CN115318318A - Preparation method and application of nitrogen-doped graphene catalyst for hydrogenation of nitroarene - Google Patents
Preparation method and application of nitrogen-doped graphene catalyst for hydrogenation of nitroarene Download PDFInfo
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- CN115318318A CN115318318A CN202111161218.1A CN202111161218A CN115318318A CN 115318318 A CN115318318 A CN 115318318A CN 202111161218 A CN202111161218 A CN 202111161218A CN 115318318 A CN115318318 A CN 115318318A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 3
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- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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Abstract
The invention discloses a preparation method and application of a nitrogen-doped graphene catalyst for hydrogenation of nitroarene, which comprises the following steps: adding g-C after GO aqueous solution is ultrasonically stripped 3 N 4 And (3) obtaining mixed powder by using a hydrothermal method, and calcining the mixed powder to obtain the nitrogen-doped graphene catalyst. The nitrogen-doped graphene catalyst has the characteristics of large specific surface area and good liquid-phase catalytic hydrogenation activity, and can solve the problems of catalyst inactivation caused by metal active component poisoning and dissolution and the like of the metal hydrogenation catalyst in a liquid-phase hydrogenation reaction, and environmental pollution caused by the catalyst inactivation. Compared with the prior art, the preparation method has the advantages of low raw material cost, simple preparation method, low production cost and good cycle performance, and develops the industrial application of the new graphene material in the aspect of catalysts.
Description
Technical Field
The invention relates to the field of new material industry, in particular to a preparation method and application of a graphene catalyst.
Background
Aniline and its derivative are important chemical materials and may be used widely in medicine, photoelectronic, dye, paint and other fields. The development of catalysts for preparing arylamine by hydrogenation of high-efficiency nitroaromatic has been a research hotspot. In the prior art, the problems of high price, poisoning of active components, agglomeration, dissolution and the like generally exist in a hydrogenation catalyst loaded by noble metal and/or base metal used in the hydrogenation reaction of nitroaromatic. Such as:
the Chinese invention patent application (application number: 2017 1 0940720. X) discloses a preparation method of a hydrogenation catalyst for nitrobenzene and derivatives thereof, which comprises the following steps: (1) Carrying out ultrasonic treatment on a carbon material and a high molecular polymer in a salt solution with a certain concentration at a certain temperature for 0.5-6 h to obtain a functionalized carbon material; (2) Preparing noble metal particles with certain size distribution from a salt solution of noble metal under the action of a protective agent and a reducing agent; (3) Carrying out ultrasonic treatment on the obtained aqueous solution or organic solution of the noble metal particles for 10min, stirring for 2-12 h, and then carrying out functional group modification on the carbon material to obtain a noble metal-supported catalyst; this application makes it possible to obtain a noble metal-supported catalyst having a size distribution and a uniform dispersion. However, this application has the disadvantages that the noble metal is expensive and the metal particles are easily lost.
In order to solve the above problems, more and more researchers have focused on non-metal catalysts that do not require metal as an active component. Carbonaceous materials have received considerable attention as non-metallic catalysts because of their ability to avoid the various disadvantages of metallic catalysts. In the prior art, most of nonmetallic catalysts for hydrogenation of nitroarenes still need to be in a strong reducing agent (such as N) 2 H 4 、 NaBH 4 ) As a hydrogen source. For example, xi et al use N, P double-doped multi-layer graphene as a highly efficient carbon material catalyst for nitrobenzene reduction (Journal of Catalysis 2018, 359. In the research, N and P double-doped multilayer graphene is obtained by stripping graphene by microwave and calcining together with hexachlorotriphosphazene and is used for NaBH 4 The hydrogenation reaction of the nitro-aromatic hydrocarbon is catalyzed, and the higher conversion rate of the amino-aromatic hydrocarbon is obtained. However, the reducing agent NaBH used in this study 4 And the application of the product as a dangerous control chemical in industrial production is difficult.
