CN114188558A - Preparation method of Fe-NC catalyst modified by oxygen vacancies - Google Patents
Preparation method of Fe-NC catalyst modified by oxygen vacancies Download PDFInfo
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- CN114188558A CN114188558A CN202111435165.8A CN202111435165A CN114188558A CN 114188558 A CN114188558 A CN 114188558A CN 202111435165 A CN202111435165 A CN 202111435165A CN 114188558 A CN114188558 A CN 114188558A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001301 oxygen Substances 0.000 title claims abstract description 55
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 30
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 11
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 62
- 230000009467 reduction Effects 0.000 abstract description 16
- 229910002556 Fe–N4 Inorganic materials 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a preparation method of a catalyst for modifying an Fe-NC active site by using an oxygen vacancy, which comprises the steps of weighing dimethyl imidazole, zinc nitrate hexahydrate and ferric acetylacetonate, and dissolving the dimethyl imidazole, the zinc nitrate hexahydrate and the ferric acetylacetonate in methanol; placing the obtained solution in an oil bath pan, violently stirring, and drying the obtained precipitate after centrifugal treatment; grinding the obtained product, then flatly paving the ground product in a porcelain boat, and then placing the porcelain boat in a tube furnace for primary high-temperature pyrolysis; grinding the obtained product, then paving the ground product in a porcelain boat, and then placing the porcelain boat in a tube furnace for secondary high-temperature pyrolysis to obtain the catalyst of the invention; the invention modifies Fe-N by introducing oxygen vacancy4Active site, changed Fe-N4The adsorption capacity of OOH promotes the reaction path of oxygen reduction two electrons, and finally the yield of hydrogen peroxide is obviously improved. At the same time, different secondary pyrolysis temperatures were studied pioneeringAnd introducing oxygen vacancies to influence the yield of the hydrogen peroxide, thereby obtaining the oxygen vacancy introducing pyrolysis temperature with the highest yield efficiency of the hydrogen peroxide.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of an Fe-NC catalyst modified by oxygen vacancies.
Background
The hydrogen peroxide and the aqueous solution thereof have large demand in industrial application and are widely applied to papermaking, sewage treatment and the like. 95% of global hydrogen peroxide is prepared by an anthraquinone method, however, the scheme has complex process and is mostly unit operation, not only the transportation condition of a reactor is harsh and is easy to cause a large amount of waste, but also the requirements for subsequent waste treatment and hydrogen peroxide purification are harsh. Therefore, the traditional method for preparing hydrogen peroxide has high cost and low efficiency. H can be generated by reducing the cathode two-electron oxygen of the fuel cell or oxidizing the anode two-electron water of the electrolytic cell2O2. Since ORR has high reaction energy barrier and slow reaction kinetics, and the reaction has two competitive paths, the ORR has slow reaction, low efficiency and poor selectivity. These problems limit the large-scale application of fuel cell cathode two-electron oxygen reduction to produce hydrogen peroxide. Therefore, the exploration of low-cost and high-activity catalysts and catalysts with strong selectivity has important significance for the scale application of hydrogen peroxide preparation by two-electron oxygen reduction of the cathode of the fuel cell. Although research work has reported on related catalysts, there is still a lack of a straightforward and efficient scheme for preparing active site-targeted catalysts with atomic dispersion levels. Therefore, the patent provides a method for modifying Fe-N embedded in Zif-8 structure by introducing oxygen vacancies at different pyrolysis temperatures 4Active site catalyst (O-FeN)4) The preparation method effectively improves the performance of preparing hydrogen peroxide by electrocatalysis.
Disclosure of Invention
The invention aims to provide a preparation method of an Fe-NC catalyst modified by oxygen vacancies, and the prepared catalyst effectively improves the yield of hydrogen peroxide prepared by oxygen reduction by adjusting the secondary pyrolysis temperature.
The technical scheme adopted by the invention is that the preparation method of the Fe-NC catalyst modified by oxygen vacancies is implemented by the following steps:
step 1, weighing dimethyl imidazole, zinc nitrate hexahydrate, ferric acetylacetonate and cobalt nitrate hexahydrate, and dissolving in methanol;
step 2, placing the solution obtained in the step 1 in an oil bath pan for violent stirring, and drying the obtained precipitate after centrifugal treatment;
step 3, grinding the product obtained in the step 2, then flatly paving the ground product in a porcelain boat, and then placing the porcelain boat in a tubular furnace for primary high-temperature pyrolysis;
and 4, grinding the product obtained in the step 3, paving the ground product in a porcelain boat, and then putting the porcelain boat in a tubular furnace for secondary high-temperature pyrolysis to obtain the catalyst.
