CN115747866A - Ferrovanadium based nitride carbide heterojunction nano composite material, preparation method and application - Google Patents
Ferrovanadium based nitride carbide heterojunction nano composite material, preparation method and application Download PDFInfo
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- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 39
- 229910000628 Ferrovanadium Inorganic materials 0.000 title claims abstract description 31
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002243 precursor Substances 0.000 claims abstract description 59
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 39
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229960003351 prussian blue Drugs 0.000 claims abstract description 38
- 239000013225 prussian blue Substances 0.000 claims abstract description 38
- 239000002086 nanomaterial Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 20
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims abstract description 15
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims abstract description 15
- 239000001509 sodium citrate Substances 0.000 claims abstract description 14
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000007740 vapor deposition Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 24
- 239000001301 oxygen Substances 0.000 abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 abstract description 24
- 238000006722 reduction reaction Methods 0.000 abstract description 24
- 239000000446 fuel Substances 0.000 abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 229910052742 iron Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000010757 Reduction Activity Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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- Inert Electrodes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a vanadium iron based nitride heterojunction nano composite material, a preparation method and application thereof, wherein the method comprises the following steps: step 1) synthesis of a vanadium iron based Prussian blue precursor nano material with a cubic structure: dropwise adding a potassium ferricyanide solution into a mixed solution in which vanadium chloride and trisodium citrate are dissolved, ultrasonically stirring, standing, cleaning, centrifuging and drying to obtain a vanadium iron based Prussian blue precursor nano material with a cubic structure; step 2) preparation of the ferrovanadium based nitride heterojunction nano composite material: the vanadium iron based Prussian blue precursor nano material with the cubic structure prepared in the step 1) and a nitrogen source precursor are subjected to vapor deposition reaction to obtain the vanadium iron based nitrogen carbide heterojunction nano composite material. Compared with the conventional preparation of carbon nano composite materials, the vanadium iron based nitrogen carbide heterojunction nano composite material prepared by the method disclosed by the invention has the advantages that the distribution of active sites is more uniform, and the oxygen reduction reaction performance of the cathode of the fuel cell is more stable.
Description
Technical Field
The invention belongs to the technical field of fuel cell cathode oxygen reduction materials, and particularly relates to a vanadium-iron-based nitrogen carbide heterojunction nano composite material, a preparation method and application.
Background
As a new generation of energy conversion technology, fuel cells have the advantages of cleanliness, high efficiency, high energy conversion efficiency, environmental friendliness, and the like, and are considered to be one of the most effective technologies for solving energy and environmental problems. In the operation of the fuel cell, due to the inherent slow kinetics of the cathode Oxygen Reduction Reaction (ORR), the rate of the cathode Reaction becomes the rate control step of the whole fuel cell, and is also a main factor restricting the development of the fuel cell.
In order to lower the energy barrier of the cathode oxygen reduction reaction and improve the rate of the cathode oxygen reduction reaction, the use of a catalytic material is indispensable. At present, the oxygen reduction catalytic material with the best performance is platinum noble metal, and the oxygen reduction catalytic material has the defects of fatality such as resource scarcity, high cost, poor selectivity and methanol resistance and the like.
Therefore, the search for a new, cheap and stable non-noble metal oxygen reduction catalytic material as a substitute of noble metal platinum becomes a focus of current research, and the method is a necessary way for fundamentally solving the defects of high cost, short service life and the like of the fuel cell and realizing large-scale commercial application of the fuel cell.
The transition metal and nitrogen co-doped carbon-based catalytic material has the advantages of low price, simple preparation method, high catalytic activity, good stability and the like, and is considered to be one of the most promising materials for replacing a platinum-based catalytic material as a fuel cell cathode oxygen reduction reaction catalyst. The Prussian-like blue nano material has the structural advantage of becoming an ideal precursor for preparing the transition metal and nitrogen co-doped carbon-based catalytic material.
Disclosure of Invention
Aiming at the problems, the invention takes the ferrovanadium Prussian blue nano material with a unique cubic structure as the materialThe precursor is subjected to vapor deposition reaction with melamine or dicyandiamide under the high-temperature condition to prepare the material with rich V-N x /Fe-N x The vanadium iron based nitride carbide heterojunction nano composite material with active sites. The whole nitriding process is limited in the cubic nano structure, so that the agglomeration and the loss of vanadium-iron-based nitrogen carbide active species are effectively prevented, and the electrocatalytic oxygen reduction activity of the vanadium-iron-based nitrogen carbide can be more fully exerted in low-concentration electrolyte.
