CN116586079A - Monoatomic cobalt catalyst, preparation method and application - Google Patents

Monoatomic cobalt catalyst, preparation method and application Download PDF

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Publication number
CN116586079A
CN116586079A CN202310557610.0A CN202310557610A CN116586079A CN 116586079 A CN116586079 A CN 116586079A CN 202310557610 A CN202310557610 A CN 202310557610A CN 116586079 A CN116586079 A CN 116586079A
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catalyst
trifluoromethyl
monoatomic
bis
cobalt
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谭裕兴
刘清雷
张恩源
谭本祝
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Hunan Beihong New Materials Co ltd
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Hunan Beihong New Materials 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C241/02—Preparation of hydrazines
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a single-atom cobalt catalyst, a preparation method and application thereof. The metal organic framework compound is used as a carrier, and the monoatomic Co-S-C catalyst is obtained through reduction reaction, wherein the Co loading amount is 0.5-5wt%, and the non-noble metal catalyst greatly reduces the cost of synthesizing the 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl intermediate hydroazobenzene and has great industrial application value for preparing the 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.

Description

Monoatomic cobalt catalyst, preparation method and application
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a monoatomic cobalt catalyst, a preparation method and application thereof.
Background
2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl is an excellent intermediate product of material chemical industry, is also one of important raw materials for synthesizing soluble polyimide, and because two trifluoromethyl groups at 2,2' -positions in the molecular structure generate torsion angles between two benzene rings of biphenyl to cause a non-planar structure due to the steric hindrance effect, the polyimide film material of diamine monomer taking TFDB as a core has a plurality of special properties, such as high solubility, light color, high thermal stability, good mechanical strength and good light transmittance. Therefore, research into a large-scale production method of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl has great industrial value.
The synthesis method reported in Chinese patent CN101337895A takes 2-bromo-5-nitrobenzotrifluoride as a raw material, carries out coupling reaction under the catalysis of transition metals (Pd, cu and Ni) to obtain 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and then carries out catalytic hydrogenation on Cu oxide or metal Pd to obtain 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl. The method has the advantages that: the three wastes are less. The disadvantage is that the price of 2-bromo-5-nitro benzotrifluoride is high, the production cost is high, and the industrialized mass production is not facilitated. Chinese patent CN105541637a discloses a method for obtaining 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl from 2,2 '-bis (trifluoromethyl) -4,4' -dinitrobiphenyl as raw material by using anhydrous ammonium formate as a reducing agent and zinc powder as a catalyst as a reducing agent. The biggest problem of this method is that the raw material 2,2 '-bis (trifluoromethyl) -4,4' -dinitrobiphenyl must be obtained by nitration, but the present nitration reaction cannot be realized in a conventional reaction kettle, so that the raw material is not easily obtained.
The synthesis method reported in Chinese patent CN101525294A has the problems of large zinc powder consumption, large solid waste amount of waste alkali liquor and zinc oxide and the like in the reduction of industrial zinc powder, so that the environmental protection cost is high, the impurities are more, the yield is low, and the industrial production is not facilitated.
According to the method, hydrogen is used as a reducing agent, pd/C is used as a catalyst, pd loading is high, pd removal is serious after the reaction is repeated for several times, so that the catalyst is abandoned and cannot be reused, and a Pd noble metal catalyst belongs to rare resources, is high in price, and is high in cost and unsuitable for industrial production.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, which has high activity and long service life and adopts non-noble metal cobalt, and a preparation method thereof.
In order to solve the problems, the invention provides a single-atom Co-S-C catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, which takes sulfur-doped porous carbon as a carrier, and metal single-atom Co is dispersed in the carrier; the mass percentage of the metal monoatomic Co in the catalyst is 0.5-5wt%.
The second object of the present invention is to provide a method for preparing the above catalyst, specifically comprising: the metal organic framework compound MOF and cobalt salt are used as raw materials, and the monoatomic Co-S-C catalyst is obtained after reduction and calcination treatment.
According to one embodiment of the invention, the metal organic framework compound MOF is UiO66, uiO66-NH 2 One or more of UiO 66-OH.
According to one embodiment of the present invention, the preparation method specifically includes the following steps: (1) Adding the MOF into cobalt salt solution for reduction; (2) Filtering, drying and calcining under inert atmosphere to obtain the single-atom Co-S-C catalyst.
According to one embodiment of the invention, the cobalt salt is one or more of cobalt chloride, cobalt acetate and cobalt nitrate.
According to one embodiment of the invention, the concentration of the cobalt salt solution is 1-10 wt.%. The solvent of cobalt salt is one or more of methanol, ethanol, water and DMF.
According to one embodiment of the invention, in step (1), the reducing agent is sodium borohydride or lithium aluminum hydride.
According to an embodiment of the invention, in step (1), the temperature of the reduction is 60-160 ℃, preferably 100-130 ℃; the reduction time is 1 to 10 hours, preferably 1 to 6 hours.
According to one embodiment of the present invention, in step (2), the inert atmosphere is one or more of nitrogen or argon.
According to one embodiment of the invention, in step (2), the calcination is carried out at a temperature of 600-1000 ℃ for a time of 4-8 hours.
The third object of the invention is to provide the application of the catalyst or the catalyst prepared by the preparation method in the synthesis of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
According to one embodiment of the present invention, the above synthesis method comprises the steps of:
s1, dissolving m-nitro benzotrifluoride in an organic solvent, adding the catalyst into the organic solvent, placing the catalyst in a high-pressure reactor, adding an inorganic alkali aqueous solution, and introducing H 2 Reacted to H 2 Stopping when no longer absorbed, and preparing the 3,3' -bis (trifluoromethyl) diphenyl hydrazine;
