CN113285080B - Nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from phytic acid and preparation and application thereof - Google Patents
Nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from phytic acid and preparation and application thereof Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 title claims abstract description 33
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229940068041 phytic acid Drugs 0.000 title claims abstract description 32
- 235000002949 phytic acid Nutrition 0.000 title claims abstract description 32
- 239000000467 phytic acid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims description 9
- 238000000137 annealing Methods 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003929 acidic solution Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 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 description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 39
- 239000003054 catalyst Substances 0.000 abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910021389 graphene Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- GXBKELQWVXYOPN-UHFFFAOYSA-N iron tungsten Chemical compound [W][Fe][W] GXBKELQWVXYOPN-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
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- 239000012047 saturated solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
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- 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
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- H—ELECTRICITY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The invention relates to a nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid and a preparation method and application thereof, wherein the preparation method specifically comprises the following steps: (a) Taking an acidic solution A containing aniline, phytic acid and a tungsten source and an acidic solution B containing ammonium persulfate and an iron source, dropwise adding the acidic solution B into the acidic solution A for reaction, and carrying out post-treatment to obtain a FeW/N, P-C precursor; (b) Uniformly mixing the FeW/N, P-C precursor obtained in the step (a) with NaCl and KCl, and sequentially carrying out primary annealing, acid washing and secondary annealing to obtain the FeW/N, P-C composite material. Compared with the prior art, the composite material prepared by the invention has good catalytic activity, stability and methanol tolerance, can be used as a cathode oxygen reduction catalyst of a fuel cell, and is simple to operate in the preparation process.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from phytic acid and preparation and application thereof.
Background
The problems of energy shortage and environmental pollution are two major problems faced by the development of human society since the 21 st century. Therefore, it is urgent to find clean renewable energy and develop efficient energy storage and conversion technology. Fuel cells are receiving wide attention as a new energy technology most likely to be applied commercially on a large scale, and the electroreduction reaction of oxygen is one of the most important electrocatalytic reactions, and is widely applied to the fields of fuel cells, metal-air batteries and the like. However, the cathode oxygen reduction reaction of the fuel cell needs a catalyst, the current commonly used catalyst is a platinum or platinum-based catalyst, and the practical application of the catalyst is limited by the defects of high price, limited reserves, easy poisoning, serious performance loss during long-time operation and the like of metal platinum, and the development of related fields such as the fuel cell is also hindered.
In response to the shortcomings of platinum-based catalysts, carbon materials doped with certain non-metallic elements (e.g., nitrogen, sulfur, boron, phosphorus) have shown some oxygen reduction performance in recent years, but elemental doping involves more severe conditions and performance is more poor than that of commercial platinum catalysts, with greater oxygen reduction overpotentials. Therefore, the main task at present is to develop a low-cost, high-activity and high-stability cathode non-noble metal catalyst, thereby promoting the large-scale commercial application of fuel cells.
Heretofore, patent CN103920519B discloses a preparation method of an oxygen reduction electrocatalyst based on iron-tungsten bimetallic oxide enhanced nitrogen-doped graphene, which comprises the following steps: 1) Oxidizing graphite powder to prepare graphite oxide; 2) Carrying out ultrasonic treatment on the graphite oxide prepared in the step 1) to prepare graphene oxide; 3) Diluting the graphene oxide prepared in the step 2) with water, mixing the diluted graphene oxide with a nitrogen source, and carrying out hydrothermal reaction to obtain nitrogen-doped graphene; 4) Dispersing the nitrogen-doped graphene prepared in the step 3) in water, adding an iron source and a tungsten source, and heating for hydrolysis reaction; 5) Cleaning and drying the reaction product obtained in the step 4), and then carrying out heat treatment under the condition of protective gas. Although the patent discloses a preparation method of an oxygen reduction electrocatalyst based on iron-tungsten bimetallic oxide enhanced nitrogen-doped graphene, the experimental method has the advantages of high risk and harsh reaction conditions, and compared with the method, the method disclosed by the invention has the advantages of mild reaction conditions, high safety factor, strong operability, and simplicity and rapidness.
