Dehydrogenation catalysts for polymer precursors and formic acid formed therefrom

Abstract

This invention provides a dehydrogenation catalyst that enables the production of hydrogen by dehydrogenating formic acid using a continuous process with higher efficiency than conventional methods, as well as a polymer precursor that can optimally form the catalyst and a formic acid dehydrogenation catalyst formed therefrom. [Solution] The polymer precursor has a structure represented by the following general formula (1). TIFF2026073992000060.tif50163 (A and B are independently groups comprising a 5-membered or 6-membered heterocycle or oxime structure which may have substituents, Z is a 5-membered or 6-membered aromatic ligand, M is a Group 8 noble metal element, R 1 R is a hydroxyl group, an alkenyl group or alkynyl group having 1 to 12 carbon atoms, 2 (where is a halogen atom, hydrogen atom, formic acid, or water molecule, X is an anion, and n is a natural number between 1 and 12)

Description

Technical Field

[0001] The present invention relates to a dehydrogenation catalyst for dehydrogenating formic acid to obtain hydrogen gas, and particularly to a dehydrogenation catalyst for formic acid that promotes the dehydrogenation reaction with high efficiency even in continuous processing.

Background Art

[0002] In recent years, hydrogen gas has attracted attention as a next-generation fuel, and the realization of a hydrogen society is being aimed at. Hydrogen gas can be used, for example, as fuel for fuel cell vehicles. However, at present, in hydrogen stations for fuel cell vehicles in Japan, the supply cost of high-pressure hydrogen gas is high, so fuel cell vehicles have not been sufficiently popularized.

[0003] From this point, technologies for supplying hydrogen gas at low cost have been actively studied. As such a technology, dehydrogenation catalysts that generate hydrogen gas by dehydrogenating formic acid and formates are known. Such dehydrogenation catalysts are generally composed of iridium complexes.

[0004] For example, as a conventional dehydrogenation catalyst, a dehydrogenation catalyst containing an iridium complex having an amino group such as a dimethylamino group, a diethylamino group, or a pyrrolidine group at the para position (4,4'-position) of a 2,2'-bipyridine ligand or at the 4,7-positions of a 1,10-phenanthroline ligand is known (Patent Document 1).

[0005] Also, for example, as a conventional dehydrogenation catalyst, a mononuclear metal complex represented by the following formula is known (Patent Document 2).

[0006]

Chemical Formula

[0007] In the above formula, Q 1 ~Q 4 is nitrogen or nitrogen and carbon, and X 1 ~X 4is a hydroxy group or the like, and R 1 ~R 9 is a hydrogen atom, an alkyl group or the like, Y is an arbitrary ligand or does not exist, and M is a positive integer, 0, or a negative integer.

[0008] Since the conventional dehydrogenation catalyst described above dissolves in an aqueous formic acid solution or water, which is a reaction solvent, it is premised on batch processing.

[0009] However, in order to produce hydrogen on a large scale using a dehydrogenation catalyst, it is efficient to continuously generate hydrogen from formic acid by continuous processing rather than batch processing. If the above conventional dehydrogenation catalyst is applied to continuous processing, after the use of the dehydrogenation catalyst, a rare metal such as iridium, which is a main component of the catalyst, will flow out together with the solvent. In order to reactivate the dehydrogenation catalyst, an extra cost for recovering iridium will be incurred.

[0010] From the viewpoint of applying the dehydrogenation catalyst to continuous processing, a process of continuously generating hydrogen by packing an insolubilized dehydrogenation catalyst in a column and continuously flowing an aqueous formic acid solution has also been studied (Non-Patent Document 1).

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0012]

Non-Patent Document 1

Disclosure of the Invention

Problems to be Solved by the Invention

[0013] However, while some conventional dehydrogenation catalysts, such as Non-Patent Document 1, are intended for continuous processing, they still have the problem that after use, rare metals such as iridium, which are the main components of the catalyst, leach out with the solvent, requiring extra costs for iridium recovery.

[0014] Furthermore, the optimal raw materials (precursors) for producing dehydrogenation catalysts suitable for continuous processing are not yet known.

[0015] The present invention was made to solve the aforementioned problems, and provides a dehydrogenation catalyst that enables the production of hydrogen by the dehydrogenation reaction of formic acid with higher efficiency than conventional methods, using continuous processing instead of batch processing, and also provides a precursor that can optimally form this dehydrogenation catalyst. [Means for solving the problem]

[0016] The inventors of this invention diligently researched highly efficient dehydrogenation catalysts and discovered a novel dehydrogenation catalyst containing a polymer. They also discovered a novel precursor (polymer precursor) used before solidifying the dehydrogenation catalyst with the polymer, leading to the present invention.

[0017] Thus, the polymer precursor relating to the present application has a structure represented by the following general formula (1).

[0018] [ka]

[0019] In the above formula, A and B are each independently groups comprising a heterocyclic or oxime structure of a 5-membered or 6-membered ring, which may have substituents; Z is a 5-membered or 6-membered aromatic ligand; M is a Group 8 noble metal element; and R 1 R is a hydroxyl group, an alkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms.2 is a halogen atom, a hydrogen atom, formic acid or a water molecule, X is an anion, and n is a natural number from 1 to 12.

[0020] Further, the dehydrogenation catalyst for formic acid according to the present application is formed from the above polymer precursor and contains, as an active ingredient, a complex represented by the following general formula (2) or an isomer thereof.

[0021]

Chemical formula

[0022] In the above formula, A, B, Z, M, R 2 , X, and n are the same as defined in the above general formula (1), and P is a polymer.

Brief Description of the Drawings

[0023] [Figure 1] Shows the mass spectrometry (MS) measurement results of the polymer precursor according to Example 1. [Figure 2] Shows the mass spectrometry (MS) measurement results of the polymer precursor according to Example 1. [Figure 3] Shows the mass spectrometry (MS) measurement results of the polymer precursor according to Example 1.

Modes for Carrying Out the Invention

[0024] (First Embodiment) The polymer precursor according to the first embodiment has a structure represented by the following general formula (1).

