CN112371153A - Bimetallic CoNi-ZIF derived CoNi @ CN catalyst, preparation method and catalytic hydrogenation application thereof - Google Patents

Bimetallic CoNi-ZIF derived CoNi @ CN catalyst, preparation method and catalytic hydrogenation application thereof Download PDF

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CN112371153A
CN112371153A CN202011211342.XA CN202011211342A CN112371153A CN 112371153 A CN112371153 A CN 112371153A CN 202011211342 A CN202011211342 A CN 202011211342A CN 112371153 A CN112371153 A CN 112371153A
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catalyst
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alcohol
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CN112371153B (en
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鲁新环
王晨龙
夏清华
王贝贝
周丹
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Hubei University
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, a preparation method thereof and application of the catalyst in catalyzing epoxide hydrogenation, wherein the preparation method comprises the following steps: fully and uniformly mixing cobalt salt, nickel salt and alcohol to obtain a solution A; fully and uniformly mixing the P123 and alcohol to obtain a solution B; adding the solution B into the solution A in batches to obtain a mixed solution C, and uniformly stirring; mixing imidazole and alcohol uniformly, and adding the mixture into the solution C to obtain a mixed solution D; fully stirring the mixed solution D at the alcohol reflux temperature for reaction to obtain a CoNi-ZIF metal organic framework material; h2And carrying out pyrolysis reduction treatment to obtain the hydrogenation catalyst. The catalyst prepared by the invention has low cost, high conversion rate of hydrogenation reaction and good product selectivity, and can be applied to catalyzing epoxy compounds and H2Hydrogenation reactionThe aromatic alcohol, alicyclic alcohol and aliphatic alcohol compounds are prepared, and the conversion rate of epoxy compounds and the selectivity of alcohol are greatly improved.

Description

Bimetallic CoNi-ZIF derived CoNi @ CN catalyst, preparation method and catalytic hydrogenation application thereof
Technical Field
The invention relates to the field of epoxide hydrogenation, in particular to a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, a preparation method thereof and application thereof in catalyzing epoxide hydrogenation.
Background
Alcohol is an important biomass platform compound, is a basic raw material of fine chemical products such as detergents, surfactants, plastic plasticization and the like, has large using amount and high added value, and is widely applied to industries such as medicines, foods, cosmetics, plastics, antioxidants and the like.
Hydrogenation is an important means for preparing alcohol compounds from epoxy compounds, taking epoxy cyclohexane for preparing cyclohexanol as an example, the prior art mainly comprises the step of reacting epoxy cyclohexane with a hydrogenation reagent to prepare cyclohexanol, and the cyclohexanol selectivity is high. For example, Chinese patent CN110668915A describes a method for preparing cyclohexanol by hydrogenating cyclohexene oxide, wherein the catalyst is a nickel-supported catalyst comprising silicon dioxide, aluminum oxide and activated carbon, the weight content of metallic nickel is 10-60%, but alkali metal salt is required to be added in the process as an auxiliary agent, so that certain difficulty is brought to the purification and separation of subsequent products. In the hydrogenation of styrene oxide to beta-phenylethyl alcohol, homogeneous reaction and heterogeneous reaction are reported. One of the biggest drawbacks of homogeneous reactions is the difficulty in product separation, with skeletal nickel being the most commonly used catalyst in heterogeneous catalysis. British patent 760768 describes the hydrogenation of ethylene oxide over skeletal nickel alone as a catalyst, with the disadvantage of excessive ethylbenzene being produced as a by-product. US3579593 and german DE1918852 describe the production of 11% ethylbenzene over skeletal nickel and 10% phenylacetaldehyde over palladium. In chinese patent CN1546444A, the catalyst used is an isometric impregnation method to load Pd-B on NaY, MCM41, beta molecular sieve, metal oxide, and although the hydrogenation activity is high, expensive noble metal catalysts are used.
Therefore, it is required to develop a catalyst with low raw material cost and simple preparation steps, so that the catalyst has good catalytic performance and stability for epoxy compounds under mild reaction conditions.
