CN112916033A - Carbon-nitrogen-doped silicon dioxide-loaded Co catalyst and preparation method and application thereof - Google Patents

Carbon-nitrogen-doped silicon dioxide-loaded Co catalyst and preparation method and application thereof Download PDF

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CN112916033A
CN112916033A CN201911240757.7A CN201911240757A CN112916033A CN 112916033 A CN112916033 A CN 112916033A CN 201911240757 A CN201911240757 A CN 201911240757A CN 112916033 A CN112916033 A CN 112916033A
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nitrogen
carbon
catalyst
silicon dioxide
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汪学广
程功林
盛瑶
邹秀晶
尚兴付
丁伟中
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University of Shanghai for Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • 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
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • 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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Abstract

The invention relates to the technical field of catalysts, and provides a carbon-nitrogen-doped silicon dioxide loaded Co catalyst, and a preparation method and application thereof. Mixing silicon dioxide, cobalt nitrate, a carbon source, a nitrogen source and a solvent, and heating the obtained mixture until the solvent is evaporated to dryness to obtain a solid material; and roasting the solid material in a protective atmosphere to obtain the carbon-nitrogen-doped silicon dioxide loaded Co catalyst. The catalyst provided by the invention has high catalytic activity and good stability, can be recycled for multiple times, and has higher selectivity when being applied to the reduction of nitro compounds to prepare amine.

Description

Carbon-nitrogen-doped silicon dioxide-loaded Co catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a carbon-nitrogen-doped silicon dioxide-loaded Co catalyst, and a preparation method and application thereof.
Background
Selective reduction of nitro compounds is one of the basic chemical reactions for the production of amines, aniline being an important intermediate and key precursor for the manufacture of numerous agrochemicals, pharmaceuticals, polymers and fine chemicals. The conventional non-catalytic process for reducing nitro groups uses stoichiometric amounts of reducing agents (such as Fe, Zn, Sn and metal sulfides) for reduction, but such processes cause serious problems with product separation, the reactor is susceptible to corrosion hazards, and large amounts of waste acids, bases and undesirable byproducts, such as hydroxylamine, are produced.
Efforts have therefore been focused on establishing efficient and highly selective catalytic reduction of nitro groups instead of non-catalytic processes. Since the catalysts for heterogeneously catalyzed reactions are easier to separate and recover, there is a greater tendency to use heterogeneously catalyzed reactions instead of uncatalyzed processes. The loaded noble metal-based nano-catalyst is widely applied to the reaction of selectively reducing nitroaromatic into arylamine. However, most of these catalysts do not satisfy the dual requirements of activity and selectivity. The Pt-group (Pt, Pd, Rh, Ru, etc.) catalysts have high catalytic activity, but have poor chemical selectivity when reducing nitro groups and high cost, and the supply of these noble metals has limited their widespread use in numerous industrial processes.
Non-noble metal transition metal catalysts (Fe, Co, Ni, etc.) have proven to be effective for selective hydrogenation of nitro compounds, and particularly, iron, cobalt, nickel, etc. catalysts supported on alumina, carbon materials are important novel heterogeneous catalytic materials. However, such catalysts generally have low activity and are prone to deactivation during recycling.
Disclosure of Invention
In view of the above, the present invention aims to provide a carbon-nitrogen doped silica supported Co catalyst and a preparation method thereof. The catalyst provided by the invention has high selectivity and good stability, can be recycled for multiple times, and has excellent catalytic effect when being applied to selective reduction of nitro compounds.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of carbon-nitrogen doped silica supported Co catalyst comprises the following steps:
mixing silicon dioxide, cobalt nitrate, a carbon source, a nitrogen source and a solvent, and heating the obtained mixture until the solvent is evaporated to dryness to obtain a solid material;
and roasting the solid material in a protective atmosphere to obtain the carbon-nitrogen-doped silicon dioxide loaded Co catalyst.
Preferably, the carbon source comprises one or more of glucose, sucrose, glucosamine hydrochloride and glucosamine sulfate.
Preferably, the nitrogen source comprises one or more of melamine, 1, 10-phenanthroline, cyclodextrin, urea and 2-methylimidazole.
Preferably, the dosage ratio of the silicon dioxide, the cobalt nitrate, the carbon source, the nitrogen source and the solvent is 1g:1g: 0.5-5 g:50 mL.
Preferably, the solvent comprises water and ethanol; the volume ratio of the water to the ethanol is 1: 0-1.