[0025]

Chemical formula

[0026] In the above formula, A and B are each independently a group containing a 5-membered or 6-membered heterocyclic ring or an oxime structure which may have a substituent, Z is a 5-membered or 6-membered aromatic ligand, M is a Group 8 noble metal element, R1 R is a hydroxyl group, an alkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms. 2 x is a halogen atom, a hydrogen atom, formic acid, or a water molecule, x is an anion, and n is a natural number between 1 and 12.

[0027] A and B are each independently groups comprising a heterocyclic or oxime structure of a five-membered or six-membered ring, which may have substituents. In the case of a five-membered ring, A and B are preferably combinations of the positions of these three constituent atoms (functional groups), as stable aromaticity is exhibited when the oxygen, sulfur, and / or nitrogen atoms that constitute the constituent atoms (functional groups) are replaced by carbon atoms. Furthermore, in the case of a six-membered ring, A and B are generally preferred as the number of nitrogen atoms decreases, as this increases the electron-donating ability to the metal atoms in the compound, thus allowing the catalytic activity to be fully expressed.

[0028] Furthermore, if A and B are groups that independently contain the oxime structure shown below, since the oxime structure includes a structure in which a strongly electron-donating hydroxyl group is bonded to a nitrogen atom, the nitrogen atom, which enhances the reactivity of the catalyst by donating electrons to a Group 8 noble metal element M (e.g., Ir), becomes even more electron-rich, further increasing the electron-donating ability of the nitrogen atom, thereby activating the reactivity of the catalyst and further enhancing its catalytic capacity.

[0029] [ka]

[0030] The group containing this oxime structure can be substituted with various substituents R as described above. 3 The carbon atoms may be substituted by this R 3For example, carbon atoms may be substituted with lower alkyl groups such as methyl, ethyl, propyl, and butyl groups, or with amino groups such as primary, secondary, and tertiary amino groups. For instance, methyl groups or primary amino groups, which are not sterically bulky and are easy to handle, can be used.

[0031] For these reasons, A and B are preferably selected independently from the group consisting of groups comprising the following heterocyclic or oxime structures, which may have substituents, including ease of handling.

[0032] [ka]

[0033] Z is an aromatic ligand in the form of a five-membered or six-membered ring. In the case of a five-membered ring, Z is preferably a cyclopentadienyl group, in which case the hydrogen of cyclopentadiene is replaced by a metal atom, and two double bonds (four electrons) coordinate to the metal atom. In the case of a six-membered ring, Z is preferably a benzene ring, in which case three double bonds (six electrons) coordinate to the metal atom.

[0034] M is a Group 8 noble metal element and is not particularly limited, but is preferably selected from the group consisting of Ru, Pd, Ir, and Pt, for example, Ir can be used.

[0035] R 1 This group is a hydroxyl group, an alkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms. Examples of this alkenyl group include the ethenyl group, propenyl group, and butadienyl group, and for example, the ethenyl group can be used. Examples of this alkynyl group include terminal alkynes such as the ethynyl group and propagyl group, and for example, the ethynyl group can be used.

[0036] R 2This can be a halogen atom, a hydrogen atom, formic acid, or a water molecule; for example, a halogen atom can be used.

[0037] X is preferably a halogen ion, a nitrate ion, or a sulfate ion. For example, R 2 When is a halogen atom (e.g., a chlorine atom), there are no particular limitations, but X can also be a halogen ion of the same type (e.g., a chloride ion). Also, for example, R 2 While not particularly limited, X can also be a sulfate ion when X is a water molecule.

[0038] n is a natural number between 1 and 12, and since an alkyl chain of a certain length is more preferable, it is preferably a natural number between 2 and 5, and more preferably a natural number between 3 and 5.

[0039] For these reasons, examples of polymer precursors according to this embodiment include the following compounds.

[0040] [ka]

[0041] Using the above polymer precursor, compounds containing various polymers can be synthesized. In particular, the above polymer precursor has excellent dehydrogenation ability of formic acid even on its own (see the examples described later). For this reason, for example, a dehydrogenation catalyst for formic acid can also be produced using the above polymer precursor.

[0042] For example, the formic acid dehydrogenation catalyst according to this embodiment is formed from the above polymer precursor and contains a complex represented by the following general formula (2), or an isomer thereof, as an active ingredient.

[0043] [ka]

[0044] In the above formula, A, B, Z, M, R 2 X and n are the same as defined in the general formula (1) above, and P is a polymer.

[0045] The formic acid treated with the above-mentioned dehydrogenation catalyst also includes formic acid solutions and formate salts.

[0046] P is not particularly limited as long as it is a polymer, but examples include polyethylene, polypropylene, polyamide, polyethylene glycol, polyester, polystyrene, polyethyleneimine, polyurethane, epoxy resin, phenolic resin, melamine resin, and urea resin. Of these, a more preferred polymer is a crosslinked polymer or a thermosetting resin. For example, crosslinked polyethyleneimine (PEI) or crosslinked polystyrene (PS) can be used.

[0047] For the reasons described above, examples of formic acid dehydrogenation catalysts according to this embodiment include the following compounds. In the following chemical formulas containing polymers, m and n indicate the degree of polymerization of the polymer.

[0048] [ka]

[0049] As described above, the formic acid dehydrogenation catalyst according to this embodiment is characterized by a configuration in which polymer P is introduced to the functional group of Z (for example, a cyclopentadienyl group) to make the catalyst insoluble.

[0050] The formic acid dehydrogenation catalyst according to this embodiment has higher durability than a comparative example of a catalyst in which a polymer is introduced into the functional group (electron-donating ligand; for example, a bipyridyl group) of A or B.

[0051] Although this mechanism has not been fully elucidated, focusing on the bonding force of the complex constituent metal M (e.g., Ir), it can be inferred that the bonding force of the complex constituent metal M to the functional group Z (e.g., cyclopentadienyl group) is stronger than the bonding force of the functional group composed of A and B (electron-donating ligand; e.g., bipyridyl group).

[0052] From this, it can be inferred that in the formic acid dehydrogenation catalyst according to this embodiment, polymer P is introduced to the functional group Z (e.g., cyclopentadienyl group) to insolubilize the catalyst, so the complex constituent metal M remains on the insolubilized polymer P and is not cleaved from polymer P by the formic acid aqueous solution, thereby suppressing its leakage with the formic acid aqueous solution.