Disclosure of Invention
The invention aims to provide a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst and application of the bimetallic CoNi @ CN catalyst in catalyzing hydrogenation of epoxide aiming at the defects of the prior art. The method comprises the steps of firstly obtaining a CoNi-ZIF organic framework material through normal pressure rotation reaction, then preparing a CoNi-ZIF derived CoNi @ CN catalyst with high catalytic activity through thermal decomposition treatment, and applying the CoNi-ZIF derived CoNi @ CN catalyst to catalyzing epoxy compounds and H2In the preparation of aromatic alcohol, alicyclic alcohol and aliphatic alcohol compounds by hydrogenation reaction, the conversion rate of epoxide and the selectivity of alcohol compounds are greatly improved, and the generation of deoxidation product alkane is reduced.
In order to realize the aim, the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) fully and uniformly mixing cobalt salt, nickel salt and alcohol to obtain a solution A; fully and uniformly mixing the triblock copolymer P123 with alcohol to obtain a solution B; then adding the solution B into the solution A in batches to obtain a mixed solution C, and stirring to uniformly mix the mixed solution C;
2) mixing imidazole and alcohol uniformly, and adding the mixture into the mixed solution C to obtain a mixed solution D; fully stirring the mixed solution D at the alcohol reflux temperature for reaction, and after the reaction is finished, centrifugally separating, washing and drying to obtain a CoNi-ZIF metal organic framework material;
3) h is carried out on the CoNi-ZIF metal organic framework material2And (3) carrying out pyrolysis reduction treatment to obtain the CoNi @ CN catalyst derived from the CoNi-ZIF.
Preferably, the cobalt salt is selected from one of cobalt nitrate hexahydrate, cobalt acetate tetrahydrate and cobalt chloride hexahydrate; the nickel salt is selected from one of nickel nitrate hexahydrate and nickel chloride hexahydrate;
the molar ratio of the sum of the addition amounts of the cobalt salt and the nickel salt to the addition amount of the alcohol in the solution A is 1: (43.2-86.4), wherein the addition amount of the cobalt salt and the nickel salt is (6-0.5) by mol ratio: 1.
preferably, the addition amount of the triblock copolymer P123 and the alcohol in the solution B is 1: (33-65), wherein the mass ratio of the sum of the addition amount of the cobalt salt and the nickel salt in the solution A to the addition amount of the triblock copolymer P123 in the solution B is (5.5-12): 1.
preferably, the imidazole is selected from one of imidazole, 1-methylimidazole, 2-methylimidazole, N-methylimidazole, benzimidazole, 2-methylbenzimidazole and 1-benzylimidazole;
the mixed solution D is prepared by mixing imidazole and alcohol according to the molar ratio of 1: (15.8-21.6) and adding the mixture into the mixed solution C after uniformly mixing.
Preferably, the alcohol is selected from one of methanol, ethanol, isopropanol and n-butanol.
Preferably, in the step 2), the mixed solution D is fully stirred and reacted at the alcohol reflux temperature for 1-3 hours. The temperature of the reaction of the mixed solution D is the temperature which ensures the sufficient reflux of the alcohol.
Preferably, the step 3) comprises placing the CoNi-ZIF metal organic framework material into a vacuum muffle furnace, and introducing H2And carrying out pyrolysis reduction treatment at the temperature of 250-500 ℃ for 1-3 h to obtain the CoNi @ CN catalyst derived from the CoNi-ZIF.
Preferably, the centrifugal separation and washing treatment after the reaction in the step 2) is specifically: performing centrifugal separation at 8000r, repeatedly washing the purple substance obtained by centrifugation with ethanol, and centrifuging for 5 times to obtain purple solid; the drying treatment specifically comprises the following steps: the purple solid was dried in a forced air drying oven at 90 ℃ for 24 h.
The triblock copolymer P123 used in the above preparation method is a commercially available product.
The invention also provides a CoNi-ZIF derived CoNi @ CN catalyst, which is prepared by the preparation method.
The invention also providesThe application of the CoNi-ZIF derived CoNi @ CN catalyst is provided, and the CoNi-ZIF derived CoNi @ CN catalyst is used for catalyzing epoxy compounds and H2Hydrogenation reaction to prepare aromatic alcohol, alicyclic alcohol or aliphatic alcohol compounds.
