPa to 100 MPa, preferably 1 MPa to 10 MPa. Pressure inside the reaction container is spontaneously increased, which allows high pressure hydrogen gas to be spontaneously supplied without pressurizing by means of external energy.

[0023] In the method for dehydrogenating formic acid (or a method for producing hydrogen) according to the present invention, a concentration of the complex catalyst is not particular limited, but depends on, for example, reaction velocity, solubility of the complex in the reaction solution, and economic efficiency. Appropriate concentration of the catalyst is 1 × 10-9 M to 1 × 10-1 M, preferably 1 × 10-7 M to 1 × 10-4 M.

[0024] In the method for dehydrogenating formic acid (or a method for producing hydrogen) according to the present invention, a ratio of an amount of substance (the number of molecules) of catalyst molecules to that of formic acid molecules is not particularly limited, but, for example, the ratio of the formic acid molecules to the catalyst molecules is 100:1 to 1:100, 000, 000 at the start of the reaction. Hydrogen can be continuously produced by additionally adding or continuously adding dropwise formic acid molecules during the reaction. As used herein, the term formic molecule includes formic acid and a formic acid salt, which may be used alone or as a mixture thereof. In the case where the mixture is used, it is generally used in a pH range of 1 to 9, preferably 1 to 6, but the formic acid may be dehydrogenated at a pH out of the above range by additionally adding an acid or a base. In the case where the formic acid salt is used alone, examples of a positive ion serving as a counter cation include, but are not limited to, various metal ions such as a lithium ion, a magnesium ion, a sodium ion, a potassium ion, a calcium ion, a barium ion, a strontium ion, an yttrium ion, a scandium ion, or a lanthanoid ion; an ammonium ion, tetramethyl ammonium, and tetraethyl ammonium. Although these counter ions may be used alone or two or more counter ions may be used in combination.

[0025] The catalyst, a tautomer or stereoisomer thereof, or a salt thereof according to the present invention can be used as a catalyst for dehydrogenation of formic acid in, for example, a formic acid fuel cell. In the case where the catalyst is used in the fuel cell, for example, the cell only has to contain therein the catalyst for dehydrogenation of formic acid according to the present invention and include a mechanism for generating hydrogen by dehydrogenating formic acid according to the above described method. A specific configuration of the fuel cell is not particularly limited, and, for example, a configuration of a known fuel cell can be appropriately applied thereto. Furthermore, an application of the catalyst for dehydrogenation of formic acid according to the present invention is not limited to those mentioned above, and, for example, the catalyst for dehydrogenation of formic acid according to the present invention can be used in every technical field in which hydrogen (H2) is needed to be supplied.

[0026] In the method for dehydrogenating formic acid according to the present invention, a reaction solvent to be used is not particularly limited. For example, the solvent may be water or an organic solvent, and one solvent may be used alone or two or more solvents may be used in combination. In the case where the complex catalyst according to the present invention is soluble in water, water is preferably used from the viewpoint of simplicity and convenience. The organic solvent is not particularly limited, but a highly polar solvent is preferable from the viewpoint of solubility of the catalyst. Examples thereof include nitriles such as acetonitrile, propionitrile, butyronitrile, or benzonitrile; primary alcohols such as methanol, ethanol, n-propyl alcohol, or n-butyl alcohol; secondary alcohols such as isopropyl alcohol or s-butyl alcohol; tertiary alcohols such as t-butyl alcohol; polyhydric alcohols such as ethylene glycol or propylene glycol; ethers such as tetrahydrofuran, dioxane, dimethoxyethane, or diethyl ether; amides such as dimethylformamide or dimethylacetamide; sulfoxides such as dimethyl sulfoxide; and esters such as ethyl acetate. Furthermore, formic acid as a raw material may be in the form of a solution or a salt.

Examples



[0027] Hereinafter, examples of the present invention will be described in more detail. However, the present invention is not limited to the following examples.