From the perspective of green and sustainable chemistry, the use of molecular hydrogen (H) is highly desirable 2 ) The method for preparing arylamine by hydrogenation of nitroaromatic hydrocarbon is cheaper, direct and clean. Therefore, it is very important to research on the nonmetallic catalyst for directly converting the nitroarene into the aminoarene by using molecular hydrogen so as to solve the defects in the prior art.
Disclosure of Invention
The invention aims to avoid the defects in the prior art and provides a green sustainable nonmetal catalyst for liquid-phase hydrogenation of nitroaromatic hydrocarbon, which has low cost and high reaction efficiency. The purpose of the invention is realized by the following technical scheme.
A preparation method of a nitrogen-doped graphene catalyst for hydrogenation of nitroarene comprises the following steps:
a. ultrasonically stripping the GO aqueous solution for 8 hours to obtain GO working solution;
b. adding g-C into the GO working solution 3 N 4 Obtaining mixed liquid;
c. treating the GO mixed solution by using a hydrothermal method, filtering and drying to obtain mixed powder;
d. and (3) placing the mixed powder in an inert atmosphere, heating to 600-1200 ℃, and naturally cooling to obtain the nitrogen-doped graphene catalyst.
Therefore, the invention uses a hydrothermal method to prepare graphite phase carbon nitride (g-C) 3 N 4 ) And in-situ generating \ loading reduced graphene oxide (rGO), and calcining the mixed powder to obtain the nitrogen-doped graphene catalyst. The nitrogen-doped graphene catalyst has the characteristics of large specific surface area and good liquid-phase catalytic hydrogenation activity.
Preferably, in step a, the preparation of said aqueous GO solution comprises the steps of:
(1) Graphite powder, sodium nitrate and concentrated sulfuric acid are mixed according to the mass ratio of 1:1:85 is placed in a reaction bottle and stirred for 6 hours at the temperature of 0 ℃;
(2) Slowly adding 6 parts by mass of potassium permanganate into the reaction bottle, and stirring for 2 hours;
(3) Transferring the reaction bottle to 45 ℃, stirring for 1h, dropwise adding 90 parts by mass of deionized water, and stirring for 1h;
(4) Transferring the reaction bottle to 95 ℃, stirring for 1.3h, adding 20 parts by mass of hydrogen peroxide, stirring for 0.3h, and centrifuging to remove the solution; stirring for 1.3h in the step (4) is a specific technical characteristic, wherein over 1.3h, black brown non-product precipitate is formed, and less than 1.3h, chemical stripping degree is insufficient;
(5) Washing the precipitate with 5% dilute hydrochloric acid and centrifuging for 3 times, washing the precipitate with deionized water and centrifuging for 3 times, and dialyzing to obtain GO water solution.
More preferably, the method also comprises a step (6) of diluting the GO aqueous solution to a concentration of 1.7-2.8 mg/mL. The specific GO aqueous solution concentration can be set to promote the reaction of GO with g-C during in-situ generation of rGO 3 N 4 Self-assembly to form a three-dimensional network structure, and the subsequent catalyst reaction activity is obviously improved. If the setting is lower than 1.7mg/mL, rGO and g-C are subjected to hydrothermal process 3 N 4 Forming a sandwich-like laminated structure, reducing the catalyst reactivity. Above 2.8mg/mL results in rGO and g-C 3 N 4 Aggregate into lumps, resulting in a decrease in the reactivity of the catalyst.
Preferably, in step a, the concentration of the GO aqueous solution is 1.75-2.10 mg/mL. By setting 1.75-2.10 mg/mL, the hydrothermal rGO can form a three-dimensional net structure without being aggregated into an integrated block. The catalyst obtained with the setting of 1.95mg/mL had the best catalytic effect.
Preferably, g to C in step b 3 N 4 The preparation method comprises the following steps: placing the raw materials in a covered crucible, heating to 550 deg.C at 5 deg.C/min, maintaining for 2 hr, and naturally cooling to obtain g-C 3 N 4 The raw material is selected from melamine, dicyanodiamine, thiourea or urea. g-C obtained from different raw materials 3 N 4 The properties are very different, in the present application, g-C obtained starting from thiourea and urea 3 N 4 The effect is better.