Preferably, the epoxy compound is reacted with H2The method for preparing the aromatic alcohol, alicyclic alcohol or aliphatic alcohol compound by hydrogenation comprises the following steps: adding CoNi @ CN catalyst derived from CoNi-ZIF material, epoxy compound and solvent alcohol into a pressure reaction kettle, and adding N into the pressure reaction kettle2The air in the autoclave was replaced 3 times and then charged with H2Enabling the pressure of hydrogen in the reaction kettle to reach 2.0-4.0 MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 50-80 ℃, reacting at a constant temperature for 2-10 hours to perform liquid-phase hydrogenation reaction on the epoxy compound, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally performing reduced pressure distillation operation to obtain the alcohol compound;
the additive amounts of the CoNi @ CN catalyst derived from the CoNi-ZIF material, the epoxy compound and the solvent alcohol are 1: (4.8-9.8): (250-500);
the epoxy compound is selected from one of cyclohexene oxide, alpha-pinene oxide, 4-vinyl-cyclohexene oxide, styrene oxide, 3, 4-epoxy tetrahydrofuran, epichlorohydrin, propylene oxide, butylene oxide, 1, 2-cyclohexene oxide and 1, 2-epoxydodecane; the solvent alcohol is selected from one of ethanol, methanol and isopropanol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes low-cost metal cobalt, nickel and imidazole ligand with small dosage as raw materials, prepares the CoNi-ZIF organic framework material by fully stirring and reacting at the alcohol reflux temperature, and passes through H2The CoNi @ CN catalyst is obtained through pyrolysis reduction treatment and is applied to the reaction of hydrogenating epoxy compounds to aromatic alcohol, alicyclic alcohol and aliphatic alcohol compounds.
(2) The CoNi @ CN prepared by the invention has a complete crystalline structure, the high-exposed metal active site is beneficial to the diffusion of reactant molecules and product molecules and the formation of intermediates in the catalytic reaction process, an ideal reaction site is provided for the occurrence of catalytic reaction, and the preparation method with low cost, simple synthesis and good reproducibility is beneficial to the large-scale application of the CoNi @ CN catalyst in the hydrogenation of epoxy compounds.
(3) The aromatic alcohol, alicyclic alcohol and aliphatic alcohol compounds are produced according to the steps, the process is simple, the catalyst is cheap, the catalytic activity is high, the reaction condition is mild, the conversion of the cyclohexene oxide can reach 100%, and the selectivity of the product cyclohexanol can also reach 95%.
Drawings
FIG. 1 is an X-ray diffraction pattern of CoNi-ZIF and CoNi @ CN-350 prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of CoNi-ZIF and CoNi @ CN-350 prepared in example 1 of the present invention;
FIG. 3 is a TEM image of CoNi-ZIF and CoNi @ CN-350 prepared in example 1 of the present invention;
FIG. 4 is a scanning electron microscope photograph of CoNi-ZIF (P123 free) and CoNi @ CN-350(P123 free) prepared in comparative example 1 of the present invention;
FIG. 5 is a graph showing the results of catalytic hydrogenation reactions of example 1 of the present invention and comparative examples 1,2, 3,4 and 5.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
Example 1:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt nitrate hexahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 864mmol methanol to obtain solution A; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 16g of methanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of methanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 1h, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24h to obtain a CoNi-ZIF metal organic framework material;
3) placing the CoNi-ZIF metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5 hours, yielding the CoNi-ZIF-derived CoNi @ CN catalyst, which was reported as CoNi @ CN-350-1.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the CoNi @ CN catalyst comprises the following steps: adding 20mg of CoNi @ CN-350-1 catalyst prepared above, 98mg (1mmol) of epoxy cyclohexane and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of the epoxy cyclohexane is 98.7%, and the selectivity of the product cyclohexanol is 95.4%.
Example 2:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt acetate tetrahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 432mmol methanol, and obtaining solution A after uniform dissolution; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 16g of methanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 632mmol of methanol, and adding the solution into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 2 hours, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24 hours to obtain a CoNi-ZIF metal organic framework material;
3) placing the CoNi-ZIF metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5 hours, yielding the CoNi-ZIF-derived CoNi @ CN catalyst, which was reported as CoNi @ CN-350-2.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the CoNi @ CN catalyst comprises the following steps: adding 20mg of CoNi @ CN-350-2 catalyst prepared above, 98mg (1mmol) of epoxy cyclohexane and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 95.2%, and the selectivity of the product cyclohexanol is 94.3%.
Example 3:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt chloride hexahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 864mmol ethanol to obtain solution A; fully and uniformly dissolving 0.25g of triblock copolymer P123 and 12.6g of ethanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of ethanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 2 hours, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24 hours to obtain a CoNi-ZIF metal organic framework material;
3) placing the CoNi-ZIF metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5h, to finally obtain the CoNi-ZIF-derived CoNi @ CN catalyst, which was designated CoNi @ CN-350-3.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the CoNi @ CN catalyst comprises the following steps: adding 20mg of CoNi @ CN-350-3 catalyst prepared above, 98mg (1mmol) of epoxy cyclohexane and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 91.8%, and the selectivity of the product cyclohexanol is 92.9%.