[0053] In contrast, in the comparative example described above, the catalyst is insolubilized by introducing a polymer to the functional group (electron-donating ligand; e.g., bipyridyl group) composed of A and B. Therefore, when the formic acid aqueous solution is flowed through, the solution around the catalyst becomes acidic, inactivating the functional group (electron-donating ligand; e.g., bipyridyl group) composed of A and B. This causes them to cleave with the complex constituent metal M (e.g., Ir), and further makes it difficult for them to re-bond with the complex constituent metal. It is presumed that the complex constituent metal will then be leached out along with the formic acid aqueous solution.

[0054] In other words, when regenerating the catalyst, the catalyst in the comparative example above requires re-reaction with components containing expensive complex constituent metals (e.g., Ir), but the formic acid dehydrogenation catalyst according to this embodiment only requires reaction with inexpensive functional groups (electron-donating ligands; e.g., bipyridyl groups) composed of A and B.

[0055] As a method for obtaining the formic acid dehydrogenation catalyst according to this embodiment, for example, in the case where polystyrene is introduced as the polymer, the polymer precursor and the halogenated polymer can be combined with a solvent and stirred while applying heat of 100°C or less, as shown in the following chemical reaction equation, to introduce the polymer into the precursor. By washing this polymerized dehydrogenation catalyst with water and an organic solvent, the desired solidified dehydrogenation catalyst can be obtained.

[0056] [ka]

[0057] In addition, as a method for obtaining the dehydrogenation catalyst according to this embodiment, for example, in the case of introducing polyethyleneimine as a polymer, the polymer (polyethyleneimine in this example) can be introduced into the precursor by adding the polymer precursor, polyethyleneimine, and a base (for example, potassium t-butoxide) as shown in the following chemical reaction equation and reacting at 70°C for about 2 days. By washing this polymerized dehydrogenation catalyst with water and an organic solvent, the desired solidified dehydrogenation catalyst can be obtained.

[0058] [ka]

[0059] The formic acid dehydrogenation catalyst obtained in this embodiment can be used to produce hydrogen gas from a formic acid solution or formate salt by the following dehydrogenation reaction.

[0060] [ka]

[0061] (Examples) The following describes embodiments of the present invention, but these embodiments are merely examples and do not limit the present invention.

[0062] (Example 1) Production of polymer precursors and dehydrogenation catalysts (1) Polymer precursors using polystyrene as the polymer were prepared according to the following procedure. Compound identification was performed using the method described below. The polymer precursors were identified using mass spectrometry (MS) and nuclear magnetic resonance (NMR). Mass spectrometry (MS) was performed using a Waters LCT Premier XE to measure the molecular weight of the structure using either the ESI or ASAP method, confirming that the target substance had been synthesized. The structure was determined by NMR (nuclear magnetic resonance analysis) measurements using JEOL ECZ400 and ECS400. The dehydrogenation catalyst solidified with polymer was identified using the solid-state NMR and ICP-MS (inductively coupled plasma mass spectrometry) methods described above. ICP-MS measurements were performed using an Agilent 7900 ICP-MS from Agilent Technologies.

[0063] The compounds and intermediates produced in each example will be referred to by the following categorized abbreviations. • Cx (Catalyst): Polymer precursor • Lx (Low molecular weight compound): A low molecular weight compound that constitutes a polymer precursor. ·Px(Polymer): Dehydrogenation catalyst ·Rx(Reference): Comparative example compound

[0064] [ka]

[0065] (Synthesis of low molecular weight compound L01) According to the above chemical reaction equation, under an Ar atmosphere, metallic lithium (396 mg, 57.1 mmol) was added to 6.5 mL of anhydrous diethyl ether using a three-necked flask fitted with a reflux tubing. 2-bromo-2-butene (4.0 g, 29.6 mmol) was added to this suspension, and reflux was confirmed. Subsequently, 7.5 mL of diethyl ether was added, and the mixture was stirred at room temperature for 1 hour and under reflux for 17 hours. After cooling to room temperature, ε-caprolactone (1.66 g, 14.5 mmol) was added, and the mixture was stirred for 1 hour. After the reaction was complete, 30 mL of saturated ammonium chloride aqueous solution was added, and the mixture was extracted with dichloromethane. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was mixed with 12% hydrochloric acid aqueous solution and stirred at room temperature. After 1 hour, it was extracted with dichloromethane, and the organic layer was dried over magnesium sulfate. The solvent was removed under reduced pressure (2 hPa, 40 °C), and the resulting residue was distilled under reduced pressure to obtain 749 mg (24.6 mmol, 25%) of the low molecular weight compound L01. The obtained compound was confirmed by MS and NMR. The results of the MS measurements are shown in Figure 1. ·m / z = 209[M+1] + · 1 H NMR (DMSO-d6, 400MHz) δ3.64(dt, 2H, J=6.5 Hz, J=1.5 Hz), 2.45-2.72(m, 1H), 2.14-2.16(m, 2H), 1.82(s, 6H), 1.78(s, 6H), 1.32-1.72(m, 6H), 1.00(dd, 2H, J=7.6 Hz, J=3.2 Hz)

[0066] [ka]

[0067] According to the above chemical reaction equation, iridium chloride hydrate (254 mg, 0.85 mmol) was added to 30 mL of a methanol solution of 265 mg (1.27 mmol) of 1-(5-hydroxypentyl)-2,3,4,5-tetramethylcyclopentadiene (low molecular weight compound L01), and the mixture was refluxed overnight. After the reaction was complete, the solvent was removed under reduced pressure. The resulting residue was recrystallized using dichloromethane ether to obtain 188 mg (47%) of low molecular weight compound L02. The obtained compounds were confirmed by MS and NMR. The results of the MS measurements are shown in Figure 2. ·m / z = 941[M+1] + · 1 H NMR (DMSO-d6, 400MHz) δ3.64(dt, 2H, J=6.5 Hz, J=1.5 Hz), 2.14-2.17(m, 2H), 1.63(s, 6H), 1.58(s, 6H), 1.32-1.54(m, 4H), 1.00(dd, 2H, J=7.5 Hz, J=3.0 Hz)

[0068] [ka]

