A supported non-precious metal single-atom catalyst and its application

Abstract

The invention discloses the preparation of a supported non-precious metal single-atom catalyst and its application in the carboxylation reaction of unsaturated alkynes, wherein the active component is metal Ni and the carrier is nitrogen-doped carbon. Wherein, the loading amount of the active metal on the carrier is 0.1wt%-5.0wt%, and the doping amount of nitrogen in the nitrogen-doped carbon is 0.1wt%-10wt%; the metal Ni is in a single-atom dispersion state. Preparation of the catalyst: The nitrogen-doped carrier and the compound containing metal Ni are placed in the same reactor and treated for a certain time at a certain temperature, pressure and suitable atmosphere. Metal Ni is spontaneously dispersed on the carrier in the form of a single atom to generate a single-atom active center, which is used for the carboxylation reaction of unsaturated alkynes, and the catalyst has good activity and selectivity. Compared with the homogeneous carbonyl nickel, nickel salt or palladium-phosphine complex reported in other patent documents as a catalyst, and the system in which highly corrosive sulfuric acid, sulfonic acid or other acids are added as an auxiliary agent, the multiphase reaction process provided by the invention has the advantages of being environmentally friendly, simple to operate, and the catalyst can be recycled.

Description

Technical Field

[0001] The invention relates to the preparation of a supported non-noble metal single-atom catalyst and its application in the carboxylation reaction of unsaturated alkynes Background Art

[0002] The carboxylation of unsaturated alkynes is a very important chemical reaction. It is an atom-economic reaction for preparing esters containing C=C functional groups. For example, the carboxylation of acetylene can prepare methyl acrylate. At present, this type of reaction is mainly catalyzed by homogeneous catalysts. Ni(CO)4, Ni salt or Pd(PPh)3 are used as main catalysts in industry, and trifluoromethanesulfonic acid and benzenesulfonic acid are used as auxiliary agents. Such catalysts are difficult to recover and separate, and corrode equipment. Therefore, for this type of reaction, it is urgent to find a highly active and environmentally friendly heterogeneous catalyst. Single-atom catalysts have the characteristics of a single active site, a controllable coordination environment, and 100% atomic utilization. They are considered to be a bridge connecting heterogeneous catalysts and homogeneous catalysts. However, the current common preparation methods of single-atom catalysts are wet chemical methods or high-temperature vapor deposition methods. The catalysts obtained by this method are either low in activity or poor in stability in the carboxylation of alkynes and cannot be recycled. Therefore, it is urgent to find a single-atom catalyst that can stably and efficiently catalyze the carboxylation of unsaturated alkynes under reaction conditions.

[0003] Many patents describe catalysts for the carboxylation of unsaturated alkynes.

[0004] Patent 1 (CN 105753700 A) uses pyridyl diphenylphosphine (2-PyPPH) as an organic ligand and connects vinyl groups, polymerizes with polymer hinges to form an organic ligand polymer (N-PPOL) to immobilize palladium acetate to prepare an immobilized Pd-based catalyst, and the catalyst acetylene carboxymethyl ester reacts at 30-80°C and 1.2-6.5Mpa, with high activity and selectivity. However, the reaction process still requires organic acid as an auxiliary agent, and all metal components are lost after the hot filtration experiment. In addition, the organic ligand (2-PyPPH) is expensive, the grafting process is complicated, and it is difficult to apply on a large scale.

[0005] Patent 2 (CN 102190583 A) uses palladium acetate, an acid auxiliary, and a nitrogen-phosphorus ligand as a catalyst to catalyze the acetylene carboxylation reaction at 10-100°C and a total pressure of 0.5-3 MPa, wherein Pd reacts with an organic acid and a nitrogen-phosphorus ligand to generate an active center in situ under the reaction conditions. The catalytic system is difficult to recycle, and the organic acid corrodes the equipment.

