CN112657530A - Non-noble metal immobilized nitrogen-doped carbon nanotube catalyst, and preparation method and application thereof - Google Patents
Non-noble metal immobilized nitrogen-doped carbon nanotube catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal, a preparation method and application thereof, which are applied to the technical fields of pesticide synthesis, drug production, fine chemical manufacture and the like. The catalyst has a bamboo-like tubular shape, part of the carbon nano tubes contain metal nano particles, and all the carbon nano tubes are of hollow structures; i of the catalystD/IGThe value range is 0.95-0.98, the nitrogen content is 2.54-3.13 wt%, and the specific surface area is 166.2-307.3 m2·g‑1The pore volume ranges from 0.626 cm to 2.490cm3·g‑1The pore diameter is 3.93-3.95 nm, and belongs to a mesoporous material. The catalyst is used in methanol/ethanol/isopropanol reaction mediumThe aromatic amine is prepared by catalytic hydrogenation of the para-nitroaromatic in the medium, and the high-selectivity catalytic conversion of the nitroaromatic substrate is realized under the mild reaction condition.
Description
Technical Field
The invention relates to a nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal, a preparation method and application thereof, which are applied to the technical fields of pesticide synthesis, drug production, fine chemical manufacture and the like.
Background
The carbon nano tube is used as a novel tubular carbon material, has high specific surface area, abundant and uniform pore passages and good corrosion resistance, and is an excellent catalyst carrier. However, carbon nanotubes as a support lack binding sites for metal active species, so that metal species, especially non-noble metals, are difficult to embed inside the carbon nanotubes and are very easily lost in the reaction. Therefore, it is very critical to modify the surface of the carbon nanotube with the heteroatom.
The non-noble metal carbon-based catalyst is expected to become an effective substitute of a commercial noble metal immobilized catalyst in the fields of fine chemical synthesis and practical fuel cells due to the unique chemical property and excellent catalytic/electrocatalytic activity. Driven by these potential advantages, non-noble metal (Fe, Co, Ni) based carbon nanotube catalysts based on heteroatom doping (heteroatoms like phosphorus, boron, sulfur and nitrogen) have become highly developed new heterogeneous catalysts that are efficient and stable. In particular, nitrogen-doped carbon catalytic materials are uniquely challenging in such heteroatom-doped carbon nanotube materials, which results from nitrogen atom doping that leads to superior chemical stability, good solvent wettability, and anchoring to non-noble metal nanoparticles. Generally, the nitrogen-doped carbon nanotube based on non-noble metal is prepared by mainly using various metal salts and carbon-nitrogen-rich organic matters as precursors and performing high-temperature heat treatment in an inert atmosphere in the presence of different templates. However, these methods mostly use various complicated pretreatment and post-treatment steps, and anions (acetate, halide, etc.) introduced by adding non-noble metal salts may have adverse effects on catalyst performance. Therefore, a non-noble metal-based monomolecular complex is urgently needed to be used as a precursor for directly preparing a non-noble metal-based nitrogen-doped carbon nanotube catalyst so as to improve the catalytic performance of the current nitrogen-doped carbon nanotube.
Disclosure of Invention
The invention is significant in developing a novel preparation method for nitrogen-doped carbon nanotube catalyst by directly carrying out high-temperature heat treatment on novel non-noble metal-based monomolecular organic complex dicyanamide salt serving as a precursor. Because the traditional method for preparing the nitrogen-doped carbon nanotube catalyst by taking the non-noble metal salt and the organic compound rich in carbon and nitrogen as the raw materials has relatively complicated pretreatment and post-treatment steps and uncertain influence caused by anions, the key point of the invention is to search for a non-noble metal-based nitrogen-doped carbon nanotube catalytic material prepared by taking a monomolecular organic complex as a single raw material and performing simple heat treatment.
In order to achieve the purpose, the invention adopts the following technical scheme:
the nitrogen-doped carbon nanotube catalyst immobilized by non-noble metal has the bamboo-like tubular shape, part of the carbon nanotubes contain metal nanoparticles, and all the carbon nanotubes are of hollow structures; i of the catalystD/IGThe value range is 0.95-0.98, the nitrogen content is 2.54-3.13 wt%, and the specific surface area is 166.2-307.3 m2·g-1The pore volume ranges from 0.626 cm to 2.490cm3·g-1The pore diameter is 3.93-3.95 nm, and belongs to a mesoporous material.