[0069] According to the above chemical reaction equation, 130 mg (0.44 mmol) of 4,4'-dipyrrolidinyl-2,2'-bipyridine was dissolved in 30 mL of methanol. Subsequently, 188 mg (0.2 mmol) of 1-(5-hydroxypentyl)-2,3,4,5-tetramethylcyclopentadiene iridium dichloride dimer (low molecular weight compound L02) was added, and the mixture was refluxed for 17 hours. After the reaction was complete, the solvent was removed under reduced pressure to obtain 157 mg of polymer precursor C01. The obtained compound was confirmed by MS and NMR. The results of the MS measurements are shown in Figure 3. · m / z = 730[M] + · 1H NMR (DMSO-d6, 400MHz) δ8.22(d, 2H, J=6.8 Hz), 7.43(s, 2H), 6.70(d, 2H, J=6.8 Hz), 3.54(m, 2H), 3.30(m, 8H), 2.14-2.17(m, 2H), 2.00(m, 8H), 1.82(s, 6H), 1.78(s, 6H), 1.35-1.65(m, 4H), 1.01(t, 2H, J=7.7 Hz)

[0070] [ka]

[0071] (Synthesis of low molecular weight compound L03) According to the above chemical reaction equation, under an Ar atmosphere, 2.67 g (110 mmol) of metallic Mg was added to 10 mL of anhydrous THF using a three-necked flask fitted with a reflux tubing. Four drops of 1,2-dibromoethane were added to this suspension to activate the metallic Mg. Subsequently, 100 mL of 10 mL (ca. 100 mmol) of 4-bromo-1-butene-THF solution was added while maintaining reflux, and after the addition was complete, the mixture was stirred at room temperature for another hour. The reaction mixture was cooled to 0 °C, and 12 mL (ca. 80 mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone was added and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, 90 mL of 4 N hydrochloric acid was added and the mixture was stirred for 4 hours. After the reaction was complete, the mixture was extracted with heptane, and the organic layer was washed with saturated NaCO3 aqueous solution and saline solution. The obtained organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by column chromatography (SiO2, heptane) to obtain 12.5 g (89%) of the low molecular weight compound L03. ·m / z = 177[M+1] + · 1 H NMR (CDCl3, 400MHz) δ5.71-5.89(m, 1H), 4.86-5.05(m, 2H), 2.01-2.51(m, 2H), 1.51-1.82(m, 12H), 0.96-1.06(m, 3H)

[0072] [ka]

[0073] (Synthesis of low molecular weight compound L04) 8.8 g (50 mmol) of the above low molecular weight compound L03 was added to 41.5 mL of anhydrous THF and cooled to 0 °C. 125 mL of 0.5 M 9-borabicyclo[3.3.1]nonane was added and the mixture was stirred at room temperature. After 1 hour, the mixture was cooled to 0 °C, and 20 mL of 3 M NaOH aqueous solution and 20 mL of 30% H2O2 aqueous solution were added and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, 63 mL of water was added and potassium carbonate was added until the solution was homogeneous. Subsequently, the mixture was extracted with diethyl ether, and the organic layer was washed with water and saline solution. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure, and the resulting residue was distilled under reduced pressure to obtain 8.18 g (84%, bp 120 °C, 20 Pa) of low molecular weight compound L04. ·m / z = 195[M+1] + · 1 H NMR (CDCl3, 400MHz) δ3.56-4.14(m, 2H), 2.00-2.06(m, 1H), 1.75-1.82(m, 6H), 1.51-1.55(m, 6H), 0.99-1.02(m, 1H), 0.96(d, 2H, J=6.8Hz)

[0074] [ka]

[0075] (Synthesis of low molecular weight compound L05) 353 mg (1.0 mmol) of iridium chloride hydrate and 311 mg (1.6 mmol) of the low molecular weight compound L04 were added to 2 mL of t-butyl alcohol. After degassing with Ar, the mixture was stirred at room temperature to confirm the formation of bubbles, and then stirred at 75 °C for 24 hours. After the reaction was complete, the solvent was removed under reduced pressure. The resulting residue was washed with diethyl ether to obtain 366 mg (80%) of the low molecular weight compound L05. · m / z = 912[M] + · 1 H NMR (DMSO-d6, 400MHz) δ3.35-3.38(m, 4H), 2.01-2.03(m, 4H), 1.62(s, 12H), 1.59 (s, 12H), 1.38-1.47(m, 8H)

[0076] [ka]

[0077] (Synthesis of polymer precursor CO2) 91 mg (0.1 mmol) of the above low molecular weight compound L05 and 51 mg (0.21 mmol) of 4,4'-diamino-2,2'-bipyridine were added to 4 mL of DMF and stirred at room temperature for 4 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 99 mg (77%) of polymer precursor C02.

[0078] [ka]

[0079] (Synthesis of polymer precursor C03) 91 mg (0.1 mmol) of the above low molecular weight compound L05 and 50.9 mg (0.21 mmol) of 4,4'-bis(dimethylamino)-2,2'-bipyridine were added to 4 mL of DMF and stirred at room temperature for 1 hour. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 112.2 mg (80.1%) of polymer precursor C03. · m / z = 663[M] + · 1H NMR (DMSO-d6, 400MHz) δ8.23(d, 2H, J=6.9 Hz), 7.56(d, 2H, J=2.8 Hz), 6.84(dd, 2H, J=6.9 Hz, J=2.8 Hz), 3.34-3.35(m, 2H), 3.18(s, 6H), 1.75-2.01(m, 2H), 1.58(s, 12H), 1.40-1.41(m, 4H)

[0080] [ka]

[0081] (Synthesis of polymer precursor C04) 152 mg (0.17 mmol) of the low molecular weight compound L05 and 108 mg (0.37 mmol) of 4,4'-bis(pyrrolidine-1-yl)-2,2'-bipyridine were added to 3 mL of methanol and stirred at room temperature for 1 hour. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 147 mg (59%) of polymer precursor C04.