[0006] Patent 3 (CN 107051576 A) uses acidic molecular sieves and inert oxides as carriers, nickel compounds, and nickel compounds loaded on inert carriers to jointly catalyze the carbonylation and esterification of acetylene. The reaction needs to be carried out at a pressure of 5-10Mpa and 170-220°C. In this system, the nickel salt is loaded on the carrier and dried without any reduction treatment. During the actual reaction, Ni will be lost in the form of nickel salts, thereby corroding the equipment, and the lost components are difficult to recover; the reaction needs to be at least 5Mpa pressure to occur, and the gas CO under this pressure will also cause corrosion to the equipment.

[0007] Patent 4 (CN 107382732 A) uses non-halogen compounds of nickel and salt ligands of β-diketone and corresponding compounds as catalysts to catalyze the carbonylation of acetylene to synthesize acrylate at 170-250°C and 3-10Mpa without acid additives. This catalytic system is difficult to recycle, and the price of nickel acetylacetonate or acetylacetonate salt is relatively expensive, which is not suitable for industrial use. In addition, acetylacetonate salt is easy to react with nickel salt to form highly toxic carbonyl nickel under CO conditions.

[0008] Patent 5 (CN 106831425 A) uses nickel salt and bidentate ligand containing N and group VI elements as catalysts to catalyze the carboxylation of acetylene, with a reaction temperature of 160-250°C and a reaction pressure of 3-12Mpa, and no carbon deposition during the reaction. This catalytic system is difficult to recycle, the ligand is expensive, and in the actual reaction process, the ligand (such as 2-pyridinecarboxylic acid) often has carboxyl groups, sulfonic acid groups, etc., so it is impossible to eliminate its corrosiveness to the equipment. Summary of the invention

[0009] This article discloses the preparation of a supported non-precious metal single-atom catalyst and its application in the carboxylation reaction of unsaturated alkynes. The active metal nickel of the catalyst is in a single-atom dispersed state, there is no metal loss during the reaction, and the catalyst can be recycled. The catalyst shows excellent activity and selectivity in the carboxylation reaction of unsaturated alkynes. The reaction conditions are mild, no acid auxiliary agent is required, the catalyst is low in price, and has prospects for industrial application.

[0010] Another object of the present invention is to provide a method for preparing a single-atom metal catalyst under carbon monoxide atmosphere conditions. The method has a simple process flow and is easy to control. The obtained single-atom catalyst will not aggregate or flow away under the reaction environment.

[0011] In order to achieve the above object, the technical solution adopted by the present invention is:

[0012] A preparation of a supported non-precious metal single-atom catalyst and its application in the carboxylation reaction of unsaturated alkynes, characterized in that the active component of the metal catalyst is Ni, the carrier is nitrogen-doped carbon, and the active component Ni is dispersed in the nitrogen-doped carbon carrier in the form of single atoms. The single-atom Ni loading is 0.2%-5.0wt%, and the mass content of nitrogen in the nitrogen-doped carbon carrier is 0.1wt%-10.0wt%. The preparation process of the supported non-precious metal single-atom catalyst is as follows:

[0013] The organic polymer precursor is placed in a tube furnace, a gas with a certain flow rate is introduced, the temperature is raised to a specified temperature, heated for a certain time, and then cooled to room temperature to obtain a nitrogen-doped carbon carrier;

[0014] The organic polymer precursor is one or more of poly 2,6-diaminopyridine, polyaniline, melamine, polypyrrole, polypyridine, dicyandiamide, etc.; the gas flow rate is 20-200 ml / s, preferably 50-100 ml / s; the heating temperature is 500-1200°C, preferably 700-900°C, the heating rate is 5-10°C / min, and the heating time is 2-4h; the gas is an inert gas containing ammonia, wherein the volume concentration of ammonia is 5%-100%, preferably 20-80%.

