CN112547123B

CN112547123B - Ir catalyst, preparation method and application thereof, and method for preparing hydrogen by using Ir catalyst

Info

Publication number: CN112547123B
Application number: CN201910854929.3A
Authority: CN
Inventors: 周小春; 白闯
Original assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Current assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority date: 2019-09-10
Filing date: 2019-09-10
Publication date: 2023-05-26
Anticipated expiration: 2039-09-10
Also published as: CN112547123A

Abstract

The invention provides an Ir catalyst, a preparation method and application thereof, and a method for preparing hydrogen by using the Ir catalyst. The Ir catalyst provided by the invention can realize the efficient hydrogen production by using methanol at a lower temperature (30-100 ℃) and normal pressure without adding an organic solvent and a strong alkaline substance, and the prepared gas mixture has low CO content (less than 10 ppm) and is beneficial to the utilization of subsequent gas products.

Description

Ir catalyst, preparation method and application thereof, and method for preparing hydrogen by using Ir catalyst

Technical Field

The invention belongs to the technical field of new energy, and relates to an Ir catalyst, a preparation method and application thereof, and a method for preparing hydrogen by using the Ir catalyst.

Background

The hydrogen energy is used as a high-efficiency and clean energy form, and is more and more concerned in the fields of national production and scientific research, but the low-temperature storage and preparation of hydrogen are the problems to be solved urgently for the long-term large-scale application of the hydrogen energy. Methanol is used as a hydrogen carrier, the hydrogen content can reach 12.5wt%, and the methanol is low in price and convenient to store and transport, is an ideal hydrogen source, and can provide a great arm help for the use of portable hydrogen energy.

At present, the mode of obtaining hydrogen from methanol mainly comprises the steps of preparing hydrogen by reforming methanol, and the mode of preparing hydrogen by using methanol and water as reaction raw materials can not only reduce the reaction activation energy from methanol to hydrogen, but also can additionally enable water to be a hydrogen source, so that the atom utilization rate is greatly improved. The current art has mainly used supported solid phase catalysts of metals or metal alloys for methanol reforming to produce hydrogen, such as Rozovskii et al (Topics in Catalysis,2003,22 (3-4): 137-150) using Cu-based catalysts to achieve methanol and CO ₂ Conversion between CO. Lin et al (Nature, 2017,544 (7648):80) have utilized Pt/alpha-MoC to achieve a stable methanol reforming hydrogen production reaction at 150-190 ℃. Although the heterogeneous catalysis of the methanol reforming hydrogen production has achieved some results, the methanol reforming hydrogen production approach still has the advantages of high working temperature and high CO content in the gas>1%) and the like, which can make such techniques difficult to obtain in portable, gentle situationsTo the application. At present, the technology of homogeneously catalyzing methanol reforming hydrogen production by using a metal complex catalyst has the advantages of high selectivity and low reaction temperature. For example, campos et al (Inorganic chemistry,2015,54 (11): 5079-5084) found that Ir azaheterocyclic compounds can be used to effect methanol reforming reactions at 90℃with the aid of a strong base. Fujita et al (Angewandte Chemie International Edition,2015,54 (31): 9057-9060) found that bipyridyl compounds of Ir can achieve efficient methanol reforming hydrogen production reactions with the assistance of small amounts of strong bases at temperatures below 100 ℃.

Because strong base substances still have inconvenience in application in portable and mild hydrogen production scenes, a new Ir catalyst is desired to be developed to expand the application of Ir, and the purpose of hydrogen production can be realized under the assistance of weak base at a lower reaction temperature by the catalyst.

Disclosure of Invention

The invention aims to provide an Ir catalyst, a preparation method and application thereof, and a method for preparing hydrogen by using the Ir catalyst. The Ir catalyst provided by the invention has the advantages of simple preparation method and higher yield. The method for preparing hydrogen provided by the invention can realize the aim of high-efficiency hydrogen production at the reaction temperature of about 80 ℃ under the assistance of weak base.

To achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides an Ir catalyst comprising a compound having the structure of formula I and/or formula II:

wherein R is ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from-H, alkoxy, alkyl, aryl, acetyl or cyclopentadienyl.

R ₆ 、R ₁₁ Each independently selected from the group consisting of-H, -OH, -COOH, alkylidenethiol, alkylideneamine alkyl, pyrrolyl and derivatives thereof, imidazolyl and derivatives thereof, thienyl and derivatives thereof, and thiazolyl and derivatives thereof.

R ₇ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₂ 、R ₁₃ 、R ₁₄ Each independently selected from the group consisting of-H, -OH, -COOH, -SH, -NH ₂ 、-NO ₂ Halogen, alkoxy or alkyl.

X is Cl ^- 、NH ₃ 、H ₂ O、OTf ^- 、SO ₄ ^2- Or NO ₃ ^- Any one or a combination of at least two of these.

n is 1 or 2, m is an integer from 0 to 3, such as 0, 1, 2, 3, etc.

In the present invention, the alkoxy group is-OR and R is an alkyl group.

The alkylene mercapto is-R-SH, and R is alkylene.

The alkylene amine group is-R-NH ₂ R is an alkylene group.

The alkylene aminoalkyl group is-R _a -NH-R _b ，R _a Is alkylene, R _b Is alkyl.

The Ir catalyst provided by the invention can realize the aim of efficiently producing hydrogen at the reaction temperature of about 80 ℃ under the assistance of weak base.

For the cyclopentadiene ring and the derivative ligand thereof, the resonance stable anion structure of the cyclopentadiene ring is mainly utilized to coordinate with the Ir metal core and provide a good coordination precursor, and the cyclopentadiene ring with different substituents has certain difference in specific catalytic performance, but the main functions are unchanged, so the examples of the invention are only to be illustrative.

Preferably, said R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from-H, C1-C5 alkoxy, C1-C5 alkyl, phenyl, acetyl or cyclopentadienyl, further preferably-H-OCH ₃ 、-CH ₃ 、-CH ₂ CH ₃ Phenyl, acetyl or cyclopentadienyl.