The invention is also characterized in that:
wherein in the step 1, dimethyl imidazole, zinc nitrate hexahydrate, ferric acetylacetonate, cobalt nitrate hexahydrate and methanol are weighed according to a molar ratio of 10:1: 0.25-0.5: 1306-1500;
Wherein the reaction temperature in the oil bath kettle in the step 2 is 20-30 ℃, and the reaction time is 23-25 h;
wherein the drying temperature in the step 2 is 55-65 ℃, and the drying time is 8-14 h;
wherein the reaction temperature of the tubular furnace in the step 3 is 900-1000 ℃, the heating rate is 3-5 ℃/min, the heat preservation time is 1-3 h, and the protective gas is nitrogen;
wherein the reaction temperature of the tubular furnace in the step 4 is 240-400 ℃, the heating rate is 3-5 ℃/min, the heat preservation time is 1-3 h, and the protective gas is oxygen.
The invention has the beneficial effects that:
the preparation method of the Fe-NC catalyst modified by the oxygen vacancy forms high-load O-FeN by adjusting different temperatures of oxygen vacancy introduced by secondary pyrolysis4The site Zif-8 structure obtains a stable carbon substrate framework and more oxygen vacancies promote high-density O-FeN4Formation of (2), change of FeN4Adsorption of OOH to the site, thereforThe performance of the obtained catalyst for preparing hydrogen peroxide by oxygen reduction is obviously improved; as a design scheme of the catalyst for preparing hydrogen peroxide by oxygen reduction, the method has the characteristics of simple and feasible experimental method, high catalytic selectivity and the like, is a feasible electro-catalyst synthesis scheme for preparing hydrogen peroxide by applying oxygen reduction, provides a new direction for the development of preparing hydrogen peroxide by oxygen reduction, and has profound significance.
Drawings
FIG. 1 is a graph comparing hydrogen peroxide yields of an oxygen vacancy modified Fe-NC catalyst in example 1 and an Fe-NC catalyst in comparative example 1 in a production method of an Fe-NC catalyst modified with oxygen vacancies according to the present invention;
FIG. 2 is a graph comparing the hydrogen peroxide yields of the oxygen vacancy modified Fe-NC catalyst in example 2 and the Fe-NC catalyst in comparative example 1 in a manufacturing method of the Fe-NC catalyst modified with oxygen vacancies according to the present invention;
FIG. 3 is a graph showing a comparison of hydrogen peroxide yields of an oxygen vacancy modified Fe-NC catalyst in example 3 and an Fe-NC catalyst in comparative example 1 in a production method of an Fe-NC catalyst modified with oxygen vacancies according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a Fe-NC catalyst modified by oxygen vacancies, which is implemented according to the following steps;
step 1, weighing dimethyl imidazole, zinc nitrate hexahydrate, ferric acetylacetonate and methanol according to a molar ratio of 10:1: 0.25-0.5: 1306-1500;
step 2, placing the mixed solution prepared in the step 1 in an oil bath pan at the temperature of 20-30 ℃ and violently stirring for 23-25 hours to obtain a precipitation solution, and placing the obtained precipitate in a vacuum oven at the temperature of 55-65 ℃ for 8-14 hours after centrifugal treatment;
Step 3, grinding the dried precipitate into powder and transferring the powder into a porcelain boat, putting the porcelain boat into a tubular furnace for high-temperature pyrolysis, introducing nitrogen, wherein the pyrolysis temperature is 25-1000 ℃, and the heating rate is 3-5 ℃/min;
and 4, grinding the product after the primary pyrolysis into powder, transferring the powder into a porcelain boat again, putting the porcelain boat into a tubular furnace for high-temperature pyrolysis, introducing oxygen, wherein the pyrolysis temperature is 240-400 ℃, and the heating rate is 3-5 ℃/min to obtain the catalyst.
Comparative example 1: Fe-NC catalyst:
dimethyl imidazole, zinc nitrate hexahydrate, ferric acetylacetonate and cobalt nitrate hexahydrate are dissolved in 150ml of methanol according to a molar ratio of 10:1: 0.25. Placing the precipitate in a 25 ℃ oil bath kettle, violently stirring for 24 hours to obtain a precipitate solution, placing the precipitate in a 60 ℃ vacuum oven for 12 hours after centrifugal treatment, then grinding the dried precipitate into powder and transferring the powder into a porcelain boat, placing the porcelain boat in a tubular furnace for high-temperature pyrolysis, introducing nitrogen, wherein the pyrolysis temperature is 25-950 ℃, and the heating rate is 5 ℃/min; the catalyst of the invention is obtained.
