CN109704301B - Preparation method and application of cobalt-sulfur co-doped mesoporous carbon - Google Patents
Preparation method and application of cobalt-sulfur co-doped mesoporous carbon Download PDFInfo
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Abstract
The invention discloses cobalt-sulfur co-doped mesoporous carbon and a preparation method and application thereof, wherein citric acid monohydrate, magnesium nitrate hexahydrate and cobalt salt are used as raw materials, so that the preparation method is simple, the manufacturing cost is low, the popularization is easy, and the large-scale manufacturing can be carried out; meanwhile, the prepared cobalt-sulfur co-doped mesoporous carbon product has high stability, and can be used for preparing aromatic amine compounds; when the aromatic amine compound is prepared, the reaction is easy to operate, good reaction can be carried out under the conditions of normal pressure and 50-70 ℃, and the reaction condition is easier to realize compared with the generation method in the prior art; meanwhile, the cobalt-sulfur co-doped mesoporous carbon material has wide applicability, can play a good catalytic effect on various nitro compounds, greatly shortens the reaction time, has the highest yield of 98%, and has remarkably improved yield and higher economic benefit compared with a common preparation method in the prior art.
Description
Technical Field
The invention relates to the field of catalyst synthesis, in particular to a preparation method and application of cobalt-sulfur co-doped mesoporous carbon.
Background
Aromatic amine compounds are industrially important raw materials, have wide application range, and can be used for producing dyes, medicines, agricultural chemicals, additives, surfactants, textile assistants, chelating agents, polymers, flame retardants and the like.
In the prior art, aromatic amines are prepared mainly by reducing nitro groups, and the reduction methods mainly include the following methods: 1. reduction of metals in acidic, neutral and alkaline systems; 2, chemical reduction method: including sodium sulfide reduction, NaBH4, hydrazine hydrate reduction, and the like; 3. catalytic hydrogenation reduction method. In addition, there are many documents on the production of aniline by reduction reaction using nitrobenzene as a raw material, which is widely available and inexpensive, but this method usually requires a large amount of transition metals, and a large amount of inorganic waste is also generated in the whole production process. In 2005, the second army medical university of the people's liberation army of China (CN 169351 [ P ].2005-11-23) realized the synthesis of the trizandol antifungal compound through the process of reduction under the catalysis of active nickel and the reduction of hydrazine hydrate; in 2012, Pralay Das et al (Tetrahedron Lett, 2012, 53: 4858-. In 2015, Vicente et al (chem. eng.j, 2015, 261:53-59.) catalyzed reduction of p-nitrophenol using a catalyst with silver nanoparticles supported on copper doped titanium dioxide; in 2006, in the process of preparing 5-azaindole, Zhejiang university (CN1321118C [ P ].2006-1), the precursor of 5-azaindole needs to be reduced by 3-dimethylamine vinyl-4-nitropyridine nitrogen oxide by using palladium/carbon as a catalyst to obtain corresponding amine; in 2013, Suzhou Yongjian biological medicine limited company (CN103265457A [ P ].2013-08-28) discovered a synthesis method for synthesizing (R) -4-aminophenylethyl- (2-hydroxy-2-phenylethyl) -tert-butyl carbamate by catalytic reduction with palladium/carbon as a catalyst and hydrogen as a reducing agent; in 2015, the university of Henan university (CN104892427A [ P ].2015-09-09) discovered a preparation method of aminophenylethylamine, which adopts P-nitroanisole as a raw material, firstly reduces the para-nitro group of the P-nitroanisole into amino through catalytic hydrogenation, then protects the para-amino group through Boc anhydride, and then leads hydroxyl group to have substitution reaction with sulfonyl chloride compound to obtain sulfonic acid compound, then aminated, and finally removes Boc group to obtain the P-aminophenylethylamine. The above-mentioned preparation methods are effective for preparing aromatic amines, but have many problems including that the catalysts used are expensive, the preparation of the catalysts is very troublesome, or the reaction conditions are severe and need to be carried out under high pressure of hydrogen. These all limit the industrial popularization and application of the existing preparation technology.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method and application of cobalt-sulfur co-doped mesoporous carbon.
