CN116135312A - Multi-activation-site catalyst and preparation method and application thereof - Google Patents

Multi-activation-site catalyst and preparation method and application thereof Download PDF

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CN116135312A
CN116135312A CN202111356677.5A CN202111356677A CN116135312A CN 116135312 A CN116135312 A CN 116135312A CN 202111356677 A CN202111356677 A CN 202111356677A CN 116135312 A CN116135312 A CN 116135312A
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杨启华
刘鑫
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • C07C29/136—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 of >C=O containing groups, e.g. —COOH
    • C07C29/143—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 of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—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 of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations

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Abstract

The invention discloses a multi-activation-site catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The catalyst is uniformly spread on SiO with COF 2 Surface prepared COF/SiO 2 The composite material is taken as a carrier, a wet impregnation method is adopted to load metal salt on the carrier, and the corresponding supported metal nanoparticle catalyst is further obtained through reduction; to be used forThe total weight of the catalyst is 1-30% of COF and 0.2-5% of metal. The interaction between the functional group and carbonyl on the COF of the catalyst can activate carbonyl preferentially, and the metal nano particles rapidly dissociate H 2 The obtained active hydrogen overflows to hydrogenate carbonyl activated by COF to generate alcohol, and multi-site activation enables the catalyst to catalyze aldehyde/ketone compounds to selectively hydrogenate to generate corresponding alcohol compounds with high activity and high selectivity under relatively mild conditions, so that the catalyst has important application prospects in the selective hydrogenation of aldehyde/ketone compounds to generate alcohol.

Description

Multi-activation-site catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a multi-activation-site catalyst, a preparation method and application thereof in selective hydrogenation of aldehyde/ketone compounds.
Background
The selective hydrogenation reaction has extremely important significance in the synthesis of spices, pesticides and medicines and the purification of industrial raw materials, such as the preparation of ethylene by acetylene hydrogenation, the preparation of hydroxylamine by nitrobenzene hydrogenation and the preparation of aromatic alcohol by aromatic ketone hydrogenation. The selective reduction of unsaturated ketone/aldehyde into unsaturated alcohol is one basic conversion in organic synthetic chemistry, and has important application in the fields of green chemistry and chemical industry. A particular objective in the selective hydrogenation of unsaturated ketones/aldehydes is to hydrogenate c=o to the corresponding alcohol, while other unsaturated bonds within the molecule (e.g. c=c, c≡c, benzene rings, etc.) are not affected. Since substrates containing a plurality of unsaturated groups are involved, it is an object that the high selectivity to the corresponding alcohol compounds is not easy to achieve. The selectivity of the product in the selective hydrogenation reaction is mainly determined by the competitive adsorption and activation of different unsaturated groups and the relative adsorption strength of reactants, intermediates and products on the surface of the metal nanoparticles, so that the factors need to be considered in designing the catalyst.
In recent years, different strategies have been developed to improve the catalytic performance of supported metal nanoparticles, including reducing the metal nanoparticle size to monoatoms, forming bimetallic alloys, creating Strong Metal Support Interactions (SMSI), modifying the metal surface with organic ligands, and the like. These strategies, while effective, have remained a challenging task to increase both the activity and selectivity of the unsaturated ketone/aldehyde selective hydrogenation reaction.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a multi-activation-site catalyst, a preparation method and a preparation method thereofApplication in selective hydrogenation of aldehyde/ketone compounds and comparison catalyst M/SiO 2 Compared with the catalyst, the catalyst can carry out the selective hydrogenation reaction of aldehyde/ketone compounds with high activity and high selectivity to generate corresponding alcohol.
The invention aims at realizing the following steps:
the invention provides a multi-activation-site catalyst which is uniformly spread on SiO by COF 2 Surface prepared COF/SiO 2 The composite material is used as a carrier, a wet impregnation method is adopted to load metal salt on the carrier, and the corresponding supported metal nanoparticle catalyst is obtained through reduction.
Based on the technical scheme, preferably, the COF content of the catalyst is 1-30% and the metal content of the catalyst is 0.2-5% based on the total weight of the catalyst.