Preferably, said R ₆ 、R ₁₁ Each independently selected from the group consisting of-H, -OH, -COOH, C1-C5 alkylmercapto, C1-C5 alkylamino, C1-C5 alkyleneaminoalkyl, pyrrolyl and derivatives thereof, imidazolyl and derivatives thereof, thienyl and derivatives thereof, and thiazolyl and derivatives thereof, further preferred are-H, -OH, -COOH, -CH ₂ SH、-CH ₂ NH ₂ 、-CH ₂ NHCH ₃ Pyrrolyl and its derivatives, imidazolyl and its derivatives, thienyl and its derivatives, or thiazolyl and its derivatives.

Preferably, said R ₇ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₂ 、R ₁₃ 、R ₁₄ Each independently selected from the group consisting of-H, -OH, -COOH, -SH, -NH ₂ 、-NO ₂ (R) -Cl, C1-C5 alkoxy or C1-C5 alkyl, more preferably-H, -OH, -COOH, -SH, -NH ₂ 、-NO ₂ 、-Cl、-OCH ₃ or-CH ₃ 。

In the present invention, the C1-C5 may be C1, C2, C3, C4, C5, etc.

In a second aspect, the present invention provides a method for preparing the Ir catalyst according to the first aspect, comprising the steps of:

the Ir catalyst precursor reacts with pyridine ligands and/or pyrimidine ligands to obtain the Ir catalyst.

Wherein, the Ir catalyst precursor has the following structure:

the pyridine ligand has the following structure:

the pyrimidine ligand has the following structure:

R ₁ -R ₁₄ is the same as the definition of the first aspect.

Preferably, the mass ratio of the total amount of pyridine-based ligand and/or pyrimidine-based ligand to the Ir catalyst precursor is (0.5-5): 1, e.g. 0.8:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, etc.

Preferably, the temperature of the reaction is 0 to 100 ℃, for example, 10 ℃,20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃, etc., more preferably 25 to 80 ℃.

Compared with the prior art which generally adopts a solvent and needs to reach the reflux temperature of the solvent, the Ir catalyst can be prepared in a wider temperature range, and can be introduced into a constant temperature oven or react at room temperature by utilizing the characteristic of reflux condensation, and can be prepared in the oven by using a flat bottom container.

Preferably, the reaction time is from 10min to 24h, for example 1h, 3h, 5h, 7h, 9h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, etc., further preferably from 2 to 12h.

Preferably, the reaction is carried out in a solvent.

Preferably, the solvent is selected from polar organic solvents and/or water.

Preferably, the polar organic solvent is methanol and/or ethanol.

Pure water can be selected as a solvent, and the Ir catalyst can be successfully prepared under the conditions of no organic solvent addition and room temperature preparation temperature, so that the method is environment-friendly and saves resources.

Preferably, in the reaction system, a base is also included.

The invention can make Ir catalyst preparation successful in the presence of alkali or alkali-free, and if a certain amount of alkali is added, the reaction can be promoted, so that the preparation reaction can be more thoroughly carried out in a relatively short time.

Preferably, the molar amount of the base is 0.2 to 10 times, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, etc., preferably 0.8 to 1.8, e.g., 0.9, 1.0, 1.2, 1.4, 1.6, etc., times that of the pyridine-based ligand and/or pyrimidine-based ligand.

When the ligand is pyridine ligand, the alkali dosage is 0.2-10 times of pyridine ligand, when the ligand is pyrimidine ligand, the alkali dosage is 0.2-10 times of pyrimidine ligand, when the ligand is combination of pyridine ligand and pyrimidine ligand, the alkali dosage is 0.2-10 times of total mass of pyridine ligand and pyrimidine ligand,

preferably, the base is selected from organic bases and/or inorganic bases.

Preferably, the organic base is selected from any one or a combination of at least two of ammonia, tetramethylammonium hydroxide or triethylamine.

Preferably, the inorganic base is selected from any one or a combination of at least two of sodium hydroxide, potassium carbonate or sodium carbonate.

Preferably, the preparation method of the Ir catalyst precursor comprises the following steps:

and (3) reacting chloroiridium acid with cyclopentadiene derivatives to obtain the Ir catalyst precursor.

Preferably, the reaction is carried out under a protective atmosphere.

Preferably, the protective atmosphere is nitrogen.

Preferably, the molar ratio of chloroiridium acid to cyclopentadiene derivative is 1 (0.5-3), such as 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:2.8, etc., further preferably 1 (0.8-2.5), such as 1:0.9, 1:1, 1:1.5, 1:1.8, 1:2, 1:2.3, etc.

Preferably, the reaction is carried out in a solvent.

Preferably, the solvent is anhydrous methanol.

Preferably, the reaction temperature of the reaction is 55-85 ℃, e.g., 58 ℃, 64 ℃, 69 ℃, 73 ℃, 78 ℃, 83 ℃ and the like, and the reaction time is 24-48 hours, e.g., 26 hours, 32 hours, 38 hours, 47 hours and the like.

In a third aspect, the present invention provides the use of an Ir catalyst according to the first aspect for the preparation of hydrogen.

Preferably, the starting material for the preparation of hydrogen is selected from compounds with hydroxyl and/or carbonyl groups.

The Ir catalyst provided by the invention has certain catalytic hydrogen production capacity on common compounds containing hydroxyl and/or carbonyl.

Preferably, the raw material is selected from any one or a combination of at least two of methanol, formic acid, ethanol, isopropanol, glucose or formaldehyde; formic acid and/or methanol are more preferable, and methanol is still more preferable.

In a fourth aspect, the present invention provides a method for preparing hydrogen from methanol, the method using a catalyst comprising the Ir catalyst of the first aspect.

Meanwhile, the Ir catalyst provided by the invention has certain catalytic hydrogen production capacity on general compounds containing hydroxyl and/or carbonyl, so that in the method for preparing hydrogen by utilizing methanol, hydroxyl or carbonyl impurities commonly contained in the methanol cannot influence the catalytic performance of the Ir catalyst, namely the Ir catalyst provided by the invention cannot have the phenomenon of catalyst poisoning and deactivation.