In order to achieve the purpose, the invention provides the following technical scheme: the cobalt-sulfur co-doped mesoporous carbon comprises the following substances in parts by weight:
5-10 parts of citric acid monohydrate;
3-7 parts of magnesium nitrate hexahydrate;
1-3 parts of cobalt salt.
As a further improvement of the invention, the cobalt salt is any one of cobalt sulfate heptahydrate and cobalt sulfamate.
As a further improvement of the invention, the preparation method of the cobalt-sulfur co-doped mesoporous carbon comprises the following steps:
the method comprises the following steps: weighing required substances according to a formula, adding citric acid monohydrate and magnesium nitrate hexahydrate into deionized water, stirring and dissolving to form a solution, and then placing the solution into an oven for reaction to prepare a precursor;
step two: stirring and mixing the precursor and cobalt salt to form a mixture; then putting the mixture into an atmosphere furnace for calcining under the protection of nitrogen; and after calcining, cooling to room temperature to obtain the cobalt-sulfur co-doped mesoporous carbon.
As a further improvement of the invention, the temperature of the oven is set to be 80-150 ℃ in the first step when the first step is placed in the oven for reaction, and the reaction time is 12-36 h.
As a further improvement of the invention, the temperature of the atmosphere furnace is set to be 700-900 ℃ when the calcination is carried out in the second step, and the calcination time is 0.5-3 h.
As a further improvement of the invention, the cobalt-sulfur co-doped mesoporous carbon is used as a catalyst for preparing aromatic amine compounds.
As a further improvement of the invention, the specific method of using the cobalt-sulfur co-doped mesoporous carbon as the catalyst comprises the steps of reacting a nitrobenzene ring compound and hydrazine hydrate at 50-70 ℃ for 4-24h under the catalysis of the cobalt-sulfur co-doped mesoporous carbon, filtering, extracting, washing with water, and drying to finally obtain the aromatic amine compound.
As a further improvement of the invention, the nitrobenzene ring compound is characterized in that a benzene ring has a nitro substituent, and at least one position except for the substituted nitro has an R substituent, wherein the R substituent is any one of H, C1-C6 alkoxy, halogen, C1-C6 alkyl, aryl, NR1R2 and naphthalene ring, and R1 and R2 are any one of H, C1-C6 alkyl, benzyl or aryl.
As a further improvement of the invention, the nitrobenzene ring compound and hydrazine hydrate react in a solvent, wherein the solvent is any one of toluene, water, ethanol, acetonitrile, dichloromethane and cyclohexane.
As a further improvement of the invention, the molar ratio of the nitrobenzene ring compound to the hydrazine hydrate is 1:1.5-1: 3; the molar ratio of the dosage of the nitrobenzene ring compound to the dosage of the cobalt-sulfur co-doped mesoporous carbon is 1:0.05-1: 0.2.
The invention has the beneficial effects that: the citric acid monohydrate, the magnesium nitrate hexahydrate and the cobalt salt are used as raw materials, so that the preparation method is simple, the preparation cost is low, the popularization is easy, and the large-scale preparation can be realized; meanwhile, the prepared cobalt-sulfur co-doped mesoporous carbon product has high stability, and can be used for preparing aromatic amine compounds; when the aromatic amine compound is prepared, the reaction is easy to operate, good reaction can be carried out at normal pressure and 50-70 ℃, and the reaction condition is easier to realize compared with the generation method in the prior art; meanwhile, the cobalt-sulfur co-doped mesoporous carbon material has wide applicability, can play a good catalytic effect on various nitrobenzene ring compounds, greatly shortens the reaction time, has the highest yield of 98%, and has remarkably improved yield and higher economic benefit compared with a common preparation method in the prior art.
Drawings
Fig. 1 is a detection diagram of a cobalt-sulfur co-doped mesoporous carbon material prepared in example 1 of the present invention; wherein 1a is a Scanning Electron Micrograph (SEM); 1b is a Transmission Electron Micrograph (TEM); 1c is a high power transmission electron micrograph (HRTEM); and 1d is an absorption and desorption curve.
Fig. 2 is an XPS diagram of the cobalt-sulfur co-doped mesoporous carbon material prepared in example 1 of the present invention.