Preferably, the heating temperature for heating until the solvent is evaporated to dryness is 40-60 ℃.
Preferably, the roasting temperature is 500-900 ℃, and the roasting time is 1-5 h.
Preferably, the protective atmosphere is nitrogen.
The invention provides a carbon-nitrogen-doped silicon dioxide loaded Co catalyst prepared by the preparation method in the scheme.
The invention provides application of the carbon-nitrogen-doped silicon dioxide-loaded Co catalyst in the scheme in selective reduction of nitro compounds to prepare amine.
The invention provides a preparation method of a carbon-nitrogen doped silicon dioxide loaded Co catalyst, which comprises the following steps: mixing silicon dioxide, cobalt nitrate, a carbon source, a nitrogen source and a solvent, and heating the obtained mixture until the solvent is evaporated to dryness to obtain a solid material; and roasting the solid material in a protective atmosphere to obtain the carbon-nitrogen-doped silicon dioxide loaded Co catalyst. The carbon source, the nitrogen source, the cobalt nitrate and the silicon dioxide are mixed firstly, and are evaporated to dryness to form a complex, in the roasting process, the cobalt nitrate is firstly decomposed into cobalt and cobalt oxide particles, meanwhile, the carbon source and the nitrogen source are subjected to polymerization and decomposition to form a nitrogen-doped carbon material, in the further roasting process, carbon can reduce the cobalt oxide into metal Co, and finally the carbon-nitrogen-doped silicon dioxide supported Co catalyst is obtained. The preparation method provided by the invention has simple steps, is easy to operate and is easy for industrial production.
The invention provides the catalyst prepared by the preparation method in the scheme. The catalyst provided by the invention has very high catalytic activity under the condition that hydrogen is used as a reducing agent, and has higher activity than the prior reported similar non-noble metal catalysts, and compared with other Fe, Co and Ni catalysts, the catalyst provided by the invention has better stability and can be recycled for multiple times. The results of the examples show that when the catalyst provided by the invention is applied to the selective reduction of o-chloronitrobenzene, the conversion rate can reach 78.3%, the selectivity can reach more than 99%, and after the catalyst is exposed in the air for 3 months, the performance of the catalyst is stable, and the activity is basically unchanged.
Drawings
FIG. 1 is an XRD pattern of catalysts prepared in example 1 and comparative examples 1 to 3;
fig. 2 is a TEM image of the catalyst prepared in example 1.
Detailed Description
The invention provides a preparation method of a carbon-nitrogen doped silicon dioxide loaded Co catalyst, which comprises the following steps:
mixing silicon dioxide, cobalt nitrate, a carbon source, a nitrogen source and a solvent, and heating the obtained mixture until the solvent is evaporated to dryness to obtain a solid material;
and roasting the solid material in a protective atmosphere to obtain the carbon-nitrogen-doped silicon dioxide loaded Co catalyst.
The method comprises the steps of mixing silicon dioxide, cobalt nitrate, a carbon source, a nitrogen source and a solvent, heating the obtained mixture until the solvent is evaporated to dryness, and obtaining a solid material. In the present invention, the silica is preferably industrial silica; the particle size of the silicon dioxide is preferably 3-5 mm; the cobalt nitrate is preferably cobalt nitrate hexahydrate; the carbon source preferably comprises one or more of glucose, sucrose, glucosamine hydrochloride and glucosamine sulfate; the nitrogen source preferably comprises one or more of melamine, 1, 10-phenanthroline, cyclodextrin, urea and 2-methylimidazole; the solvent preferably comprises water and ethanol; the volume ratio of the water to the ethanol is preferably 1: 0-1, and more preferably 1: 0.3-0.8; when the dosage of the ethanol is 0, the solvent is water; the water is preferably deionized water; the dosage ratio of the silicon dioxide, the cobalt nitrate, the carbon source, the nitrogen source and the solvent is preferably 1g:1g: 0.5-5 g:50mL, and more preferably 1g:1g: 1-3 g:50 mL.
In the invention, the heating temperature for heating to evaporate the solvent to dryness is preferably 40-60 ℃, and more preferably 45-55 ℃; the heating to evaporate the solvent to dryness is preferably carried out under stirring conditions; according to the invention, the solvent is heated and evaporated to dryness, so that the cobalt nitrate, the carbon source and the nitrogen source form a complex with a certain structure.