Disclosure of Invention
The invention aims to provide a nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid and a preparation method and application thereof, solves the technical problems of large consumption of Pt/C catalyst noble metal, low catalyst utilization rate, low catalytic activity and the like in the prior art, and the prepared composite material has good catalytic activity, stability and methanol tolerance, can be used as a fuel cell cathode oxygen reduction catalyst and is simple to operate in the preparation process.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid specifically comprises the following steps:
(a) And dropwise adding the acidic solution B into the acidic solution A for reaction, and performing post-treatment to obtain a FeW/N, P-C precursor, wherein the FeW/N, P-C precursor is dark green. Aniline can be used as a carbon source and a nitrogen source at the same time, phytic acid can be used as a carbon source and a phosphorus source at the same time, the aniline and the phytic acid form a carbon carrier together, and ammonium persulfate can be used as an initiator to induce aniline self-polymerization reaction;
(b) Uniformly mixing the FeW/N, P-C precursor obtained in the step (a) with NaCl and KCl, and sequentially carrying out primary annealing, acid washing and secondary annealing to obtain the FeW/N, P-C composite material.
In the step (a), the acidic solution A is prepared from H with the concentration of 0.5M 2 SO 4 The solution and the ultrapure water are prepared according to the volume ratio of 1 (0.5-1), the volume is 15-30mL, and the solution contains aniline, phytic acid and a tungsten source;
the acid solution B is prepared from H with the concentration of 0.5M 2 SO 4 Prepared with ultrapure water according to the volume ratio of 1 (0.5-1), and contains ammonium persulfate and iron source. The purpose of using an acidic solution is because aniline polymerizes under acidic conditions to have better conductivity.
In the step (a), the tungsten source adopts phosphotungstic acid, the iron source adopts ferric acetylacetonate, and the two organic compounds are used as the tungsten source and the iron source to react with aniline and phytic acid more easily.
In the step (a), the molar ratio of aniline, phytic acid, ammonium persulfate and iron source is (1-2): 0.1-0.3): 0.5-1): 0.01-0.1, preferably 1.
In the step (a), the initial temperature of the reaction is 0-5 ℃, preferably 0 ℃, an ice water bath can be adopted in the initial stage of the reaction, after the reaction is carried out for 1-4 hours (preferably 2 hours) at a low temperature, the temperature is raised to room temperature, the reaction is continued for 20-24 hours, preferably 22 hours, and stirring is carried out while the reaction is carried out. The method comprises the following steps of firstly inducing aniline self-polymerization reaction at low temperature, controlling initial reaction rate, effectively adjusting reaction progress, and then heating to room temperature to accelerate reaction.
In the step (a), the post-treatment process specifically comprises: and (3) carrying out suction filtration on the reaction solution after the reaction is finished, washing the obtained filter residue to be neutral by using water, then washing the filter residue for a plurality of times by using an organic solvent, and then carrying out vacuum drying at the drying temperature of 50-70 ℃, preferably 60 ℃ for 10-12h, preferably 10h.
In the step (b), the mass ratio of the FeW/N, P-C precursor to NaCl to KCl is 1 (5-20) to (5-20), and the preference is 1. As template compounds, naCl and KCl are gradually melted into liquid phase along with the increase of temperature in the annealing process, so that all parts of the composite material are completely carbonized at high temperature.
In the step (b), the temperature of the primary annealing is 800-950 ℃, the optimization is 850 ℃, the time of the primary annealing is 1-4h, the optimization is 2h, the temperature rise rate is 1-5 ℃/min, the optimization is 3 ℃/min, and the annealing process is carried out in the inert atmosphere
Then, the mixture is naturally cooled to room temperature. The inert atmosphere may be nitrogen or argon as a shielding gas from the catalyst. If the annealing temperature is lower, the graphitization degree of the material is poorer, and the conductivity of the material is poor; if the annealing temperature is too high, the material can collapse to some extent and active sites can be gathered, and the overall performance of the material, including the catalytic performance, can be affected.
In the step (b), the acid washing process specifically comprises the following steps: dispersing the intermediate product after primary annealing in H with the concentration of 0.5M 2 SO 4 Stirring the solution at 50-80 deg.C (preferably 60 deg.C) for 10-12h (preferably 12 h), filtering to obtain filter residue, washing the filter residue with water to neutrality, washing with organic solvent several times, and vacuum drying at 50-70 deg.C (preferably 60 deg.C) for 10-12h (preferably 10 h). The acid washing can remove the nano particles and clusters aggregated at high temperature and excessive NaCl and KCl compounds.
