CN113244957A - Polymeric carbene iridium catalyst and preparation method and application thereof - Google Patents

Polymeric carbene iridium catalyst and preparation method and application thereof Download PDF

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CN113244957A
CN113244957A CN202110505581.4A CN202110505581A CN113244957A CN 113244957 A CN113244957 A CN 113244957A CN 202110505581 A CN202110505581 A CN 202110505581A CN 113244957 A CN113244957 A CN 113244957A
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reaction
catalyst
formate
hydrogenation
carbene
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CN113244957B (en
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张志炳
周政
胡兴邦
周磊
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Nanjing Anlige Co ltd
Nanjing University
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Nanjing Institute of Microinterface Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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    • B01J2531/827—Iridium
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Abstract

The invention provides a polymerization carbene iridium catalyst, a preparation method and application thereof, wherein the chemical structural formula of the polymerization carbene iridium catalyst is as follows:
Figure DDA0003058287020000011
wherein
Figure DDA0003058287020000012
The polymerization carbene iridium catalyst is a heterogeneous catalyst, so that water can be used as a solvent in the actual catalytic reaction process, the hydrophobicity and the thermal stability of the polymerization carbene iridium catalyst are obviously enhanced, and the protection of Ir-H bonds is greatly facilitated.

Description

Polymeric carbene iridium catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of preparation of a polymeric carbene iridium catalyst, and particularly relates to a polymeric carbene iridium catalyst, and a preparation method and application thereof.
Background
Formic acid (Formic acid), commonly known as Formic acid, is the simplest organic carboxylic acid, and has both carboxyl and aldehyde groups in its molecule compared to other organic acids, so Formic acid has both acid and aldehyde properties. As an important chemical raw material, formic acid has wide application in rubber, leather making, medicines, pesticides, dyes, fuel cells, catalytic hydrogen production, agriculture, environmental protection and other various industries, and the demand of formic acid in China is increased by more than 10% in recent years. It is noteworthy that the current commercial processes for the carbonylation of methanol to produce formic acid are neither environmentally friendly nor economical. Over the past decades, CO2It is considered a promising carbon source due to its non-toxic, readily available and renewable nature. Thus CO2The hydrogenation of formic acid is a promising alternative.
CO2The reaction for preparing formic acid by hydrogenation needs to add an alkaline solvent into a reaction system, so that the reaction is thermodynamically feasible. Meanwhile, the weak base is added, so that formate can be formed with the generated formic acid to promote the reaction to be continuously carried out rightwards, the generated formate is easy to separate from a reaction system and then decomposed, the formic acid is obtained on one hand, the base is recovered on the other hand, and the recycling of the base is realized. Research shows that noble metal catalysts (Ir, Ru, Rh and the like) and cheap transition metals (Cu, Fe and the like) have certain activity for hydrogenation reaction, but the disadvantage is that the catalytic reaction generally needs to be carried out at higher reaction temperature. Cyclo (alkyl) (amino) carbenes (CAACs) have proven to be excellent ligands for transition metals, and are widely used in the field of catalysis because they have advantages in activating small molecules and thermally strong bonds.
In CO2In the hydrogenation process, the metal reacts with H2The interaction to form metal hydrides (M-Hs) is crucial, then CO2May be inserted into the M-H bond. In general, M-Hs are not stable in water except for water-soluble ligands (e.g., tppms, tppts, pta)Or polar substituents such as acidic (-SO)3H、-CO2H) Basic (-NR)2) In addition, the catalysts used at present can only be used in organic solvents. Exploring catalyst pair containing high-stability M-Hs active center for improving CO2The hydrogenation efficiency is of great significance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a polymerization carbene iridium catalyst with a novel structure, wherein the carbene iridium catalyst with the structure is heterogeneous, water can be used as a solvent, sodium hydroxide is used as an alkali, and CO is reacted at room temperature2The method has the advantages that the defect that organic solvents are needed to be used as solvents in the past is overcome by converting the catalyst into formate, the method is green and environment-friendly, and meanwhile, the hydrophobicity and the thermal stability of the catalyst are remarkably enhanced, so that the protection of Ir-H bonds is greatly facilitated.
The second purpose of the invention is to provide a preparation method of the polymerized carbene iridium catalyst, which is simple, has close front-to-back connection of operation steps, and is worthy of wide popularization and application.