[0082] [ka]

[0083] (Synthesis of polymer precursor C05) 91 mg (0.1 mmol) of the low molecular weight compound L05 and 31 mg (0.21 mmol) of 2-(1H-imidazole-2-yl)pyridine were added to 4 mL of DMF and stirred at room temperature for 3.5 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether and extracted with dichloromethane. The organic layer was desoldered to obtain 16 mg (13%) of the polymer precursor C05. · m / z = 566 [M] + · 1H NMR(DMSO-d6, 400 MHz) δ8.87(d, 1H, J=5.3 Hz), 8.41(d, 1H, J=7.9 Hz), 8.23(dt, 1H, J=7.9 Hz, J=1.3 Hz), 7.81(d, 1H, J=1.4 Hz), 7.62-7.66(m, 2H), 3.34(m, 2H), 2.08-2.11(m, 2H), 1.67-1.68(m, 12H), 1.41-1.44(m, 4H)

[0084] [ka]

[0085] (Synthesis of polymer precursor C06) 91 mg (0.1 mmol) of the low molecular weight compound L05 and 28 mg (0.2 mmol) of 2,2'-biimidazole were added to 2 mL of methanol and stirred at room temperature for 3.5 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 59 mg (50%) of polymer precursor C06. m / z = 555 [M] + · 1 H NMR(DMSO-d6, 400 MHz) δ7.61(d, 2H, J=0.2 Hz), 7.56(d, 2H, J=0.2 Hz), 3.37-3.41 (m, 2H), 2.14-2.17(m, 2H), 1.70(s, 6H), 1.70(s, 6H), 1.40-1.45(m, 4H)

[0086] [ka]

[0087] (Synthesis of polymer precursor C07) 137 mg (0.15 mmol) of the low molecular weight compound L05 and 38 mg (0.32 mmol) of dimethylglyoxime were added to 3 mL of methanol and stirred at room temperature for 20 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 161 mg (94%) of polymer precursor C07.

[0088] [ka]

[0089] (Synthesis of polymer precursor C08) 91 mg (0.1 mmol) of the low molecular weight compound L05 and 25 mg (0.21 mmol) of diaminoglyoxime were added to 4 mL of DMF and stirred at room temperature for 1.5 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether and dichloromethane and extracted with ethanol. The solvent was removed to obtain 56 mg (97%) of the polymer precursor C08. · m / z = 539[M] + · 1 H NMR(DMSO-d6, 400 MHz) δ7.61(br, 4H), 3.31-3.42(m, 2H), 2.08-2.11(m, 2H), 1.67 (s, 6H), 1.65(s, 6H), 1.35-1.43(m, 4H)

[0090] [ka]

[0091] (Synthesis of low molecular weight compound L06) Under an Ar atmosphere, 0.535 g (22 mmol) of metallic Mg was added to 2 mL of anhydrous THF using a two-necked flask fitted with a reflux tubing. A small piece of iodine was added to this suspension to activate the metallic Mg. Subsequently, 16 mL of 2.67 mL (approx. 20 mmol) of 6-bromo-1-hexane-THF solution was added while maintaining reflux, and after the addition was complete, the mixture was stirred at room temperature for another hour. The reaction mixture was cooled to 0 °C, and 2.4 mL (approx. 16 mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone was added, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, 18 mL of 4 N hydrochloric acid was added, and the mixture was stirred for another 4 hours. After the reaction was complete, the mixture was extracted with heptane, and the organic layer was washed with saturated NaCO3 aqueous solution and saline solution. The resulting organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by column chromatography (SiO2, heptane) to obtain 2.94 g (90%) of the low molecular weight compound L06. ·m / z = 205[M+1] + · 1 H NMR (DMSO-d6, 400MHz) δ5.75-5.85(m, 1H), 4.89-5.01(m, 2H), 3.25-3.60(m, 3H), 1.95-2.02(m, 2H), 1.60-1.61(m, 6H), 1.58(s, 6H), 1.14-1.47(m, 6H)

[0092] [ka]

[0093] (Synthesis of low molecular weight compound L07) 1.92 g (9.4 mmol) of the above low molecular weight compound L06 was added to 9.4 mL of anhydrous THF and cooled to 0 °C. 28.8 mL of 0.5 M 9-borabicyclo[3.3.1]nonane was added, and the mixture was stirred at room temperature for 10 minutes, then stirred at 40 °C for 16 hours. After that, the mixture was cooled to 0 °C and 0.6 mL of water was added. Subsequently, 3.8 mL of 3 M NaOH aqueous solution and 4.2 mL of 30% H2O2 aqueous solution were added and the mixture was stirred at room temperature for 20 hours. After the reaction was complete, the mixture was extracted with diethyl ether, the organic layer was washed with water and saline solution, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by column chromatography (SiO2, heptane) to obtain 1.39 g (66%) of the low molecular weight compound L07. ·m / z = 223[M+1] + · 1 H NMR (DMSO-d6, 400MHz) δ3.33(s, 1H), 3.22(s, 12H), 1.62-1.60(m, 12H), 1.38-1.26(m, 1H)

[0094] [ka]

[0095] (Synthesis of low molecular weight compound L08) 705 mg (2 mmol) of iridium chloride hydrate and 712 mg (3.2 mmol) of the low molecular weight compound L07 were added to 4 mL of t-butyl alcohol. After degassing with Ar, the mixture was stirred at room temperature to confirm the formation of bubbles, and then stirred at 75 °C for 24 hours. After the reaction was complete, the solvent was removed under reduced pressure. The resulting residue was washed with diethyl ether to obtain 0.55 g (57%) of the low molecular weight compound L08. ·m / z = 970[M+1] + · 1 H NMR (DMSO-d6, 400MHz) δ3.26-3.35(m, 4H), 1.99-2.03(m, 4H), 1.61-1.64(m, 12H), 1.58(s, 12H), 1.23-1.46(m, 16H)

[0096] [ka]

[0097] (Synthesis of polymer precursor C09) 96.9 mg (0.1 mmol) of the low molecular weight compound L08 and 50.9 mg (0.21 mmol) of 4,4'-bis(dimethylamino)-2,2'-bipyridine were added to 4 mL of DMF and stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 118 mg (81%) of polymer precursor C09. · m / z = 691[M] + · 1 H NMR(DMSO-d6, 400 MHz) δ8.24(d, 1H, J=6.9 Hz) 7.57(d, 1H, J=3.5 Hz), 6.84(dd, 1H, J=6.9 Hz, J=2.8 Hz), 3.26-3.33(m, 2H), 3.18(s, 6H), 1.76-1.99(m, 2H), 1.58(s, 12H), 1.19-1.45(m, 8H)

[0098] [ka]

