CN114700100A - Preparation method of catalyst for nitrogen reduction reaction - Google Patents

Preparation method of catalyst for nitrogen reduction reaction Download PDF

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CN114700100A
CN114700100A CN202210355499.2A CN202210355499A CN114700100A CN 114700100 A CN114700100 A CN 114700100A CN 202210355499 A CN202210355499 A CN 202210355499A CN 114700100 A CN114700100 A CN 114700100A
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catalyst
nitrogen
source
reduction reaction
nitrogen reduction
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CN114700100B (en
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丁辉
赵瑞
赵丹
徐曦萌
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Tianjin University
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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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a catalyst for nitrogen reduction reaction and a preparation method thereof, belonging to the technical field of catalyst preparation. The catalyst is prepared by a liquid phase one-pot method, wherein a carbon source and a nitrogen source are pyrolyzed together to form a nitrogen-doped carbon structure carrier, and the carrier has a huge specific surface area and is rich in defect sites, so that adsorption and activation of nitrogen molecules are realized. The active phase metal atoms loaded in the catalyst realize the activation of hydrogen molecules, and simultaneously, a non-metal element boron element can form a stable CN-B carrier at high temperature after being doped, so that the catalyst has a promotion effect on ammonia synthesis under mild conditions. The catalyst prepared by the invention can efficiently synthesize ammonia under a reaction condition with mild atmospheric pressure.

Description

Preparation method of catalyst for nitrogen reduction reaction
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a catalyst for nitrogen reduction reaction.
Background
As an important chemical product, ammonia has good application prospect in the fields of agricultural production, energy storage and transportation, green energy development and the like. At present, more than 90% of ammonia in China comes from a Haber-Bosch process, but the process has extremely harsh reaction conditions, high energy consumption, large carbon emission and poor safety. This high energy consumption, high carbon production model has severely changed the environment on which we live, leading to increasingly frequent extreme weather, and thus it is seen that research into new methods capable of replacing the Haber-Bosch process for ammonia synthesis is of great importance for industrial production as well as for human sustainable development.
The photocatalytic synthesis of ammonia, the electrocatalytic synthesis of ammonia, the low-temperature plasma synthesis of ammonia and the thermocatalytic synthesis of ammonia are the main research directions for synthesizing ammonia under mild conditions. Considering that the demand of ammonia is huge, large-scale production is needed, the requirements on ammonia yield, energy utilization efficiency, technical maturity and the like are high, the thermal catalytic synthesis ammonia process is most suitable under the existing chemical system, and the traditional heterogeneous thermal catalytic process can be improved only by preparing an efficient reaction thermal catalyst, so that the synthesis of ammonia at normal temperature and normal pressure is realized. In the development of thermal catalytic synthesis of ammonia, supported Ru-based catalysts, intermetallic electronic compounds, metal nitrides, metal hydride catalysts and the like are developed, but the advantages and disadvantages coexist, and the problems that the yield of NRR reaction is low and the production scale is far from reaching the industrial requirement still exist. Therefore, the preparation of the high-efficiency thermal catalyst for NRR reaction, which has the advantages of low energy consumption, mild reaction conditions and simple preparation conditions, is still urgently applied to practical production.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a catalyst for nitrogen reduction reaction, which constructs a carbon-nitrogen-loaded metal atom-level active site catalyst (M/CN-B catalyst, where M is a metal element loaded in the catalyst), and improves the activity of the catalyst by doping and modifying with a heteroatom. The method realizes the catalytic hydrogenation reduction of the nitrogen to synthesize the ammonia under the condition of relatively mild reaction temperature under one atmospheric pressure, greatly reduces the energy consumption and pollution of the synthesized ammonia, and further realizes green production.