The third purpose of the invention is to provide the application of the polymeric carbene iridium catalyst, and the reaction process has the advantages of mild condition, high reaction rate, environmental protection and the like compared with the traditional reaction process by adopting the catalyst, and is CO2The method for preparing the formate by hydrogenation provides an efficient and feasible new method.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a polymerization carbene iridium catalyst, which has a chemical structural formula as follows:
Figure BDA0003058287000000021
wherein
Figure BDA0003058287000000022
In the prior art, M-Hs is not stable in water except for water soluble ligands (e.g., tppms, tppts)Pta) or polar substituents such as acidic (-SO)3H、-CO2H) Basic (-NR)2) In addition, the general catalyst in the prior art can only be used in an organic solvent, and the stability and catalytic performance of the catalyst are general, the invention provides a heterogeneous catalyst for solving the technical problems, and the catalyst belongs to a polymeric carbene iridium catalyst from the structural general formula of the catalyst, so that the catalyst still has high catalytic effect under the condition of taking water as a solvent, and the hydrophobicity and thermal stability of the catalyst are also strong.
Preferably, as a further implementable scheme, the catalyst is mainly prepared from raw materials of cycloalkyl amino carbene ligand, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, wherein the adopted raw materials comprise the cycloalkyl amino carbene ligand which is carbene iridium catalyst frequently used as catalyst in the prior art, and the structure of the catalyst also belongs to the prior art.
Preferably, as a further implementable variant, the molar ratio of cycloalkylaminocarbocarbene ligand, dimethoxymethane, benzene and iridium 1, 5-cyclooctadienechloride is 1: (1-10): (1-10):1. The proportion of the raw materials for synthesizing the catalyst has certain influence on the catalytic effect of the catalyst, particularly the proportion of dimethoxymethane and benzene can influence the dispersion degree of metal elements in a polymer, the activity of catalyst clusters can be reduced due to too small dispersion degree, the concentration of the catalyst can be reduced due to too high dispersion degree, and the reaction is not facilitated, so that the proportion is preferably controlled within a proper proportion range.
The invention also provides a preparation method of the polymerization carbene iridium catalyst, which comprises the following steps:
all raw materials are subjected to reaction synthesis at the temperature of 60-150 ℃, and the reaction chemical equation is as follows:
Figure BDA0003058287000000031
in the specific preparation process, the operation conditions are preferably controlled properly, for example, the preparation temperature is controlled between 60 ℃ and 150 ℃, because although the temperature rise is favorable for accelerating the reaction, the reaction is exothermic from the thermodynamic point of view, so the effect is slightly reduced after the temperature reaches a certain limit, and the temperature needs to be controlled in a proper range.
Preferably, as a further implementable variant, the reaction time is from 40 to 80 h. The reaction time should also be controlled within a suitable range because although it is advantageous to extend the reaction time toward the forward direction, the reaction approaches equilibrium and the increase in catalytic effect is reduced when the time is increased to a certain extent.
The invention can catalyze CO by the polymerization carbene iridium catalyst2The effective application is carried out in the aspect of preparing formate by hydrogenation.
Preferably, CO is catalyzed2In the reaction process of preparing formate by hydrogenation, the dosage of the polymeric carbene iridium catalyst is based on the iridium-containing molar quantity, and the dosage of the relative solvent is 0.000002mmol-0.0002mmol of the catalyst per milliliter of the solvent.
Preferably, as a further implementable solution, CO is catalyzed2The reaction temperature for preparing the formate by hydrogenation is 30-100 ℃.
Preferably, as a further implementable solution, CO is catalyzed2The reaction time for preparing the formate by hydrogenation is 12-48 h, and the reaction pressure is 5-7 MPa.
Preferably, as a further implementable solution, CO2And H2The inlet volume ratio of (1): (2-3).
Catalysis of CO2After the reaction for preparing formate by hydrogenation is finished, the TON of the reaction can be calculated by the following formula:
Figure BDA0003058287000000041
wherein TON denotes the number of substrate conversions per mole of active center of the catalyst, n1Denotes the amount of formate formed, ncatDenotes the amount of iridium-containing material in the catalyst used. The amount of formate is determined by a hydrogen spectrum nuclear magnetic internal standard method, and the internal standard substance is isopropanol and deuterium water lock field.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a heterogeneous polymerization carbene iridium catalyst with a novel structure, which can take water as a solvent and sodium hydroxide as alkali to react CO at room temperature2Converted to formate.
(2) The polymeric carbene iridium catalyst has better solubility in a reaction system and better applicability to the current mainstream production process.
(3) The preparation method of the polymeric carbene iridium catalyst provided by the invention is simple, the operation steps are connected front and back tightly, and the polymeric carbene iridium catalyst is worthy of wide popularization and application.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a nuclear magnetic carbon spectrum of a polymeric carbene iridium catalyst provided in example 1 of the present invention;
fig. 2 is an infrared spectrum of the polymeric iridium carminative catalyst provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Example 1 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0001mmol catalyst, 5g sodium hydroxide and 50mL water are added into a 500mL high-pressure reaction kettle, CO is introduced after air is removed22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthetic conditions are 60 ℃ and 40 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 30 ℃, and a sample is taken out for testing after the reaction is carried out for 12 hours. Under these conditions, a TON of 5760 was obtained and the confirmation spectrum of the catalyst obtained is shown in FIGS. 1-2, FIG. 1The formants at 1, 2, 3, 4 and 5 are assigned to carbon, cyclooctadiene, aromatic carbon, quaternary carbon and methylene carbon, respectively.