[0015] The metal Ni precursor and the nitrogen-doped carbon carrier are separated and placed in a reactor, wherein the metal Ni precursor is at the upstream end of the gas and the nitrogen-doped carbon carrier is at the downstream end of the gas, a gas containing CO is introduced and increased to a certain pressure, the temperature is raised to a specified temperature, heated for a certain time, cooled to room temperature, and used after passivation;

[0016] Among them, the metal Ni precursor is its simple substance and / or compound, wherein the simple substance or compound of metal Ni includes one or more of metal nickel powder, nickel acetylacetonate, carbonyl nickel, nickel oxide, nickel sulfide, etc.; the gas containing carbon monoxide includes pure carbon monoxide gas or a mixture of carbon monoxide and one or two of hydrogen and inert gas, wherein the volume concentration of carbon monoxide is 1-100%, preferably the volume concentration is 20-100%; the mass ratio of the metal nickel precursor to the nitrogen-doped carbon carrier is 0.01-1, and the preferred ratio is 0.01-0.6; the carbon monoxide gas flow rate is 1.25-250ml / s.gcat, and the preferred gas flow rate is 2.5-50ml / s.gcat; the gas pressure is 0.1Mpa-4Mpa, and the preferred pressure is 0.5-2Mpa; the heating temperature is 20-400°C, and the preferred temperature is 80-300°C; the heating time is 1-12h, and the preferred heating time is 4-6h.

[0017] Passivation process: After the reactor is cooled to room temperature, the pressure is released to normal pressure, the gas containing CO is turned off, and the passivation gas is re-introduced into the reactor, and the reactor is purged at normal pressure at room temperature, wherein the passivation gas is an inert gas containing oxygen, wherein the volume concentration of oxygen is 0.1%-1.0%, preferably the volume concentration is 0.5%-1.0%, the gas flow rate is 0.5-2.0ml / s.gcat, preferably the gas flow rate is 0.5-1.0ml / s.gcat, and the purging time is 12-24h. The reaction is carried out in a solvent, and the reaction solvent is one or a mixture of two or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol, and n-butanol in any ratio; the unsaturated alkyne is any one or more of acetylene, propyne, 1-butyne, diacetylene, phenylacetylene (gasified), etc., and the molar ratio of the catalyst active component to the reaction substrate is 1×10 -2 to 5.

[0018] The alkyne carboxylation reaction can be carried out in a reactor or in a fixed bed reactor, wherein the initial pressure of carbon monoxide and unsaturated alkyne gas at room temperature is 0.01-5 MPa, the reaction temperature is 50-300° C., and the reaction time is not less than 1 hour.

[0019] The catalyst in the reactor can be recycled for more than 3 times without significant decrease in conversion rate and selectivity, and the catalyst is easily separated from the reaction solution. The catalyst in the fixed bed can react stably for more than 80 hours.

[0020] The activity test method of the catalyst provided by the present invention is as follows:

[0021] The reactor is a high-pressure reactor. The reaction substrate, internal standard and solvent are prepared into a reaction solution of a certain concentration. A certain amount of the reaction solution is taken with a pipette for each reaction. The initial pressure of the unsaturated alkyne and carbon monoxide in the reactor at room temperature is 0.01-5Mpa, the reaction temperature is 50-300°C, and the reaction time is not less than 1 hour. After the reaction is completed and cooled to room temperature, a sample is taken for gas chromatography analysis.

[0022] The reactor is a high-pressure fixed bed. The gas reactants enter the fixed bed pipeline through a high-pressure flowmeter. The solvent is injected using a high-pressure pump. The pressure of unsaturated alkynes and carbon monoxide in the fixed bed at room temperature is 0.01-5Mpa, the flow rate is 0.05-0.1ml / s, the reaction temperature is 50-300℃, and the reaction time is not less than 1 hour. The reaction process is analyzed online using gas chromatography.