In another aspect, the present invention provides a method for preparing the multi-activation site catalyst, which mainly comprises the following steps:
(1) Preparing COF/SiO by colloid method or solvothermal method 2 And (3) a carrier: adding the COF monomer into a reaction container, adding a solvent and a catalyst, stirring and mixing uniformly, and then adding SiO 2 Stirring for 12-48h or stirring for 1-12h, heating to 90-120deg.C, maintaining for 12-48h, filtering, performing Soxhlet extraction, and drying to obtain COF/SiO 2 A carrier;
(2) The M/COF/SiO is prepared by adopting a wet impregnation method 2 : COF/SiO 2 The carrier is dispersed in H 2 Adding metal salt precursor solution into O, stirring at room temperature for 4-24 hr, centrifuging, drying the obtained solid, and adding into H 2 Reducing at 150-300 deg.C for 0.5-3 hr.
Based on the above technical scheme, preferably, the COF monomer in the step (1) is composed of a monomer one and a monomer two, wherein the monomer one is one of 1,3, 5-tricarboxyl phloroglucinol, 2, 4-dihydroxy-1, 3, 5-trimellitic aldehyde, 2-hydroxy-1, 3, 5-trimellitic aldehyde and trimellitic aldehyde, the monomer two is one of 2,4, 6-tris (4' -aminophenyl) -1,3, 5-triazine and 1,3, 5-tris (4-aminophenyl) benzene, and the molar ratio of the monomer one to the monomer two is 1:1.
Based on the technical scheme, preferably, the solvent in the step (1) is one of dimethyl sulfoxide and dioxane; the catalyst is acetic acid solution, and the mole ratio of the catalyst to the monomer I is (100-1000): 1.
Based on the above technical scheme, it is preferable that the concentration of the monomer I in the step (1) in the reaction system is 0.0001-0.01mol/L.
Based on the technical scheme, preferably, siO in the step (1) 2 Is SiO 2 Nanospheres or SiO 2 Microsphere, COF and SiO 2 The mass ratio of (2) to (100) is 1.
Based on the technical scheme, the COF/SiO is preferably prepared by a colloid method in the step (1) 2 In the carrier process, after solvent is added, a cationic surfactant solution (CTAB) and an anionic surfactant solution (SDS) are also added, the mole ratio of the cationic surfactant to the monomer I is (10-50) 1, and the mole ratio of the anionic surfactant to the monomer I is (0.5-10) 1.
Based on the technical scheme, preferably, the solvent for Soxhlet extraction in the step (1) is tetrahydrofuran or ethanol, the temperature of Soxhlet extraction is 100-120 ℃, and the time is 12-48h.
Based on the above technical scheme, preferably, the metal salt precursor added in the step (2) is chloroplatinic acid, chloroplatinic acid salt, chloropalladate acid or chloropalladate salt.
Based on the technical proposal, preferably, the metal salt precursor and the COF/SiO added in the step (2) are 2 The mass ratio of the carrier is (2-50): 1000.
Based on the technical scheme, the specific drying process in the step (2) is preferably to dry in flowing air at 50-100 ℃ for 1-5h.
Based on the technical scheme, preferably, H in the step (2) 2 The reduction is carried out in a tube furnace, H 2 The flow rate is 10-20mL/min, the heating rate is 1-5 ℃/min, the reduction temperature is 165-200 ℃, and the reduction time is 1-3h.
Another object of the present invention is to provide the above catalyst M/COF/SiO 2 The application in the selective hydrogenation reaction of aldehyde/ketone compounds.
Based on the technical scheme, the preferable selective hydrogenation reaction conditions of the aldehyde/ketone compounds are as follows: the aldehyde/ketone compound, alcohol and the catalyst are put into a closed high-pressure reaction kettle, and hydrogenolysis reaction is carried out for 0.5 to 4 hours under the conditions of 1 to 4MPa of hydrogen pressure and 50 to 80 ℃, and the temperature is reduced and the catalyst is separated, thus obtaining the corresponding hydrogenation product.