[Example 1]


[Catalyst synthesis] (Synthesis of sulfate of complex catalyst represented by General Formula (1) or (2))



[0028] [Cp*Ir(H2O)3]SO4 and a ligand corresponding to it in an equal amount were dissolved into water, followed by stirring at room temperature under an argon stream for 12 hours. The resultant reaction liquid was filtered. The resultant filtrate was concentrated under reduced pressure. The resultant product was dried at 50°C under reduced pressure for 12 hours, to thereby the intended product.

[0029] The spectral data of the resultant complex catalysts are presented below.

[Example 1-1] (illustrative, not of the invention)



[0030] The spectral data of the compound represented by the following Formula (22) is presented below.



[0031] 1H NMR (400 MHz, D2O): δ = 8.95 (dt, J = 5.6, 1.1 Hz, 1H), 8.22 - 8.06 (m,2H), 7.65 (ddd, J = 7.4, 5.6, 1.6 Hz, 1H), 7.56 (dd, J = 19.2, 1.6 Hz, 2H), 1.63 (s, 15H); IR (KBr): 1622, 1474, 1203, 1110, 791cm-1; UV/Vis: λmax 272 nm; ESI-MS (m/z): [M-SO4-H2O-H]+; found, 472.1; Elemental analysis calcd. for C18H24IrN3O5S+H2O: C, 34.83; H, 4.22; N, 6.77. Found: C, 34.74; H, 4.38; N, 6.52.

[Example 1-2] (illustrative, not of the invention)



[0032] The spectral data of the compound represented by the following Formula (23) is presented below.



[0033] 1H NMR (400 MHz, D2O): δ = 8.91 (d, J = 5.7 Hz, 1H), 8.19 - 8.07 (m,2H), 8.04 (d, J = 2.9 Hz, 1H), 7.63 (ddd, J = 7.3, 5.7, 1.9 Hz, 1H), 7.09 (d, J = 2.9 Hz, 1H), 1.63 (s, 15H); IR (KBr):1615, 1458, 1192, 1113, 782cm-1; UV/Vis: λmax 300 nm (shoulder peak); ESI-MS (m/z): [M-SO4-H2O-H]+; found, 472.1; Elemental analysis calcd. for C18H24IrN3O5S+H2O: C, 34.83; H, 4.22; N, 6.77. Found: C, 35.22; H, 4.39; N, 6.85.

[Example 1-3] (illustrative, not of the invention)



[0034] The spectral data of the compound represented by the following Formula (24) is presented below.



[0035] 1H NMR (400 MHz, D2O): δ = 9.11 (d, J = 5.4 Hz, 1H), 8.37 (d, J = 7.8 Hz, 1H), 8.30 (t, J = 7.9 Hz, 1H), 7.91 - 7.75 (m,3H), 7.59 - 7.52 (m,2H), 1.67 (s, 15H); IR (KBr): 1625, 1459, 1118, 1027, 764cm-1; UV/Vis: λmax 330 nm; ESI-MS (m/z): [M-SO4-H2O-H]+; found, 522.1; Elemental analysis calcd. for C22H26IrN3O5S+H2O: C, 39.39; H, 4.21; N, 6.26. Found: C, 39.52; H, 4.19; N, 6.00.

[Example 1-4] (illustrative, not of the invention)



[0036] The spectral data of the compound represented by the following Formula (25) is presented below.

1H NMR (400 MHz, D2O): δ = 7.52 (t, J = 1.6 Hz, 2H), 7.41 (t, J = 1.6 Hz, 2H), 1.67 (s, 15H); UV/Vis: λmax 289 nm; ESI-MS (m/z): [M-SO4-H2O-H]+; found, 461.59.

[Example 1-5] (illustrative, not of the invention)



[0037] The spectral data of the compound represented by the following Formula (26) is presented below.



[0038] 1H NMR (400 MHz, D2O): δ = 2.18 (d, J = 1.4 Hz, 6H), 2.27 (d, J = 1.4 Hz, 6H), 1.57 (d, J = 1.5 Hz, 15H); IR (KBr): 1593, 1193, 1114, 799 cm-1; UV/Vis: λmax 314 nm; ESI-MS(m/z): [M-SO4-H2O-H]+; found, 517.1; Elemental analysis calcd. for C20H31IrN4O5S: C, 38.02; H, 4.95; N, 8.87. Found: C, 38.07; H, 4.78; N, 8.63.