Example 1: an Fe-NC catalyst modified by oxygen vacancy is specifically carried out according to the following steps:
Dimethyl imidazole, zinc nitrate hexahydrate and ferric acetylacetonate in a molar ratio of 10:1:0.25 are dissolved in 150ml of methanol. And (2) placing the mixture in a 25 ℃ oil bath kettle, violently stirring for 24 hours to obtain a precipitation solution, placing the obtained precipitate in a 60 ℃ vacuum oven for 12 hours after centrifugal treatment, then grinding the dried precipitate into powder and transferring the powder into a porcelain boat, placing the porcelain boat in a tubular furnace for high-temperature pyrolysis, introducing nitrogen, wherein the pyrolysis temperature is 25-950 ℃, and the heating rate is 5 ℃/min. Grinding the product after the primary pyrolysis into powder, transferring the powder into a porcelain boat again, putting the porcelain boat into a tubular furnace for high-temperature pyrolysis, introducing oxygen, wherein the pyrolysis temperature is 240 ℃, and the heating rate is 5 ℃/min to obtain the catalyst of the invention; the catalyst of the invention is obtained.
Example 2: an Fe-NC catalyst modified by oxygen vacancy is specifically carried out according to the following steps:
dimethyl imidazole, zinc nitrate hexahydrate and ferric acetylacetonate in a molar ratio of 10:1:0.25 are dissolved in 150ml of methanol. Placing the precipitate in a 25 ℃ oil bath kettle, violently stirring for 24 hours to obtain a precipitate solution, placing the precipitate in a 60 ℃ vacuum oven for 12 hours after centrifugal treatment, then grinding the dried precipitate into powder and transferring the powder into a porcelain boat, placing the porcelain boat in a tubular furnace for high-temperature pyrolysis, introducing nitrogen, wherein the pyrolysis temperature is 25-950 ℃, and the heating rate is 5 ℃/min; grinding the product after the primary pyrolysis into powder, transferring the powder into a porcelain boat again, putting the porcelain boat into a tubular furnace for high-temperature pyrolysis, introducing oxygen, wherein the pyrolysis temperature is 320 ℃, and the heating rate is 5 ℃/min to obtain the catalyst of the invention; the catalyst of the invention is obtained.
Example 3: an Fe-NC catalyst modified by oxygen vacancy is specifically carried out according to the following steps:
dimethyl imidazole, zinc nitrate hexahydrate and ferric acetylacetonate in a molar ratio of 10:1:0.25 are dissolved in 150ml of methanol. And (2) placing the mixture in a 25 ℃ oil bath kettle, violently stirring for 24 hours to obtain a precipitation solution, placing the obtained precipitate in a 60 ℃ vacuum oven for 12 hours after centrifugal treatment, then grinding the dried precipitate into powder and transferring the powder into a porcelain boat, placing the porcelain boat in a tubular furnace for high-temperature pyrolysis, introducing nitrogen, wherein the pyrolysis temperature is 25-950 ℃, and the heating rate is 5 ℃/min. Grinding the product after the primary pyrolysis into powder, transferring the powder into a porcelain boat again, putting the porcelain boat into a tube furnace for high-temperature pyrolysis, introducing oxygen, wherein the pyrolysis temperature is 400 ℃, and the heating rate is 5 ℃/min to obtain the catalyst. The catalyst of the invention is obtained.
O-FeN prepared by the invention at different pyrolysis temperatures4The test of the catalyst of the site for preparing hydrogen peroxide by oxygen reduction is carried out in a three-electrode reaction device. The prepared catalyst is coated on a glassy carbon electrode to be used as a working electrode, and cyclic voltammetry (C-V) test is carried out in 0.1M KOH. Of these, comparative example 1 is to exclude the influence of oxygen vacancy on the catalyst in the primary pyrolysis. Fig. 1, 2 and 3 show graphs of hydrogen peroxide yield curves of catalysts prepared in examples 1, 2 and 3 of the present invention and comparative example 1 in this order. Comparing the three figures, the comparison is made with Fe-N without secondary pyrolysis 4O-Fe-N after secondary pyrolysis4In the full reduction potential interval, the yield of the hydrogen peroxide is improved, and the yield of the hydrogen peroxide can show a trend that the yield is increased firstly and then reduced in the full potential range along with the increase of the secondary pyrolysis temperature. Further, Experimental example 2Prepared O-Fe-N after secondary pyrolysis4And in the reduction potential range of 0.57-0.73V, the yield of hydrogen peroxide is the highest and reaches more than 60 percent.