Preferably, the method comprises the steps of:

an aqueous methanol solution containing a basic substance is mixed with the Ir catalyst of the first aspect and reacted to obtain hydrogen.

Preferably, the amount of the substance of the Ir catalyst is 1-100000ppm, such as 10, 100, 500, 1000, 2000, 5000, 8000, 10000, 50000, 80000, etc., more preferably 100-10000ppm, of the amount of the methanol substance.

Preferably, the concentration of the methanol in the reaction system is 0.2 to 24.6M, for example, 1M, 5M, 7M, 8M, 9M, 10M, 12M, 14M, 15M, 18M, 20M, 22M, 24M, etc., and further preferably 7.68 to 24.6M.

Preferably, the basic compound is added in an amount of 0.2 to 300 times, such as 1, 10, 20, 40, 50, 60, 80, 150, 200, 250, etc., more preferably 0.5 to 100 times, the amount of the substance of the Ir catalyst.

Preferably, the basic compound comprises an inorganic base and/or an organic base.

Preferably, the inorganic base comprises potassium hydroxide and/or sodium hydroxide.

Preferably, the organic base comprises tetramethylhydroxylamine and/or triethylamine.

Compared with the prior art that only strong alkali or even a large amount of strong alkali can be used as a catalyst in the homogeneous methanol reforming hydrogen production, the invention can use strong alkali or weak alkali to realize the efficient hydrogen production by using methanol under the condition of lower temperature.

Preferably, the reaction is carried out in a closed environment.

Preferably, the reaction temperature of the reaction is 30 to 150 ℃, for example, 40 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃, 110 ℃, 140 ℃, etc., further preferably 60 to 100 ℃.

The Ir catalyst provided by the invention can realize high-efficiency hydrogen production at a lower temperature (30-100 ℃) and normal pressure without adding an organic solvent and a strong alkaline substance, and the prepared gas mixture has low CO content (less than 10 ppm), thereby being beneficial to the utilization of subsequent gas products.

As a preferred technical solution, the method comprises the following steps:

in a closed environment, heating a methanol aqueous solution containing an alkaline compound and having a methanol concentration of 0.2-24.6M to 30-150 ℃, adding the Ir catalyst according to claim 1 or 2, mixing and reacting to obtain hydrogen.

Wherein the amount of the Ir catalyst substance is 1-100000ppm of the methanol substance.

The addition amount of the basic compound is 0.2 to 300 times the amount of the substance of the Ir catalyst.

Compared with the prior art, the invention has the following beneficial effects:

(1) The Ir catalyst provided by the invention can realize the efficient hydrogen production by using methanol at a lower temperature (30-100 ℃) and normal pressure without adding an organic solvent and a strong alkaline substance, and the prepared gas mixture has low CO content (less than 10 ppm) and is beneficial to the utilization of subsequent gas products.

(2) The Ir catalyst provided by the invention has certain catalytic hydrogen production capacity on general compounds containing hydroxyl and/or carbonyl, so that in the method for preparing hydrogen by utilizing methanol, hydroxyl or carbonyl impurities commonly contained in the methanol cannot influence the catalytic performance of the Ir catalyst, namely the Ir catalyst provided by the invention cannot have the phenomenon of catalyst poisoning and deactivation.

(3) In the process of preparing hydrogen by utilizing methanol, the TOF (within 0.5 h) of the catalyst can reach 490h at most by adopting the Ir catalyst ^-1 The above.

Drawings

FIG. 1 is a graph showing the peak contrast of the CO gas chromatograph.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

Preparation example 1

An Ir catalyst A-1 has the following structure:

the preparation method comprises the following steps:

(1) Preparing a precursor:

0.10mmol of chloroiridic acid and 750. Mu.L (0.15 mmol) of pentamethylcyclopentadiene are added to 6mL of absolute methanol under nitrogen protection, and the mixture is refluxed for 37h under stirring at a constant temperature of 65 ℃. Cooling the reacted mixtureFiltering after reaching 0 ℃, washing the obtained solid by using anhydrous diethyl ether, and drying in vacuum to obtain a reddish brown solid product [ Cp x IrCl ] ₂ ] ₂ 。

¹ H NMR(400MHz,DMSO-d6):δ＝1.63(s,1H).

(2) Preparation of Ir catalyst:

29.4mg (0.037 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 7.8mg (0.08 mmol) of 2-hydroxypyridine and 4.7mg (0.08 mmol) of KOH were added and stirred for 4h at constant temperature of 25 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 32.7mg of a yellow solid product in 89.8% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝11.56(s,1H),7.44-7.38(m,1H),7.35(d,J＝6.1Hz,1H),6.30(d,J＝9.2Hz,1H),6.15(t,J＝6.6Hz,1H),1.63(s,15H).

Preparation example 2

An Ir catalyst A-2 has the following structure:

the preparation method comprises the following steps:

(1) Ir catalyst [ Cp ] IrCl was prepared using the precursor prepared in preparation example 1 ₂ ] ₂ ；

(2) 31.0mg (0.039 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 11.0mg (0.09 mmol) of 2-pyridinecarboxylic acid and 5.2mg (0.09 mmol) of KOH were added and stirred for 4 hours at a constant temperature of 25 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 33.2mg of a yellow solid product in 87.7% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝8.81(d,J＝5.5Hz,1H),8.14(t,J＝8.3Hz,1H),7.90(d,J＝7.6Hz,1H),7.80-7.75(m,1H),1.63(s,15H).

Preparation example 3

An Ir catalyst A-3 has the following structure:

the preparation method comprises the following steps:

(2) 49.9mg (0.06 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of water under nitrogen, 18.3mg (0.13 mmol) of 6-hydroxy-2-pyridinecarboxylic acid was added and stirred for 8h at a constant temperature in an oil bath at 25 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 59.5mg of a yellow solid product in 94.8% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝7.27(dd,J＝8.7,6.6Hz,1H),6.51(dd,J＝6.6,1.3Hz,1H),6.30(dd,J＝8.7,1.2Hz,1H),1.67(s,15H).

Preparation example 4

The only difference from preparation example 3 is that in this preparation example, water was replaced with the same volume of absolute ethanol.