[0023] The metal Ni is spontaneously dispersed in the form of single atoms on the carrier to generate single-atom active centers, which are used for the carboxylation reaction of unsaturated alkynes, and the catalyst has good activity and selectivity. Compared with the systems reported in other patent documents that use homogeneous carbonyl nickel, nickel salts or palladium-phosphine complexes as catalysts and add highly corrosive sulfuric acid, sulfonic acid or other acids as additives, the multiphase reaction process provided by the invention has the advantages of being environmentally friendly, simple to operate, and the catalyst can be recycled.

[0024] The present invention has the following effects:

[0025] 1. The present invention provides a preparation method of a supported non-precious metal single-atom catalyst and its application in the carboxylation reaction of unsaturated alkynes. The reaction does not require an acid auxiliary agent, the catalyst is easy to prepare, recyclable, and can be recycled for multiple times. During use, no active components are lost and the activity is not significantly reduced.

[0026] 2. The product obtained by the carboxylation reaction of unsaturated alkynes is an important organic monomer in industry, such as synthetic organic glass, advanced optical lenses, water-based coatings and advanced molds, etc. The present invention provides a supported non-precious metal single-atom catalyst with high activity and selectivity for such reactions.

[0027] 3. The present invention provides a supported non-precious metal single-atom catalyst that is easy to separate from the reaction solution after the reaction and is easy to operate.

[0028] In summary, the present invention achieves efficient and highly selective conversion of unsaturated alkynes, carbon monoxide and alcohols to prepare ester compounds. Compared with industrial homogeneous catalyst systems, the catalyst provided by the present invention is green and friendly in the process of such reactions, saves costs, and is expected to be applied in industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is an electron microscope image of nickel sulfide in the Ni-NC catalyst prepared in Example 1.

[0030] Figure 2 This is the local spherical aberration electron microscope image of the catalyst Ni-NC in Example 1.

[0031] Figure 3 Schematic diagram of the preparation operation. DETAILED DESCRIPTION

[0032] The present invention is further described below in conjunction with the accompanying drawings and specific implementation modes, but the present invention is not limited thereto.

[0033] The preparation process of the nitrogen-doped carbon carrier used in the following examples is as follows: 3.0 g of poly 2,6-diaminopyridine is placed in a tubular furnace, and a mixed gas of 55% NH3-45% He by volume is introduced at a gas flow rate of 65 ml / s. The temperature is increased to 800°C at a rate of 10°C / min and then heated for 4 hours. The nitrogen-doped carbon carrier is obtained after being cooled to room temperature. The mass content of nitrogen in the product nitrogen-doped carbon carrier is 8.5 wt%.

[0034] Embodiment 1:

[0035] At room temperature, 10 mg of nickel sulfide was placed in a reactor, quartz wool was added to separate it, and 40 mg of nitrogen-doped carbon carrier was added to the other end. Pure CO gas was introduced, and the gas flow rate was controlled to be 10 ml / s to ensure that nickel sulfide was at the upstream end of the gas and nitrogen-doped carbon was at the downstream end of the gas. The reactor pressure was increased, and the flow rate was set to 0.2 ml / s after reaching 1 MPa. The reactor temperature was increased to 160 ° C. After maintaining the state for 4 hours, it was naturally cooled to room temperature. The reactor was restored to normal pressure, and pure CO was replaced with a passivation gas of 1% O2-99% N2 (volume concentration, the same below), and the flow rate was 0.5 ml / s to purge for 12 hours, and the carrier part was taken out separately for standby use. It can be seen from the electron microscope that Ni is dispersed as a single atom on the treated carrier. The mass content of active metal Ni is 2.5wt%.