After the solid material is obtained, the solid material is roasted under the protective atmosphere to obtain the carbon-nitrogen-doped silicon dioxide loaded Co catalyst. In the invention, the roasting temperature is preferably 500-900 ℃, more preferably 600-800 ℃, and the roasting time is preferably 1-5 h, more preferably 2-4 h; the protective atmosphere is preferably nitrogen. During firing, cobalt nitrate is first decomposed into metallic Co or Co oxide particles (Co)3O4Etc.) while the carbon and nitrogen precursors undergo a process of polymerization and decomposition to form a nitrogen-doped carbon material, the carbon reduces the Co oxide to metallic Co during further firing. In addition, during firing, the nitrogen source polymerizes to form a layered graphitic carbon nitride (g-C)3N4) With carbon source in g-C3N4Interlayer polymerization is carried out to form a carbon skeleton, cobalt nanoparticles are embedded in the layered structure, and the cobalt nanoparticles catalyze the carbon layer to generate nitrogen doping along with the continuous roastingThe carbon tube and the nanometer Co particle are coated by several layers of graphite carbon, and the special structure can avoid the oxidation of the cobalt nanometer particle and improve the stability of the catalyst.
The invention provides a carbon-nitrogen doped silicon dioxide loaded Co catalyst prepared by the preparation method in the scheme, which comprises a silicon dioxide carrier and nitrogen doped carbon coated metal cobalt nanoparticles loaded on the silicon dioxide carrier; and a notch is formed on the nitrogen-doped carbon material coating layer on the surface of the metal cobalt nano-particle, so that reactant molecules can be contacted with the cobalt nano-particle; in the invention, the loading amount of the metal cobalt nanoparticles in the catalyst is preferably 20-40 wt%; the preferable load amount of carbon in the nitrogen-doped carbon material coating layer is 23-28 wt%, and the preferable load amount of nitrogen is 5-8 wt%; the catalyst provided by the invention has the following advantages: the nanometer Co particles are wrapped by the nitrogen-doped carbon material, and the metal particles are separated from each other in space due to the existence of the carbon layer, so that the loss and agglomeration of the metal particles in the reaction process can be prevented, and the catalyst has better stability; the coated nano Co particles have magnetism, the whole coating structure also has magnetism, and the catalyst is easy to recycle after the reaction is finished; in some reactions, the substrate molecule contains nitrogen, sulfur and other heteroatoms (such as quinoline, picoline and the like), the heteroatoms have strong coordination capacity with metals and easily deactivate metal catalysts, and the existence of a carbon layer can reduce or eliminate the influence; the introduction of heteroatom nitrogen improves the electronic property of the carbon layer, increases the dispersion degree of the catalyst in a polar solution, enhances the adsorption capacity of a substrate on the surface of the catalyst, and simultaneously facilitates the dispersion of nano Co particles.
The invention also provides application of the carbon-nitrogen-doped silicon dioxide loaded Co catalyst in the scheme in selective reduction of nitro compounds to prepare amine. The present invention is not particularly limited to the specific method of application, and may be applied by methods known to those skilled in the art.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1g of technical silica, 1g of cobalt nitrate hexahydrate, 0.5g of sucrose, 5g of urea in 50mL of ethanol: water 1: 1 (volume ratio), stirring and evaporating at 60 ℃, roasting the obtained solid for 1h at 800 ℃ in a nitrogen atmosphere, and obtaining the target catalyst after roasting.
Example 2
1g of technical silica, 1g of cobalt nitrate hexahydrate, 1g of glucosamine hydrochloride, 2g of urea in 50mL of ethanol: water 1: 1 (volume ratio), stirring and evaporating at 40 ℃, roasting the obtained solid for 3h at 700 ℃ in a nitrogen atmosphere, and obtaining the target catalyst after roasting.
Example 3
1g of technical silica, 1g of cobalt nitrate hexahydrate, 0.5g of glucose, 3g of melamine were dissolved in 50mL of ethanol: water 1: 1 (volume ratio), stirring and evaporating at 50 ℃, roasting the obtained solid for 1h at 500 ℃ in a nitrogen atmosphere, and obtaining the target catalyst after roasting.