Preparation example 5

The only difference from preparation example 4 is that in this preparation example, the reaction temperature is 80 ℃.

Preparation example 6

The difference from preparation example 5 is that in this preparation example the constant temperature oil bath is replaced by a constant temperature oven.

Preparation example 7

The only difference from preparation example 3 is that in this preparation example, the preparation method is as follows:

65.5mg (0.08 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 25.9mg (0.18 mmol) of 6-hydroxy-2-pyridinecarboxylic acid and 11.9mg (0.20 mmol) of KOH were added and stirred for 4h at a constant temperature in an oil bath at 25 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 79.2mg of a yellow solid product in 96.2% yield.

Preparation example 8

An Ir catalyst A-4 has the following structure:

the preparation method comprises the following steps:

54.6mg (0.11 mmol) of the Ir catalyst obtained in preparation 3 are dissolved in 10mLCH under nitrogen ₂ Cl ₂ In this, 18.7mg (0.11 mmol) of AgNO was added ₃ Stirring for 0.5h at constant temperature of 25 ℃. After the reaction was completed, the resulting off-white precipitate was filtered off, and the filtrate was dried by spin-drying in vacuo to give 49.8mg of an orange-yellow solid product in 86.6% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝8.03-7.96(m,1H),7.38(d,J＝7.0Hz,1H),7.17(d,J＝8.1Hz,1H),1.66(s,15H).

Preparation example 9

An Ir catalyst A-5 has the following structure:

the preparation method comprises the following steps:

(2) 38.4mg (0.05 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 14.7mg (0.10 mmol) of 6-amino-2-pyridinecarboxylic acid and 6.2mg (0.10 mmol) of KOH were added and stirred for 4h at a constant temperature of 25 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 41.5mg of a yellow solid product in 86.0% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝7.70-7.64(m,1H),7.07(d,J＝7.1Hz,1H),7.02(d,J＝8.4Hz,1H),6.42(s,2H),1.58(s,15H).

Preparation example 10

An Ir catalyst A-6 has the following structure:

the preparation method comprises the following steps:

(2) 32.4mg (0.04 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 13.0mg (0.09 mmol) of 5-hydroxy-2-pyridinecarboxylic acid and 5.98mg (0.10 mmol) of KOH were added and stirred for 4 hours at a constant temperature of 25 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 29.6mg of a yellow solid product in 72.7% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝11.29(s,1H),8.26(d,J＝2.5Hz,1H),7.72(d,J＝8.6Hz,1H),7.46(dd,J＝8.6,2.5Hz,1H),1.61(s,15H).

PREPARATION EXAMPLE 11

An Ir catalyst A-7 has the following structure:

the preparation method comprises the following steps:

(2) 33.0mg (0.04 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of absolute ethanol under nitrogen, 18.0mg (0.08 mmol) of 5-bromo-6-hydroxypyridine-2-carboxylic acid was added, and the mixture was refluxed with stirring at a constant temperature of 80℃for 8h. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 38.0mg of a yellow solid product in 79.0% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝7.77(d,J＝7.3Hz,1H),6.44(d,J＝7.3Hz,1H),1.63(s,11H).

Preparation example 12

An Ir catalyst A-8 has the following structure:

the preparation method comprises the following steps:

(2) 34.3mg (0.04 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolving in 8mL of absolute ethanol under the protection of nitrogen, adding 14.8mg (0.08 mmol) of 2, 6-pyridine dicarboxylic acid, heating in a constant temperature oven at 80 ℃ for 8 hours (the reaction is carried out in a sealed flat-bottom glass bottle when the constant temperature oven is used as a heating source, and the reaction is carried out) under the protection of nitrogen, cooling to 0 ℃ and filtering, washing the obtained solid by using cold methanol, and vacuum drying to obtain 35.8mg of yellow solid product with the yield of 77.4 percent.

¹ H NMR(400MHz,DMSO-d6):δ＝8.20-8.15(m,1H),7.94(d,J＝7.9Hz,2H),1.57(s,15H).

Preparation example 13

An Ir catalyst A-9 has the following structure:

the preparation method comprises the following steps:

(1) The precursor was prepared by the method of preparation example 1, except that R ₁ -R ₅ to-Ph (phenyl) to obtain precursor [5Ph-Cp ] IrCl ₂ ] ₂ 。

¹ H NMR(400MHz,DMSO-d6):δ＝5.29-4.94(m,25H)。

(2) 62.4mg (0.04 mmol) [5Ph-Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of absolute ethanol under nitrogen, 13mg (0.09 mmol) of 6-hydroxy-2-pyridinecarboxylic acid was added, and the mixture was heated in an oil bath at a constant temperature of 80℃for 12 hours. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 47.4mg of a solid product in 64.5% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝7.85(m,1H),7.31(d,J＝7.3Hz,1H),7.08(d,J＝7.9Hz,1H),4.57(m,25H).

PREPARATION EXAMPLE 14

An Ir catalyst A-10 has the following structure:

the preparation method comprises the following steps:

(1) The precursor was prepared by the method of preparation example 1, except that R ₁ -R ₅ to-H to obtain precursor [5H-Cp ] IrCl ₂ ] ₂ 。

₁ H NMR(400MHz,DMSO-d6):δ＝5.7-5.0(m,5H)。

(2) 32.5mg (0.05 mmol) of [5H-Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of absolute ethanol under nitrogen protection, 14.5mg (0.10 mmol) of 6-hydroxy-2-pyridinecarboxylic acid was added, and the mixture was heated in an oil bath at a constant temperature of 80℃for 8 hours. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 36.5mg of a solid product in 78.9% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝8.12(m,1H),7.49(d,J＝6.8Hz,1H),7.32(d,J＝7.7Hz,1H),5.8(s,5H).

Preparation example 15

An Ir catalyst A-11 has the following structure:

the preparation method comprises the following steps:

(2) 31.9mg (0.04 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 11.2mg (0.09 mmol) of pyrimidine-2-carboxylic acid and 5.2mg (0.09 mmol) of KOH were added and stirred for 5h at constant temperature of 25 ℃. The mixture after the reaction was cooled to 0℃and filtered, the resulting solid was washed with cold methanol and dried in vacuo to give 35.1mg of a solid productThe yield was 90.2%.