s2, under the protection of nitrogen, 3' -bis (trifluoromethyl) diphenyl hydrazine is taken as a raw material, and a rearrangement reaction is carried out under the action of inorganic acid, so that 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl is prepared.
The reaction scheme is as follows:
according to one embodiment of the invention, in step S1, the reaction temperature is 10-100deg.C, preferably 50-70deg.C; the pressure of the reaction is 0.1-1Mpa, preferably 0.3-0.6Mpa.
According to an embodiment of the present invention, in step S1, the organic solvent is one or more of methanol, ethanol, DMF, preferably methanol.
According to one embodiment of the present invention, in step S2, the inorganic acid is hydrochloric acid or sulfuric acid.
The beneficial effects are that:
the catalyst modified by the method has lower load, can be repeated for more than 10 times, still has higher yield and higher stability, and therefore, the cost is lower. The invention obtains a non-noble metal monoatomized Co-S-C catalyst based on the prior art. The catalyst has the characteristics of low load, good stability, repeated use (more than 30 times), low cost and the like, belongs to a non-noble metal catalyst, is used for catalyzing m-nitrobenzotrifluoride to prepare 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, and remarkably reduces the production cost of the 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl. The invention has the advantages that the catalyst loaded by single-atom Co is prepared by taking a metal organic framework compound as a carrier, the Co loading amount is 0.5-5wt% through the reduction reaction of the single-atom Co-S-C catalyst, and the non-noble metal catalyst greatly reduces the cost of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl intermediate hydroazobenzene and has great industrial application value for preparing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
Drawings
FIG. 1 is an XRD pattern of Co-S-C-1 catalyst prepared in preparation example 1;
FIG. 2, panel a, is a TEM characterization of the UiO66 pyrolytic carbon;
FIG. 2 b is a TEM characterization of Co-S-C-1 prepared in preparation example 1;
FIG. 3 is a cobalt single-atom catalyst spherical aberration electron microscope of Co-S-C-1 prepared in preparation example 1.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure. It should also be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, since various insubstantial modifications and adaptations of the invention to those skilled in the art based on the foregoing disclosure are intended to be within the scope of the invention and the specific process parameters and the like set forth below are merely one example of a suitable range within which one skilled in the art would choose from the description herein without being limited to the specific values set forth below.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto, and the apparatus and reagents used in the examples of the present disclosure are those commonly used by those skilled in the art unless otherwise specified.
Preparation example 1
A5 wt% cobalt chloride solution was prepared, and UiO66 was placed in the above solution and reduced with sodium borohydride as a reducing agent at 25℃for 5 hours. Filtering, drying, and adding nitrogen N 2 Calcining for 5 hours at 600 ℃ under the atmosphere to obtain the monoatomic catalyst Co-S-C-1, wherein the content of Co is 1.2 weight percent.
Preparation example 2
Preparing 5wt% cobalt chloride solution, and adding UiO66-NH 2 Placing the mixture in the solution, and reducing the mixture for 5 hours at the temperature of 25 ℃ by taking lithium aluminum hydrogen as a reducing agent. Filtering, drying, and calcining at 600 ℃ for 5 hours under argon atmosphere to obtain the monoatomic catalyst Co-S-C-2, wherein the content of Co is 1.8wt%.
Preparation example 3
A5 wt% cobalt chloride solution was prepared, and UiO66-OH was placed in the above solution and reduced at 25℃for 5 hours with sodium borohydride as a reducing agent. Filtering, drying, and calcining for 5 hours at 600 ℃ in nitrogen atmosphere to obtain the single-atom catalyst Co-S-C-3, wherein the content of Co is 2wt%.
Preparation example 4
A5 wt% cobalt chloride solution was prepared, uiO66-OH was placed in the above solution, and lithium aluminum hydrogen was used as a reducing agent, and the solution was reduced at 25℃for 5 hours. Filtering, drying, and calcining for 5 hours at 600 ℃ under argon atmosphere to obtain the monoatomic catalyst Co-S-C-4, wherein the content of Co is 1.5wt%.
Preparation example 5
A5 wt% cobalt chloride solution was prepared, uiO66-OH was placed in the above solution, and lithium aluminum hydrogen was used as a reducing agent, and the solution was reduced at 25℃for 5 hours. Filtering, drying, and calcining for 5 hours at 600 ℃ in nitrogen atmosphere to obtain the single-atom catalyst Co-S-C-5, wherein the content of Co is 1.5wt%.
Example 1
43.8g (0.225 mol) of m-nitrobenzotrifluoride are dissolved in 1 in a 1000mL autoclave00.0mL of methanol was charged with 1.5g of monoatomic catalyst Co-S-C-1, 13.7g of 40% aqueous sodium hydroxide solution, and H was introduced 2 Pressurizing to 0.4MPa and 25 ℃, and carrying out vigorous stirring reaction for 4 hours until hydrogen is not absorbed any more, stopping stirring reaction, filtering and recovering the monoatomic catalyst Co-S-C-1 to obtain 42g of 3,3' -bis (trifluoromethyl) diphenyl hydrazine methanol solution with the GC content of 99.5 percent.
Under the protection of nitrogen, 120 g of 30wt% hydrochloric acid solution is added into a 1000m L three-neck flask, stirring is started, all 42g of 3,3' -bis (trifluoromethyl) diphenyl hydrazine-containing methanol solution obtained in the process is dripped at 20 ℃ to react for 3h, standing and sampling are used for high-efficiency liquid chromatographic analysis, 25wt% Na OH solution is prepared for neutralization until p H is 9-10 after the reaction is finished, a large amount of light yellow solid is precipitated in the solution, the solution is filtered, washed by clear water and recrystallized by ethanol, and a white crystal product 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl is obtained, and the yield is 72.5wt%.
Examples 2 to 5
Other conditions were the same as in example 1 except that the catalysts prepared in preparation examples 2 to 5 were used in this order, and specific parameters and results are shown in Table 1.
Comparative example 1
Other conditions were the same as in example 1 except that the catalyst added was a commercially available palladium on carbon catalyst having a Pd loading of 5% by weight, and specific parameters and results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the catalyst prepared by the invention can realize higher yield of the target product under the condition of lower metal Co loading. In addition, the price of the metal Co is far lower than Pd, so the catalyst prepared by the invention can greatly reduce the cost on the basis of ensuring higher yield compared with the palladium-carbon catalyst in the prior art.