Preferably, GO and g-C in the GO working solution 3 N 4 The mass ratio of (1): 1 to 20. Setting the mass and g-C of GO in GO working solution 3 N 4 Mass ratio to modulate different nitrogen doping ratio.
More preferably, GO and g-C in the GO working solution in the step b 3 N 4 The mass ratio of (1): 5. the increase of the nitrogen doping proportion does not bring about the improvement of the liquid phase catalytic hydrogenation effect, and GO and g-C are arranged in the invention 3 N 4 The mass ratio of (1): 5, the better catalytic effect can be achieved.
Preferably, in step d, the temperature is raised to 800 ℃ at a rate of 2 ℃/min. Too fast a temperature rise rate can cause the graphene sheet layer to curl more violently when hydrothermal rGO is subjected to thermal reduction, and finally the catalyst preparation fails, and at the same time, too fast a temperature rise rate can reduce the yield of thermal reduction.
Preferably, in step c, the temperature of the hydrothermal method is 180 ℃ and the time is 8h.
The second purpose of the present invention is to provide a nitrogen-doped graphene catalyst obtained by the above preparation method. C in the nitrogen-doped graphene catalyst: n: the ratio of O elements is 86-93: 4 to 8:3 to 6. The BET specific surface area is 600-800 m 2 /g。
The invention also aims to provide the application of the nitrogen-doped graphene catalyst in the liquid-phase hydrogenation catalytic reaction of nitroarene.
Preferably, the catalyst and the nitroaromatic hydrocarbon are added into the reaction solvent, and the catalytic reaction is carried out in the presence of hydrogen.
Further, the reaction solvent is one or a mixture of more than two of methanol, ethanol or isopropanol.
More preferably, the reaction solvent is ethanol, and the mass part ratio of the catalyst, the nitroaromatic hydrocarbon and the ethanol is 5-100.
Preferably, the catalytic temperature is 140-190 ℃, the reaction time is 4-24 hours, the hydrogen pressure is 2-4 Mpa, and the stirring speed is 600rpm.
Preferably, the catalytic temperature is 170 ℃, the reaction time is 6 hours, and the hydrogen pressure is 4MPa.
Preferably, the nitroaromatic hydrocarbon is nitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrotoluene, o-nitrobenzaldehyde, p-nitrophenol, m-nitrophenol, p-nitroaniline or p-nitroacetophenone.
The invention has the beneficial effects that:
the invention relates to a preparation method of a nitrogen-doped graphene catalyst for hydrogenation of nitroarene, which comprises the following steps: adding g-C after GO aqueous solution is ultrasonically stripped 3 N 4 And (3) obtaining mixed powder by using a hydrothermal method, and calcining the mixed powder to obtain the nitrogen-doped graphene catalyst. The nitrogen-doped graphene catalyst obtained by the invention has the characteristics of large specific surface area and good liquid-phase catalytic hydrogenation activity. The method can solve the problems of metal active component poisoning, catalyst inactivation caused by dissolution and desorption, environmental pollution and the like of the metal hydrogenation catalyst in the liquid phase hydrogenation reaction. Compared with the prior art, the invention has the following advantages:
1. the prepared nitrogen-doped graphene catalyst can directly use molecular hydrogen to carry out liquid-phase hydrogenation reaction on nitroarene, and has high reaction activity;
2. the non-metal catalyst has the advantages of cheap raw materials, simple preparation method, low production cost and good cycle performance;
3. the invention expands the industrial application of the new graphene material in the aspect of catalysts and lays a foundation for further utilizing carbon nano materials.
Drawings
FIG. 1 is an SEM picture of N-rGO-3N in example 1;
FIG. 2 is the XPS energy spectra of N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N of example 2;
FIG. 3 is a Raman spectrum of N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N of example 2;
FIG. 4 is a graph of a cycling experiment for N-rGO-1N in example 5.
Detailed Description
The process provided by the present invention is further described in connection with the following examples, but the invention is not limited thereto.