Example 4:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt nitrate hexahydrate, 2mmol of nickel chloride hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 648mmol methanol, and obtaining solution A after uniform dissolution; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 16g of methanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 748mmol of methanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 1h, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24h to obtain a CoNi-ZIF metal organic framework material;
3) placing the CoNi-ZIF metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5 hours, yielding the CoNi-ZIF-derived CoNi @ CN catalyst, which was reported as CoNi @ CN-350-4.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the CoNi @ CN catalyst comprises the following steps: adding 20mg of CoNi @ CN-350-4 catalyst prepared above, 147mg (1.5mmol) of epoxy cyclohexane and 6g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 95.1%, and the selectivity of the product cyclohexanol is 94.8%.
Example 5:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt nitrate hexahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 432mmol isopropanol, and obtaining solution A after uniform dissolution; fully and uniformly dissolving 0.25g of triblock copolymer P123 and 16g of isopropanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 632mmol of isopropanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 3 hours, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24 hours to obtain a CoNi-ZIF metal organic framework material;
3) placing the CoNi-ZIF metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5 hours, yielding the CoNi-ZIF-derived CoNi @ CN catalyst, which was reported as CoNi @ CN-350-5.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the CoNi @ CN catalyst comprises the following steps: adding 10mg of CoNi @ CN-350-5 catalyst prepared above, 98mg (1mmol) of epoxy cyclohexane and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 88.5%, and the selectivity of the product cyclohexanol is 84.2%.
Example 6:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt nitrate hexahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 864mmol n-butanol to obtain solution A; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 12g of n-butanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of n-butanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 120 ℃ for reflux reaction for 1h, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24h to obtain a CoNi-ZIF metal organic framework material;
3) placing CoNi-ZIF metal organic framework material in a vacuum chamberH in an empty muffle furnace2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5 hours, yielding the CoNi-ZIF-derived CoNi @ CN catalyst, which was reported as CoNi @ CN-350-6.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the CoNi @ CN catalyst comprises the following steps: adding 20mg of CoNi @ CN-350-6 catalyst prepared above, 98mg (1mmol) of epoxy cyclohexane and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 92.6%, and the selectivity of the product cyclohexanol is 83.9%.
Examples 7 to 11
Examples 7-11 are the same as example 1 except for the following, and the results are shown in the following table.
The catalyst CoNi @ CN-35020 mg and 98mg (1mmol) of cyclohexene oxide prepared in examples 7 to 11 were accurately weighed, and 5g of ethanol as a solvent were subjected to a reaction at 70 ℃ under a condition of H2Cyclohexanol was obtained at a pressure of 3.0MPa for 8h, with the results given in Table 1 below:
TABLE 1
Figure BDA0002758833470000101
Examples 12 to 15
In examples 12 to 15, the sum of the amounts of the substances (cobalt salt + nickel salt) in example 1 was 10mmol, with the following exceptions, and the results are shown in the following table.
The catalyst CoNi @ CN-35020 mg prepared in examples 12 to 15 and 98mg (1mmol) of cyclohexene oxide were accurately weighed, and 5g of ethanol as a solvent were added at a reaction temperature of 70 ℃ under H2Cyclohexanol was obtained at a pressure of 3.0MPa for 8h, with the results shown in Table 2 below:
TABLE 2
Figure BDA0002758833470000102
Examples 16 to 19
Examples 16-19 are the same as example 1 except for the following, and the results are shown in the following table.
The catalyst CoNi @ CN-x 20mg prepared in examples 16-19 and 98mg (1mmol) of cyclohexene oxide were weighed accurately, and 5g of ethanol as a solvent were reacted at 70 ℃ under H2Cyclohexanol was obtained at a pressure of 3.0MPa for 8h, with the results shown in Table 3 below:
TABLE 3
Figure BDA0002758833470000111
Examples 20 to 22
Examples 20-22 are the same as example 1 except for the following, and the results are shown in the following table.
The catalyst CoNi @ CN-x 20mg prepared in examples 20-22 and 98mg (1mmol) of cyclohexene oxide were weighed accurately, and 5g of ethanol as a solvent were reacted at 70 ℃ under H2Cyclohexanol was obtained at a pressure of 3.0MPa for 8h, with the results shown in Table 4 below:
TABLE 4
Figure BDA0002758833470000112
Examples 23 to 26
Examples 23-26 are the same as example 1 except for the following, and the results are shown in the following table.