¹ H NMR(400MHz,DMSO-d6):δ＝9.26(d,J＝6.5Hz,1H),7.85(t,J＝8.2Hz,1H),8.76(d,J＝7.2Hz,1H),1.64(s,15H).

PREPARATION EXAMPLE 16

An Ir catalyst A-12 has the following structure:

the preparation method comprises the following steps:

(2) 39.6mg (0.05 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 15.7mg (0.10 mmol) of 4, 6-dihydroxypyrimidine-2-carboxylic acid and 5.8mg (0.10 mmol) of KOH were added and stirred for 5 hours at a constant temperature of 25℃in an oil bath. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 47.7mg of a solid product in 92.6% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝4.81(s,1H),4.44(s,1H),1.66(s,15H).

Preparation example 17

An Ir catalyst A-13 has the following structure:

the preparation method comprises the following steps:

(2) 39.1mg (0.05 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 14.0mg (0.10 mmol) of 3-hydroxy-2-pyridinecarboxylic acid was added, and the mixture was stirred for 10 hours at a constant temperature of 80 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 44.5mg of a solid product in 90.5% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝12.89(s,1H),8.36(d,J＝4.6Hz,1H),7.68-7.59(m,2H),1.63(s,12H).

PREPARATION EXAMPLE 18

An Ir catalyst A-14 has the following structure:

the preparation method comprises the following steps:

(2) 31.9mg (0.04 mmol) of [ Cp ] IrCl ₂ ] ₂ Dissolved in 8mL of anhydrous methanol under nitrogen, 12.5mg (0.09 mmol) of 4-hydroxy-2-pyridinecarboxylic acid and 5.7mg (0.10 mmol) of KOH were added and stirred for 5 hours at a constant temperature in an oil bath at 25 ℃. The mixture after the reaction was cooled to 0 ℃ and filtered, and the resulting solid was washed with cold methanol and dried in vacuo to give 25.6mg of solid product in 64.0% yield.

¹ H NMR(400MHz,DMSO-d6):δ＝11.92(s,1H),8.45(d,J＝6.3Hz,1H),7.21(d,J＝2.8Hz,1H),7.08(dd,J＝6.3,2.9Hz,1H),1.61(s,15H).

The reaction conditions for preparation examples 1-18 are shown in Table 1:

TABLE 1

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According to the preparation example and the structural characterization, the Ir catalyst is successfully prepared, the reaction temperature range of the Ir catalyst is wider, the number of optional solvents is more, the Ir catalyst can be successfully prepared under the condition that alkaline substances exist or not, and the yield is more than 64 percent, and can be up to more than 98 percent.

Meanwhile, the preparation method can carry out the reaction in a constant temperature environment (such as a constant temperature oven), so that the preparation method can simultaneously carry out a plurality of groups of reactions, and the yield is reduced, but the reaction batches can be increased, and the yield of single batch is improved.

The following examples are examples of hydrogen production using the Ir catalysts provided in preparations 1-18.

Example 1

A method for preparing hydrogen by using methanol comprises the following steps:

transferring 3.8mL of a mixed solution of methanol containing sodium hydroxide and water into a 15mL round-bottom flask, connecting a U-shaped pipe and keeping the reaction device sealed; after the temperature was raised to 57℃in an oil bath at constant temperature and the reaction was stabilized for 10 minutes, 100. Mu.L of an aqueous solution of catalyst A-3 was injected into the reaction mixture, and the reaction mixture was reacted at constant temperature with stirring with a magnet, wherein [ MeOH ] =8.61M, [ A-3] =3.23 mM, and [ NaOH ] =4.68 mM.

Example 2

transferring 3.9mL of a mixed solution of methanol and water containing sodium carbonate into a 15mL round-bottom flask, connecting a U-shaped pipe and keeping the reaction device sealed; heating the oil bath at constant temperature to 78 ℃, stabilizing for 10min, injecting 100 mu L of aqueous solution of catalyst A-2 into the system, and finally adding [ MeOH ] into the reaction solution]＝23.2M，[A-2]＝0.50mM，[Na ₂ CO ₃ ]＝1.58mM。

Example 3

transferring 3.9mL of a mixed solution of methanol and water containing sodium carbonate into a 15mL round-bottom flask, connecting a U-shaped pipe and keeping the reaction device sealed; heating to 68deg.C with constant temperature oil bath, stabilizing for 10min, injecting 100 μl of aqueous solution of catalyst A-6 into the system, and adding MeOH into the final reaction solution]＝23.2M，[A-6]＝0.50mM，[Na ₂ CO ₃ ]＝1.58mM。

Example 4

3.9mL of a mixed solution of methanol and water containing sodium carbonate was removed to a 15mL round bottom flaskA U-shaped tube was connected and kept sealed. After the constant temperature oil bath is heated to 78 ℃, 100 mu L of aqueous solution of catalyst A-5 is injected into the system, and the [ MeOH ] in the final reaction solution]＝23.2M，[A-5]＝0.50mM，[Na ₂ CO ₃ ]＝1.58mM。

Example 5

3.9mL of a mixed solution of methanol and water containing triethylamine was removed to a 15mL round bottom flask, a U-shaped tube was attached and the reaction apparatus was kept sealed. After the temperature of the oil bath was raised to 57 ℃, 100 μl of an aqueous solution of catalyst a-3 was injected into the system, and [ MeOH ] =23.2M, [ a-3] =0.50 mM, and [ triethylamine ] =9.02 mM were contained in the final reaction solution.

Example 6

3.9mL of methanol solution containing tetramethylammonium hydroxide was removed into a 15mL round bottom flask, a U-tube was attached and the reaction apparatus was kept sealed. After the temperature of the oil bath was raised to 78 ℃, 100 μl of a methanol solution of catalyst a-3 was injected into the system, and [ MeOH ] =24.6M, [ a-3] =0.50 mM, and [ tetramethylammonium hydroxide ] =1.18 mM were contained in the final reaction solution.