Based on the technical scheme, preferably, the aldehyde/ketone compounds comprise acetophenone, p-methylacetophenone, m-methylacetophenone, o-methylacetophenone, p-methoxyacetophenone, p-tert-butylacetophenone, p-isobutylacetophenone, p-trifluoromethyl acetophenone, benzaldehyde, acetone, butyraldehyde, 4-phenyl-2-butanone, 4-methyl-2-pentanone, 2-hexanone and dodecanal.
The catalyst prepared by the invention has the following advantages:
1. COF/SiO prepared by the invention 2 The carrier is uniformly coated, and the prepared metal nano particles loaded by the multi-active site catalyst have smaller particle size and uniform distribution and have no obvious agglomeration.
2. M/COF/SiO prepared by the invention 2 The interaction between the functional group on the COF and the carbonyl in the catalyst can activate the carbonyl preferentially, and the metal nano particles rapidly dissociate H 2 The obtained active hydrogen overflows to hydrogenate carbonyl activated by COF to generate alcohol, the multi-site activation enables the catalyst to catalyze aldehyde/ketone compounds to selectively hydrogenate to generate corresponding alcohol compounds with high activity and high selectivity under relatively mild conditions, the selectivity and activity in the selective hydrogenation reaction of aldehyde/ketone compounds can be obviously improved, and the catalytic effect is obviously better than that of a comparative catalyst M/SiO 2 The catalyst has important application prospect in selective hydrogenation of aldehyde/ketone compounds to generate alcohol, and the synergistic catalysis of multi-site activation provides an effective way for simultaneously improving the hydrogenation activity and selectivity of the polyfunctional group substrate.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described.
FIG. 1 shows the COF-1/SiO obtained in example 1 2 Transmission Electron Microscope (TEM) photographs of the carrier;
FIG. 2 is a COF-2/SiO obtained in example 2 2 Transmission Electron Microscope (TEM) photographs of the carrier;
FIG. 3 is a COF-3/SiO obtained in example 3 2 Transmission Electron Microscope (TEM) photographs of the carrier;
FIG. 4 shows the COF-4/SiO obtained in example 4 2 Transmission Electron Microscope (TEM) photographs of the carrier;
FIG. 5 shows the COF-5/SiO obtained in example 5 2 Transmission Electron Microscope (TEM) photographs of the carrier;
FIG. 6 shows the COF-6/SiO obtained in example 6 2 Transmission Electron Microscope (TEM) photographs of the carrier;
FIG. 7 is a COF-7/SiO obtained in example 7 2 Transmission Electron Microscope (TEM) photographs of the carrier;
FIG. 8 is a high resolution transmission electron microscope (HR-TEM) photograph of the catalyst obtained in example 8;
FIG. 9 is an argon adsorption/desorption graph of the catalyst obtained in example 8;
FIG. 10 is a high resolution transmission electron microscope (HR-TEM) photograph of the catalyst obtained in comparative example 1;
FIG. 11 is an argon adsorption/desorption graph of the catalyst obtained in comparative example 1.
Detailed Description
The following examples serve to further illustrate the invention without however limiting the scope of the invention as defined by the appended claims.
Example 1: COF-1/SiO synthesized by colloid method 2 Carrier body
2.3mg of 1,3, 5-tricarboxyl phloroglucinol and 3.9mg of 2,4, 6-tris (4' -aminophenyl) -1,3, 5-triazine were added to a round bottom flask, followed by 0.1mL of dimethyl sulfoxide and mixed well. 84mg of CTAB and 2.4mg of SDS were dissolved in 9.5mL of water, added to the above-mentioned COF monomer solution and mixed again uniformly, then 0.5mL of acetic acid was added, and stirred and mixed uniformly. After 48 hours 500mg of SiO was added 2 Nanospheres (COF 1% -30% of the total catalyst by adjusting SiO) 2 Is adjusted by the amount of (1% COF/SiO in this example) 2 ) StirringFiltering for 24 hours, extracting with ethanol for 48 hours, and drying to obtain COF-1/SiO 2 A carrier.