The invention provides a preparation method of a catalyst for nitrogen reduction reaction, wherein the catalyst is prepared by adopting a liquid phase one-pot method, and comprises the following steps:
s1, weighing and mixing a nitrogen source, a carbon source, a boron source and a metal source, adding ethanol and deionized water, and performing ultrasonic mixing to obtain a mixed solution;
s2, placing the mixed solution in a vacuum drying oven, reacting for 30-40 min at the temperature of 80-100 ℃, then heating to 150-200 ℃, and continuously drying for 60-90 min to form a fluffy porous structure; cooling to room temperature, grinding, and sieving with a 20-40 mesh sieve to obtain uniform powder;
s3, putting the powder obtained in the step S2 into a covered crucible, calcining the powder at 350-650 ℃ for 60-90 min, and raising the temperature at a rate of 4-10 ℃ per min-1Heating to 350-650 ℃, keeping for 90-150 min, and naturally cooling to room temperature to form a block sample;
s4, taking out the block sample, grinding, sieving with a 40-70-mesh sieve, transferring to a tube furnace, heating to 600-1000 ℃ under the protection of nitrogen, calcining for 100-180 min, and naturally cooling to room temperature to obtain the catalyst.
Preferably, in step S1, the nitrogen source is any one of dicyandiamide, melamine, ethylenediaminetetraacetic acid and urea.
Preferably, the carbon source in step S1 is any one of glucose, ethylene diamine tetraacetic acid, carbonized straw, and soluble starch.
Preferably, in step S1, the boron source is any one of boric acid and borate.
Preferably, the metal source in step S1 is any one of palladium chloride and nickel nitrate hexahydrate.
Preferably, the mass ratio of the carbon source to the nitrogen source in the step S1 is 1-12: 5; the addition amount of the boron source is 2.5-15% of the total mass of the carbon source and the nitrogen source; the addition amount of the metal source is 1-4.5% of the total mass of the carbon source and the nitrogen source.
Preferably, the volume-to-mass ratio of the ethanol to the nitrogen source in the step S1 is 2-12 mL/g; the volume-mass ratio of the deionized water to the nitrogen source is 1-9 mL/g.
Preferably, the temperature rise rate in the step S4 is 6-12 ℃ min-1The nitrogen flow rate is 80-120 mL/min-1。
Another object of the present invention is to provide a catalyst for nitrogen reduction reaction prepared by the above method, which has active sites on atomic scale, denoted as M/CN-B.
The catalyst for nitrogen reduction reaction prepared by the invention can be used for synthesizing ammonia by nitrogen reduction reaction under mild conditions, the reaction pressure is one atmosphere, and the reaction temperature is 80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a catalyst for nitrogen reduction reaction, which realizes the high-efficiency activation of nitrogen and hydrogen molecules by constructing a catalyst with M/CN-B atomic level active sites. The nitrogen-doped carbon structure carrier formed by co-pyrolysis of the carbon source and the nitrogen source has a huge specific surface area and is rich in defect sites, so that adsorption and activation of nitrogen molecules are realized; the loaded active phase metal atoms realize the activation of hydrogen molecules; after being doped, the non-metallic element boron can form a stable CN-B carrier at high temperature, and has the promotion effect on ammonia synthesis under mild conditions. Thereby preparing the atomic-level active site catalyst capable of synthesizing ammonia under mild conditions.
Detailed Description
The invention provides a preparation method of an atomic-scale active site catalyst for synthesizing ammonia under mild conditions, and in order to make the purposes, technical schemes and advantages of the invention clearer, the technical schemes of the invention are clearly and completely described below by combining with embodiments. It is to be understood that the described embodiments are only some of the embodiments of the invention. The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the starting materials and auxiliaries are, unless specified otherwise, either obtained from customary commercial sources or prepared in customary manner.