Example 2 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0001mmol catalyst, 5g sodium hydroxide and 50mL water are added into a 500mL high-pressure reaction kettle, CO is introduced after air is removed22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:10:10:1, and the synthetic conditions are 60 ℃ and 40 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 30 ℃, and a sample is taken out for testing after the reaction is carried out for 12 hours. Under these conditions, TON was 4560.
Example 3 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0001mmol catalyst, 5g sodium hydroxide and 50mL water are added into a 500mL high-pressure reaction kettle, CO is introduced after air is removed22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthetic conditions are 150 ℃ and 40 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 30 ℃, and a sample is taken out for testing after the reaction is carried out for 12 hours. Under this condition, TON obtained was 5660.
Example 4 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0002mmol of catalyst, 5g of sodium hydroxide and 50mL of water are placed in a 500mL autoclave, air is removed and CO is introduced22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, the synthetic conditions are 60 ℃ and 80 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 30 ℃, and a sample is taken out for testing after the reaction is carried out for 12 hours. Under these conditions, a TON of 6400 was obtained.
Example 5 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0001mmol of catalyst is added into a 500ml high-pressure reaction kettle5g of sodium hydroxide and 50mL of water, air being excluded and CO being introduced again22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthetic conditions are 60 ℃ and 40 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 100 ℃, and a sample is taken out for testing after the reaction is carried out for 12 hours. Under these conditions, the TON obtained was 7970.
Example 6 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0001mmol catalyst, 5g sodium hydroxide and 50mL water are added into a 500mL high-pressure reaction kettle, CO is introduced after air is removed22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthetic conditions are 60 ℃ and 40 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 30 ℃, and a sample is taken out for testing after 48 hours of reaction. Under these conditions, the TON obtained was 7880.
Example 7 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0001mmol catalyst, 5g sodium hydroxide and 50mL water are added into a 500mL high-pressure reaction kettle, CO is introduced after air is removed22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthetic conditions are 60 ℃ and 40 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 30 ℃, and a sample is taken out for testing after the reaction is carried out for 12 hours. Under these conditions, TON was obtained as 3280.
Example 8 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0005mmol of catalyst, 5g of sodium hydroxide and 50mL of water are placed in a 500mL autoclave, air is removed and CO is introduced22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:5:5:1, the synthetic conditions are 100 ℃ and 60 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 50 DEG CAnd taking out a sample for testing after reacting for 24 hours. Under these conditions, the TON obtained was 5890.
Example 9 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.00002mmol of catalyst, 5g of sodium hydroxide and 50mL of water are added into a 500mL high-pressure reaction kettle, air is removed, and then CO is introduced22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:10:10:1, and the synthetic conditions are 150 ℃ and 80 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 100 ℃, and a sample is taken out for testing after 48 hours of reaction. Under this condition, the TON obtained was 10680.
Example 10 catalysis of CO2The reaction process for preparing the formate by hydrogenation comprises the following steps:
0.0005mmol of catalyst, 5g of sodium hydroxide and 50mL of water are placed in a 500mL autoclave, air is removed and CO is introduced22MPa and H24MPa, the raw materials of the synthetic catalyst are naphthenic amino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:2:2:1, and the synthetic conditions are 70 ℃ and 60 hours. CO 22The reaction temperature for preparing the formate by hydrogenation is 70 ℃, and a sample is taken out for testing after 36 hours of reaction. Under this condition, the TON obtained was 7650.
Experimental example 1
The following process steps are used to catalyze CO2Formate salts were prepared by hydrogenation, by varying the molar ratio between the feeds, to compare the TON obtained in the reaction.
The specific process comprises the following steps: the molar ratios of cycloalkylaminocarbobine, dimethoxymethane, benzene and iridium chloride 1, 5-cyclooctadiene were as shown in Table 1 below, respectively, and the synthesis conditions were 100 ℃ and 70 hours. Reaction conditions are as follows: 0.00001mmol catalyst, 0.5g sodium hydroxide and 5mL water, CO2 2MPa，H2 4MPa。CO2The reaction temperature for preparing the formate by hydrogenation is 100 ℃, and a sample is taken out for testing after 48 hours of reaction.