The invention discloses a new method for synthesizing a series of non-noble metal dicyanamides by performing a displacement reaction between silver dicyanamide precipitates and different non-noble metal bromides; the metal salt molecule consists of non-noble metal ions and dicyandiamide radical ions, cyano groups inside the molecule can generate a condensation reaction to generate a graphite-phase nitrogen-doped carbon-anchored cobalt intermediate in the high-temperature heat treatment process, reduced cobalt species can cause carbon nitride to generate graphitization transformation and form a carbon nano tube-coated cobalt nano particle catalyst when the temperature is continuously raised, the cobalt nano particle is coated by the nitrogen-doped carbon layer and has strong oxidation resistance and high stability, and the in-situ coated cobalt nano particle catalyst has good circulation stability for the selective hydrogenation reaction of a nitroarene substrate.
The preparation method of the nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal comprises the following steps:
step 3, after sweeping the non-noble metal dicyanamide solid by using inert gas, firstly heating to 550 ℃ and keeping the temperature for 1-2 hours, then heating to 700-1000 ℃ and keeping the temperature for 1-2 hours, wherein the heating rate is 2-5 ℃/min, so as to obtain a black solid;
and 4, placing the obtained black solid in acid for etching, performing suction filtration, washing the black solid to be neutral by using deionized water, drying and activating to obtain the black non-noble metal immobilized nitrogen-doped carbon nanotube catalyst.
The catalyst is non-noble metal dicyanamide salt (M ═ Fe, Co and Ni), and the synthesis is as follows:
further, the mass ratio of silver nitrate, deionized water and sodium dicyandiamide in the step 1 is 2.1-8.6: 30-100: 1.1 to 4.5.
Further, the stirring reaction time in the step 1 is 1-2 h. Further, in the step 2, the non-noble metal bromide is one of cobalt bromide, ferrous bromide and nickel bromide, and the molar ratio of the non-noble metal bromide to the silver nitrate is 0.4-0.45: 1, the concentration of the non-noble metal bromide aqueous solution is 0.1-0.5 mol/L.
Further, the inert gas in the step 3 is one or two of nitrogen and argon mixed according to any ratio.
Further, the flow rate of the inert gas in the step 3 is 50-300 mL/min. Further, in the step 4, the etching time is 12-18 h, and the etching times are 1-2; the activation temperature is 700 ℃, and the activation time is 1-2 h.
Application of non-noble metal-supported nitrogen-doped carbon nanotube catalyst in preparation of aromatic amine by catalytic hydrogenation of paranitroarene in methanol/ethanol/isopropanol reaction medium under mild reaction condition (0.1-0.2 MPa H)2And the temperature is 30-60 ℃ for 2-8 h) to realize the high-selectivity catalytic conversion of the nitroarene substrate.
Compared with the prior art, the invention has the following advantages:
the hydrogenation reaction of the non-noble metal catalyst on the nitroaromatic hydrocarbon can be realized generally under the conditions of high temperature, high pressure and longer reaction time, the cobalt nanoparticles synthesized by the technology are wrapped inside the nitrogen-doped carbon nanotube in situ, and the catalyst has higher oxidation resistance and corrosivity and can realize the high-selectivity hydrogenation of the nitroaromatic hydrocarbon under the mild condition. The method can effectively avoid the use of high-temperature and high-pressure special equipment, reduce the cost of catalytic hydrogenation and simplify the reaction process, and provides a novel non-noble metal catalyst for the low-temperature and low-pressure conversion of the nitroaromatic.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of a dicyandiamide cobalt complex synthesized with a dicyandiamide sodium raw material;
FIG. 2 is a scanning electron micrograph of a nitrogen doped carbon nanotube Co @ NCNTs-T (T700-;
FIG. 3 is an X-ray diffraction pattern of a nitrogen-doped carbon nanotube Co @ NCNTs-T (T700-;
FIG. 4 is a graph of the physical adsorption of a nitrogen-doped carbon nanotube Co @ NCNTs-T (T700-;
FIG. 5 is a Raman spectrum of the nitrogen-doped carbon nanotube Co @ NCNTs-T (T700-.