Comparative example 1
Otherwise as in example 1, with no sucrose added, the catalyst obtained was noted as Co-SiO2-N。
Comparative example 2
Otherwise as in example 1, with no urea addition, the catalyst obtained is described as Co-SiO2-C。
Comparative example 3
Otherwise, as in example 1, with no addition of sucrose and urea, the catalyst obtained is marked as Co-SiO2。
Comparative example 4
Otherwise, as in example 1, only cobalt nitrate hexahydrate was replaced by iron nitrate to obtain a carbon-nitrogen-doped silica-supported Fe catalyst.
Comparative example 5
Otherwise, as in example 1, only cobalt nitrate hexahydrate was replaced with nickel nitrate to obtain a carbon-nitrogen-doped silica-supported Ni catalyst.
XRD test: x-ray diffraction tests were carried out on the catalysts prepared in example 1 and comparative examples 1 to 3 to obtain XRD patternsAs shown in FIG. 1, the catalyst prepared in example 1 is represented as Co-SiO2-CN. As can be seen from FIG. 1, Co/SiO2-N and Co/SiO2Because no carbon source is added, elemental cobalt cannot be obtained by reduction through carbon, and obvious triple-strong peaks of the elemental Co are not found in XRD curves of the two catalysts; Co/SiO2C is added with a carbon source, but the particle size of the loaded cobalt cannot be restricted due to the absence of N element, so that the Co nano-particle size is coarse; Co/SiO2Due to the simultaneous addition of the carbon source and the nitrogen source, the-CN enhances the strong interaction with the metal-carrier between the cobalt nanoparticles, reduces the particle size of the simple substance cobalt, and also enhances the adhesion stability of the cobalt particles. Meanwhile, due to the introduction of nitrogen atoms, the electronic structure of the whole carbon material is changed, new defect sites are created, and active sites are increased. Co-SiO can be seen from the XRD pattern2Grain size of Co particles in-CN is larger than that of Co/SiO2the-C is small, the Co particles are mainly exposed to the outside and are Co (111) crystal planes and Co (200) crystal planes, and the Co (111) crystal planes and Co (200) crystal planes are active sites of hydrogenation reaction, and the XRD test result shows that the catalyst prepared by the method has higher activity and stability, which is also consistent with the combination of actual test.
TEM test: the catalyst prepared in example 1 was subjected to TEM test, and the results are shown in fig. 2, and from the TEM image, the lattice fringes of cobalt (solid portion of the central black region) and the lattice fringes of the carbon layer (dotted portion) were observed at the same time.
Application example
(1) The catalyst prepared in the embodiment 1 and the comparative examples 4-5 is applied to catalyze the hydrogenation reduction reaction of o-chloronitrobenzene, and the reaction conditions are as follows: 6mmol of o-chloronitrobenzene, 30mg of catalyst and 20mL of ethanol, the reaction temperature is 120 ℃, and the reaction pressure is H2: 2MPa and the reaction time is 2 h.
The results obtained, calculated as conversion and selectivity of the reaction, are shown in table 1:
TABLE 1 catalysis results of the catalysts obtained in example 1 and comparative examples 4 to 5
Catalyst and process for preparing same Conversion (%) Selectivity (%)
Comparative example 4 7.9 >99％
Comparative example 5 13.3 >99％
Example 1 87.2 >99％
According to the data in the table 1, the carbon-nitrogen-doped silicon dioxide loaded Co catalyst prepared by the invention is applied to the selective reduction of nitro compounds, and has the advantages of high conversion rate, high selectivity and good catalytic effect.
(2) And (3) testing the cycling stability: and (3) testing the circulation stability by using nitrobenzene as a raw material, wherein other conditions are consistent with those in the step (1), the nitrobenzene is recycled for 6 times, the loss of the target catalyst in recycling is assumed to be 10%, other reaction conditions are changed according to the same proportion, and the proportion is consistent.
The results show that the conversion rate of nitrobenzene into aniline when the catalyst is used for the first time is 88%, the conversion rate of nitrobenzene into aniline for the third time, the conversion rate for the fifth time and the conversion rate for the sixth time are nearly 90% and can basically reach the level of a fresh catalyst, and XPS and TEM tests of the catalyst after the catalyst is used up in a circulating sleeve show that the phenomenon of Co particle aggregation does not occur, but the content of Co is slightly reduced, and the reason that the conversion rate for circulating sleeve application is increased is probably because the assumed 10% loss amount of the catalyst is too much, the actual loss is not 10%, and the amount of a substrate is correspondingly reduced, so that the conversion rate is increased.