[0036] Embodiment 2:

[0037] At room temperature, 10 mg of nickel sulfide was placed in a reactor, quartz wool was added to separate it, and 40 mg of nitrogen-doped carbon carrier was added to the other end. A 50% CO-50% H2 mixed gas was introduced, and the gas flow rate was controlled to be 10 ml / s to ensure that the nickel sulfide was at the upstream end of the gas and the nitrogen-doped carbon was at the downstream end of the gas. The reactor pressure was increased, and the flow rate was set to 0.2 ml / s after reaching 1 MPa. The reactor temperature was increased to 160 ° C, and the state was maintained for 4 hours before naturally cooling to room temperature. The reactor was restored to normal pressure, and the 50% CO-50% H2 mixed gas was changed to a passivation gas of 1% O2-99% N2, and the flow rate was 0.5 ml / s to purge for 12 hours, and the carrier part was taken out separately for standby use. It can be seen from the electron microscope that the Ni on the treated carrier is dispersed as a single atom. The mass content of active metal Ni is 0.5wt%.

[0038] Embodiment 3:

[0039] At room temperature, 10 mg of nickel acetylacetonate was placed in a reactor, quartz wool was added to separate, and 40 mg of nitrogen-doped carbon carrier was added to the other end, pure CO gas was introduced, and the gas flow rate was controlled to be 10 ml / s, ensuring that nickel acetylacetonate was at the upstream end of the gas and nitrogen-doped carbon was at the downstream end of the gas. The reactor pressure was increased, and the flow rate was set to 0.2 ml / s after reaching 1 MPa, and the reactor temperature was increased to 200 ° C. After maintaining the state for 4 hours, it was naturally cooled to room temperature, and the reactor was restored to normal pressure. The CO gas was changed to a passivation gas of 1% O2-99% N2, and the flow rate was 0.5 ml / s to purge for 12 hours, and the carrier part was taken out separately for standby use. It can be seen from the electron microscope that Ni is dispersed as a single atom on the treated carrier. The mass content of active metal Ni is 4.0wt%.

[0040] Embodiment 4:

[0041] At room temperature, 10 mg of reduced nickel powder was placed in a reactor, quartz wool was added to separate, and 40 mg of nitrogen-doped carbon carrier was added to the other end. A 50% CO-50% H2 mixed gas was introduced, and the gas flow rate was controlled to be 10 ml / s to ensure that the reduced nickel powder was at the upstream end of the gas and the nitrogen-doped carbon was at the downstream end of the gas. The reactor pressure was increased, and the flow rate was set to 0.2 ml / s after reaching 1 MPa. The reactor temperature was increased to 160 ° C, and the state was maintained for 4 hours before naturally cooling to room temperature. The reactor was restored to normal pressure, and the pure 50% CO-50% H2 mixed gas was changed to a passivation gas of 1% O2-99% N2, and the flow rate was 0.5 ml / s to purge for 12 hours, and the carrier part was taken out separately for standby use. It can be seen from the electron microscope that the Ni on the treated carrier is dispersed as a single atom. The mass content of active metal Ni is 0.2wt%.

[0042] Embodiment 5:

[0043] At room temperature, 10 mg of nickel oxide powder was placed in a reactor, quartz wool was added to separate, and 40 mg of nitrogen-doped carbon carrier was added to the other end. A 50% CO-50% H2 mixed gas was introduced, and the gas flow rate was controlled to be 10 ml / s to ensure that the nickel oxide was at the upstream end of the gas and the nitrogen-doped carbon was at the downstream end of the gas. The reactor pressure was increased, and the flow rate was set to 0.2 ml / s after reaching 1 MPa. The reactor temperature was increased to 180 ° C, and the state was maintained for 4 hours before naturally cooling to room temperature. The reactor was restored to normal pressure, and the 50% CO-50% H2 mixed gas was changed to a passivation gas of 1% O2-99% N2, and the flow rate was 0.5 ml / s for 12 hours. The carrier part was taken out separately for standby use. It can be seen from the electron microscope that the Ni on the treated carrier is dispersed as a single atom. The mass content of active metal Ni is 0.1wt%.