In the step (b), the temperature of the secondary annealing is 800-950 ℃, preferably 850 ℃, the time of the secondary annealing is 1-4h, preferably 2h, the heating rate is 1-5 ℃/min, preferably 5 ℃/min, the annealing process is carried out in an inert atmosphere, and then the annealing is naturally cooled to the room temperature. The inert atmosphere can be nitrogen or argon, the inert atmosphere is used as protective gas and does not react with the composite material, the structure of the carbon skeleton can be damaged by acid washing, and the carbon skeleton is stabilized by secondary annealing treatment.
The nitrogen-phosphorus-codoped FeW/N, P-C composite material derived from phytic acid and prepared by the preparation method is of a porous lamellar structure, and the pore volume of the FeW/N, P-C composite material is 0.693cm 3 737.93m in specific surface area/g 2 (iv) g. The FeW/N, P-C composite material comprises a nitrogen-phosphorus co-doped carbon carrier and Fe and W which are loaded on the carbon carrier and exist in a highly dispersed atomic form.
The application of the nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from the phytic acid in the fuel cell can efficiently catalyze the 4 e-oxygen reduction reaction, has good catalytic activity, stability and methanol tolerance, and can be used as a cathode oxygen reduction catalyst of the fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the density of active sites is increased by accurately controlling the coordination environment and/or the pore volume of the structure, the nitrogen-phosphorus-doped FeW/N, P-C flaky composite material is prepared, and O in the reaction process can be promoted 2 And diffusion of water, transfer of protons, transfer of electrons in the carbon skeleton, and the like, thereby improving the catalytic performance. The composite material has high catalytic activity, good stability and methanol tolerance, shows excellent catalytic activity to ORR, and can be used as a cathode material of a fuel cell.
2. Compared to commercial Pt-based catalysts, the FeW/N, P-C composites of the present invention have ORR catalytic activity in alkaline media exceeding commercial 20-percent Pt/C catalysts and have greater stability and methanol resistance.
3. The raw materials adopted by the invention are low in price and rich in sources, the preparation process is simple, the large-scale production is facilitated, and the method has high practical value.
4. The catalyst of the invention can overcome the technical problems of large consumption of noble metal, low utilization efficiency of the catalyst, low catalytic activity and the like of the traditional Pt/C catalyst.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the FeW/N, P-C composite material prepared in example 1;
FIG. 2 is an XRD pattern of a FeW/N, P-C composite material prepared in example 1;
FIG. 3 is an XPS plot of the FeW/N, P-C composite prepared in example 1;
FIG. 4 is a comparison of the linear polarization curve test of the catalysts of example 1 and comparative examples 1 and 2 in 0.1M KOH solution;
FIG. 5 is a graph comparing the chronoamperometry of the catalysts of example 1 and comparative example 1 in 0.1M KOH solution;
FIG. 6 is a graph comparing methanol tolerance tests in 0.1M KOH solutions for the catalysts of example 1 and comparative example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from phytic acid is in a porous sheet structure and is prepared by the following steps:
(1) Preparation of FeW/N, P-C precursor
2mmol of aniline, 0.25mmol of phytic acid and 0.0025mmol of phosphotungstic acid are uniformly dissolved and dispersed in 20mL of acidic solution (prepared from 0.5M H 2 SO 4 The solution and the ultrapure water are mixed according to the volume ratio of 1); 1.5mmol ammonium persulfate and 0.05mmol ferric acetylacetonate are uniformly dissolved and dispersed in an acidic solution (prepared from H with the concentration of 0.5M) 2 SO 4 The volume ratio of the solution to the ultrapure water is 1). Slowly dripping the solution B into the solution A under the reaction condition of ice-water bath (0 ℃), heating to room temperature after reacting for 2 hours, continuously stirring and reacting for 20 hours, then carrying out suction filtration on the reaction solution after the reaction is finished, washing the obtained filter residue for several times by using an organic solvent, and then washing at 60 DEG CVacuum drying is carried out for 12h, and a dark green FeW/N, P-C precursor is obtained.