Performance test 1

The method for producing hydrogen provided in examples 1-6 was characterized as follows:

(1) TOF of catalyst (0.5 h): the reaction is carried out at constant temperature under the stirring of a magnet, the gas type and the content in the system are tested by gas chromatography (TCD and FID) during the reaction, the change of the gas volume in the system is tested by a U-shaped tube, and TOF (h) of the catalyst in 0.5h is calculated according to the following formula ^-1 )；

Wherein V (H) ₂ ) L is the volume of hydrogen measured; v (V) _RT The volume of the gas is 1mol at room temperature, and the volume is 24L at 20 ℃; t is the reaction time, h; n is n _cat The amount of the catalyst used, mol.

The test results are shown in Table 2:

TABLE 2

According to the embodiment and the test result, when the Ir catalyst provided by the invention is used as a catalyst of a methanol hydrogen production process, alkali in the hydrogen production process can be selected as weak alkali, the concentration of the alkali is low, and in the hydrogen production process, the alkali can play a role by providing certain alkali, and the hydrogen production process does not need to be performed by adopting strong alkali.

Example 7

3.9mL of a mixed solution of methanol and water containing sodium carbonate was removed to a 15mL round bottom flask, a U-shaped tube was attached and the reaction apparatus was kept sealed. Heating the oil bath at constant temperature to 57 ℃, stabilizing for 10min, injecting 100 mu L of aqueous solution of catalyst A-3 into the system, and finally adding [ MeOH ] into the reaction solution]＝4.61M，[A-3]＝0.50mM，[Na ₂ CO ₃ ]＝7.20mM。

Examples 8 to 12

The difference from example 7 is only that in this example, the concentration of methanol was 12.3M (example 8), 15.4M (example 9), 20.9M (example 10), 23.2M (example 11), 24.4M (example 12).

Example 13

3.9mL of a mixed solution of methanol and water containing sodium carbonate was removed to a 15mL round bottom flask, a U-shaped tube was attached and the reaction apparatus was kept sealed. Heating the oil bath at constant temperature to 78 ℃, stabilizing for 10min, injecting 100 mu L of aqueous solution of catalyst A-3 into the system, and finally adding [ MeOH ] into the reaction solution]＝3.20M，[A-3]＝0.50mM，[Na ₂ CO ₃ ]＝1.58mM。

Examples 14 to 17

The difference from example 13 is only that in this example, the concentration of methanol was 12.3M (example 14), 15.4M (example 15), 20.9M (example 16), 23.2M (example 17).

Performance test 2

Examples 7-17 were characterized with reference to performance test 1 and the results are shown in Table 3:

TABLE 3 Table 3

Sample of	Temperature/. Degree.C	Methanol concentration/M	Alkali dosage/mM	TOF/h ^-1
					Example 7	57	4.61	7.20	0.598
Example 8	57	12.3	7.20	2.20
					Example 9	57	15.4	7.20	2.26
Example 10	57	20.9	7.20	1.51
					Example 11	57	23.2	7.20	0.77
Example 12	57	24.4	7.20	0.76
					Example 13	78	3.08	1.58	1.44
Example 14	78	12.3	1.58	21.9
					Example 15	78	15.4	1.58	57.8
Example 16	78	20.9	1.58	77.9
					Example 17	78	23.2	1.58	377

The embodiment and the performance test show that the concentration of the reaction raw materials has a certain influence on the performance of the Ir catalyst provided by the invention for catalyzing methanol to prepare hydrogen, and the hydrogen preparation efficiency is higher when the concentration of the methanol is in the range of 7.68-24.6M.

Example 18

The only difference from example 17 is that in this example the reaction temperature was 47 ℃ (example 18), 57 ℃ (example 19), 68 ℃ (example 20), 72 ℃ (example 21), 74 ℃ (example 22), 89 ℃ (example 23).

Performance test 3

Examples 18-23 were characterized with reference to performance test 1 and the results are shown in Table 4:

TABLE 4 Table 4

Sample of	Temperature/. Degree.C	TOF/h ^-1
			Example 18	47	1.84
Example 19	57	8.22
			Example 20	68	14.1
Example 21	72	24.0
			Example 22	74	156
Example 23	89	491

From the examples and the test results, in the present invention, the performance of the catalyst for catalyzing the reforming of methanol to prepare hydrogen is improved with the increase of the reaction temperature, and the TOF of the catalyst is close to 500h at 89 DEG C ^-1 In the present invention, the reaction temperature is preferably in the range of 60 to 100℃in view of the possibility that the increase in temperature may waste resources on the one hand and may cause the catalyst to be decomposed or the structure to be changed on the other hand.

Example 24

The only difference from example 17 is that in this example, methanol was replaced with ethanol and the ethanol concentration was 16.1M.

Example 25

The only difference from example 17 is that in this example methanol was replaced with isopropanol and the isopropanol concentration was 12.3M.

Example 26

The only difference from example 17 is that in this example, methanol was replaced with glucose and the glucose concentration was 0.63M.

Example 27

The only difference from example 17 is that in this example methanol was replaced with formaldehyde and the formaldehyde concentration was 13.6M.

Example 28

The only difference from example 27 is that in this example, the formaldehyde concentration is 2.88M.

Example 29

The only difference from example 17 is that in this example methanol was replaced with formic acid and the formic acid concentration was 0.15M.

Example 30

The difference from example 29 is only that in this example, the formic acid concentration is 0.33M.

Performance test 4

Examples 24-30 were characterized with reference to performance test 1 and the results are shown in Table 5:

TABLE 5

The example and the test result show that the Ir catalyst provided by the invention has certain catalytic hydrogen production capacity on common compounds containing hydroxyl and/or carbonyl, and has higher catalytic performance on formic acid than methanol.

Therefore, in the method for preparing hydrogen by using methanol, hydroxy or carbonyl impurities commonly contained in the methanol cannot influence the catalytic performance of the Ir catalyst, namely the Ir catalyst provided by the invention cannot be subjected to the phenomenon of catalyst poisoning and deactivation.