(3) Stability test
After the conventional non-noble metal Co catalyst is exposed in the air for a period of time, the catalyst can be quickly deactivated, the simple Co is easily oxidized into cobaltosic oxide again in the air state, and the catalyst prepared in example 1 is exposed in the air without protection to test the stability of the catalyst. The results show that after 3 months the catalyst was still very stable with little apparent change in activity.
The catalysts obtained in examples 2 to 3 were subjected to the same tests as in (1) to (3), and the results were similar to those of example 1.
The embodiment shows that the carbon-nitrogen-doped silicon dioxide loaded Co catalyst with high catalytic activity, good stability and high selectivity is prepared by doping carbon and nitrogen atoms in the preparation method provided by the invention, and has wide application prospect in the preparation of amine compounds by selectively reducing nitro compounds.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the carbon-nitrogen-doped silicon dioxide loaded Co catalyst is characterized by comprising the following steps of:
mixing silicon dioxide, cobalt nitrate, a carbon source, a nitrogen source and a solvent, and heating the obtained mixture until the solvent is evaporated to dryness to obtain a solid material;
and roasting the solid material in a protective atmosphere to obtain the carbon-nitrogen-doped silicon dioxide loaded Co catalyst.
2. The method according to claim 1, wherein the carbon source comprises one or more of glucose, sucrose, glucosamine hydrochloride, and glucosamine sulfate.
3. The method according to claim 1, wherein the nitrogen source comprises one or more of melamine, 1, 10-phenanthroline, cyclodextrin, urea, and 2-methylimidazole.
4. The method according to claim 1, wherein the amount of the silica, the cobalt nitrate, the carbon source, the nitrogen source, and the solvent is 1g:1g: 0.5-5 g:50 mL.
5. The production method according to claim 1 or 4, wherein the solvent comprises water and ethanol; the volume ratio of the water to the ethanol is 1: 0-1.
6. The method according to claim 1, wherein the heating temperature for heating to evaporate the solvent to dryness is 40 to 60 ℃.
7. The preparation method according to claim 1, wherein the roasting temperature is 500-900 ℃ and the roasting time is 1-5 h.
8. The method of claim 1, wherein the protective atmosphere is nitrogen.
9. The carbon-nitrogen doped silica supported Co catalyst prepared by the preparation method of any one of claims 1 to 8.
10. Use of the carbon-nitrogen doped silica supported Co catalyst of claim 9 in the selective reduction of nitro compounds to amine.
CN201911240757.7A 2019-12-06 2019-12-06 Carbon-nitrogen-doped silicon dioxide-loaded Co catalyst and preparation method and application thereof Pending CN112916033A (en)

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CN113663727A (en) * 2021-09-18 2021-11-19 黔南高新区绿色化工技术研究院有限公司 Preparation method of supported catalyst with high specific surface area and application of supported catalyst in p-nitroaniline synthesis
CN113694916A (en) * 2021-09-17 2021-11-26 黔南高新区绿色化工技术研究院有限公司 Method for synthesizing p-nitroaniline based on hierarchical porous carbon fiber supported phase transfer catalyst
CN114210332A (en) * 2022-01-10 2022-03-22 兰州市三青化学有限公司 Preparation method of cobalt metal-nitrogen co-doped carbon material catalyst
CN114308104A (en) * 2021-12-27 2022-04-12 华南理工大学 Preparation method and application of nitrogen-doped carbon material loaded bimetallic cobalt and vanadium catalyst
CN114345387A (en) * 2022-01-10 2022-04-15 兰州市三青化学有限公司 Preparation method of nitrogen-doped carbon-supported cobalt catalyst
CN114471656A (en) * 2022-01-21 2022-05-13 浙江大学 Catalyst suitable for selective hydrogenation preparation of pioglitazone and preparation and application thereof
CN114700488A (en) * 2022-04-11 2022-07-05 河北省科学院能源研究所 Preparation method of Ni/Co alloy coated with nitrogen-doped porous carbon microspheres
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CN115382566A (en) * 2022-08-30 2022-11-25 浙江大学 Lewis base modified porous carbon catalyst suitable for preparing pioglitazone through hydrogenation and preparation and application thereof
CN115518669A (en) * 2022-11-02 2022-12-27 苏州大学 Supported cobalt cluster catalyst for ammonia synthesis and preparation method and application thereof
CN116273120A (en) * 2023-03-07 2023-06-23 淮安禾之盛新材料技术开发服务有限公司 Carbon-nitrogen doped supported cobalt-based catalyst and preparation method and application thereof
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