The technical scheme adopted by the invention is as follows: a method for preparing a ferrovanadium based nitride heterojunction nanocomposite, the method comprising the steps of:
step 1) synthesis of a vanadium iron based Prussian blue precursor nano material with a cubic structure:
dropwise adding a potassium ferricyanide solution into a mixed solution in which vanadium chloride and trisodium citrate are dissolved, ultrasonically stirring, standing, and then cleaning, centrifuging and drying to obtain a ferrovanadium Prussian blue precursor nano material with a cubic structure;
step 2) preparation of the ferrovanadium based nitride heterojunction nano composite material:
the method comprises the following steps of 1) carrying out vapor deposition reaction on a ferrovanadium Prussian blue precursor nano material with a cubic structure and a nitrogen source precursor to obtain a ferrovanadium nitride-based nitride heterojunction nano composite material.
Further, in the step 1), the potassium ferricyanide solution is 8-10mmol; 8-10mmol of vanadium chloride solution; the trisodium citrate solution is 18-20mmol.
Further, in the step 1), standing for 24-48 h after ultrasonic stirring for 60-120 min.
Further, the step 1) of carrying out vapor deposition reaction on the vanadium iron based prussian blue precursor nano material with the cubic structure and a nitrogen source precursor specifically comprises the following steps:
placing a ferrovanadium Prussian blue precursor nano material with a cubic structure and a nitrogen source precursor at two ends of a quartz porcelain boat, heating to a preset temperature at a certain heating rate in a tube furnace under a protective atmosphere, and roasting for a preset time.
Further, the nitrogen source precursor is at least one of urea, dicyandiamide or melamine.
Further, the protective atmosphere is argon or nitrogen.
Further, the heating rate is 1-5 ℃/min; the preset temperature is 650-750 ℃; the preset time is 2-4 h.
Further, the preset temperature is 700 ℃; the preset time is 2.5h.
Further, the mass ratio of the ferrovanadium-based prussian blue precursor nano material with the cubic structure to the nitrogen source precursor is 1:10-30.
Further, the mass ratio of the vanadium iron-based prussian blue precursor nano material with the cubic structure to the nitrogen source precursor is 1.
The invention also provides the vanadium iron based nitride heterojunction nano composite material prepared by the preparation method.
Meanwhile, the invention also provides an application of the ferrovanadium nitride-based nitride heterojunction nano composite material, and the ferrovanadium nitride-based nitride heterojunction nano composite material is applied to preparation of an electro-catalytic reduction material.
Compared with the conventional preparation of carbon nano composite materials, the vanadium iron based nitrogen carbide heterojunction nano composite material prepared by the preparation method has the advantages that the active sites of the vanadium iron based nitrogen carbide heterojunction nano composite material are more uniformly distributed, and the oxygen reduction reaction performance of the cathode of a fuel cell is more stable; the doping of the functionalized nitrogen atoms shows more prominent V-N x With Fe-N x The synergistic effect between the two components promotes the excellent oxygen reduction activity. In addition, the preparation cost is greatly reduced compared with the commercial noble metal fuel cell cathode oxygen reduction material.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The invention provides a ferrovanadium nitride heterojunction nano composite material, a preparation method and application, and the ferrovanadium nitride heterojunction nano composite material with abundant electrocatalytic oxygen reduction active sites is prepared by matching a vapor deposition nitridation auxiliary synthesis strategy through a high-temperature roasting process on the basis of a ferrovanadium Prussian blue precursor nano material with a unique cubic structure.
The invention provides a preparation method of a vanadium iron based nitride heterojunction nano composite material, which comprises the following steps:
step 1) synthesis of a vanadium iron based Prussian blue precursor nano material with a cubic structure:
dropwise adding a potassium ferricyanide solution into a mixed solution in which vanadium chloride and trisodium citrate are dissolved, ultrasonically stirring, standing, cleaning, centrifuging and drying to obtain a vanadium iron based Prussian blue precursor nano material with a cubic structure;
step 2) preparation of the ferrovanadium based nitride heterojunction nano composite material:
the method comprises the following steps of 1) carrying out vapor deposition reaction on a ferrovanadium Prussian blue precursor nano material with a cubic structure and a nitrogen source precursor to obtain a ferrovanadium nitride-based nitride heterojunction nano composite material.
In the preparation method, the using amount of the potassium ferricyanide solution is 8-10mmol; the using amount of the vanadium chloride solution is 8-10mmol; the dosage of the trisodium citrate solution is 18-20mmol. In the process of synthesizing the vanadium iron based Prussian blue precursor nano material with the cubic structure, potassium ferricyanide solution is used as a raw material for preparing the vanadium iron based Prussian blue precursor to provide an iron source; a vanadium chloride solution is used as a raw material for preparing a vanadium iron based Prussian blue precursor to provide a vanadium source); the trisodium citrate solution is used as a catalyst for preparing the vanadium iron Prussian blue precursor, and potassium ferricyanide and vanadium chloride are promoted to react to generate the vanadium iron Prussian blue precursor nano material with a cubic structure.