The carrier COF-1/SiO was subjected to a transmission electron microscope (FIG. 1) 2 Characterization can be seen to be COF-1/SiO 2 Is a pellet with particle diameter of about 26nm, COF vs. SiO 2 The coating of (2) is relatively uniform.
Example 2: COF-2/SiO synthesized by colloid method 2 Carrier body
This example is essentially the same as example 1 except that the COF monomer used is changed from 2,4, 6-tris (4' -aminophenyl) -1,3, 5-triazine to 1,3, 5-tris (4-aminophenyl) benzene and the resulting support is designated COF-2/SiO 2 。
Example 3: COF-3/SiO synthesized by colloid method 2 Carrier body
The procedure of this example is essentially the same as that of example 1, except that the COF monomer used is changed from 1,3, 5-tricarboxyl phloroglucinol to trimellitic aldehyde, and the resulting carrier is designated as COF-3/SiO 2 。
Example 4: solvothermal method for synthesizing COF-4/SiO 2 Carrier body
Into a round bottom flask were added 2.3mg of 1,3, 5-tricarboxyl phloroglucinol and 3.9mg of 2,4, 6-tris (4' -aminophenyl) -1,3, 5-triazine, followed by 10mL of dioxane and 0.1mL of acetic acid, and the mixture was stirred and mixed well. 500mg of amino-modified SiO are added 2 Microspheres (COF 1% -30% of the total catalyst by adjusting SiO) 2 Is adjusted by the amount of (1% COF/SiO in this example) 2 ) After stirring for 4 hours, the temperature was raised to 100℃and maintained for 24 hours. Filtering and Soxhlet extracting in tetrahydrofuran for 24 hr, and drying to obtain COF-4/SiO 2 A carrier.
Example 5: solvothermal synthesis of COF-5/SiO 2 Carrier body
This example is essentially the same as example 4 except that the COF monomer used is changed from 2,4, 6-tris (4' -aminophenyl) -1,3, 5-triazine to 1,3, 5-tris (4-aminophenyl) benzene and the resulting support is designated COF-5/SiO 2 。
Example 6: solvothermal method for synthesizing COF-6/SiO 2 Carrier body
The procedure of this example is essentially the same as that of example 4, except that the COF monomer used is changed from 1,3, 5-tricarboxyl phloroglucinol to 2, 4-dihydroxy-1, 3, 5-trimesic aldehyde, and the resulting carrier is designated as COF-6/SiO 2 。
Example 7: solvothermal method for synthesizing COF-7/SiO 2 Carrier body
The procedure of this example is essentially the same as that of example 4, except that the COF monomer used is changed from 1,3, 5-tricarboxyl trimellitic acid to 2-hydroxy-1, 3, 5-trimesic aldehyde, and the resulting carrier is designated as COF-7/SiO 2 。
Example 8: synthesis of Pt/COF-1/SiO by wet impregnation method 2
At 2mL H 2 200mg of COF-1/SiO are added to O 2 Then H with the mass concentration of 7.6mg/mL is added 2 PtCl 6 0.1-2.9 mL of aqueous solution, stirring at room temperature for 12h, centrifuging, and pouring out supernatant. The solid obtained is dried in flowing air at 100deg.C for 1 hour, and at 200deg.C with H 2 Reduction was carried out for 2 hours to give catalyst A.
When H is added 2 PtCl 6 When the water solution is 0.1mL, the Pt metal content in the prepared catalyst is 0.2%; when H is added 2 PtCl 6 At 2.9mL of the aqueous solution, the Pt metal content of the prepared catalyst was 5%.
Catalyst a was characterized by transmission electron microscopy (fig. 8) and it was seen that Pt nanoparticles were approximately 1.6nm in size, well dispersed, and free of significant agglomeration. The argon adsorption result shows that the specific surface area of the material is 133m 2 g -1 (FIG. 9).
Examples 9 to 14: synthesis of Pt/COF-2-7/SiO by wet impregnation method 2
Examples 9 to 14 are essentially identical to example 8, except that the carriers used are COF-2 to 7/SiO, respectively 2 Catalysts B to G are obtained.