The catalysts CoNi @ CN-x 20mg prepared in examples 23-26 and 98mg (1mmol) of cyclohexene oxide were weighed accurately, 5g of ethanol solvent was reacted at 70 ℃ for 8 hours to obtain cyclohexanol, and the results are shown in Table 5 below:
TABLE 5
Figure BDA0002758833470000121
Examples 27 to 29
Examples 27-29 are the same as example 1 except for the following differences, and the results are shown in the following table.
The catalyst CoNi @ CN-x 20mg prepared in examples 27 to 29, 98mg (1mmol) of cyclohexene oxide, 5g of ethanol as a solvent, and H were accurately weighed2Cyclohexanol was obtained at a pressure of 3.0MPa for 8h, with the results as given in Table 6 below:
TABLE 6
Figure BDA0002758833470000122
Examples 30 to 33
Examples 30-33 the results are given in example 1, with the following exceptions, and are shown in the following table.
The catalyst CoNi @ CN-x 20mg prepared in examples 30 to 33, 98mg (1mmol) of cyclohexene oxide, 5g of ethanol as a solvent, and H were accurately weighed2Pressure 3.0MPa, reaction temperature 70 ℃ to obtain cyclohexanol, the results of which are given in Table 7 below:
TABLE 7
Figure BDA0002758833470000131
Examples 34 to 42
Examples 34-42 the hydrogenation substrates for examples 34-42 were, in order, respectively: 4-vinylcyclohexane oxide, alpha-pinene oxide, 3, 4-tetrahydrofuran oxide, styrene oxide, propylene oxide, epichlorohydrin, butylene oxide, 1, 2-epoxyhexane, 1, 2-epoxydodecane, and the rest of the procedure was the same as in example 1, and the results were shown in the following table.
The catalysts CoNi @ CN-x 20mg prepared in examples 34-42 and 1mmol of epoxy compound and 5g of ethanol and H serving as solvents are accurately weighed2The pressure was 3.0MPa, the reaction temperature was 70 ℃ and the reaction time was 8 hours, to obtain an alcohol compound, the results of which are shown in Table 8 below:
TABLE 8
Figure BDA0002758833470000132
Figure BDA0002758833470000141
Comparative example 1:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt nitrate hexahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 864mmol methanol to obtain solution A;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of methanol, and adding the solution into the solution A in batches to obtain a mixed solution B; fully stirring the solution B at the temperature of 90 ℃ for reflux reaction for 1h, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid by using ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24h to obtain a CoNi-ZIF (P123 free) metal organic framework material;
3) placing the CoNi-ZIF metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5 hours, resulting in the CoNi-ZIF-derived CoNi @ CN catalyst, which was designated CoNi @ CN-350(P123 free).
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the CoNi @ CN (P123 free) catalyst comprises the following steps: adding 20mg of CoNi @ CN-350-1 catalyst prepared above, 98mg (1mmol) of cyclohexene oxide and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2Making the hydrogen pressure in the reaction kettle reach 3.0MPa, starting stirring, heating the reaction kettle to make the catalytic reaction temperature be 70 ℃, making constant-temperature reaction for 8h to make epoxy cyclohexane liquid-phase hydrogenation reaction, after the reaction is finished, centrifugally separating catalyst and reaction liquor, finally making reduced-pressure distillation operation so as to obtain cyclohexanol compound whose epoxy cyclohexane conversion rate is 3.0MPa48.7 percent and the selectivity of the product cyclohexanol is 83.2 percent.
Comparative example 2:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst, which comprises the following steps:
1) 8mmol of cobalt nitrate hexahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 864mmol methanol to obtain solution A; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 16g of methanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of methanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 1h, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24h to obtain a CoNi-ZIF metal organic framework material;
(2) a process for catalyzing the hydrogenation of an epoxy compound comprising the steps of: adding 20mg of the prepared CoNi-ZIF metal organic framework material, 98mg (1mmol) of epoxy cyclohexane and 5g of ethanol into a stainless steel high-pressure reaction kettle, and adding N into the reaction kettle2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 1.7%, and the selectivity of the product cyclohexanol is 100%.