In the preparation method, the mass ratio of the vanadium iron based Prussian blue precursor nano material with the cubic structure to the nitrogen source precursor is 1:10-30, preferably 1.
In the preparation method, the nitrogen source precursor is at least one of urea, dicyandiamide or melamine. When the roasting temperature is gradually increased, volatile substances from pyrolysis of urea, melamine or dicyandiamide are captured by the vanadium iron based Prussian blue precursor nano material with a cubic structure, so that the precursor is nitrided, and a corresponding vanadium iron based nitride carbide heterojunction nano composite material is formed.
In the preparation method, the vanadium iron based Prussian blue precursor nano material with a cubic structure and a corresponding nitrogen source are placed at two ends of a quartz ceramic boat, and are heated to 650-750 ℃ at a heating rate of 1.5 ℃/min in a tubular furnace under a protective atmosphere for roasting for 2-4h, preferably, the roasting temperature is 700 ℃ and the roasting time is 2.5h. The protective atmosphere is argon or nitrogen.
In the present invention, V-N x With Fe-N x The synergy between the two components and the roasting temperature greatly influence the electrocatalytic oxygen reduction performance of the prepared vanadium iron based nitride heterojunction nano composite material. According to the invention, the roasting temperature is controlled to be 650-750 ℃, and if the roasting temperature is lower than 650 ℃, the carbon-nitrogen bond in the prepared product can not be converted into the carbon-carbon bond; if the roasting temperature is higher than 750 ℃, carbon-carbon bonds can be broken due to overhigh temperature, so that the cubic structure of the ferrovanadium Prussian blue precursor nano material is damaged. When the temperature of a carbon-nitrogen bond introduced by potassium ferricyanide is 650-750 ℃, the carbon-nitrogen bond is broken, nitrogen generated gas escapes, and carbon are mutually combined to form a ring, so that a graphitized structure is formed; when the temperature is lower than 650 ℃, the carbon-oxygen bond can not be broken, and a carbon structure can not be formed; when the temperature is higher than 750 ℃, the reaction is too violent due to too high temperature, and the ring formation of carbon and carbon can be damaged too quickly due to the escape of nitrogen.
The iron-based nitride carbide heterojunction nano composite material prepared by the preparation method is tested in a low-concentration KOH alkaline solution for the performance of the fuel cell cathode oxygen reduction reaction, and shows excellent oxygen reduction activity and stability. The iron-based nitride-carbide heterojunction nano composite material is applied to preparation of an electro-catalytic reduction material, and is particularly used as a fuel cell cathode oxygen reduction material.
In order to further illustrate the present invention, the following will describe the preparation method of an iron-based nitride carbide heterojunction nanocomposite material provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1:
step 1): under the condition of normal temperature, quickly dropwise adding 200mL of solution dissolved with 8mmol of potassium ferricyanide into the solution dissolved with 8mmol of vanadium chloride and 18mmol of trisodium citrate, stirring and carrying out ultrasonic treatment until the vanadium chloride and the trisodium citrate are completely mixed, standing for 30h after stirring for 60min, then washing with deionized water and ethanol for multiple times, and centrifuging to obtain the ferrovanadium Prussian blue precursor nano material with a cubic structure; and placing the mixture in a vacuum drying oven for drying for 40 hours for later use;
step 2): placing the vanadium iron based Prussian blue precursor nano material with a cubic structure and nitrogen source precursor urea at two ends of a quartz porcelain boat, heating to 650 ℃ at the speed of 1.5 ℃/min in a tubular furnace under argon atmosphere, and roasting for 2.5h to obtain the vanadium iron based nitrogen carbide heterojunction nano composite material.
The iron-based nitride heterojunction nanocomposite prepared in example 1 is tested in a low-concentration KOH alkaline solution for the performance of oxygen reduction reaction of a fuel cell cathode, the current ratio of an oxidation peak to a reduction peak is 0.98, the difference between the oxidation potential and the reduction potential is 0.12V less than that of an electrode prepared from a conventional iron-based nitride, and excellent oxygen reduction activity and stability are shown.
Example 2:
step 1): under the condition of normal temperature, quickly dropwise adding 200mL of solution in which 9mmol of potassium ferricyanide is dissolved into solution in which 9mmol of vanadium chloride and 19mmol of trisodium citrate are dissolved, stirring and carrying out ultrasonic treatment until the vanadium chloride and the trisodium citrate are completely mixed, standing for 32 hours after stirring for 80 minutes, then washing for multiple times by deionized water and ethanol, and centrifuging to obtain a ferrovanadium Prussian blue precursor nano material with a cubic structure; and placing the mixture in a vacuum drying oven for drying for 40 hours for later use;
step 2): placing the ferrovanadium Prussian blue precursor nano material with a cubic structure and a nitrogen source precursor dicyandiamide at two ends of a quartz porcelain boat, heating to 700 ℃ at a speed of 3 ℃/min in a tube furnace under an argon atmosphere, and roasting for 3h to obtain the ferrovanadium nitride based nitride carbide heterojunction nano composite material.