Detailed Description
Example 1: the preparation method of the cobalt-sulfur co-doped mesoporous carbon comprises the following specific steps:
adding 4g of citric acid monohydrate and 2.5g of magnesium nitrate hexahydrate into 10mL of deionized water, stirring at the speed of 200rad/min for 15min to form a solution, then putting the solution into an oven at 120 ℃, and standing for 24 hours to obtain a foamy solid (precursor); and stirring the prepared precursor and 1g of cobalt sulfate heptahydrate at the speed of 300rad/min for 10min, mixing to form a mixture, then placing the mixture in an atmosphere furnace under the protection of nitrogen, calcining for 1 hour at the temperature of 800 ℃, and cooling to 25 ℃ after calcining to obtain the cobalt-sulfur Co-doped mesoporous carbon (SMC-Co).
Example 2: nitrobenzene reduction reaction catalyzed by cobalt-sulfur co-doped mesoporous carbon
Nitrobenzene (1mmol, 104ul), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 6 h. The product is extracted by ethyl acetate, and then filtered, extracted, washed by water and dried to finally obtain the brown yellow aniline with the yield of 98%.1H NMR(500MHz,CDCl3)7.12(t,J＝7.5Hz,2H),6.73(t,J＝7.5Hz,1H),6.61(d,J＝7.5Hz,2H),3.56(s,2H).13C NMR(500MHz,CDCl3)146.3,129.1,118.3,114.9。
Example 3: cobalt-sulfur co-doped mesoporous carbon catalyzed p-methyl nitrobenzene reduction reaction
P-methylnitrobenzene (1mmol,0.137mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 6 h. The product was extracted with ethyl acetate, filtered, extracted, washed with water, and then dried to finally obtain light yellow p-toluidine with a yield of 96%.1H NMR(500MHz,CDCl3)6.99(d,J＝8Hz,2H),6.63(d,J＝8Hz,2H),3.55(s,2H),2.27(s,3H).13C NMR(500MHz,CDCl3)143.8,129.7,127.7,115.2,20.38.
Example 4: o-methyl nitrobenzene reduction reaction catalyzed by cobalt-sulfur co-doped mesoporous carbon
O-methylnitrobenzene (1mmol,0.137mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 6 h. The product was extracted with ethyl acetate, filtered, extracted, washed with water, and then dried to obtain pale yellow o-toluidine with a yield of 96%.1H NMR(500MHz,CDCl3)7.09(t,J＝8Hz,2H),6.77(t,J＝8Hz,1H),6.71(d,J＝8Hz,2H),3.62(s,2H),2.21(s,3H).13C NMR(500MHz,CDCl3)144.5,130.3,126.9,122.2,118.5,114.8,17.2.
Example 5: cobalt-sulfur co-doped mesoporous carbon catalyzed reduction reaction of m-methyl nitrobenzene
O-methylnitrobenzene (1mmol,0.137mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 6 h. Extracting the product with ethyl acetate, filtering, extracting, washing with water, and drying to obtain the final productM-toluidine as a colored oil in 93% yield.1H NMR(500MHz,CDCl3)7.09(t,J＝7.5Hz,1H),6.62(d,J＝7.5Hz,1H),6.54-6.52(m,2H),3.61(s,2H),2.30(s,3H).13C NMR(500MHz,CDCl3)146.3,139.0,129.1,119.4,115.9,112.2,21.34.
Example 6: cobalt-sulfur co-doped mesoporous carbon catalyzed p-bromonitrobenzene reduction reaction
Para-bromonitrobenzene (1mmol,0.202mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 8 h. The product is extracted by ethyl acetate, and then filtered, extracted, washed by water and dried to finally obtain gray p-bromoaniline with the yield of 92 percent.1H NMR(500MHz,CDCl3)7.20(d,J＝8.5Hz,2H),6.52(d,J＝8.5Hz,2H),3.63(s,2H).13C NMR(500MHz,CDCl3)147.7,130.5,122.9,121.2,117.7,113.6.
Example 7: o-bromonitrobenzene reduction reaction catalyzed by cobalt-sulfur co-doped mesoporous carbon
O-bromonitrobenzene (1mmol,0.202mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 8 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed by water and dried to finally obtain the white o-bromoaniline with the yield of 93 percent.1H NMR(500MHz,CDCl3)7.42(d,J＝8Hz,1H),7.12(t,J＝8Hz,1H),6.77(d,J＝8Hz,1H),6.64(t,J＝8Hz,1H),4.10(s,2H).13C NMR(500MHz,CDCl3)144.0,132.5,128.3,119.3,115.7,109.2.