Detailed Description
Example 1
The preparation method of the nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal comprises the following steps:
And 2, dropwise adding 100mL of 0.45 silver nitrate molar equivalent nickel bromide aqueous solution under stirring at the rotation speed of 1000rpm/min, stirring for 12 hours in a dark place, collecting filtrate, performing rotary evaporation to remove water, and performing vacuum drying to obtain pink dicyandiamide cobalt powder.
Step 3, continuously introducing argon into the furnace at a flow rate of 50mL/min to purge the sample, then carrying out temperature programming, raising the temperature of the furnace body to 550 ℃ and keeping for 2 hours, then raising the temperature to 700 ℃ at a temperature raising rate of 2 ℃/min and keeping for 2 hours, and naturally cooling to room temperature to obtain black solid powder;
and 4, adding the obtained black powder into 100mL of 1M dilute sulfuric acid solution, stirring at room temperature for 12 hours, repeating the step for 1 time, repeatedly washing with deionized water, and activating at 700 ℃ for 1 hour to obtain the Co @ NCNTs-700 catalyst.
The Co @ NCNTs-700 catalyst has a bamboo-like tubular shape, a part of carbon nano tubes contain metal nano particles, and all the carbon nano tubes are of hollow structures; i isD/IGThe value ranges from 0.95, the nitrogen content is 3.13 wt%, and the specific surface area is 166.2m2·g-1Pore volume of 0.945cm3·g-1The aperture is 3.94nm, belonging to mesoporous materials.
Example 2
The preparation method of the nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal comprises the following steps:
And 2, dropwise adding 100mL of 0.45 silver nitrate molar equivalent nickel bromide aqueous solution under stirring at the rotation speed of 1000rpm/min, stirring for 12 hours in a dark place, collecting filtrate, performing rotary evaporation to remove water, and performing vacuum drying to obtain pink dicyandiamide cobalt powder.
And 3, continuously introducing inert gas nitrogen into the furnace at the flow rate of 100mL/min to purge the sample, then carrying out temperature programming, raising the temperature of the furnace body to 550 ℃ and keeping for 2 hours, and then raising the temperature to 800 ℃ at the temperature raising rate of 3 ℃/min and keeping for 2 hours.
And 4, adding the obtained black powder into 100mL of 1M dilute sulfuric acid solution, stirring at room temperature for 12 hours, repeating the step for 1 time, repeatedly washing with deionized water, and activating at 700 ℃ for 1 hour to obtain the Co @ NCNTs-800 catalyst.
The catalytic reaction conditions are as follows: 1mmol nitrobenzene, 40mg Co @ NCNTs-800 catalyst, 5mL ethanol were added to a 35mL glass reaction flask with H2After 3 times of replacement and maintaining the pressure in the bottle at 0.1MPa at 30 ℃. Stirring and reacting for 3 hours at the rotating speed of 1200rpm/min, centrifuging to separate out the catalyst, analyzing the supernatant through gas chromatography or gas chromatography-mass spectrometry, using n-tetradecane as an internal standard to catalyze the reduction of nitrobenzene into aniline, wherein the conversion rate and the selectivity of the nitrobenzene are both over 99 percent.
The Co @ NCNTs-800 catalyst has a bamboo-like tubular shape, a part of carbon nano tubes contain metal nano particles, and the catalyst is of a hollow structure; i isD/IGThe value was 0.96, the nitrogen content was 2.60% by weight, and the specific surface area was 215.7m2·g-1The pore volume is 1.371cm3·g-1The aperture is 3.94nm, belonging to mesoporous materials.
Example 3
The preparation method of the nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal comprises the following steps:
And 2, dropwise adding 100mL of 0.45 silver nitrate molar equivalent nickel bromide aqueous solution under stirring at the rotation speed of 1000rpm/min, stirring for 12 hours in a dark place, collecting filtrate, performing rotary evaporation to remove water, and performing vacuum drying to obtain pink dicyandiamide cobalt powder.
And 3, continuously introducing argon into the furnace at the flow rate of 200mL/min to purge the sample, then carrying out temperature programming, raising the temperature of the furnace body to 550 ℃ and keeping the temperature for 2 hours, and then raising the temperature to 900 ℃ at the temperature raising rate of 4 ℃/min and keeping the temperature for 2 hours.