TABLE 1 Effect of different molar ratios on the TON of the reaction
CAAC DMM Benzene IrCOD/Synthesis molar ratio TON
1:1:1:1 8500
1:2:2:1 10200
1:5:5:1 13400
1:8:8:1 11300
1:10:10:1 7800
As can be seen from Table 1 above, adjusting the ratio of dimethoxymethane to benzene can affect the dispersion degree of the metal elements in the polymer, too small a dispersion degree can cause the activity of the catalyst clusters to be reduced, and too high a dispersion degree can cause the concentration of the catalyst to be reduced and the reaction to be unfavorable.
Experimental example 2
The following process steps are used to catalyze CO2And (3) hydrogenation to prepare formate, and comparing TON obtained by the reaction by changing the reaction temperature.
The specific process comprises the following steps: the molar ratio of the naphthenic amino carbene to the dimethoxymethane to the benzene to the 1, 5-cyclooctadiene iridium chloride is 1:5:5:1, and the synthesis condition is 100 ℃ and 70 hours. Reaction conditions are as follows: 0.00001mmol catalyst, 0.5g sodium hydroxide and 5mL water, CO22MPa，H2 4MPa。CO2The specific reaction temperature for preparing formate by hydrogenation is shown in the following table2, taking out a sample for testing after reacting for 48 hours.
TABLE 2 Effect of reaction temperature on reaction TON
Temperature of hydrogenation reaction TON
30 5900
50 7200
70 9900
90 14600
100 13400
As can be seen from table 2 above, an increase in temperature is advantageous for accelerating the reaction, but the reaction itself is an exothermic reaction from the thermodynamic viewpoint, so that the effect is slightly reduced after the temperature reaches a certain limit.
Experimental example 3
The following process steps are used to catalyze CO2The formate was prepared by hydrogenation, with variation of the reaction time, to compare the TON obtained in the reaction.
The specific process comprises the following steps: the molar ratio of the naphthenic amino carbene to the dimethoxymethane to the benzene to the 1, 5-cyclooctadiene iridium chloride is 1:5:5:1, and the synthesis condition is 100 ℃ and 70 hours. Reaction conditions are as follows: 0.00001mmol catalyst, 0.5g sodium hydroxide and 5mL water, CO22MPa，H2 4MPa。CO2And (3) preparing formate by hydrogenation, wherein the specific reaction temperature is 90 ℃, the reaction time is shown in the following table 3, and a sample is taken out after the reaction for testing.
TABLE 3 Effect of reaction time on reaction TON
Hydrogenation reaction time TON
12 4300
18 6700
24 9700
36 13500
48 14600
As can be seen from Table 3 above, it is advantageous to extend the reaction time in the forward direction, but when the reaction time is increased to a certain extent, the reaction approaches equilibrium and the catalytic effect is reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A polymeric carbene iridium catalyst is characterized in that the chemical structural formula of the polymeric carbene iridium catalyst is as follows:
Figure FDA0003058286990000011
wherein
Figure FDA0003058286990000012
2. The polymeric carbene iridium catalyst of claim 1, wherein the polymeric carbene iridium catalyst is mainly prepared from a cycloalkyl amino carbene ligand, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride as raw materials.
3. The polymeric carbene iridium catalyst of claim 1, wherein the molar ratio of the cycloalkylaminocarbocarbene ligand, dimethoxymethane, benzene and iridium 1, 5-cyclooctadiene chloride is 1: (1-10): (1-10):1.
4. The method for preparing a polymeric carbene iridium catalyst according to any one of claims 1 to 3, comprising the steps of:
all raw materials are subjected to reaction synthesis at the temperature of 60-150 ℃, and the reaction chemical equation is as follows:
Figure FDA0003058286990000013
5. the process according to claim 4, wherein the reaction time is 40 to 80 hours.
6. The polymerized carbene iridium catalyst of any one of claims 1 to 3 and the polymerized carbene iridium catalyst prepared by the preparation method of any one of claims 4 to 5 in catalyzing CO2Application in preparing formate by hydrogenation.
7. Use according to claim 6, characterized in that CO is catalysed2In the reaction process of preparing formate by hydrogenation, the dosage of the polymeric carbene iridium catalyst is based on the iridium-containing molar quantity, and the dosage of the relative solvent is 0.000002mmol-0.0002mmol of the catalyst per milliliter of the solvent.
8. Use according to claim 6, characterized in that CO is catalysed2The reaction temperature for preparing the formate by hydrogenation is 30-100 ℃.
9. Use according to claim 6, characterized in that CO is catalysed2The reaction time for preparing the formate by hydrogenation is 12-48 h, and the reaction pressure is 5-7 MPa.
10. Use according to claim 6, wherein CO is2And H2The inlet volume ratio of (1): (2-3).
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