Example 8: cobalt-sulfur co-doped mesoporous carbon catalyzed m-bromonitrobenzene reduction reaction
M-bromonitrobenzene (1mmol,0.202mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 8 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed by water and dried to finally obtain the light yellow m-bromoaniline with the yield of 93 percent.1H NMR(500MHz,CDCl3)7.09(t,J＝7.5Hz,1H),6.62(d,J＝7.5Hz,1H),6.54-6.52(m,2H),3.61(s,2H),2.30(s,3H).13C NMR(500MHz,CDCl3)146.3,139.0,129.1,119.4,115.9,112.2,21.34.
Example 9: cobalt-sulfur co-doped mesoporous carbon catalyzed p-fluoronitrobenzene reduction reaction
Parafluoronitrobenzene (1mmol,0.141mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 8 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed by water and dried to finally obtain the light yellow para-fluoroaniline with the yield of 92 percent. 1H NMR (500MHz, CDCl3)6.87(t, J ═ 9Hz,2H),6.62-6.59(m,2H),3.50(s,2H).13C NMR(500MHz,CDCl3)157.2,155.3,142.4,116,115.9,115.5,115.4.
Example 10: cobalt-sulfur co-doped mesoporous carbon catalyzed p-chloronitrobenzene reduction reaction
P-chloronitrobenzene (1mmol,0.158mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 6 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed and dried to finally obtain light yellow parachloroaniline with the yield of 98%.1H NMR(500MHz,CDCl3)7.10(d,J＝8.5Hz,2H),6.60(d,J＝8.5Hz,2H),3.66(s,2H).13C NMR(500MHz,CDCl3)144.9,129.0,123.0,116.2.
Example 11 Co-S codoped mesoporous carbon catalyzed reduction of P-iodonitrobenzene
P-iodonitrobenzene (1mmol,0.249mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 70 ℃ for 24 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed and dried to finally obtain white p-iodoaniline with the yield of 96%.1H NMR(500MHz,CDCl3)7.36(d,J＝8.5Hz,2H),6.41(d,J＝8.5Hz,2H),3.63(s,2H).13C NMR(500MHz,CDCl3)146.0,137.7,117.1,79.1.
Example 12: reduction reaction of p-methoxynitrobenzene catalyzed by cobalt-sulfur co-doped mesoporous carbon
P-methoxynitrobenzene (1mmol,0.153mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 8 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed by water and dried to finally obtain light yellow p-anisidine with the yield of 87%.1H NMR(500MHz,CDCl3)6.76(d,J＝9Hz,2H),6.64(d,J＝9Hz,2H),3.75(s,3H),3.44(s,2H).13C NMR(500MHz,CDCl3)152.6,139.9,116.3,114.7,55.6.
Example 13 Co-Sulfur Co-doped mesoporous carbon catalyzed reduction of 1, 3-dimethyl-2-Nitrobenzene
1, 3-dimethyl-2-nitrobenzene (1mmol,0.151mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 8 h. Extracting the product with ethyl acetate, filtering, extracting, washing with water, and filteringAfter drying, 1, 3-dimethyl-2-phenylamine was finally obtained in a pale yellow yield of 94%.1H NMR(500MHz,CDCl3)7.03(d,J＝7.5Hz,2H),6.74(d,J＝7.5Hz,1H),3.56(s,2H),2.26(s,6H).13C NMR(500MHz,CDCl3)142.6,128.1,121.6,117.9,17.5.
Example 14 Co-Sulfur Co-doped mesoporous carbon catalyzed reduction of 3-nitropyridine
3-Nitropyridine (1mmol,0.124mg), SMC-Co (20mg), toluene (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 4 h. The product was extracted with ethyl acetate, filtered, extracted, washed with water, and then dried to give pale yellow 3-aminopyridine in 82% yield.1H NMR(500MHz,DMSO)7.95(d,J＝3.5Hz,1H),7.73(d,J＝3.5Hz,1H),7.03(dd,J1＝3.5Hz,J2＝8.5Hz,1H),6.93(d,J＝8.5Hz,1H),5.28(s,2H).13C NMR(500MHz,DMSO)145.0,136.9,136.2,123.8,120.1.