(2) Preparation of FeW/N, P-C composite material
And (2) taking 50mg of the FeW/N, P-C precursor obtained in the step (a) according to the mass ratio of 1 3 737.93m in specific surface area/g 2 (ii) in terms of/g. Wherein: the temperature of the primary annealing is 850 ℃, the time of the primary annealing is 2h, the heating rate is 3 ℃/min, and the annealing process is carried out under the protection of nitrogen in inert atmosphere; the pickling process specifically comprises the following steps: dispersing the intermediate product after primary annealing in H with the concentration of 0.5M 2 SO 4 Stirring the solution at 60 ℃ for 10h, then carrying out suction filtration to obtain filter residue, washing the filter residue to be neutral, washing the filter residue for a plurality of times by using an organic solvent, and then carrying out vacuum drying at 60 ℃ for 12h; the temperature of the secondary annealing is 850 ℃, the annealing time is 2h, the heating rate of the secondary annealing is 5 ℃/min, and the annealing process is carried out under the inert atmosphere nitrogen.
The Transmission Electron Microscope (TEM) image of the FeW/N, P-C composite material is shown in FIG. 1 (the left image is 200 nm), and it can be seen that the prepared FeW/N, P-C composite material has an obvious sheet structure, and the existence of Fe and W nano particles is not observed, which indicates that the Fe and W elements may not form clusters or particles and may exist in a highly dispersed atomic form, and the small image in the right image indicates that the composite material is a polycrystalline substance, which also indicates the reliability of the synthesis method of the invention.
The XRD pattern of the FeW/N, P-C composite material is shown in figure 3, and it can be seen that no crystalline particles such as Fe, W and the like are formed in the composite material, only the graphitized carbon peak is formed, which indicates that Fe, W may exist in the catalyst in a doped form, and the combination of figures 2 and 3 shows that the prepared material is indeed FeW/N, P-C.
The FeW/N, P-C composite material is used as an oxygen reduction catalyst to carry out a linear polarization test, and the test conditions are as follows: with 0.1M KOH solution, the test parameters were-0.8-0.2V, the sweep rate was 5mV/s, and the rotation rate was 1600rpm (the same applies below), and the results are shown in FIG. 4, where FeW/N, P-C composite material was observedThe initial potential of (2) was 0.995V (vs. RHE), the half-wave potential was 0.877V (vs. RHE), and the limiting current density at 0.85V was-3.36 mA cm -2 。
The FeW/N, P-C composite material is subjected to a timing current test under the following test conditions: by the use of O 2 In a saturated solution with a concentration of 0.1M KOH, the test parameters were-0.15V, the rotation speed was 1600rpm, and the test time was 50000s (the same applies below), and as a result, as shown in FIG. 5, it can be seen that the stability of the FeW/N, P-C composite material gradually decreased with the passage of the test time, but the rate of decrease was very slow, and the FeW/N, P-C composite material could maintain 93.92% of the initial current density after the 50000s test.
The FeW/N, P-C composite material is subjected to a methanol resistance test under the following test conditions: by the use of O 2 Saturated KOH solution with concentration of 0.1M, test parameter of-0.15V, rotation speed of 1600rpm, test time of 5000s. At 1000s from the start of the test, 3M methanol was rapidly added to the KOH solution (the same applies below), and as a result, as shown in FIG. 6, it can be seen that the current of the FeW/N, P-C composite material was changed only slightly after the addition of methanol.
Comparative example 1
A commercial catalyst JM20% Pt/C, purchased from Johnson-Matthery, was subjected to a linear polarization curve test in an alkaline solution, and the results are shown in FIG. 4 in particular, and it can be seen that the initial potential of JM20% Pt/C: 0.990V; half-wave potential: 0.861V; limiting current density at 0.85V: -3.01mAcm -2 . Chronoamperometric tests were conducted on the commercial catalyst and, as a result, it can be seen in fig. 5 that the stability of JM20% Pt/C gradually decreased with the passage of test time, but the rate of decrease was very rapid, and the current density of commercial JM20% Pt/C remained only at 44.57% of the initial current density after 50000s testing. The methanol resistance test of the commercial catalyst was conducted, and as a result, as shown in FIG. 6, it can be seen that, after adding methanol, the current of the JM 20-th Pt/C catalyst was significantly changed, that is, the JM 20-th Pt/C catalyst underwent a severe oxidation reaction in an alkaline solution containing methanol.