Example 1
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 1.26g of melamine, 2.70g of glucose, 0.49g of boric acid and 0.1634g of nickel nitrate hexahydrate, placing the materials in a beaker, adding 10mL of ethanol and 10mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 30min to obtain a mixed solution;
s2, placing the mixed solution obtained in the step S1 in a vacuum drying oven at 100 ℃ for reaction for 30min, and continuously drying the oven at the temperature rise value of 180 ℃ for 70min to form a fluffy porous structure; taking out the dried sample, cooling to room temperature, placing the sample in a mortar for grinding, and sieving by a 40-mesh sieve to obtain uniform powder;
s3, placing the powder obtained in the step S2 into a covered crucible, placing the crucible into a muffle furnace, calcining the powder at 500 ℃ for 80min, and raising the temperature at 6 ℃ min-1Heating to 500 ℃, keeping for 120min, and naturally cooling to room temperature to form a block sample;
s4, taking out the block sample in the step S3, grinding the block sample uniformly, sieving the block sample with a 70-mesh sieve, transferring the block sample to a tubular furnace, heating the block sample to 700 ℃ in the presence of nitrogen, calcining the block sample for 120min, and enabling the nitrogen flow to be 100 ml/min-1The heating rate is 6 ℃ min-1And naturally cooling to room temperature to obtain the catalyst Ni/CN-B, which is marked as A.
Example 2
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 8.76g of ethylenediamine tetraacetic acid (used as a carbon source and a nitrogen source), 0.25g of sodium borate and 0.2451g of nickel nitrate hexahydrate, placing the sodium borate and the 0.2451g of nickel nitrate hexahydrate in a beaker, adding 20mL of ethanol and 15mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 40min to obtain a mixed solution;
s2, placing the mixed solution obtained in the step S1 in a vacuum drying oven at 90 ℃ for reaction for 40min, and continuously drying the oven at the temperature rise value of 150 ℃ for 100min to form a fluffy porous structure; taking out the dried sample, cooling to room temperature, placing the sample in a mortar for grinding, and sieving by a 30-mesh sieve to obtain uniform powder;
s3, placing the powder obtained in the step S2 into a covered crucible, placing the crucible into a muffle furnace, calcining the powder at 400 ℃ for 90min, and raising the temperature at 4 ℃ per min-1Heating to 400 ℃, keeping for 150min, and naturally cooling to room temperature to form a block sample;
s4, taking out the block sample in the step S3, grinding the block sample evenly, sieving the block sample with a 50-mesh sieve, transferring the block sample to a tubular furnace, heating the block sample to 600 ℃ in the presence of nitrogen, calcining the block sample for 180min, and enabling the nitrogen flow to be 80 ml/min-1The heating rate is 8 ℃ min-1And naturally cooling to room temperature to obtain the catalyst Ni/CN-B, which is marked as B.
Example 3
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 1.80g of urea, 4.05g of water-soluble starch, 0.47g of boric acid and 0.06g of palladium chloride, placing the materials in a beaker, adding 10mL of ethanol and 15mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 50min to obtain a mixed solution;
s2, placing the mixed solution obtained in the step S1 in a vacuum drying oven at 100 ℃ for reaction for 30min, and continuously drying the oven at 190 ℃ for 60min to form a fluffy porous structure; taking out the dried sample, cooling to room temperature, placing the sample in a mortar for grinding, and sieving by a 40-mesh sieve to obtain uniform powder;
s3, placing the powder obtained in the step S2 into a covered crucible, placing the crucible into a muffle furnace, calcining the powder at 650 ℃ for 60min, and raising the temperature at a rate of 10 ℃ min-1Heating to 650 ℃, keeping for 90min, and then naturally cooling to room temperature to form a block sample;
s4, taking out the block sample in the step S3, grinding the block sample uniformly, sieving the block sample with a 70-mesh sieve, transferring the block sample to a tubular furnace, heating the block sample to 1000 ℃ in the presence of nitrogen, calcining the block sample for 100min, and ensuring the nitrogen flow to be 110 ml/min-1The heating rate is 10 ℃ min-1And naturally cooling to room temperature to obtain the catalyst Pd/CN-B which is marked as C.