Claims (10)

1. The monoatomic Co-S-C catalyst for synthesizing 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl is characterized in that sulfur-doped porous carbon is used as a carrier, and metal monoatomic Co is dispersed in the carrier; the mass percentage of the metal monoatomic Co in the catalyst is 0.5-5wt%.
2. The method for preparing the catalyst according to claim 1, wherein the monoatomic Co-S-C catalyst is obtained by taking metal organic framework compound MOF and cobalt salt as raw materials and performing reduction and calcination treatment.
3. The method of claim 2, wherein the metal organic framework compound MOF is UiO66, uiO66-NH 2 One or more of UiO 66-OH.
4. A method of preparation according to claim 3, comprising the specific steps of:
(1) Adding the MOF into cobalt salt solution for reduction;
(2) Filtering, drying and calcining under inert atmosphere to obtain the single-atom Co-S-C catalyst.
5. The method according to claim 4, wherein the cobalt salt is one or more of cobalt chloride, cobalt acetate and cobalt nitrate.
6. The method according to claim 4, wherein the concentration of the cobalt salt solution is 1 to 10wt%.
7. The method according to claim 4, wherein in the step (1), the reducing agent is sodium borohydride or lithium aluminum hydride.
8. The method according to claim 4, wherein in step (1), the temperature of the reduction is 60-160 ℃, preferably 100-130 ℃; the reduction time is 1 to 10 hours, preferably 1 to 6 hours.
9. The method according to claim 4, wherein in the step (2), the calcination is performed at 600 to 1000℃for 4 to 8 hours.
10. Use of the catalyst of claim 1 or the catalyst prepared by the method of any one of claims 2-9 in the synthesis of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
CN202310557610.0A 2023-05-17 2023-05-17 Monoatomic cobalt catalyst, preparation method and application Pending CN116586079A (en)

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