[Example 1-6] (illustrative, not of the invention)



[0039] The spectral data of the compound represented by the following Formula (27) is presented below.



[0040] 1H NMR (400 MHz, D2O): δ = 2.31 (s, 6H), 2.18 (s, 6H), 1.59 (s, 15H); IR (KBr): 1622, 1413, 1140 cm-1; UV/Vis: λmax 317 nm; ESI-MS (m/z): [M-SO4-H2O-H]+; found, 427.1; Elemental analysis calcd. for C20H31RhN4O6S+1.3H2O: C, 42.6; H, 5.65; N, 9.94. Found: C, 42.8; H, 5.68; N, 9.65.

[Example 1-7]



[0041] The spectral data of the compound represented by the Formula (15) is presented below.

[0042] 1H NMR (D2O, 400 MHz): 7.38 (s, 1H), 7.19 (s, 1H), 6.01 (s, 1H), 1.63 (s, 15H). 1H NMR (DMSO-d6, 400 MHz): 10.89 (s, 1H), 7.86 (s, 1H), 7.57 (s, 1H), 6.12 (s, 1H), 1.69 (s, 15H); ESI-MS (+): m/z 505.2 [M-H2O-H]+.

[Example 1-8]



[0043] The spectral data of the compound represented by the Formula (16) is presented below.

[0044] 1H NMR (D2O, 400 MHz):8.68 (d, J = 3.2 Hz, 1H), 8.37 (d, J = 3.2 Hz, 1H), 8.00 (t, J = 4.0 Hz, 1H), 7.42 (d, J = 8 Hz, 1H), 6.98 (t, J = 3.2 Hz, 2H), 1.69 (s, 15H); 13C NMR (D2O, 125 MHz): δ = 164.09, 146.86, 145.24, 143.88, 132.22, 112.45, 110.61, 101.99, 89.77, 8.97. ESI-MS (+): m/z 488.1 [M-H2O-H]+.

[Example 1-9]



[0045] The spectral data of the compound represented by the Formula (17) is presented below.

[0046] 1H NMR (DMSO-d6, 400 MHz): 11.38 (s, 1H), 8.65 (s, 1H), 8.45 (s, 1H), 7.03 (s, 1H), 5.29 (s, 1H), 1.73 (s, 15H); 13C NMR (DMSO-d6, 125MHz): 169.56, 168.59, 145.18, 133.44, 111.97, 96.26, 87.89, 8.83; ESI-MS: 505.1 [M-H2O-H]+. Anal. Calc. for C17H23IrN4O7S·0.5H2O: C 32.48, H 3.85, N 8.91. Found: C 32.62, H 3.63, N 8.66.

[Example 1-10]



[0047] The spectral data of the compound represented by the Formula (18) is presented below.

[0048] 1H NMR (D2O, 400 MHz): δ = 7.38 (s, 1H), 7.19 (s, 1H), 6.01 (s, 1H), 1.63 (s, 15H). 1H NMR (d6-DMSO, 400 MHz): 10.89 (s, 1H), 7.86 (s, 1H), 7.57 (s, 1H), 6.12 (s, 1H), 1.69 (s, 15H). 13C NMR (d6-DMSO, 125 MHz): δ = 168.71, 157.91, 127.47, 123.18, 95.95, 87.73, 84.72, 55.90, 8.99. ESI-MS (+): m/z 505.2 [M-H2O-H]+.