Comparative example 3:
(1) the invention provides a preparation method of a bimetallic CoNi-ZIF 'derived CoNi @ CN' catalyst, which comprises the following steps:
1) 8mmol of cobalt nitrate hexahydrate, 2mmol of nickel nitrate hexahydrate (cobalt salt: nickel salt 4: 1) dissolving in 864mmol methanol to obtain solution A; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 16g of methanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of methanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; adding the mixed solution D into a polytetrafluoroethylene lining, then placing the mixed solution D into a stainless steel closed reaction kettle, then placing the sealed reaction kettle into an oven, starting to heat the reaction kettle to 90 ℃ for static crystallization reaction for 3 hours, taking out the reaction kettle after the reaction is finished, naturally cooling the reaction kettle, after the reaction is finished, carrying out centrifugal separation and centrifugation on the obtained purple solid, repeatedly washing the obtained purple solid with ethanol, and carrying out centrifugation for 5 times, then placing the obtained purple solid in a blast drying oven for drying for 24 hours at 90 ℃ to obtain a CoNi-ZIF' metal organic framework material;
3) placing the CoNi-ZIF' metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 ℃ and the pyrolysis time was 2h, finally obtaining the CoNi-ZIF ' derived CoNi @ CN ' catalyst, which was designated as CoNi @ CN-350 '.
(2) A method for catalyzing hydrogenation of an epoxy compound by using a CoNi @ CN' catalyst comprises the following steps: adding 20mg of CoNi @ CN-350' catalyst prepared above, 98mg (1mmol) of epoxy cyclohexane and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 69.2%, and the selectivity of the product cyclohexanol is 87.6%.
Comparative example 4:
(1) the invention provides a preparation method of a single metal Co-ZIF derived Co @ CN catalyst, which comprises the following steps:
1) dissolving 10mmol of cobalt nitrate hexahydrate in 864mmol of methanol, and obtaining a solution A after uniform dissolution; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 16g of methanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of methanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 1h, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24h to obtain a Co-ZIF metal organic framework material;
3) placing the Co-ZIF metal organic framework material in a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5 hours, to finally obtain the Co-ZIF derived Co @ CN catalyst, which was designated as Co @ CN-350.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the Co @ CN catalyst comprises the following steps: adding 20mg of the Co @ CN-350 catalyst prepared above, 98mg (1mmol) of cyclohexene oxide and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 89.0%, and the selectivity of the product cyclohexanol is 79.1%.
Comparative example 5:
(1) the invention provides a preparation method of a single metal Ni-ZIF derived Ni @ CN catalyst, which comprises the following steps:
1) dissolving 10mmol of nickel nitrate hexahydrate in 864mmol of methanol, and uniformly dissolving to obtain a solution A; fully and uniformly dissolving 0.36g of triblock copolymer P123 and 16g of methanol to obtain solution B, adding the solution B into the solution A in batches to obtain mixed solution C, and stirring for 20min to uniformly mix the mixed solution C;
2) uniformly dissolving 40mmol of 2-methylimidazole and 864mmol of methanol, and adding the mixture into the mixed solution C in batches to obtain a mixed solution D; fully stirring the mixed solution D at the temperature of 90 ℃ for reflux reaction for 1h, after the reaction is finished, centrifugally separating, repeatedly washing and centrifuging the obtained purple solid with ethanol for 5 times, and drying the obtained purple solid in an air-blast drying oven at the temperature of 90 ℃ for 24h to obtain the Ni-ZIF metal organic framework material;
3) putting the Ni-ZIF metal organic framework material into a vacuum muffle furnace for H2Reduction treatment by pyrolysis in an atmosphere H2The flow rate was 35ml/min, the pyrolysis temperature was controlled at 350 deg.C, and the pyrolysis time was 2.5h, to finally obtain the Ni-ZIF derived Ni @ CN catalyst, which was designated as Ni @ CN-350.
(2) The method for catalyzing the hydrogenation of the epoxy compound by using the Ni @ CN catalyst comprises the following steps: adding 20mg of the prepared Ni @ CN-350 catalyst, 98mg (1mmol) of cyclohexene oxide and 5g of ethanol into a stainless steel high-pressure reaction kettle, and reacting with N2Replacing air in the reaction kettle for three times, and then filling H2And (2) enabling the hydrogen pressure in the reaction kettle to reach 3.0MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 70 ℃, carrying out constant-temperature reaction for 8 hours to carry out epoxy cyclohexane liquid-phase hydrogenation reaction, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally carrying out reduced pressure distillation operation to obtain the cyclohexanol compound, wherein the conversion rate of epoxy cyclohexane is 7.5%, and the selectivity of the product cyclohexanol is 60.3%.