[0099] (Synthesis of low molecular weight compound L09) Under an Ar atmosphere, 1.34 g (55 mmol) of metallic Mg was added to 5 mL of anhydrous THF using a two-necked flask fitted with a reflux tubing. A small piece of iodine was added to this suspension to activate the metallic Mg. Subsequently, 40 mL of 8-bromo-1-octane 8.6 mL (approx. 50 mmol)-THF solution was added while maintaining reflux, and after the addition was complete, the mixture was stirred at room temperature for another hour. The reaction mixture was cooled to 0 °C, and 6.4 mL (approx. 40 mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone was added and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, 45 mL of 4 N hydrochloric acid was added and the mixture was stirred for 16 hours. After the reaction was complete, the mixture was extracted with heptane, and the organic layer was washed with saturated NaCO3 aqueous solution and saline solution. The resulting organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by column chromatography (SiO2, heptane) to obtain 7.59 g (82%) of the low molecular weight compound L09. ·m / z = 233[M+1] + · 1 H NMR (DMSO-d6, 400MHz) δ5.73-5.83(m, 1H), 4.88-4.98(m, 2H), 1.99-2.04(m, 2H), 1.74-1.79(m, 10H), 1.25-1.37(m, 10H), 0.94-1.00(m, 3H)

[0100] [ka]

[0101] (Synthesis of low molecular weight compound L10) 4.4 g (18.8 mmol) of low molecular weight compound L09 was added to 19 mL of anhydrous THF and cooled to 0 °C. 56 mL of 0.5 M 9-borabicyclo[3.3.1]nonane was added, and the mixture was stirred at room temperature for 10 minutes, then stirred at 40 °C for 16 hours. After that, the mixture was cooled to 0 °C and 1.2 mL of water was added. Subsequently, 7.5 mL of 3 M NaOH aqueous solution and 7.6 mL of 30% H2O2 aqueous solution were added and the mixture was stirred at room temperature for 20 hours. After the reaction was complete, the mixture was extracted with diethyl ether, the organic layer was washed with water and saline solution, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by column chromatography (SiO2, heptane) to obtain 3.71 g (79%) of low molecular weight compound L10. ·m / z = 251[M+1] + · 1 H NMR (CDCl3, 400MHz) δ3.63(t, 2H, J=6.76 Hz), 2.06-2.63(m, 1H), 1.81(s, 6H), 1.77(s, 6H), 1.26-1.61(m, 12H), 1.00(q, 1H, J = 5.7 Hz), 0.99(q, 1H, J=8.5 Hz)

[0102] [ka]

[0103] (Synthesis of low molecular weight compound L11) 705 mg (2 mmol) of iridium chloride hydrate and 801 mg (3.2 mmol) of low molecular weight compound L10 were added to 4 mL of t-butyl alcohol. After degassing with Ar, the mixture was stirred at room temperature to confirm the formation of bubbles, and then stirred at 75 °C for 24 hours. After the reaction was complete, the solvent was removed under reduced pressure. The resulting residue was washed with diethyl ether to obtain 0.36 g (70%) of low molecular weight compound L11. · m / z = 1025[M] + · 1H NMR (DMSO-d6, 400MHz) δ3.31-3.34(m, 4H), 1.99-2.03(t, 6H), 1.74-1.77(m, 6H), 1.61(s, 12H) 1.59(s, 16H) 1.06(s, 12H)

[0104] [ka]

[0105] (Synthesis of polymer precursor C10) 103 mg (0.1 mmol) of the low molecular weight compound L11 and 50.9 mg (0.21 mmol) of 4,4'-bis(dimethylamino)-2,2'-bipyridine were added to 4 mL of DMF and stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 131 mg (86%) of polymer precursor C10. · m / z = 719[M] + · 1 H NMR (DMSO-d6, 400 MHz) δ8.24(d, 1H, J=6.8 Hz), 7.55(d, 1H, J=2.9 Hz), 6.84(dd, 1H, J=6.8 Hz, J=2.9 Hz), 3.32-3.35(m, 2H), 3.18(s, 12H), 1.76-1.98(m, 2H), 1.58(s, 6H), 1.57(s, 6H), 1.20-1.35(m, 8H)

[0106] [ka]

[0107] (Synthesis of polymer precursor C11) 51 mg (0.05 mmol) of the low molecular weight compound L11 and 18.6 mg (0.16 mmol) of dimethylglyoxime were added to 1 mL of methanol and stirred at room temperature for 16 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 37.2 mg (59%) of the polymer precursor C11. · m / z = 275 [M+1] + · 1 H NMR(DMSO-d6, 400MHz) δ3.32(t, 2H, J=6.6 Hz), 2.59(s, 1H), 2.30 (s, 3H), 1.99-2.11(m, 2H), 1.88(s, 2H), 1.59-1.67(m, 12H), 1.15-1.40(m, 12H)

[0108] [ka]

[0109] (Synthesis of polymer precursor C12) 51 mg (0.05 mmol) of the low molecular weight compound L11 and 25 mg (0.21 mmol) of diaminoglyoxime were added to 2 mL of methanol and stirred at room temperature for 16 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 42.4 mg (76%) of polymer precursor C12. · m / z = 275 [M+1] + · 1 H NMR(DMSO-d6, 400MHz) δ7.83(br, 4H), 3.36-3.43(m, 2H), 2.09-2.13(m, 2H), 1.70(s, 6H), 1.68(s, 6H), 1.20-1.39(m, 12H)

[0110] [ka]

[0111] (Synthesis of polymer precursor C13) 51 mg (0.05 mmol) of low molecular weight compound L11 and 15 mg (0.08 mmol) of 4,4'-bis(dimethylamino)-2,2'-bipyridine were added to 2 mL of DMF and stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 54.5 mg (75%) of polymer precursor C13. · m / z = 275 [M+1] + · 1 H NMR(DMSO-d6, 400MHz)d8.17-8.19(d, 2H, J=6.8 Hz), 7.19-7.20(d, 2H, J=2.5 Hz), 6.76-6.78(dd, 2H, J=6.5 Hz, J=2.4 Hz), 3.38-3.35(m, 2H), 1.97-2.00(m, 2H), 1.60(s, 6H), 1.59(s, 6H), 1.10-1.43(m, 12H)