[0044] Embodiment 6:

[0045] Place 10 mg of nickel bromide in a reactor at room temperature, add quartz wool to separate, and add 40 mg of nitrogen-doped carbon carrier at the other end, pass pure 10% CO-90% He gas, control the gas flow rate to 10 ml / s, ensure that nickel bromide is at the upstream end of the gas, and nitrogen-doped carbon is at the downstream end of the gas, increase the reactor pressure, and set the flow rate to 0.2 ml / s after reaching 1 MPa, increase the reactor temperature to 160 ° C, maintain the state for 4 hours, and then cool naturally to room temperature, the reactor returns to normal pressure, and the pure 10% CO-90% He gas is changed to 1% O2-99% N2 passivation gas, the flow rate is 0.5 ml / s to purge for 12 hours, and the carrier part is taken out separately for standby. It can be seen from the electron microscope that Ni is dispersed as a single atom on the treated carrier. The mass content of active metal Ni is 2.0wt%.

[0046] Embodiment 7:

[0047] Place 10 mg of nickel carbonate in a reactor at room temperature, add quartz wool to separate, and add 40 mg of nitrogen-doped carbon carrier at the other end, pass pure 50% CO-50% H2 gas, control the gas flow rate to 10 ml / s, ensure that nickel carbonate is at the upstream end of the gas, and nitrogen-doped carbon is at the downstream end of the gas, increase the reactor pressure, and set the flow rate to 0.2 ml / s after reaching 1 MPa, increase the reactor temperature to 160 ° C, maintain the state for 4 hours, and then cool to room temperature naturally, the reactor returns to normal pressure, and the pure 50% CO-50% H2 gas is changed to 1% O2-99% N2 passivation gas, the flow rate is 0.5 ml / s to purge for 12 hours, and the carrier part is taken out separately for standby. It can be seen from the electron microscope that Ni is dispersed as a single atom on the treated carrier. The mass content of active metal Ni is 0.2wt%.

[0048] Embodiment 8:

[0049] At room temperature, 10 mg of carbonyl nickel (frozen at 0 ° C) was placed in a reactor, and quartz wool was added to separate the two. 40 mg of nitrogen-doped carbon carrier was added to the other end. Pure CO gas was introduced, and the gas flow rate was controlled to be 10 ml / s to ensure that the carbonyl nickel (frozen at 0 ° C) was at the upstream end of the gas and the nitrogen-doped carbon was at the downstream end of the gas. The reactor pressure was increased, and the flow rate was set to 0.2 ml / s after reaching 1 MPa. The reactor temperature was increased to 140 ° C, and the state was maintained for 4 hours before naturally cooling to room temperature. The reactor was restored to normal pressure, and the CO-H2 mixed gas was changed to a passivation gas of 1% O2-99% N2, and the flow rate was 0.5 ml / s for 12 hours. The carrier part was taken out separately for standby use. It can be seen from the electron microscope that the Ni on the treated carrier is dispersed as a single atom. The mass content of active metal Ni is 5.0wt%.

[0050] Application Example 1:

[0051] 40 mg of the catalyst was placed in a reaction kettle, and 5 ml of methanol reaction solution was added using a pipette. The reaction conditions were 0.05 MPa acetylene, 0.95 MPa carbon monoxide (initial pressure), and 160°C.

[0052] The specific experimental results are as follows:

[0053] Results of non-noble metal Ni catalysts prepared from different precursors in the carboxymethylation of acetylene

Claims

1. Application of a supported non-precious metal single-atom catalyst in the carboxylation reaction of unsaturated alkynes, characterized in that: The active component of the metal catalyst is Ni, the carrier is nitrogen-doped carbon, and the active component Ni is dispersed in the nitrogen-doped carbon carrier in the form of single atoms; The mass content of active metal Ni is 0.1wt%-5.0wt%, and the mass content of nitrogen in the nitrogen-doped carbon carrier is 0.1wt%-10.0wt%; The alkyne carboxylation reaction is carried out in a reactor; the initial pressure of carbon monoxide and unsaturated alkyne gas at room temperature is 0.01-5Mpa, and the reaction temperature is 50-300 o C, reaction time is not less than 1 hour; The reaction solvent is one of methanol, ethanol, n-propanol, isopropanol, tert-butanol, and n-butanol, or a mixture of two or more in any ratio; the unsaturated alkyne is acetylene, and the molar ratio of the catalyst active component to the reaction substrate is 1×10 -2 to 5.