Example 1
One embodiment of the preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroarene provided by the invention comprises the following steps:
(1) Placing 1g of graphite powder, 1g of sodium nitrate and 85g of concentrated sulfuric acid in a 250mL round-bottom flask, and stirring for 6 hours in a cooling bath at 0 ℃;
(2) Slowly adding 6g of potassium permanganate into the round-bottom flask, and continuously stirring for 2 hours;
(3) Transferring the round bottom flask into a 45 ℃ oil bath, stirring for 1h, dropwise adding 90g of deionized water by using a constant-pressure dropping funnel, and stirring for 1h;
(4) Transferring the round-bottom flask into a 95 ℃ oil bath, stirring for 1.3h, adding 20g of hydrogen peroxide, stirring for 0.3h, centrifuging (8000rpm, 5min), and removing the solution;
(5) Washing the precipitate with 5% (v/v) hydrochloric acid and centrifuging for 3 times, washing the precipitate with deionized water and centrifuging for 3 times to obtain GO colloid, filling the GO colloid into a D3500 dialysis bag, and dialyzing for 7 days to obtain GO aqueous solution;
(6) Diluting the GO aqueous solution with deionized water until the concentration is 1.78mg/mL, and determining the concentration detection by an ultraviolet spectrophotometer;
(7) Ultrasonically stripping 1.78mg/mL GO aqueous solution for 8 hours by using an ultrasonic cleaner (250W, 25 ℃) to obtain GO working solution;
(8) Adding graphite phase carbon nitride (g-C) into 100mL of GO working solution 3 N 4 ) 0.975g to obtain a mixed solution;
(9) Reduction by hydrothermal method: putting the mixed solution into a 150mL hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a constant-temperature oven at 180 ℃ for 8 hours, cooling, filtering under reduced pressure, and freeze-drying the obtained gray powder;
(10) And (3) placing the dried powder in a porcelain boat, heating to 800 ℃ at the speed of 2 ℃/min under the protection of nitrogen, keeping for 2 hours, and naturally cooling to obtain the nitrogen-doped graphene catalyst which is marked as N-rGO-3N.
Specifically, g to C in step (8) 3 N 4 The preparation method comprises the following steps: placing 20g of melamine in a covered crucible, heating to 550 ℃ at a speed of 5 ℃/min, keeping for 2 hours, and naturally cooling to obtain g-C 3 N 4 。
FIG. 1 is a scanning electron micrograph of N-rGO-3N in this example, from which it can be seen that the nitrogen-doped graphene catalyst shows a porous three-dimensional honeycomb network structure after calcination at 800 ℃.
The hydrogenation catalyst N-rGO-3N in the embodiment is applied to the nitrobenzene liquid phase hydrogenation catalytic reaction. 0.05g of catalyst, 0.05g of nitrobenzene and 20mL of ethanol are placed in a high-pressure reaction kettle for reaction, the catalysis temperature is 170 ℃, the reaction time is 6 hours, and the hydrogen pressure is 4Mpa. The reaction solution was analyzed by gas chromatography, and the conversion of nitrobenzene into aniline was 70.52% with a selectivity of 84.15%.
Example 2
In one embodiment of the preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroarene, the main technical scheme of this embodiment 2 is substantially the same as that of embodiment 1, and features that are not explained in this embodiment 2 are explained in embodiment 1, and are not described herein again. The present example differs from example 1 in that:
(6) Diluting the GO aqueous solution with deionized water until the concentration is 1.95mg/mL, and determining the concentration detection by an ultraviolet spectrophotometer;
(7) Ultrasonically stripping 1.95mg/mL GO aqueous solution for 8 hours by using an ultrasonic cleaner (250W, 25 ℃) to obtain GO working solution;
specifically, step (8) is carried out using g-C 3 N 4 The preparation method comprises the following steps: placing 20g of raw materials in a covered crucible, heating to 550 ℃ at a speed of 5 ℃/min, keeping for 2 hours, and naturally cooling to obtain g-C 3 N 4 The raw material is selected from melamine, dicyanodiamine, thiourea or urea.