[0112] [ka]

[0113] (Synthesis of low molecular weight compound L12) Under an Ar atmosphere, 0.534 g (22 mmol) of metallic Mg was added to 2 mL of anhydrous THF using a two-necked flask fitted with a reflux tubing. A small piece of iodine was added to this suspension to activate the metallic Mg. Subsequently, 16 mL of 4.6 mL (approx. 20 mmol) of 11-bromo-1-undecene solution in THF was added while maintaining reflux, and after the addition was complete, the mixture was stirred at room temperature for another hour. The reaction mixture was cooled to 0°C, and 2.41 mL (approx. 16 mmol) of 2,3,4,5-tetramethyl-2-cyclopentenone was added and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, 18 mL of 4 N hydrochloric acid was added and the mixture was stirred for 16 hours. After the reaction was complete, the mixture was extracted with heptane, and the organic layer was washed with saturated NaCO3 aqueous solution and saline solution. The resulting organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The resulting residue was purified by column chromatography (SiO2, heptane) to obtain 1.75 g (40%) of the low molecular weight compound L12. ·m / z=275 [M+1] + · 1 H NMR(CDCl3, 400 MHz) δ5.87(m, 1H), 4.91-5.02(m, 2H), 2.01-2.07(m, 1H), 1.29-1.57(m, 12H), 1.18-1.26(m, 15H), 0.84-1.04(m, 2H)

[0114] [ka]

[0115] (Synthesis of low molecular weight compound L13) 1.51 g (5.5 mmol) of low molecular weight compound L12 was added to 6 mL of anhydrous THF and cooled to 0 °C. 17 mL of 0.5 M 9-borabicyclo[3.3.1]nonane was added, and the mixture was stirred at room temperature for 10 minutes, then stirred at 40 °C for 16 hours. After that, the mixture was cooled to 0 °C and 0.5 mL of water was added. Subsequently, 2.2 mL of 3 M NaOH aqueous solution and 2.2 mL of 30% H2O2 aqueous solution were added and the mixture was stirred at room temperature for 20 hours. After adding 9 mL of water, 11 g of potassium carbonate was added and the mixture was stirred. After the reaction was complete, the mixture was extracted with diethyl ether, the organic layer was washed with water and saline solution, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by column chromatography (SiO2, dichloromethane) to obtain 0.636 g (40%) of low molecular weight compound L13. ·m / z = 293 [M+1] + · 1 H NMR (CDCl3, 400MHz) δ3.64(t, 2H, J=6.6 Hz), 1.77-1.96(m, 1H), 1.18-1.60(m, 30H)

[0116] [ka]

[0117] (Synthesis of low molecular weight compound L14) 423 mg (1.2 mmol) of iridium chloride hydrate and 562 mg (1.92 mmol) of low molecular weight compound L13 were added to 2.4 mL of t-butyl alcohol. After degassing with Ar, the mixture was stirred at room temperature to confirm the formation of bubbles, and then stirred at 75 °C for 24 hours. After the reaction was complete, the solvent was removed under reduced pressure. The resulting residue was washed with diethyl ether to obtain 0.177 g (27%) of low molecular weight compound L14. ·m / z=1110 [M+1] + · 1H NMR (DMSO-d6, 400MHz) δ3.33(t, 2H, J=6.5Hz), 1.99-2.03(m, 2H), 1.62(s, 6H), 1.59(s, 6H), 1.18-1.25(m, 18H)

[0118] [ka]

[0119] (Synthesis of polymer precursor C14) 111 mg (0.1 mmol) of the low molecular weight compound L14 and 51 mg (0.21 mmol) of 4,4'-bis(dimethylamino)-2,2'-bipyridine were added to 4 mL of DMF and stirred at room temperature for 2 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with diethyl ether to obtain 131 mg (79%) of polymer precursor C14. ·m / z=761 [M] + · 1 H NMR (DMSO-d6, 400MHz) δ8.24(d, 2H, J=7.0 Hz), 7.55(d, 2H, J=2.7 Hz), 6.84 (dd, 2H, J=7.0 Hz, J=2.7 Hz), 3.30-3.37(m, 2H), 3.26(s, 6H), 1.58(s, 6H), 1.57(s, 6H), 1.16-1.23(m, 18H)

[0120] Synthesis of cross-linked polyethyleneimine (PEI)

[0121] [ka]

[0122] 2.13 g of polyethylene and 573 mg of 1,3-dibromopropane were added to a pressure vessel with 2.04 g of water and heated at 130°C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, added to liquid nitrogen, and pulverized. The resulting powder was washed with water, ethanol, and dichloromethane to obtain 1.29 g of a yellow solid.

[0123] Synthesis of polymer-introduced dehydrogenation catalysts

[0124] [ka]

[0125] Next, following the chemical reaction equation above, 19.2 mg (0.4 mmol) of sodium hydride was added to 10 mL of 153 mg (0.2 mmol) of polymer precursor C01-THF under a nitrogen atmosphere. The mixture was stirred at 60 °C for 1 hour. The reaction mixture was cooled to room temperature, 200 mg (0.4 mmol Cl) of chloromethyl polystyrene was added, and the mixture was stirred overnight at 60 °C. After the reaction was complete, the mixture was poured into 50 mL of water and filtered. The residue was further washed with 20 mL x 3 of methanol to obtain 150 mg of dehydrogenation catalyst P01.

[0126] [ka]

[0127] 14 mg (0.02 mmol) of polymer precursor C03, 17 mg of PEI, and 2.2 mg (0.02 mmol) of potassium t-butoxide were added to 2 mL of THF and stirred at 70 °C for 24 hours. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with ethanol to obtain 23.7 mg of dehydrogenation catalyst P02.

[0128] [ka]

[0129] 15 mg (0.02 mmol) of polymer precursor C04, 17 mg of PEI, and 2.2 mg (0.02 mmol) of potassium t-butoxide were added to 2 mL of THF and stirred at 70 °C for 2 days. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with ethanol to obtain 12 mg of dehydrogenation catalyst P03.

[0130] [ka]

[0131] 12 mg (0.02 mmol) of polymer precursor C06, 17 mg of PEI, and 2.2 mg (0.02 mmol) of potassium t-butoxide were added to 2 mL of THF and stirred at 70 °C for 2 days. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with ethanol to obtain 18 mg of dehydrogenation catalyst P04.