The iron-based nitride-carbide heterojunction nano composite material prepared in the example 2 is tested in a low-concentration KOH alkaline solution for the performance of the fuel cell cathode oxygen reduction reaction, the current ratio of an oxidation peak to a reduction peak is 1.01, and the difference between the oxidation potential and the reduction potential is 0.09V less than the electrode potential difference prepared by the conventional iron-based nitride; exhibits excellent oxygen reduction activity and stability.
Example 3:
step 1): under the condition of normal temperature, quickly dropwise adding 200mL of solution dissolved with 10mmol of potassium ferricyanide into the solution dissolved with 10mmol of vanadium chloride and 20mmol of trisodium citrate, stirring and carrying out ultrasonic treatment until the vanadium chloride and the trisodium citrate are completely mixed, standing for 48h after stirring for 120min, then washing with deionized water and ethanol for multiple times and centrifuging to obtain a ferrovanadium Prussian blue precursor nano material with a cubic structure, and drying the ferrovanadium Prussian blue precursor nano material in a vacuum drying oven for 40h for later use;
step 2): placing a vanadium iron based Prussian blue precursor nano material with a cubic structure and a nitrogen source precursor melamine at two ends of a quartz porcelain boat, heating to 750 ℃ at a speed of 5 ℃/min in a tubular furnace under an argon atmosphere, and roasting for 3.5h to obtain the vanadium iron based nitrogen carbide heterojunction nano composite material.
The iron-based nitrogen carbide heterojunction nano composite material prepared in the example 3 is tested for the oxygen reduction reaction performance of the cathode of a fuel cell in a low-concentration KOH alkaline solution, the current ratio of an oxidation peak to a reduction peak is 0.99, and the difference between the oxidation potential and the reduction potential is 0.11V less than the difference between electrode potentials prepared by conventional iron-based nitrogen carbide; exhibits excellent oxygen reduction activity and stability.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (12)
1. A method for preparing a ferrovanadium based nitride heterojunction nanocomposite, the method comprising the steps of:
step 1) synthesis of a ferrovanadium Prussian blue precursor nano material with a cubic structure:
dropwise adding a potassium ferricyanide solution into a mixed solution in which vanadium chloride and trisodium citrate are dissolved, ultrasonically stirring, standing, cleaning, centrifuging and drying to obtain a vanadium iron based Prussian blue precursor nano material with a cubic structure;
step 2) preparation of the ferrovanadium based nitride heterojunction nano composite material:
the vanadium iron based Prussian blue precursor nano material with the cubic structure prepared in the step 1) and a nitrogen source precursor are subjected to vapor deposition reaction to obtain the vanadium iron based nitrogen carbide heterojunction nano composite material.
2. The method according to claim 1, wherein in the step 1), the potassium ferricyanide solution is 8-10mmol; 8-10mmol of vanadium chloride solution; the trisodium citrate solution is 18-20mmol.
3. The method as claimed in claim 1, wherein in the step 1), the mixture is kept standing for 24-48 h after ultrasonic stirring for 60-120 min.
4. The method according to claim 1, wherein the step 1) of carrying out vapor deposition reaction on the vanadium iron based Prussian blue precursor nanomaterial with the cubic structure and the nitrogen source precursor comprises the following specific steps:
placing a vanadium iron based Prussian blue precursor nano material with a cubic structure and a nitrogen source precursor at two ends of a quartz ceramic boat, heating to a preset temperature at a certain heating rate in a tubular furnace under a protective atmosphere, and roasting for a preset time.
5. The method of claim 4, wherein the nitrogen source precursor is at least one of urea, dicyandiamide, or melamine.
6. The method of claim 4, wherein the protective atmosphere is argon or nitrogen.
7. The method according to claim 4, wherein the temperature increase rate is 1 to 5 ℃/min; the preset temperature is 650-750 ℃; the preset time is 2-4 h.
8. The method of claim 7, wherein the preset temperature is 700 ℃; the preset time is 2.5h.
9. The method according to any one of claims 4 to 8, wherein the mass ratio of the ferrovanadium-based Prussian blue precursor nanomaterial of cubic structure to the nitrogen source precursor is 1:10-30.
10. The method according to claim 9, wherein the mass ratio of the vanadium iron based prussian blue precursor nanomaterial of cubic structure to the nitrogen source precursor is 1.
11. A vanadium iron based nitride heterojunction nano composite material prepared by the preparation method according to any one of claims 1 to 10.
12. Use of a ferrovanadium based nitride heterojunction nanocomposite as claimed in claim 11 in the preparation of an electrocatalytic reduction material.
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