As shown in fig. 5, compared with comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5, the catalytic activity of the catalyst CoNi @ CN prepared by the present invention is significantly higher than that of the catalyst CoNi @ CN (P123 free) precursor CoNi-ZIF prepared by the comparative example 1, the CoNi-ZIF precursor material prepared by the comparative example 2, the catalyst CoNi-ZIF prepared by the comparative example 3 in a static crystallization manner, the monometallic catalyst Co @ CN prepared by the comparative example 4 and the monometallic catalyst Ni @ CN prepared by the comparative example 5, so that the hydrogenation catalyst CoNi @ CN prepared by the stirring reflux reaction plus the pyrolytic reduction treatment is an effective catalyst for hydrogenation of epoxy compounds.
And (3) performance detection:
x-ray diffraction
X-ray diffraction on a Rigaku D/MAX-IIIC X-ray diffractometer (CuK α:
Figure BDA0002758833470000181
) And (4) carrying out measurement. Grinding the sample sufficiently, taking about 20mg of the sample, loading into a tablet press at 500kg/cm2Pressed into a sheet under pressure.
As can be seen from FIG. 1, an XRD spectral line of the CoNi-ZIF prepared in the embodiment 1 of the invention has characteristic diffraction peaks of the CoNi-ZIF, and diffraction peaks with 2 theta of 5-50 degrees in the figure are all skeleton characteristic diffraction peak data of the CoNi-ZIF; the diffraction peaks of the CoNi @ CN-350 material prepared by pyrolyzing the CoNi-ZIF at 2 theta of 44.3 degrees, 51.5 degrees and 75.8 degrees are respectively assigned as Co (111), Co (200) and Co (220). Illustrates that the cobalt ions of the thermally treated CoNi @ CN-350 catalyst sample of example 1 were reduced to the zero valent metal cobalt.
Scanning electron microscopy
Scanning Electron microscope the measurement was carried out on a JSM-6510A scanning electron microscope manufactured by Japan Electron Ltd. The scanning voltage of the tungsten lamp is 30 KV.
As can be seen from FIG. 2, the CoNi-ZIF metal organic framework film material prepared in the embodiment 1 of the invention is a uniform and regular crystal material with a cubic structure; the CoNi @ CN-350 material prepared by pyrolyzing the CoNi-ZIF exposes a certain defect position, but the shape of a metal-organic framework is still maintained integrally.
As can be seen from fig. 4, the CoNi-ZIF (P123 free) metal organic framework film material prepared in comparative example 1 of the present invention is a crystal material with a cubic structure, but the size is different, and it is obvious from the scanning electron microscope image of the CoNi @ CN-350(P123 free) catalyst after heat treatment that a certain cavity defect site is exposed, but the basic framework structure of the material is completely disappeared, which indicates that the framework structure of the material itself is very unstable.
Transmission electron microscopy images
Scanning electron microscopy was performed on a transmission electron microscope model Tecnai20, FEI Inc., USA. The test voltage was 200 kV.
As can be seen from FIG. 3, the CoNi-ZIF metal organic framework membrane material prepared in the embodiment 1 of the invention is a regular crystal material with a cubic structure; the CoNi @ CN-350 material prepared by pyrolyzing CoNi-ZIF exposes a certain cavity defect position.

Claims (10)

1. A preparation method of a bimetallic CoNi-ZIF derived CoNi @ CN catalyst is characterized by comprising the following steps: the method comprises the following steps:
1) fully and uniformly mixing cobalt salt, nickel salt and alcohol to obtain a solution A; fully and uniformly mixing the triblock copolymer P123 with alcohol to obtain a solution B; then adding the solution B into the solution A in batches to obtain a mixed solution C, and stirring to uniformly mix the mixed solution C;
2) mixing imidazole and alcohol uniformly, and adding the mixture into the mixed solution C to obtain a mixed solution D; fully stirring the mixed solution D at the alcohol reflux temperature for reaction, and after the reaction is finished, centrifugally separating, washing and drying to obtain a CoNi-ZIF metal organic framework material;
3) h is carried out on the CoNi-ZIF metal organic framework material2And (3) carrying out pyrolysis reduction treatment to obtain the CoNi @ CN catalyst derived from the CoNi-ZIF.