[0132] [ka]

[0133] 12 mg (0.02 mmol) of polymer precursor C08, 17 mg of PEI, and 2.2 mg (0.02 mmol) of potassium t-butoxide were added to 2 mL of THF and stirred at 70 °C for 2 days. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with ethanol to obtain 20 mg of dehydrogenation catalyst P05.

[0134] [ka]

[0135] 14.5 mg (0.02 mmol) of polymer precursor C09, 17 mg of PEI, and 2.2 mg (0.02 mmol) of potassium t-butoxide were added to 2 mL of THF and stirred at 70 °C for 2 days. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with ethanol to obtain 23.3 mg of dehydrogenation catalyst P06.

[0136] [ka]

[0137] 15 mg (0.02 mmol) of polymer precursor C10, 17 mg of PEI, and 2.2 mg (0.02 mmol) of potassium t-butoxide were added to 2 mL of THF and stirred at 70 °C for 2 days. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with ethanol to obtain 21 mg of dehydrogenation catalyst P07.

[0138] [ka]

[0139] 16 mg (0.02 mmol) of polymer precursor C14, 17 mg of PEI, and 2.2 mg (0.02 mmol) of potassium t-butoxide were added to 2 mL of THF and stirred at 70 °C for 2 days. After the reaction was complete, the mixture was concentrated under reduced pressure. The resulting residue was washed with ethanol to obtain 21 mg of dehydrogenation catalyst P08.

[0140] (Comparative Example 1) A conventional dehydrogenation catalyst was produced as a comparative example using the following procedure.

[0141] [ka]

[0142] According to the above chemical reaction equation, 398 mg (0.5 mmol) of 1,2,3,4,5-pentamethylcyclopentadienyliridium dichloride dimer and 312 mg (1 mmol) of silver(II) sulfate were added to 3.5 mL of water and stirred at room temperature for 18 hours. After the reaction was complete, the resulting precipitate was filtered. The obtained filtrate was dried under reduced pressure to obtain 349 mg (73%) of comparative example compound R01. The structure of the obtained compound was confirmed by MS and NMR.

[0143] [ka]

[0144] 2.13 g of PEI and 0.64 g (2.84 mmol) of 4,4'-dichloro-2,2'-bipyridine were added to a pressure vessel with 2.04 g of water and heated at 130 °C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, added to liquid nitrogen, and pulverized. The resulting powder was washed with water, ethanol, and dichloromethane to obtain 1.68 g of comparative compound R02.

[0145] [ka]

[0146] 600 mg of comparative compound R02 was added to 10 mL of an aqueous solution of comparative compound R01 containing 11.6 mg (24.3 μmol), and the mixture was stirred overnight at room temperature. After the reaction was complete, the solid was filtered off. The obtained solid was washed with water, ethanol, and dichloromethane to obtain 512 mg of comparative compound R03.

[0147] (Example 3) First, 88% formic acid was diluted to prepare a 3 M formic acid aqueous solution, and 20 mL of 3 M formic acid and 2 μmol of catalyst were added to a 30 mL Schlenk tube. An exhaust pipe was attached to the Schlenk tube, and a digital flow meter was connected with a rubber tube. The Schlenk tube containing the formic acid and catalyst was heated to 80 °C to carry out the dehydrogenation reaction. The amount of gas generated per minute during the reaction was measured, and the point at which the gas generation rate stabilized after a certain period of time was defined as the catalyst characteristic.

[0148] [Table 1]

[0149] (Example 4) The irr content of polymer-introduced irr complexes was investigated using ICP-MS. First, the sample was weighed, a 60% nitric acid aqueous solution was added, and the mixture was heated at 220 °C for 15 minutes while irradiating with microwaves. After cooling to room temperature, water was added to the residue to make a total volume of 50 mL. The irr content of the prepared solution was measured by ICP-MS.

[0150] [Table 2]

[0151] (Example 5) Based on the results obtained in Example 4, the catalyst was weighed out so that the Ir content was 1 μmol, and the dehydrogenation reaction was carried out in the same manner as in Example 3. For comparison, the comparative compound R03 was also subjected to the same dehydrogenation reaction.

[0152] [Table 3]

[0153] Both the polymer precursor of Example 3 and the polymer compound of Example 5 were confirmed to exhibit high catalytic properties. The materials obtained by the present invention show high dehydrogenation ability compared to existing materials, and by solidifying the polymer precursor with a polymer, a catalyst that can be repeatedly used as a catalyst can be provided.

Claims

1. A polymer precursor characterized by having a structure represented by the following general formula (1). 【Chemistry 1】 （１） (wherein A and B are each independently groups comprising a five-membered or six-membered heterocycle or oxime structure which may have substituents, Z is a five-membered or six-membered aromatic ligand, M is a Group 8 noble metal element, R １ R is a hydroxyl group, an alkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms. ２ (where is a halogen atom, a hydrogen atom, formic acid, or a water molecule, X is an anion, and n is a natural number between 1 and 12)

2. The polymer precursor according to claim 1, characterized in that M is selected from the group consisting of Ru, Pd, Ir, and Pt.

3. The polymer precursor according to claim 1, characterized in that A and B are each independently selected from the group consisting of groups comprising the following heterocyclic or oxime structures, which may have substituents. 【Chemistry 2】

4. The polymer precursor according to claim 1, characterized in that Z is a cyclopentadienyl group or a benzene ring.

5. A dehydrogenation catalyst for formic acid, characterized in that it is formed from a polymer precursor according to any one of claims 1 to 4 and contains a complex represented by the following general formula (2), or an isomer thereof, as an active ingredient. 【Transformation 3】 (In the formula, A, B, Z, M, R ２ X and n are the same as defined in the general formula (1) above, and P is a polymer.

6. The dehydrogenation catalyst for formic acid according to claim 5, characterized in that P is selected from the group consisting of polyethylene, polypropylene, polyamide, polyethylene glycol, polyester, polystyrene, polyethyleneimine, polyurethane, epoxy resin, phenolic resin, melamine resin, and urea resin.

7. The dehydrogenation catalyst for formic acid according to claim 5, characterized in that X is a halogen ion, a nitrate ion, or a sulfate ion.

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