[Example 2] Dehydrogenation reaction of formic acid



[0049] A solution of the complex catalyst represented by the General Formula (1) or (2) in water was degassed. Thus prepared catalyst solution was added to a 1 M degassed solution of formic acid in water (10 mL), followed by stirring with heating. An amount of gas released was measured by means of a gas meter (Shinagawa W-NK-05). A gas component released was measured by means of a gas chromatography GL SCIENCES (GC390), hydrogen was measured by means of a thermal conductivity detector (TCD), and carbon dioxide and carbon monoxide were measured by means of a methanizer and a hydrogen flame ionization detector (FID). As a result, it was found that hydrogen and carbon dioxide were released in a ratio of 1:1, and that carbon monoxide was not able to be detected (equal to or lower than the detection threshold of 10 ppm). From the reaction results presented in Table 1, all catalysts including a ligand containing a 5-membered ring, which were according to the present invention, exhibited a high catalytic activity. As described in NPL 18, in the dehydrogenation reaction of formic acid, it has been found that a catalyst is activated by the electron-donating action of a substituent on a ligand in the catalyst. Based on this finding, the catalyst represented by the General Formula (26), which was obtained by introducing four methyl groups to the catalyst represented by the General Formula (25), exhibited a turnover frequency (TOF: the number of substrate (i.e., formic acid) molecules on which the catalyst acts per 1 molecule of the catalyst per 1 hour) 1.75 times higher than that of the catalyst represented by the General Formula (25). Further, when a strong electron-donating hydroxyl group was introduced, the complex represented by the General Formula (15) in which the hydroxyl group had been substituted exhibited the TOF 5 times or more higher than that of the unsubstituted complex represented by the General Formula (22).
Table 1: Dehydrogenation reaction of formic acid using complex catalyst
Catalyst (Concentration/mM)Concentration of formic acid (M)Time (h)Temperature (°C)TOF (h-1)Turnover number of catalystConversion rate (%)
(22) / 0.5 1 4 60 810 1,970 98
(23) / 0.5 1 7 60 400 2,000 >99
(24) / 0.5 1 6 60 570 2,000 >99
(25) / 0.1 1 5 60 3,980 10,000 100
(26) / 0.1 1 2 60 7,020 10,000 100
(27) / 0.5 2 8 60 250 1,020 26
(26) / 0.1 1 0.5 80 34,000 10,000 100
(15) / 0.1 1 5 60 4,290 10,000 100
(16) / 0.1 1 7 60 2,740 10,000 100
(17) / 0.1 1 3.5 60 5,150 10,000 100
(18) / 0.1 1 7 60 7,050 10,000 100
(19) / 0.1 1 2.5 60 6,300 10,000 100
(20) / 0.1 1 3 60 290 - -
(21) / 0.1 1 3 60 6,620 10,000 100

[Example 3] Dehydrogenation reaction of formic acid



[0050] A solution of the complex catalyst represented by the General Formula (18) in water was degassed. Thus prepared catalyst solution (1 µmol) was added to an 80% degassed solution of formic acid in water (10 mL), followed by stirring with heating. The catalytic reaction proceeded for 150 hours or longer. After the reaction, the formic acid was completely decomposed. A time-dependent change in an amount of a gas released is illustrated in FIG. 1. This complex catalyst was able to exhibit stable catalytic performance without deteriorating for 1 week or longer even in a high-concentration formic acid solution.

[Example 4]



[0051] A solution of the complex catalyst represented by the General Formula (18) in water was degassed. Thus prepared catalyst solution (100 µL, 1 µmol) was added to a 1 M degassed solution of formic acid/sodium formate (100/0 to 0/100) in water (10 mL) of which pH had been adjusted, followed by stirring at 60°C. A pH-dependent change in reaction velocity is illustrated in FIG. 2.

[Example 5]



[0052] An 8 M degassed solution of formic acid in water (50 mL) containing the complex catalyst represented by the General Formula (18) (5 µmol) was placed into a glass autoclave. The reaction container was stirred with heating at 80°C, and amounts and ratios of gases released from a back pressure valve at 2 MPa were measured (FIGs. 3 and 4). As a result, a turnover efficiency of the catalyst was extremely high, i.e., 34,000 times per 1 hour. It was confirmed that hydrogen and carbon dioxide were released in a ratio of approximately 1:1 and that 99% or more of the formic acid was decomposed after the reaction. These results indicate that hydrogen is released without deteriorating the complex catalyst even under severe reaction conditions, that is, in a high-concentration aqueous formic acid solution, at a high temperature of 80°C and high pressure of 2 MPa.