Example 15: 1-nitronaphthalene reduction reaction catalyzed by cobalt-sulfur co-doped mesoporous carbon
1-nitronaphthalene (1mmol,0.173mg), SMC-Co (30mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 20 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed by water and dried to finally obtain the white 1-aminonaphthalene with the yield of 90 percent.1H NMR(500MHz,DMSO)8.14(d,J＝8Hz,1H),7.75(d,J＝8Hz,1H),7.43-7.37(m,2H),7.25(t,J＝8Hz,1H),7.12(d,J＝8Hz,1H),6.77(d,J＝8Hz,1H),5.76(s,2H).13C NMR(125MHz,DMSO)144.7,134.3,127.9,126.8,125.5,123.7,122.9,122.4,115.6,107.7.
Example 16 Co-S codoped mesoporous carbon catalyzed reduction of p-Nitrobenzamide
p-Nitrobenzamide (1mmol,0.166mg), SMC-Co (20mg), water (2mL), hydrazine hydrate (2.4mmol,146ul) were added in one portion to a 20mL reaction tube and reacted at 60 ℃ for 8 h. The product is extracted by ethyl acetate, and then is filtered, extracted, washed by water and dried to finally obtain the white p-aminobenzamide with the yield of 97 percent.1H NMR(500MHz,DMSO)7.63(d,J＝6Hz,3H),6.96(s,1H),6.55(d,J＝6Hz,2H),5.63(s,2H).13C NMR(500MHz,DMSO)167.5,153.2,131.3,117.0,112.6.
In the invention, the product is extracted by using ethyl acetate as an extraction liquid.
The molecular structural formula of the nitrobenzene ring compound is shown as
The R group is any one of H, C1-C6 alkoxy, halogen, C1-C6 alkyl, aryl and NR1R2 and a naphthalene ring, wherein R1 and R2 are any one of H, C1-C6 alkyl, benzyl or aryl.
Respectively detecting the sample prepared in the first step by using a scanning electron microscope, a transmission electron microscope and a high-magnification transmission electron microscope to obtain a graph 1a, a graph 1b and a graph 1 c; as can be seen from fig. 1a,1b, and 1c in combination with fig. 1d, the sample obtained in example 1 has a multilayer sheet structure.
The sample prepared in example 1 was examined with an X-ray photoelectron spectrometer to obtain fig. 2; as can be seen from FIG. 2, the sample obtained in example 1 had a sulfur content of 9.30%, a cobalt content of 12.00% and a carbon content of 28.59%.
According to the cobalt-sulfur co-doped mesoporous carbon and the preparation method and application thereof, when the cobalt-sulfur co-doped mesoporous carbon is prepared, citric acid monohydrate, magnesium nitrate hexahydrate and cobalt salt are used as raw materials, and since sulfur elements are doped into the raw materials, cobalt sulfate heptahydrate and cobalt sulfamate are selected as the cobalt salt; deionized water is used as a solvent, citric acid monohydrate and magnesium nitrate hexahydrate are stirred and mixed, the mixture is placed in a drying oven with the temperature of 80-150 ℃ for reaction for 12-36 hours, and a precursor which is a foamy solid is obtained after the reaction is finished; then stirring and mixing the prepared precursor and sulfur-containing cobalt salt, and then calcining the mixture in an atmosphere furnace at the temperature of 700-900 ℃ for 0.5 to 3 hours under the protection of nitrogen, wherein the calcining aims at forming mesoporous carbon, and the catalytic effect of the invention is improved; after calcining and sintering, cooling to room temperature to obtain the cobalt-sulfur co-doped mesoporous carbon. The preparation method is simple, low in raw material cost, easy to popularize and suitable for large-scale manufacturing.