2. The use according to claim 1, characterized in that: The mass content of active metal Ni is 0.2wt%-4.0wt%, and the mass content of nitrogen in the nitrogen-doped carbon carrier is 6.0%-10.0%wt.

3. The use according to claim 1, characterized in that: The preparation method of the carrier nitrogen-doped carbon is as follows: The organic polymer precursor is placed in a tube furnace, a gas with a certain flow rate is introduced, the temperature is raised to a specified temperature, heated for a certain time, and then cooled to room temperature to obtain a nitrogen-doped carbon carrier; wherein the organic polymer precursor is one or more of poly-2,6-diaminopyridine, polyaniline, melamine, polypyrrole, polypyridine, and dicyandiamide; the gas flow rate is 20-200 ml / s; the heating temperature is 500-1200 o C, the heating rate from room temperature to heating temperature is 5-10 o C / min, heating time is 2-4h; the gas is an inert gas containing ammonia, wherein the volume concentration of ammonia is 5%-100%.

4. The use according to claim 3, characterized in that: The gas flow rate is 50-100 ml / s; the heating temperature is 700-900 o C, ammonia volume concentration is 20-80%.

5. The use according to claim 1, characterized in that The preparation method of the supported non-precious metal single atom catalyst is as follows: The metal Ni precursor and the nitrogen-doped carbon carrier are separated and placed in a reactor, wherein the metal Ni precursor is at the upstream end of the gas and the nitrogen-doped carbon carrier is at the downstream end of the gas. A gas containing CO is introduced and increased to a certain pressure. The gas first passes through the metal Ni precursor and then the nitrogen-doped carbon carrier. After heating to a specified temperature, it is heated for a certain time, cooled to room temperature, and used after passivation. Wherein, the metal Ni precursor is a single substance and / or compound thereof, selected from one or more of metal nickel powder, nickel acetylacetonate, carbonyl nickel, nickel oxide, and nickel sulfide; the gas containing carbon monoxide is selected from pure carbon monoxide gas or a mixture of carbon monoxide and one or more of hydrogen and inert gas, wherein the volume concentration of carbon monoxide is 1-100%; the mass ratio of the metal nickel precursor to the nitrogen-doped carbon carrier is 0.01-1; the carbon monoxide gas flow rate is 1.25-250ml / s. gcat; the gas pressure is 0.1Mpa-4Mpa; the heating temperature is 20-400°C, and the heating time is 1-12h; Passivation process: After the reactor is cooled to room temperature, the pressure is released to normal pressure, the gas containing CO is turned off, and the passivation gas is reintroduced into the reactor, and purged at normal pressure at room temperature. The passivation gas is an inert gas containing oxygen, wherein the oxygen volume concentration is 0.1%-1.0%, the gas flow rate is 0.5-2.0ml / s. gcat, and the purging time is 12-24h.

6. The use according to claim 5, characterized in that The volume concentration of carbon monoxide is 20-100%; the mass ratio of the metal nickel precursor to the nitrogen-doped carbon carrier is 0.01-0.6; the carbon monoxide gas flow rate is 2.5-50ml / s. gcat; the gas pressure is 0.5-2Mpa; the heating temperature is 80-300°C, and the heating time is 4-6h; The oxygen volume concentration is 0.5%-1.0%, and the gas flow rate is 0.5-1.0ml / s.gcat.

7. The use according to claim 3 or 5, characterized in that: The inert gas is one or more of nitrogen, argon and helium.

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