And 4, adding the obtained black powder into 100mL of 1M dilute sulfuric acid solution, stirring at room temperature for 12 hours, repeating the step for 1 time, repeatedly washing with deionized water, and activating at 700 ℃ for 1 hour to obtain the Co @ NCNTs-900 catalyst.
The Co @ NCNTs-900 catalyst has a bamboo-like tubular shape, a part of carbon nano tubes contain metal nano particles, and the catalyst is of a hollow structure; i isD/IGThe value was 0.96, the nitrogen content was 2.54% by weight, and the specific surface area was 307.3m2·g-1Pore volume range of 2.490cm3·g-1The pore diameter is within 3.94nm, belonging to mesoporous materials.
Example 4
The preparation method of the nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal comprises the following steps:
And 2, dropwise adding 100mL of 0.45 silver nitrate molar equivalent nickel bromide aqueous solution under stirring at the rotation speed of 1000rpm/min, stirring for 12 hours in a dark place, collecting filtrate, performing rotary evaporation to remove water, and performing vacuum drying to obtain pink dicyandiamide cobalt powder.
And 3, continuously introducing nitrogen into the furnace at the flow rate of 300mL/min to purge the sample, then raising the temperature by a program, raising the temperature of the furnace body to 550 ℃ and keeping the temperature for 2 hours, then raising the temperature to 1000 ℃ at the temperature raising rate of 5 ℃/min and keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain black solid powder.
And 4, adding the obtained black powder into 100mL of 1M dilute sulfuric acid solution, stirring at room temperature for 12 hours, repeating the step for 1 time, repeatedly washing with deionized water, and activating at 700 ℃ for 1 hour to obtain the Co @ NCNTs-1000 catalyst.
The Co @ NCNTs-1000 catalyst has a bamboo-like tubular shape, a part of carbon nano tubes contain metal nano particles, and the catalyst is of a hollow structure; i isD/IGThe value was 0.98, the nitrogen content was 2.44% by weight, and the specific surface area was 133.2m2·g-1Pore volume range of 0.626cm3·g-1The pore diameter is within 3.95nm, belonging to mesoporous materials.
Example 5
The preparation method of the nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal comprises the following steps:
And 2, dropwise adding 50mL of 0.4 silver nitrate molar equivalent nickel bromide aqueous solution under stirring at the rotation speed of 800rpm/min, stirring for 12 hours in a dark place, collecting filtrate, performing rotary evaporation to remove water, and performing vacuum drying to obtain pink dicyandiamide cobalt powder.
And 3, continuously introducing argon into the furnace at the flow rate of 50mL/min to purge the sample, then carrying out temperature programming, raising the temperature of the furnace body to 550 ℃ and keeping for 1 hour, then raising the temperature to 800 ℃ at the temperature raising rate of 2 ℃/min and keeping for 1 hour, and naturally cooling to room temperature to obtain black solid powder.
And 4, adding the obtained black powder into 100mL of 0.1M dilute sulfuric acid solution, stirring for 15 hours at room temperature, repeating the step for 1 time, repeatedly washing with deionized water, and activating for 2 hours at 700 ℃ to obtain the Co @ NCNTs-800 catalyst.
Example 6
The preparation method of the nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal comprises the following steps:
And 2, dropwise adding 50mL of 0.45 silver nitrate molar equivalent nickel bromide aqueous solution under stirring at the rotation speed of 1500rpm/min, stirring for 12 hours in a dark place, collecting filtrate, performing rotary evaporation to remove water, and performing vacuum drying to obtain pink dicyandiamide cobalt powder.
And 3, continuously introducing argon into the furnace at the flow rate of 50mL/min to purge the sample, then carrying out temperature programming, raising the temperature of the furnace body to 550 ℃ and keeping for 1 hour, then raising the temperature to 800 ℃ at the temperature raising rate of 2 ℃/min and keeping for 1 hour, and naturally cooling to room temperature to obtain black solid powder.
And 4, adding the obtained black powder into 100mL of 0.5M dilute sulfuric acid solution, stirring at room temperature for 18 hours, repeating the step for 1 time, repeatedly washing with deionized water, and activating at 700 ℃ for 1.5 hours to obtain the Co @ NCNTs-800 catalyst.