The cobalt-sulfur co-doped mesoporous carbon can be used as a catalyst for preparing aromatic amine compounds; when the aromatic amine compound is prepared, the reaction operation is simple; the reaction can be carried out well under normal pressure and at the temperature of 50-70 ℃, and the reaction condition is easier to realize compared with the generation method in the prior art; the reaction formula is
R can be various substituents of 2-, 3-or 4-on the benzene ring. R may be H, C1-C6 alkoxy, halogen (fluorine, chlorine, bromine), C1-C6 alkyl, aryl, NR1R2(R1, R2 is H, C1-C6 alkyl, benzyl or aryl, etc.). R also represents a benzo-aromatic ring, such as a naphthalene ring. The aryl group is preferably a phenyl group, a substituted phenyl group (the substituent is a C1-C6 alkyl group, a C1-C6 alkoxy group), a naphthyl group or the like. Therefore, the cobalt-sulfur co-doped mesoporous carbon material has a wide application range, can play a good catalytic effect on various nitrobenzene ring compounds, greatly shortens the reaction time, achieves the highest yield of 98%, and has the advantages of remarkably improved yield and higher economic benefit compared with a common preparation method in the prior art.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. A preparation method of cobalt-sulfur co-doped mesoporous carbon is characterized by comprising the following steps: the cobalt-sulfur co-doped mesoporous carbon comprises the following substances in parts by weight:
5-10 parts of citric acid monohydrate;
3-7 parts of magnesium nitrate hexahydrate;
1-3 parts of cobalt salt;
the cobalt salt is any one of cobalt sulfate heptahydrate and cobalt sulfamate;
the preparation method of the cobalt-sulfur co-doped mesoporous carbon comprises the following steps:
the method comprises the following steps: weighing required substances according to a formula, adding citric acid monohydrate and magnesium nitrate hexahydrate into deionized water, stirring and dissolving to form a solution, and then placing the solution into an oven for reaction to prepare a precursor;
step two: stirring and mixing the precursor and cobalt salt to form a mixture; then putting the mixture into an atmosphere furnace for calcining under the protection of nitrogen; and after calcining, cooling to room temperature to obtain the cobalt-sulfur co-doped mesoporous carbon.
2. The method for preparing cobalt and sulfur co-doped mesoporous carbon according to claim 1, wherein the method comprises the following steps: in the first step, the temperature of the oven is set to be 80-150 ℃ when the oven is placed in the oven for reaction, and the reaction time is 12-36 h.
3. The method for preparing cobalt and sulfur co-doped mesoporous carbon according to claim 1, wherein the method comprises the following steps: and setting the temperature of the atmosphere furnace to be 700-900 ℃ during the calcination in the second step, wherein the calcination time is 0.5-3 h.
4. Use of a cobalt sulphur co-doped mesoporous carbon according to any of claims 1 to 3, wherein: the cobalt-sulfur co-doped mesoporous carbon is used as a catalyst for preparing aromatic amine compounds.
5. The use of the cobalt and sulfur co-doped mesoporous carbon according to claim 4, wherein: the specific method of using the cobalt-sulfur co-doped mesoporous carbon as the catalyst comprises the steps of reacting a nitrobenzene ring compound and hydrazine hydrate at 50-70 ℃ for 4-24 hours under the catalysis of the cobalt-sulfur co-doped mesoporous carbon, filtering, extracting, washing with water, and drying to finally obtain the aromatic amine compound.
6. The use of the cobalt and sulfur co-doped mesoporous carbon according to claim 5, wherein: the nitrobenzene ring compound is characterized in that a nitro substituent is arranged on a benzene ring, and an R group substituent is arranged on at least one position except for the position of the substituted nitro, wherein the R group is any one of H, C1-C6 alkoxy, halogen, C1-C6 alkyl, aryl and NR1R2 and naphthalene ring, and R1 and R2 are any one of H, C1-C6 alkyl, benzyl or aryl.
7. The use of the cobalt and sulfur co-doped mesoporous carbon according to claim 6, wherein: reacting a nitrobenzene ring compound with hydrazine hydrate in a solvent, wherein the solvent is any one of toluene, water, ethanol, acetonitrile, dichloromethane and cyclohexane.
8. The use of the cobalt and sulfur co-doped mesoporous carbon according to claim 7, wherein: the molar ratio of the nitrobenzene ring compound to the hydrazine hydrate is 1:1.5-1: 3; the molar ratio of the dosage of the nitrobenzene ring compound to the dosage of the cobalt-sulfur co-doped mesoporous carbon is 1:0.05-1: 0.2.
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