More specifically, g-C is selected according to 3 N 4 The raw materials are different, and the nitrogen-doped graphene catalysts obtained by taking melamine, dicyanodiamine, thiourea or urea as the raw materials are respectively marked as N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N.
The hydrogenation catalysts N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N in the embodiment are used for the application of nitrobenzene liquid phase hydrogenation catalytic reaction. 0.05g of catalyst, 0.05g of nitrobenzene and 20mL of ethanol are placed in a high-pressure reaction kettle for reaction, the catalysis temperature is 170 ℃, the reaction time is 6 hours, and the hydrogen pressure is 4Mpa. The reaction solution was analyzed by gas chromatography, and the conversion and selectivity of nitrobenzene to aniline were as shown in the following table.
Respectively carrying out N on N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N 2 The BET specific surface areas of the compounds in the physical adsorption experiment are 604.9m respectively 2 /g，785.8m 2 /g，602.9m 2 G and 692.6m 2 (ii) in terms of/g. FIG. 2 is an XPS spectrum of N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N, indicating that N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N contain only three elements, carbon, nitrogen and oxygen, and are non-metallic catalysts. FIG. 3 is a laser Raman spectrum of N-rGO-3N, N-rGO-2N, N-rGO-SN and N-rGO-1N, with 4 catalysts all showing a spectrum of graphene-like materials, 4 catalysts I D /I G The values are similar.
Example 3
In one embodiment of the preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroarene, the main technical scheme of this embodiment 3 is substantially the same as that of embodiment 1, and features that are not explained in this embodiment 3 are explained in embodiment 1, and are not described herein again. The present example differs from example 1 in that:
step (8) taking 100mL of GO working solution, and adding graphite-phase carbon nitride (g-C) with different mass ratios 3 N 4 ) Obtaining mixed liquid; specifically, GO with different mass ratios: g-C 3 N 4 Is 1: 1. 1: 2. 1: 3. 1: 4. 1:5 and 1:10;
specifically, g to C in step (8) 3 N 4 The preparation method comprises the following steps: placing 20g of melamine in a covered crucible, heating to 550 ℃ at a speed of 5 ℃/min, keeping for 2 hours, and naturally cooling to obtain g-C 3 N 4 。
The hydrogenation catalyst N-rGO-3N in the embodiment is applied to the nitrobenzene liquid phase hydrogenation catalytic reaction. 0.05g of catalyst, 0.05g of nitrobenzene and 20mL of ethanol are placed in a high-pressure reaction kettle for reaction, the catalysis temperature is 170 ℃, the reaction time is 6 hours, and the hydrogen pressure is 4Mpa. The reaction solution was analyzed by gas chromatography, and the conversion and selectivity of nitrobenzene to aniline were as shown in the following table.
Example 4
One embodiment of the preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroarene according to the present invention is that the main technical solution of this example 4 is substantially the same as that of example 1, and features that are not explained in this example 4 are explained in example 1, and are not described again here. This example differs from example 1 in that:
the hydrogenation catalyst N-rGO-3N in the embodiment is applied to the hydrogenation catalytic reaction of the nitroaromatic phase. 0.05g of catalyst, 0.05g of nitroarene and 20mL of ethanol are placed in a high-pressure reaction kettle for reaction, the catalytic temperature is 170 ℃, the reaction time is 6 hours, and the hydrogen pressure is 4Mpa. The nitro aromatic hydrocarbon is o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrotoluene, o-nitrobenzaldehyde, p-nitrophenol, m-nitrophenol, p-nitroaniline or p-nitroacetophenone. Thin-layer chromatography analysis is carried out on the reaction liquid to obtain the catalyst of the application, and the nitro aromatic hydrocarbon can be converted into arylamine.