Example 4
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 1.26g of dicyandiamide, 0.36g of carbonized straws, 0.24g of sodium borate and 0.04g of palladium chloride, putting the materials into a beaker, adding 15mL of ethanol and 10mL of deionized water, uniformly stirring, and carrying out ultrasonic treatment for 60min to obtain a mixed solution;
s2, placing the mixed solution obtained in the step S1 in a vacuum drying oven at 90 ℃ for reaction for 40min, and continuously drying the oven at the temperature rise value of 160 ℃ for 90min to form a fluffy porous structure; taking out the dried sample, cooling to room temperature, placing the sample in a mortar for grinding, and sieving by a 20-mesh sieve to obtain uniform powder;
s3, placing the powder obtained in the step S2 into a covered crucible, placing into a muffle furnace, calcining for 80min at 600 ℃,at a heating rate of 8 ℃ for min-1Heating to 600 ℃, keeping for 110min, and naturally cooling to room temperature to form a block sample;
s4, taking out the block sample in the step S3, grinding the block sample uniformly, sieving the block sample with a 40-mesh sieve, transferring the block sample to a tube furnace, heating the block sample to 800 ℃ in the presence of nitrogen, calcining the block sample for 160min, and enabling the nitrogen flow to be 120 ml/min-1The heating rate is 12 ℃ min-1And naturally cooling to room temperature to obtain the catalyst Pd/CN-B which is marked as D.
Comparative example 1
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 0.1634g of nickel nitrate hexahydrate and 0.31g of boric acid, placing the nickel nitrate hexahydrate and the boric acid into a beaker, dissolving the nickel nitrate hexahydrate and the boric acid in 10mL of ethanol and 10mL of deionized water solution, and uniformly stirring.
S2, accurately weighing 1.26g of melamine and 2.70g of glucose, placing the melamine and the glucose into a covered crucible, placing the crucible into a muffle furnace, calcining the crucible at 500 ℃ for 80min, and raising the temperature at a rate of 6 ℃ min-1Heating to 500 deg.C, holding for 2h, naturally cooling to room temperature, taking out the block sample, and grinding into uniform powder.
S3, adding the ground powder obtained in the step S2 into the solution obtained in the step S1, and magnetically stirring the mixture for 5 hours at 70 ℃. The sample after the reaction was taken out and transferred to a tube furnace for calcination at a nitrogen flow of 100 mL/min-1Calcining at 600 deg.C for 2 hr at a heating rate of 6 deg.C/min-1Keeping for 2h, and naturally cooling to room temperature to obtain the catalyst Ni/CN-B, which is recorded as E.
Comparative example 2
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 2.04g of gamma-Al 2O3, 2.70g of glucose, 0.31g of boric acid and 0.1634g of nickel nitrate hexahydrate, placing the materials in a beaker, adding 10mL of ethanol and 10mL of deionized water, uniformly stirring, and carrying out ultrasound for 30 min;
s2, placing the mixed solution obtained in the step S1 in a vacuum drying oven at 100 ℃ for reaction for 30min, and continuously drying the oven at the temperature rise value of 180 ℃ for 70min to form a fluffy porous structure; taking out the dried catalyst sample, cooling to room temperature, placing the catalyst sample in a mortar, grinding the catalyst sample into uniform powder, and sieving the powder by a 40-mesh sieve;
s3, placing the catalyst powder obtained in the step S2 in a covered crucible, placing the crucible in a muffle furnace, calcining the crucible at 500 ℃ for 80min, and raising the temperature at a rate of 6 ℃ min-1Heating to 500 deg.C, maintaining for 120min, and naturally cooling to room temperature;
s4, taking out the block sample, grinding uniformly, sieving with a 70-mesh sieve, transferring to a tube furnace, calcining at 700 ℃ for 120min, and keeping nitrogen flow at 100 ml/min-1The heating rate is 6 ℃ min-1When the catalyst is naturally cooled to room temperature, the catalyst Ni/gamma-Al is obtained2O3d-B, noted as F.