Example 15: synthesis of Pd/COF-1/SiO by wet impregnation method 2
The procedure of this example was essentially the same as that of example 8, except that sodium chloropalladate was used as the metal salt to obtain catalyst H.
Examples 16 to 21: wet impregnation process of synthesizing Pd/COF-2-7/SiO 2
Examples 16 to 21 are essentially identical to example 15, except that the carriers used are COF-2 to 7/SiO, respectively 2 Catalysts I to N are obtained.
Example 22: catalyst A for selective hydrogenation of aldehyde/ketone compounds
The acetophenone hydrogenation reaction is exemplified. 69mg of solid catalyst 0.2% Pt/COF-1/SiO was weighed out 2 17mg of substrate acetophenone and 2mL of ethanol were placed in an autoclave. And replacing air in the kettle with hydrogen for 5 times, regulating the pressure of the hydrogen to 2MPa, and stirring at 60 ℃ for reaction. After the reaction, hydrogen is released, the catalyst is removed by filtration, and the reaction liquid is subjected to chromatographic analysis to obtain a catalytic result.
The remaining substrates (table 1) were reacted with varying amounts of substrate at S/c=200 (where acetone, benzaldehyde S/c=1000, furfural S/c=800) with the remaining conditions unchanged.
When the catalyst with the remaining metal content was used for this reaction, the amount of substrate was unchanged, and the amount of catalyst was changed at S/c=200.
Examples 23 to 35: catalyst B-N for selective hydrogenation reaction of aldehyde/ketone compound
Examples 23 to 35 were substantially the same as example 22 except that catalysts B to N were added to the reaction system.
Comparative example 1: synthesis of Pt/SiO 2 And is used for the selective hydrogenation of aldehyde/ketone compounds
The hydrogenation reaction of acetophenone is catalyzed by a Pt catalyst supported by silicon dioxide. The synthesis process of the catalyst is as follows: the catalyst was synthesized by the method reported in the literature (Journal of Catalysis,2004, volume 225, pages 203-212). 200mg of SiO 2 Dispersed in 1.78mL of H having a pH of 9.5 2 O was further added 4mg of Pt (NH) 3 ) 4 (NO 3 ) 2 After stirring for 1 hour, the resulting solid product was filtered, washed with water and dried in flowing air at 100 ℃Overnight. Then roasting in air at a heating rate of 1 ℃/min for 3 hours at 100 ℃, and finally, H at 250 DEG C 2 (5 ℃/min) reducing for 2 hours to obtain Pt/SiO 2 。
The catalytic reaction process is as follows: comparative example 1 was substantially the same as in example 22 except that the catalyst added was comparative example 1 catalyst with a mass of 34mg (Pt metal content in the prepared catalyst was 0.4%).
Comparative example 2: synthesis of Pd/SiO 2 And is used for the selective hydrogenation of aldehyde/ketone compounds
The hydrogenation reaction of acetophenone is catalyzed by a Pd catalyst supported by silicon dioxide as a carrier. The synthesis process of the catalyst is as follows: the catalyst was synthesized by the method reported in the literature (ACS Catalysis,2018, volume 8, pages 6476-6485). 250mg of SiO 2 Dispersed in 1.25mL of H at pH 11 2 In O, 5mg of Pt (NH) is added 3 ) 4 (NO 3 ) 2 After 30 minutes of ultrasound, the mixture was allowed to stand for 2 hours, and the filtered solid product was oven dried at 60℃for 2 hours. Then baked in air at 125 deg.C for 1 hr at a heating rate of 1 deg.C/min. Finally, H at 165 DEG C 2 (1 ℃/min) reducing for 2 hours to obtain Pd/SiO 2 。
The catalytic reaction process is as follows: comparative example 2 was substantially the same as in example 22 except that the catalyst added was the catalyst of comparative example 2, and the mass was 19mg (the Pd metal content in the prepared catalyst was 0.4%).
TABLE 1 reaction evaluation results for the catalysts of example 22 and comparative example 1
Figure BDA0003357454170000071
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Figure BDA0003357454170000081
* The catalytic results of example 22 are outside the brackets, and the catalytic results of comparative example 1 are in brackets.