[Comparative Example 1]



[0053] In a dehydrogenation reaction of formic acid using the unsubstituted bipyridine complex catalyst represented by the General Formula (28) (1 M aqueous formic acid solution, reaction temperature: 60°C), the TOF was 30. The catalyst according to the present invention exhibited significantly higher catalytic activity than that value under the same reaction conditions. The complex represented by the General Formula (29), which was an active form of the complex represented by the General Formula (28) obtained by introducing hydroxyl groups to a ligand thereof, had the TOF of 1,800. Therefore, according to the present invention, it has been found that a catalyst exhibiting excellent catalytic performance can be designed only by including a 5-membered ring skeleton on a ligand thereof. In fact, the complex catalyst represented by the General Formula (18) in which a hydroxyl group had been introduced to a ligand thereof exhibited the highest catalytic performance.


[Comparative Example 2]



[0054] The catalyst for dehydrogenation of formic acid represented by the General Formula (30) where R = H or OH described in PTLs 12 and 13 exhibits extremely high reaction velocity under the optimal reaction conditions, that is, in a formic acid solution which has a concentration of 1 M or less and of which pH has been adjusted to 3.5, and at a reaction temperature of 70°C or less. However, the catalytic performance is significantly low under conditions other than the above-described optimal reaction conditions. The conversion rate of formic acid after reaction is low (50%). On the other hand, under severe reaction conditions, that is, in a formic acid solution having a concentration of 2 M or more and/or at a temperature of 80°C or higher, the catalytic performance was significantly deteriorated within 1 hour.


Industrial Applicability



[0055] In the present invention, a metal catalyst which contains a bidentate ligand including an aromatic heterocyclic 5-membered ring having 2 or more nitrogen atoms exhibited extremely high catalytic activity and extremely high durability in production of hydrogen through dehydrogenation of formic acid. Therefore, use of the metal catalyst which contains a bidentate ligand including an aromatic heterocyclic 5-membered ring having 2 or more nitrogen atoms according to the present invention enables to easily and conveniently produce hydrogen from formic acid which can be easily transported and stored. In particular, high pressure hydrogen can be produced through a selective dehydrogenation reaction of formic acid without by-producing carbon monoxide. Therefore, hydrogen can be supplied as fuel for fuel cells without using a gas reformer.


Claims

1. A catalyst used for a dehydrogenation reaction of at least one of formic acid and a formic acid salt, the catalyst having a structure represented by any selected from the group consisting of the following Formulae (13) to (19) and (21):








 
2. A method for producing hydrogen, the method comprising:

allowing a solution comprising at least one of formic acid and a formic acid salt to react in the presence of the catalyst according to claim 1, to thereby dehydrogenate the at least one of formic acid and a formic acid salt.


 


Ansprüche

1. Ein Katalysator, der für eine Dehydrogenierungsreaktion mindestens eines von Ameisensäure und Ameisensäuresalz verwendet wird, wobei der Katalysator ein Salz eines Komplexes ist, das eine Struktur aufweist, die repräsentiert wird durch irgendeine Formel ausgewählt aus der Gruppe bestehend aus den Formeln (13) bis (19) und (21):








 
2. Ein Verfahren zur Herstellung von Wasserstoff, wobei das Verfahren umfasst:

das Reagierenlassen einer Lösung, die mindestens eines von Ameisensäure und Ameisensäuresalz umfasst, in der Gegenwart eines Katalysators nach Anspruch 1, um dadurch das mindestens eine von Ameisensäure und Ameisensäuresalz zu dehydrogenieren.


 


Revendications

1. Catalyseur utilisé pour une réaction de déshydrogénation d'au moins un composé choisi parmi l'acide formique et un sel d'acide formique, le catalyseur représentant un sel d'un complexe dont la structure répond à n'importe quelle formule sélectionnée parmi le groupe constitué par les formules suivantes (13) à (19) et (21) :








 
2. Procédé pour la production d'hydrogène, le procédé comprenant le fait de :

faire réagir une solution comprenant au moins un composé choisi parmi l'acide formique et un sel d'acide formique en présence du catalyseur selon la revendication 1, dans le but de soumettre ainsi à une déshydrogénation ledit au moins un composé choisi parmi l'acide formique et un sel d'acide formique.


 




Drawing









REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description