2. The method of preparing the bimetallic CoNi-ZIF derived CoNi @ CN catalyst of claim 1, wherein: the cobalt salt is selected from one of cobalt nitrate hexahydrate, cobalt acetate tetrahydrate and cobalt chloride hexahydrate; the nickel salt is selected from one of nickel nitrate hexahydrate and nickel chloride hexahydrate;
the molar ratio of the sum of the addition amounts of the cobalt salt and the nickel salt to the addition amount of the alcohol in the solution A is 1: (43.2-86.4), wherein the addition amount of the cobalt salt and the nickel salt is (6-0.5) by mol ratio: 1.
3. the method of preparing the bimetallic CoNi-ZIF derived CoNi @ CN catalyst of claim 2, wherein: the addition amount of the triblock copolymer P123 and the alcohol in the solution B is 1: (33-65), wherein the mass ratio of the sum of the addition amount of the cobalt salt and the nickel salt in the solution A to the addition amount of the triblock copolymer P123 in the solution B is (5.5-12): 1.
4. the method of preparing the bimetallic CoNi-ZIF derived CoNi @ CN catalyst of claim 1, wherein: the imidazole is selected from one of imidazole, 1-methylimidazole, 2-methylimidazole, N-methylimidazole, benzimidazole, 2-methylbenzimidazole and 1-benzyl imidazole;
the mixed solution D is prepared by mixing imidazole and alcohol according to the molar ratio of 1: (15.8-21.6) and adding the mixture into the mixed solution C after uniformly mixing.
5. The method of preparing the bimetallic CoNi-ZIF derived CoNi @ CN catalyst of claim 1, wherein: the alcohol is selected from one of methanol, ethanol, isopropanol and n-butanol.
6. The method of preparing the bimetallic CoNi-ZIF derived CoNi @ CN catalyst of claim 1, wherein: in the step 2), the mixed solution D is fully stirred and reacted at the alcohol reflux temperature for 1-3 h.
7. The method of preparing the bimetallic CoNi-ZIF derived CoNi @ CN catalyst of claim 1, wherein: the step 3) comprises the steps of putting the CoNi-ZIF metal organic framework material into a vacuum muffle furnace, and introducing H2And carrying out pyrolysis reduction treatment at the temperature of 250-500 ℃ for 1-3 h to obtain the CoNi @ CN catalyst derived from the CoNi-ZIF.
8. A CoNi-ZIF-derived CoNi @ CN catalyst, characterized by: the CoNi-ZIF derived CoNi @ CN catalyst is prepared by the method of any one of claims 1 to 7.
9. Use of the CoNi-ZIF derivatized CoNi @ CN catalyst of claim 8, wherein: the CoNi-ZIF derived CoNi @ CN catalyst is used for catalyzing epoxy compounds and H2Hydrogenation reaction for preparing aromatic alcohol, alicyclic alcohol or aliphatic alcohol compounds。
10. The use of the CoNi-ZIF-derived CoNi @ CN catalyst according to claim 9, wherein: the epoxy compound and H2The method for preparing the aromatic alcohol, alicyclic alcohol or aliphatic alcohol compound by hydrogenation comprises the following steps: adding CoNi @ CN catalyst derived from CoNi-ZIF material, epoxy compound and solvent alcohol into a pressure reaction kettle, and adding N into the pressure reaction kettle2The air in the autoclave was replaced 3 times and then charged with H2Enabling the pressure of hydrogen in the reaction kettle to reach 2.0-4.0 MPa, starting stirring, heating the reaction kettle to enable the catalytic reaction temperature to be 50-80 ℃, reacting at a constant temperature for 2-10 hours to perform liquid-phase hydrogenation reaction on the epoxy compound, centrifugally separating the catalyst and the reaction liquid after the reaction is finished, and finally performing reduced pressure distillation operation to obtain the alcohol compound;
the additive amounts of the CoNi @ CN catalyst derived from the CoNi-ZIF material, the epoxy compound and the solvent alcohol are 1: (4.8-9.8): (250-500);
the epoxy compound is selected from one of cyclohexene oxide, alpha-pinene oxide, 4-vinyl-cyclohexene oxide, styrene oxide, 3, 4-epoxy tetrahydrofuran, epichlorohydrin, propylene oxide, butylene oxide, 1, 2-cyclohexene oxide and 1, 2-epoxydodecane; the solvent alcohol is selected from one of ethanol, methanol and isopropanol.
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