Example 5
In an embodiment of the preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroaromatic hydrocarbons, in this example 5, the catalyst N-rGO-1N obtained in example 2 is used to perform a cyclicity experiment on N-rGO-1N in a nitrobenzene liquid-phase hydrogenation catalytic reaction. 0.05g of catalyst, 0.05g of nitrobenzene and 20mL of ethanol are placed in a high-pressure reaction kettle for reaction, the catalytic temperature is 170 ℃, the reaction time is 6 hours, and the hydrogen pressure is 4Mpa. Gas chromatography analysis is carried out on the reaction liquid, and the conversion rate of nitrobenzene into aniline is 93.87%, and the selectivity is 92.77%. And centrifuging and drying the catalyst in the reaction mixed liquid after the reaction, and carrying out the next experiment. After 5 p-nitrobenzene hydrogenation experiments, the conversion rate and selectivity of nitrobenzene to aniline remained stable as shown in fig. 5.
It was shown that the activity of the catalyst in this example was not lost during the reaction. Therefore, the nonmetal catalyst of the embodiment has higher stability, and is expected to replace a metal catalyst in the liquid-phase hydrogenation reaction of the nitroarene.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped graphene catalyst for hydrogenation of nitroarene comprises the following steps:
a. ultrasonically stripping the GO aqueous solution for 8 hours to obtain GO working solution;
b. adding g-C into the GO working solution 3 N 4 Obtaining mixed solution;
c. treating the GO mixed solution by using a hydrothermal method, filtering and drying to obtain mixed powder;
d. and placing the mixed powder in an inert atmosphere, heating to 600-1200 ℃, and naturally cooling to obtain the nitrogen-doped graphene catalyst.
2. The method for preparing the nitrogen-doped graphene catalyst for hydrogenation of nitroaromatic of claim 1, wherein the g-C in the step b 3 N 4 The preparation method comprises the following steps: placing the raw materials in a covered crucible, heating to 550 deg.C at 5 deg.C/min, maintaining for 2 hr, and naturally cooling to obtain g-C 3 N 4 The raw material is taken from thiourea or urea.
3. The preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroarene according to claim 1, characterized by comprising the following steps: in the step a, the concentration of the GO aqueous solution is 1.85-2.10mg/mL.
4. The preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroarene according to claim 1, characterized by comprising the following steps: GO and g-C in GO working solution in step b 3 N 4 The mass ratio of (1): 5; in the step d, the temperature rise rate is 2 ℃/min, and the temperature rises to 800 ℃.
5. A nitrogen-doped graphene catalyst obtained by the preparation method of the nitrogen-doped graphene catalyst for hydrogenation of nitroarene according to any one of claims 1 to 4.
6. The application of the nitrogen-doped graphene catalyst of claim 5 in liquid-phase hydrogenation catalytic reaction of nitroarene, wherein the catalyst and the nitroarene are added into a reaction solvent, and the catalytic reaction is carried out in the presence of hydrogen.
7. The application of the nitrogen-doped graphene catalyst in the liquid-phase hydrogenation catalytic reaction of nitroarene according to claim 6, wherein the nitrogen-doped graphene catalyst is characterized in that: the reaction solvent is ethanol, and the mass part ratio of the catalyst to the nitroaromatic to the ethanol is 5 to 100.
8. The application of the nitrogen-doped graphene catalyst in the liquid-phase hydrogenation catalytic reaction of nitroarene according to claim 6, wherein: the catalytic temperature is 140 to 190 ℃, the reaction time is 4 to 24 hours, the hydrogen pressure is 2 to 4Mpa, and the stirring speed is 600rpm.
9. The application of the nitrogen-doped graphene catalyst in the liquid-phase hydrogenation catalytic reaction of nitroarene according to claim 8 is characterized in that: the catalytic temperature is 170 ℃, the reaction time is 6 hours, and the hydrogen pressure is 4Mpa.
10. The application of the nitrogen-doped graphene catalyst in the liquid-phase hydrogenation catalytic reaction of nitroarene according to claim 6, wherein the nitrogen-doped graphene catalyst is characterized in that: the nitro aromatic hydrocarbon is nitrobenzene, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nitrotoluene, o-nitrobenzaldehyde, p-nitrophenol, m-nitrophenol, p-nitroaniline or p-nitroacetophenone.
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