Table 1 shows the selective hydrogenation performance of different types of non-noble metal catalysts synthesized, for nitrobenzene, as follows:
table 1 selective hydrogenation performance of different types of non-noble metal catalysts synthesized on nitrobenzene.a
In Table 1, a is the reaction conditions of 1.0mmol of nitrobenzene, 40mg of catalyst, 5.0mL of ethanol, 40 ℃ and 0.1MPa of H2B is the conversion and selectivity analyzed by GC-FID with n-tetradecane as internal standard, c is DCDA: dicyandiamide, d is NaDCA which is dicyandiamide sodium, e is 10mg of KSC added, and f is after 3 times of circulating reaction.
As can be seen from Table 1, the catalysts obtained by pyrolyzing cobalt dicyanamide molecules at different temperatures have obviously different catalytic activities, wherein the Co @ NCNTs-800 catalyst has the highest catalytic activity, and the conversion rate of nitrobenzene and the selectivity of aniline are both higher than 99%. In contrast, the activity of the Fe @ NCNTs-800 and Ni @ NCNTs-800 catalysts was very low. In addition, the Co-DCDA-800 catalyst prepared by pyrolysis of a mixture of dicyandiamide and cobalt chloride and the Co-NaDCA-800 catalyst prepared by mixed pyrolysis of sodium dicyandiamide and cobalt chloride are respectively used, but the hydrogenation activity of the catalyst on a nitrobenzene substrate is less than 2 percent. Therefore, the Co @ NCNTs-800 catalyst prepared by directly thermally decomposing the self-synthesized cobalt dicyandiamide molecules serving as the precursor has the best catalytic performance. Meanwhile, the catalyst still has high catalytic activity and selectivity after 3 times of cyclic reaction.
Cobalt dicyandiamide-Co [ N (CN).)2]2At 2211cm-1And 1314cm-1Peaks at (D) correspond to stretching vibration and bending vibration peaks of-C.ident.N and-C-N bonds, respectively, which are in contact with the raw material sodium dicyandiamide-NaN (CN)2The peak positions of the two are consistent, and the successful synthesis of the cobalt dicyandiamide target molecule is proved.
Fig. 2 shows the micro-morphology of Co @ NCNTs-T (T700, 800, 900, 1000 ℃) catalyst thermally decomposed at different temperatures. It can be seen from FIG. 2a that the Co @ NCNTs-700 catalyst is composed of a large number of rough-surfaced and irregular tubular structures, which the Co @ NCNTs-800 catalyst also has and these nanotube structures become more compact and very uniformly dispersed. When the temperature is further increased to 900 ℃, the nanotube structure gradually aggregates and a collapse phenomenon occurs. The Co @ NCNTs-1000 catalyst undergoes significant collapse and produces some spherical particulate matter, mainly due to the continuous enlargement of the cobalt nanoparticles and their etching effect on the nitrogen-doped carbon nanotubes.
In fig. 3, Co @ NCNTs-T (T700, 800, 900, 1000 ℃) appears in sequence from bottom to top, and it can be seen from fig. 3 that the peaks at 26.2 ° of powder XRD of the Co @ NCNTs-T (T700, 800, 900, 1000 ℃) catalyst are attributed to the (002) diffraction peak of graphitic carbon, while the diffraction peaks at 44.2,51.5 and 75.8 ° correspond to the diffraction peaks of (111), (200) and (220) of face-centered cubic cobalt nanoparticles, respectively, whereby it can be determined that these catalysts are composed of amorphous nitrogen-doped carbon and metallic cobalt nanoparticles.
N of FIG. 42Adsorption and desorption isotherms show that these catalysts all have an obvious type IV isotherm, indicating that they have a mesoporous structure. In particular, the specific surface area, pore volume and pore diameter of the Co @ NCNTs-800 catalyst were 215.7m, respectively2·g-1，1.371cm3·g-1And 3.94 nm. The catalyst with the nanotube structure and the high specific surface area is very favorable for the diffusion of organic matters such as nitrobenzene and aniline hydrogenation products, and can obviously improve the enrichment and catalytic performance of reactants.