Example 31:

transferring 3.9mL of a mixed solution of methanol and water containing NaOH into a 15mL round-bottom flask, connecting a U-shaped pipe and keeping the reaction device sealed; after the temperature of the oil bath was raised to 78 ℃, 100 μl of an aqueous solution of catalyst a-9 was injected into the system, and [ MeOH ] =23.2M, [ a-9] =0.31 mM, and [ NaOH ] =1.58 mM were reacted at constant temperature with stirring with a magnet in the final reaction solution.

Example 32:

the difference from example 31 was only that the aqueous solution of a-9 was replaced with the aqueous solution of a-10, and [ a-10] =0.58 mM in the final reaction solution.

Example 33:

3.9mL of a mixed solution of methanol and water containing sodium carbonate was removed to a 15mL round bottom flask, a U-shaped tube was attached and the reaction apparatus was kept sealed. After the constant temperature oil bath is heated to 78 ℃, 100 mu L of aqueous solution of catalyst A-11 is injected into the system, and the [ MeOH ] in the final reaction solution]＝23.2M，[A-11]＝0.51mM，[Na ₂ CO ₃ ]＝1.58mM。

Example 34:

the difference from example 33 is only that the aqueous solution of a-11 was replaced with the aqueous solution of a-12, and [ a-12] =0.48 mM in the final reaction solution.

Example 35:

3.8mL of a mixed solution of methanol and water containing sodium carbonate was removed to a 15mL round bottom flask, a U-shaped tube was attached and the reaction apparatus was kept sealed. After the constant temperature oil bath is heated to 57 ℃, 100 mu L of aqueous solution of catalyst A-13 is injected into the system, and the [ MeOH ] in the final reaction solution]＝8.83M，[A-13]＝1.0mM，[Na ₂ CO ₃ ]=117 mM, and reacted at constant temperature with stirring with a magnet.

Example 36:

remove 3.9mL of sodium carbonateMixed solution of methanol and water into a 15mL round bottom flask, a U-tube was connected and the reaction apparatus was kept sealed. After the constant temperature oil bath is heated to 68 ℃, 100 mu L of aqueous solution of the catalyst A-14 is injected into the system, and the [ MeOH ] in the final reaction solution]＝23.2M，[A-14]＝0.50mM，[Na ₂ CO ₃ ]=1.58 mM, and the reaction was incubated under magnetic stirring.

Example 37:

the only difference from example 36 is that in this example the reaction temperature was 78 ℃.

Performance test 5

Examples 31-37 were characterized with reference to performance test 1 and the results are shown in Table 6:

TABLE 6

According to the embodiment and the performance test, the Ir catalyst provided by the invention can be used in the reaction of preparing hydrogen from methanol.

Performance test 6

The mixed product of the examples was tested for the content of CO in the product by the following method:

the increase of the catalyst consumption and the extension of the reaction time can reflect the composition of the gas product: 12mL of a mixed solution of methanol and water containing sodium carbonate was removed to a 50mL round bottom flask, 49.8mg of catalyst A-3 was added, a U-shaped tube was connected, and the reaction apparatus was kept sealed. In the reaction solution, [ MeOH ] = 23.2M, [ A-3] = 8.29mM, [ KOH ] = 24.9mM, and the gas composition in the system was detected after heating at 78 ℃ with stirring in an oil bath at constant temperature for 24 hours.

The carbon monoxide in the system is detected by a chromatographic FID detector after passing through a methane reformer by taking high-purity nitrogen, high-purity air and high-purity hydrogen as carrier gases, and the chromatographic column is Porapak Q (3 m multiplied by 3 mm).

FIG. 1 is a graph showing a peak control of a CO gas chromatography, wherein a solid line represents a gas chromatography of CO at a concentration of 10ppm, and a dotted line represents a gas chromatography of a gas component after 24 hours of reaction using the catalyst A-3 provided by the present invention, and as can be seen from FIG. 1, the CO content of the gas component produced after 24 hours of reaction under the reaction conditions for producing hydrogen using methanol provided by the present invention is significantly lower than 10ppm.

The applicant states that the present invention describes the Ir catalyst of the present invention, and its preparation method and application, and a method for preparing hydrogen comprising the same, by the above examples, but the present invention is not limited to the above detailed methods, i.e. it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. An Ir catalyst, characterized in that the catalyst comprises a compound having the structure of formula I and/or formula II:

wherein R is ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from-H, alkoxy, alkyl, aryl, acetyl or cyclopentadienyl;

R ₆ 、R ₁₁ each independently selected from the group consisting of-H, -OH, -COOH, alkylidenethiol, alkylideneamine alkyl, pyrrolyl and derivatives thereof, imidazolyl and derivatives thereof, thienyl and derivatives thereof, or thiazolyl and derivatives thereof;

R ₇ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₂ 、R ₁₃ 、R ₁₄ each independently selected from the group consisting of-H, -OH, -COOH, -SH, -NH ₂ 、-NO ₂ Halogen, alkoxy or alkyl;

x is Cl ^- 、NH ₃ 、H ₂ O、OTf ^- 、SO ₄ ^2- Or NO ₃ ^- Any one or a combination of at least two of the following;

n is 1 or 2, and m is an integer from 0 to 3.

2. Ir catalyst according to claim 1, characterized in that R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from-H, C1-C5 alkoxy, C1-C5 alkyl, phenyl, acetyl or cyclopentadienyl.

3. Ir catalyst according to claim 1, characterized in that R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ Each independently selected from-H, -OCH ₃ 、-CH ₃ 、-CH ₂ CH ₃ Phenyl, acetyl or cyclopentadienyl.

4. Ir catalyst according to claim 1, characterized in that R ₆ 、R ₁₁ Each independently selected from the group consisting of-H, -OH, -COOH, C1-C5 alkylmercapto, C1-C5 alkylamino, C1-C5 alkyleneaminoalkyl, pyrrolyl and its derivatives, imidazolyl and its derivatives, thienyl and its derivatives, or thiazolyl and its derivatives.