Comparative example 3
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 1.26g of melamine, 2.70g of glucose, 0.29g of sodium chloride and 0.1631g of cobalt nitrate hexahydrate, placing the materials in a beaker, adding 10mL of ethanol and 10mL of deionized water, stirring uniformly, and carrying out ultrasound for 30 min.
S2, placing the mixed solution obtained in the step S1 in a vacuum drying oven at 100 ℃ for reaction for 30min, and continuously drying the oven at the temperature rise value of 180 ℃ for 70min to form a fluffy porous structure; taking out the dried catalyst sample, cooling to room temperature, placing the catalyst sample in a mortar, grinding the catalyst sample into uniform powder, and sieving the powder through a 40-mesh sieve;
s3, placing the catalyst powder obtained in the step S2 in a covered crucible, placing the crucible in a muffle furnace, calcining the crucible at 500 ℃ for 80min, and raising the temperature at a rate of 6 ℃ min-1Heating to 500 deg.C, maintaining for 120min, and naturally cooling to room temperature;
s4, taking out the block sample, grinding uniformly, sieving with a 70-mesh sieve, transferring to a tube furnace, calcining at 700 ℃ for 120min, and keeping nitrogen flow at 100 ml/min-1The heating rate is 6 ℃ min-1And naturally cooling to room temperature to obtain the catalyst Co/CN-Cl which is marked as G.
Comparative example 4
A preparation method of a catalyst for nitrogen reduction reaction comprises the following steps:
s1, accurately weighing 1.26g of melamine, 2.70g of glucose, 0.87 g of dipotassium phosphate and 0.2386g of ferric nitrate nonahydrate, putting the mixture into a beaker, adding 10mL of ethanol and 10mL of deionized water, stirring uniformly, and carrying out ultrasonic treatment for 30 min;
s2, placing the mixed solution obtained in the step S1 in a vacuum drying oven at 100 ℃ for reaction for 30min, and continuously drying the oven at the temperature rise value of 180 ℃ for 70min to form a fluffy porous structure; taking out the dried catalyst sample, cooling to room temperature, placing the catalyst sample in a mortar, grinding the catalyst sample into uniform powder, and sieving the powder by a 40-mesh sieve;
s3, placing the catalyst powder obtained in the step S2 in a covered crucible, placing the crucible in a muffle furnace, calcining the crucible at 500 ℃ for 80min, and raising the temperature at 6 ℃ min-1Heating to 500 deg.C, maintaining for 120min, and naturally cooling to room temperature;
s4, taking out the block sample, grinding uniformly, sieving with a 70-mesh sieve, transferring to a tube furnace, calcining at 700 ℃ for 120min, and keeping nitrogen flow at 100 ml/min-1The heating rate is 6 ℃ min-1And naturally cooling to room temperature to obtain the catalyst Fe/CN-P, which is marked as H.
The catalysts prepared in examples 1 to 4 and comparative examples 1 to 4 were loaded into a reaction apparatus for catalytic reduction synthesis of ammonia under a reaction condition of a nitrogen flow of 10 ml/min-1Hydrogen flow 30 ml/min-1The reaction pressure is one atmosphere, the reaction temperature is 80 ℃, the reaction time is 10 hours, and the concentration of ammonia is detected by adopting a nano-grade reagent spectrophotometry. The catalytic activity is shown in table 1:
TABLE 1
Figure BDA0003582346180000061
Figure BDA0003582346180000071
As can be seen from Table 1, the M/CN-B catalyst prepared by the invention can prepare ammonia under relatively mild conditions of 80 ℃ and has higher yield. The yield of the Ni/CN-B catalyst prepared in example 1 is more remarkable than that of a catalyst doped with other elements, and the yield of ammonia can reach 0.93.