From the Raman spectrum of FIG. 5, Co @ NCNTs-T (T700, 800, 900, 1000 ℃ C.)) Catalyst is in-1350 cm-1And-1610 cm-1The characteristic peaks of D and G bands, which are ascribed to disorganized sp, appear3Carbon and graphitized sp2Carbon. Relatively high ID/IGThe ratio demonstrates the presence of a significant defect structure in these catalysts, which is mainly due to the successful doping of cobalt and nitrogen by pyrolysis of cobalt dicyanamide molecules at high temperatures.
Claims (10)
1. The nitrogen-doped carbon nanotube catalyst immobilized on non-noble metal is characterized in that the catalyst has a bamboo-like tubular shape, part of carbon nanotubes contain metal nanoparticles, and all the carbon nanotubes are of hollow structures; i of the catalystD/IGThe value range is 0.95-0.98, the nitrogen content is 2.54-3.13 wt%, and the specific surface area is 166.2-307.3 m2·g-1The pore volume ranges from 0.626 cm to 2.490cm3·g-1The pore diameter is 3.93-3.95 nm, and belongs to a mesoporous material.
2. The method of preparing a non-noble metal-supported nitrogen-doped carbon nanotube catalyst of claim 1, comprising the steps of:
step 1, dissolving silver nitrate in deionized water, adding sodium dicyandiamide, stirring for reaction, performing suction filtration, and washing a filter cake with water to obtain a white silver dicyandiamide solid;
step 2, dropwise adding a non-noble metal bromide aqueous solution into the dicyandiamide silver solid under stirring at the rotating speed of 800-1500 rpm/min, continuously stirring for 12 hours in a dark condition, performing suction filtration, discarding a faint yellow silver bromide filter cake, collecting a non-noble metal dicyandiamide filtrate, performing rotary evaporation to remove water, and performing vacuum drying to obtain a non-noble metal dicyandiamide solid;
step 3, after sweeping the non-noble metal dicyanamide solid by using inert gas, firstly heating to 550 ℃ and keeping the temperature for 1-2 hours, then heating to 700-1000 ℃ and keeping the temperature for 1-2 hours, wherein the heating rate is 2-5 ℃/min, so as to obtain a black solid;
and 4, placing the obtained black solid in acid for etching, performing suction filtration, washing the black solid to be neutral by using deionized water, drying and activating to obtain the black non-noble metal immobilized nitrogen-doped carbon nanotube catalyst.
3. The preparation method of the non-noble metal-supported nitrogen-doped carbon nanotube catalyst according to claim 2, wherein the mass ratio of silver nitrate, deionized water and sodium dicyandiamide in the step 1 is 2.1-8.6: 30-100: 1.1 to 4.5.
4. The preparation method of the non-noble metal-supported nitrogen-doped carbon nanotube catalyst according to claim 2, wherein the stirring reaction time in the step 1 is 1-2 hours.
5. The method for preparing a non-noble metal-supported nitrogen-doped carbon nanotube catalyst according to claim 2, wherein the non-noble metal bromide in the step 2 is one of cobalt bromide, ferrous bromide and nickel bromide, and the molar ratio of the non-noble metal bromide to silver nitrate is 0.4-0.45: 1, the concentration of the non-noble metal bromide aqueous solution is 0.1-0.5 mol/L.
6. The method for preparing the non-noble metal-supported nitrogen-doped carbon nanotube catalyst according to claim 2, wherein the inert gas in the step 3 is one or two of nitrogen and argon mixed in any ratio.
7. The method for preparing a non-noble metal-supported nitrogen-doped carbon nanotube catalyst according to claim 2, wherein the flow rate of the inert gas in the step 3 is 50-300 mL/min.
8. The method for preparing the non-noble metal-supported nitrogen-doped carbon nanotube catalyst according to claim 2, wherein the acid in the step 4 is dilute hydrochloric acid or dilute sulfuric acid, and the concentration of the acid is 0.1-1.0 mol/L.
9. The preparation method of the non-noble metal-supported nitrogen-doped carbon nanotube catalyst according to claim 2, wherein the etching time in the step 4 is 12-18 hours, and the etching times are 1-2 times; the activation temperature is 700 ℃, and the activation time is 1-2 h.
10. The use of the non-noble metal-supported nitrogen-doped carbon nanotube catalyst of claim 1, wherein the catalyst is used for the catalytic hydrogenation of nitroarenes in a methanol/ethanol/isopropanol reaction medium to produce aromatic amines.
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