From the above results, it can be seen that Pt/COF/SiO of the present application 2 Pt/SiO of catalyst comparative example 2 The catalyst has higher activity and selectivity in the hydrogenation reaction of aldehyde/ketone compounds, which shows that the multi-activation site catalyst can effectively improve the activity and selectivity of selective hydrogenation of aldehyde/ketone compounds to generate alcohol.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. A multi-activation site catalyst is characterized in that the catalyst is uniformly spread on SiO by COF 2 Surface prepared COF/SiO 2 The composite material is used as a carrier, a wet impregnation method is adopted to load metal salt on the carrier, and the supported metal nanoparticle catalyst is obtained through reduction.
2. The multiple activation site catalyst of claim 1, wherein the COF content is 1-30% and the metal content is 0.2-5% based on the total weight of the catalyst.
3. The method for preparing the multi-activation-site catalyst according to claim 1 or 2, which is characterized by mainly comprising the following steps:
(1) Preparing COF/SiO by colloid method or solvothermal method 2 And (3) a carrier: adding the COF monomer into a reaction container, adding a solvent and a catalyst, stirring and mixing uniformly, and then adding SiO 2 Stirring for 12-48h or stirring for 1-12h, heating to 90-120deg.C, maintaining for 12-48h, filtering, performing Soxhlet extraction, and drying to obtain COF/SiO 2 A carrier;
(2) Impregnating by wet methodThe method prepares M/COF/SiO 2 : COF/SiO 2 The carrier is dispersed in H 2 Adding metal salt precursor solution into O, stirring at room temperature for 4-24 hr, centrifuging, drying the obtained solid, and adding into H 2 Reducing at 150-300 deg.C for 0.5-3 hr.
4. The process according to claim 3, wherein the COF monomer in the step (1) is composed of a monomer one of 1,3, 5-tricarboxyl phloroglucinol, 2, 4-dihydroxy-1, 3, 5-trimellitic aldehyde, 2-hydroxy-1, 3, 5-trimellitic aldehyde and a monomer two of 2,4, 6-tris (4' -aminophenyl) -1,3, 5-triazine and 1,3, 5-tris (4-aminophenyl) benzene, and the molar ratio of the monomer one to the monomer two is 1:1.
5. The method according to claim 3, wherein the solvent in the step (1) is one of dimethyl sulfoxide and dioxane; the catalyst is acetic acid solution, and the mol ratio of the catalyst to the monomer I is (100-1000): 1; siO (SiO) 2 Is SiO 2 Nanospheres or SiO 2 Microsphere, COF and SiO 2 The mass ratio of (2) to (100) is 1.
6. The method according to claim 3, wherein the COF/SiO is prepared by a colloid method in the step (1) 2 In the carrier process, after the solvent is added, a cationic surfactant solution and an anionic surfactant solution are also added, wherein the molar ratio of the cationic surfactant to the monomer I is (10-50): 1, and the molar ratio of the anionic surfactant to the monomer I is (0.5-10): 1.
7. The process according to claim 3, wherein the solvent for Soxhlet extraction in step (1) is tetrahydrofuran or ethanol, the temperature of Soxhlet extraction is 100 to 120℃and the time is 12 to 48 hours.
8. The method according to claim 3, wherein the metal salt precursor in the step (2) is chloroplatinic acid or chlorineSodium palladium; metal salt precursors and COF/SiO 2 The mass ratio of the carrier is (2-50): 1000.
9. A process according to claim 3, wherein the drying in step (2) is carried out in a flowing air at 50-100 ℃ for 1-5 hours; h 2 The reduction is carried out in a tube furnace, H 2 The flow rate is 10-20mL/min, the heating rate is 1-5 ℃/min, the reduction temperature is 165-200 ℃, and the reduction time is 1-3h.
10. Use of the multiple activation site catalyst of claim 1 or 2 in selective hydrogenation of aldehyde/ketone compounds.
CN202111356677.5A 2021-11-16 2021-11-16 Multi-activation-site catalyst and preparation method and application thereof Pending CN116135312A (en)

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