5. Ir catalyst according to claim 1, characterized in that R ₆ 、R ₁₁ Each independently selected from the group consisting of-H, -OH, -COOH, -CH ₂ SH、-CH ₂ NH ₂ 、-CH ₂ NHCH ₃ Pyrrolyl and its derivatives, imidazolyl and its derivatives, thienyl and its derivatives, or thiazolyl and its derivatives.

6. Ir catalyst according to claim 1, characterized in that R ₇ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₂ 、R ₁₃ 、R ₁₄ Each independently selected from the group consisting of-H, -OH, -COOH, -SH, -NH ₂ 、-NO ₂ -Cl, C1-C5 alkoxy or C1-C5 alkyl.

7. Ir catalyst according to claim 1, characterized in that R ₇ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₂ 、R ₁₃ 、R ₁₄ Each independently selected from the group consisting of-H, -OH, -COOH, -SH, -NH ₂ 、-NO ₂ 、-Cl、-OCH ₃ or-CH ₃ 。

8. The process for preparing Ir catalysts according to any one of claims 1-7, characterized by comprising the steps of:

the Ir catalyst precursor reacts with pyridine ligands and/or pyrimidine ligands to obtain the Ir catalyst;

wherein, the Ir catalyst precursor has the following structure:

the pyridine ligand has the following structure:

the pyrimidine ligand has the following structure:

9. the preparation method according to claim 8, characterized in that the mass ratio of the total amount of pyridine ligands and/or pyrimidine ligands to the Ir catalyst precursor is (0.5-5): 1.

10. The method of claim 8, wherein the temperature of the reaction is 0-100 ℃.

11. The process of claim 10, wherein the temperature of the reaction is 25-80 ℃.

12. The method according to claim 8, wherein the reaction time is 10min to 24h.

13. The method of claim 12, wherein the reaction time is 2 to 12 hours.

14. The method of claim 8, wherein the reaction is carried out in a solvent.

15. The method of preparation according to claim 14, wherein the solvent is selected from polar organic solvents and/or water.

16. The method of claim 15, wherein the polar organic solvent is methanol and/or ethanol.

17. The method according to claim 8, further comprising a base in the reaction system.

18. The process according to claim 17, wherein the molar amount of the base is 0.2 to 10 times that of the pyridine-based ligand and/or pyrimidine-based ligand.

19. The process according to claim 17, wherein the molar amount of the base is 0.8 to 1.8 times that of the pyridine-based ligand and/or pyrimidine-based ligand.

20. The method of preparation according to claim 17, characterized in that the base is selected from organic and/or inorganic bases.

21. The method according to claim 20, wherein the organic base is selected from any one or a combination of at least two of ammonia, tetramethylammonium hydroxide, and triethylamine.

22. The method according to claim 20, wherein the inorganic base is selected from any one or a combination of at least two of sodium hydroxide, potassium carbonate, and sodium carbonate.

23. The preparation method of the Ir catalyst precursor according to claim 8, comprising the steps of:

24. The method of claim 23, wherein the reaction is carried out in a protective atmosphere.

25. The method of claim 24, wherein the protective atmosphere is nitrogen.

26. The method according to claim 23, wherein the molar ratio of chloroiridium acid to cyclopentadiene derivative is 1 (0.5-3).

27. The method according to claim 26, wherein the molar ratio of chloroiridium acid to cyclopentadiene derivative is 1 (0.8-2.5).

28. The method of claim 23, wherein the reaction is carried out in a solvent.

29. The method of claim 28, wherein the solvent is anhydrous methanol.

30. The method according to claim 23, wherein the reaction temperature is 55 to 85 ℃ and the reaction time is 24 to 48 hours.

31. Use of the Ir catalyst according to any one of claims 1-7 for the preparation of hydrogen.

32. Use according to claim 31, wherein the hydrogen-producing feedstock is selected from compounds bearing hydroxyl and/or carbonyl groups.

33. The use according to claim 32, wherein the raw material is selected from any one or a combination of at least two of methanol, formic acid, ethanol, isopropanol, glucose or formaldehyde.

34. Use according to claim 32, wherein the starting material is selected from formic acid and/or methanol.

35. The use according to claim 32, wherein the starting material is selected from methanol.

36. A process for the preparation of hydrogen from methanol, characterized in that the catalyst used in the process comprises the Ir catalyst according to any one of claims 1 to 7.

37. The method according to claim 36, characterized in that it comprises the steps of:

an aqueous methanol solution containing a basic compound is mixed with the Ir catalyst according to any one of claims 1 to 7 and reacted to obtain hydrogen.

38. The process according to claim 37, characterized in that the amount of material of the Ir catalyst is 1-100000ppm of the amount of methanol material.

39. The process according to claim 38, characterized in that the amount of material of the Ir catalyst is 100-10000ppm of the amount of methanol material.

40. The method according to claim 37, wherein the concentration of methanol in the reaction system is 0.2 to 24.6M.

41. The method according to claim 40, wherein the concentration of methanol in the reaction system is 7.68 to 24.6M.

42. The process according to claim 37, characterized in that the basic compound is added in an amount of 0.2-300 times the amount of the substance of the Ir catalyst.

43. The process according to claim 42, characterized in that the basic compound is added in an amount of 0.5 to 100 times the amount of the substance of the Ir catalyst.

44. The method according to claim 42 or 43, wherein the basic compound comprises an inorganic base and/or an organic base.

45. The method of claim 44, wherein the inorganic base comprises potassium hydroxide and/or sodium hydroxide.

46. The method of claim 44, wherein the organic base comprises tetramethylhydroxylamine and/or triethylamine.

47. The method of claim 37, wherein the reaction is performed in a closed environment.

48. The method of claim 37, wherein the reaction temperature of the reaction is 30-150 ℃.

49. The method of claim 48, wherein the reaction temperature of the reaction is 60-100 ℃.

50. The method according to claim 37, characterized in that it comprises the steps of:

in a closed environment, heating a methanol aqueous solution containing an alkaline compound and having a methanol concentration of 0.2-25.6M to 30-150 ℃, adding the Ir catalyst according to any one of claims 1-7, mixing and reacting to obtain hydrogen;

wherein the amount of the Ir catalyst substance is 1-100000ppm of the methanol substance;