The invention provides a preparation method of a Fe-NC catalyst modified by oxygen vacancies, which effectively improves the catalytic selectivity of hydrogen peroxide preparation by oxygen reduction. Different from the selectivity difference of the active sites of the prior catalyst, the invention introduces oxygen vacancies to modify Fe-N4Active site, oxygen vacancy strategy is effective for altering Fe-N4The electronic structure of the site modifies the unsaturated coordination field, thereby improving the selectivity of catalyzing hydrogen peroxide preparation. Adopts a simple one-pot heating method, and forms high-load O-FeN by adjusting different temperatures of oxygen vacancies introduced by secondary pyrolysis4The site Zif-8 structure, the obtained catalyst shows excellent selectivity for preparing hydrogen peroxide by oxygen reduction. It is worth noting that as the temperature of the secondary pyrolysis rises, the loop current and the hydrogen peroxide yield of the catalyst obtained by the invention increase firstly and then decrease, which indicates that O-FeN in the catalyst 4The site has a specific coupling mechanism, so that the performance of the catalyst is effectively improved.
Compared with the traditional anthraquinone method for preparing hydrogen peroxide, the design scheme of the non-noble metal catalyst has the advantages of large raw material storage amount, low cost, simple synthesis process and easy operation of the regulation and control method, and is a synthesis scheme for preparing hydrogen peroxide by oxygen reduction. The catalyst obtained by the invention is O-FeN4The specific coupling mechanism of the site has high selectivity to hydrogen peroxide prepared by oxygen reduction, low selectivity to the environment, and small influence of environmental factors such as temperature, pH and humidity on the catalytic activity, and can be used as a catalyst for preparing hydrogen peroxide by effective oxygen reduction.
Claims (6)
1. A preparation method of an Fe-NC catalyst modified by oxygen vacancies is characterized by comprising the following steps:
step 1, weighing dimethyl imidazole, zinc nitrate hexahydrate, ferric acetylacetonate and cobalt nitrate hexahydrate, and dissolving in methanol;
step 2, placing the solution obtained in the step 1 in an oil bath pan for violent stirring, and drying the obtained precipitate after centrifugal treatment;
step 3, grinding the product obtained in the step 2, then flatly paving the ground product in a porcelain boat, and then placing the porcelain boat in a tubular furnace for primary high-temperature pyrolysis;
And 4, grinding the product obtained in the step 3, paving the ground product in a porcelain boat, and then putting the porcelain boat in a tubular furnace for secondary high-temperature pyrolysis to obtain the catalyst.
2. The preparation method of the oxygen vacancy modified Fe-NC catalyst as claimed in claim 1, wherein in the step 1, dimethyl imidazole, zinc nitrate hexahydrate, ferric acetylacetonate, cobalt nitrate hexahydrate and methanol are weighed according to a molar ratio of 10:1: 0.25-0.5: 1306-1500.
3. The preparation method of the Fe-NC catalyst modified by oxygen vacancy as claimed in claim 1, wherein the reaction temperature in the oil bath kettle in the step 2 is 20-30 ℃ and the reaction time is 23-25 h.
4. The preparation method of the Fe-NC catalyst modified by oxygen vacancy as claimed in claim 1, wherein the drying process in the step 2 is as follows: and (3) after centrifugal treatment, putting the obtained precipitate into a vacuum box, wherein the temperature of the vacuum box is 55-65 ℃, and the drying time is 8-14 h.
5. The preparation method of the Fe-NC catalyst modified by the oxygen vacancy as claimed in claim 1, wherein in the step 3, the pyrolysis temperature of the tubular furnace is 25-1000 ℃, the heating rate is 3-5 ℃/min, the heat preservation time is 1-3 h, and the protective gas is nitrogen.
6. The preparation method of the Fe-NC catalyst modified by the oxygen vacancy as claimed in claim 1, wherein the pyrolysis temperature of the tube furnace in the step 4 is 240-400 ℃, the heating rate is 3-5 ℃/min, the holding time is 1-3 h, and the protective gas is oxygen.
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| CN114774980A (en) * | 2022-05-10 | 2022-07-22 | 浙江工业大学 | Vanadium oxide catalyst containing different valence states formed by controlling different calcination conditions, and synthesis method and application thereof |
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