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. A preparation method of a catalyst for nitrogen reduction reaction is characterized in that the catalyst is prepared by adopting a liquid phase one-pot method, and comprises the following steps:
s1, weighing and mixing a nitrogen source, a carbon source, a boron source and a metal source, adding ethanol and deionized water, and performing ultrasonic mixing to obtain a mixed solution;
s2, placing the mixed solution in a vacuum drying oven, reacting for 30-40 min at the temperature of 80-100 ℃, then heating to 150-200 ℃, and continuously drying for 60-90 min to form a fluffy porous structure; cooling to room temperature, grinding, and sieving with a 20-40 mesh sieve to obtain uniform powder;
s3, putting the powder obtained in the step S2 into a covered crucible, calcining the powder at 350-650 ℃ for 60-90 min, and raising the temperature at a rate of 4-10 ℃ per min-1Heating to 350-650 ℃, keeping for 90-150 min, and naturally cooling to room temperature to form a block sample;
s4, taking out the block sample, grinding, sieving with a 40-70-mesh sieve, transferring to a tube furnace, heating to 600-1000 ℃ under the protection of nitrogen, calcining for 100-180 min, and naturally cooling to room temperature to obtain the catalyst.
2. The method of producing the catalyst for nitrogen reduction according to claim 1, wherein the nitrogen source in step S1 is any one of dicyandiamide, melamine, ethylenediaminetetraacetic acid, and urea.
3. The method for preparing a catalyst for nitrogen reduction reaction according to claim 1, wherein the carbon source in step S1 is any one of glucose, ethylenediaminetetraacetic acid, carbonized straw, and soluble starch.
4. The method for producing a catalyst for nitrogen reduction reaction according to claim 1, wherein the boron source in step S1 is any one of boric acid and a borate.
5. The method for producing a catalyst for a nitrogen reduction reaction according to claim 1, wherein the metal source in step S1 is any one of palladium chloride and nickel nitrate hexahydrate.
6. The method for preparing a catalyst for a warm nitrogen reduction reaction according to claim 1, wherein the mass ratio of the carbon source to the nitrogen source in step S1 is 1 to 12: 5; the addition amount of the boron source is 2.5-15% of the total mass of the carbon source and the nitrogen source; the addition amount of the metal source is 1-4.5% of the total mass of the carbon source and the nitrogen source.
7. The method for preparing a catalyst for nitrogen reduction reaction according to claim 1, wherein the volume-to-mass ratio of the ethanol to the nitrogen source in step S1 is 2 to 12 mL/g; the volume-mass ratio of the deionized water to the nitrogen source is 1-9 mL/g.
8. The method for preparing a catalyst for nitrogen reduction according to claim 1, wherein the temperature increase rate in step S4 is 6 to 12 ℃ min-1The nitrogen flow rate is 80-120 mL/min-1。
9. A catalyst for nitrogen reduction reaction, which is produced by the method according to any one of claims 1 to 8, and which has an atomic-scale active site.
10. The use of the catalyst for nitrogen reduction according to claim 9, wherein the catalyst is used for ammonia synthesis by nitrogen reduction under mild conditions, the reaction pressure is one atmosphere, and the reaction temperature is 80 ℃.
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JPH09168739A (en) * 1995-12-20 1997-06-30 Mitsui Toatsu Chem Inc Ammonia synthesizing catalyst and production thereof
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CN111410178A (en) * 2020-04-22 2020-07-14 内蒙古民族大学 Graphitized boron carbon nitrogen material and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09168739A (en) * 1995-12-20 1997-06-30 Mitsui Toatsu Chem Inc Ammonia synthesizing catalyst and production thereof
CN110193374A (en) * 2019-07-01 2019-09-03 山东大学 Boron carbon nitrogen electrocatalysis material and preparation method thereof and the application in nitrogen reduction synthesis ammonia
CN111410178A (en) * 2020-04-22 2020-07-14 内蒙古民族大学 Graphitized boron carbon nitrogen material and preparation method and application thereof

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Title
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