FIG. 4 shows that the prepared FeW/N, P-C composite material has high catalytic activity for oxygen reduction reaction, and is comparable to commercial catalyst.
It can be seen in FIG. 5 that the current decay rate of the FeW/N, P-C composite is significantly slower than commercial JM20% Pt/C, indicating that the stability of the FeW/N, P-C composite under the above conditions is much better than commercial JM20% Pt/C.
FIG. 6 illustrates that the methanol tolerance of the FeW/N, P-C composite is better than JM20% Pt/C catalyst.
In conclusion, the invention provides a preparation method of a nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid, and the prepared composite material has a uniform porous sheet structure and shows remarkably enhanced electrochemical performance in an oxygen reduction process.
Comparative example 2
A nitrogen-doped FeW/N-C composite material prepared by the same procedure as in example 1 except that phytic acid was not added during the preparation. The test of the linear polarization curve in the alkaline solution is carried out, the result is shown in figure 4, and the initial potential of the FeW/N-C composite material can be seen: 0.893V; half-wave potential: 0.799V; limiting current density at 0.85V: -0.50mAcm -2 . FIG. 4 shows that the prepared FeW/N, P-C composite material has higher catalytic activity than FeW/N-C composite material.
Example 2
The nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from phytic acid is in a porous sheet structure and is prepared by the following steps:
(1) Preparation of FeW/N, P-C precursor
1mmol of aniline, 0.1mmol of phytic acid and 0.0005mmol of phosphotungstic acid were uniformly dissolved and dispersed in 20mL of an acidic solution (prepared from 0.5M H 2 SO 4 The volume ratio of the solution to the ultrapure water is 1; 0.5mmol ammonium persulfate and 0.01mmol ferric acetylacetonate are uniformly dissolved and dispersed in an acidic solution (prepared from H with the concentration of 0.5M) 2 SO 4 Solution B was recorded in a volume ratio of 1. Slowly dripping the solution B into the solution A under the reaction condition of 5 ℃, after reacting for 1h, heating to room temperature and continuing stirring to react for 20h, and then adding the reaction solution after the reaction is finishedAnd (3) carrying out suction filtration, washing the obtained filter residue to be neutral, then washing the filter residue for a plurality of times by using an organic solvent, and then carrying out vacuum drying at 50 ℃ for 12h to obtain a dark green FeW/N, P-C precursor.
(2) Preparation of FeW/N, P-C composite material
And (2) taking 50mg of the FeW/N, P-C precursor obtained in the step (a) according to a mass ratio of 1. Wherein: the temperature of the primary annealing is 800 ℃, the time of the primary annealing is 4h, the heating rate is 3 ℃/min, and the annealing process is carried out under the protection of nitrogen in inert atmosphere; the pickling process specifically comprises the following steps: dispersing the intermediate product after primary annealing in H with the concentration of 0.5M 2 SO 4 Stirring the solution at 80 ℃ for 10h, then carrying out suction filtration to obtain filter residue, washing the filter residue to be neutral, washing the filter residue for a plurality of times by using an organic solvent, and then carrying out vacuum drying at 70 ℃ for 10h; the temperature of the secondary annealing is 800 ℃, the annealing time is 4h, the heating rate of the secondary annealing is 5 ℃/min, and the annealing process is carried out under the inert atmosphere nitrogen.
Example 3
The nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from phytic acid is in a porous sheet structure and is prepared by the following steps:
(1) Preparation of FeW/N, P-C precursor
2mmol of aniline, 0.3mmol of phytic acid and 0.0025mmol of phosphotungstic acid are uniformly dissolved and dispersed in 20mL of acidic solution (prepared from 0.5M H 2 SO 4 The volume ratio of the solution to the ultrapure water is 1; 1mmol ammonium persulfate and 0.1mmol ferric acetylacetonate are uniformly dissolved and dispersed in an acidic solution (prepared from H with the concentration of 0.5M) 2 SO 4 Solution B was recorded in a volume ratio of 1. Slowly dropwise adding the solution B into the solution A under the reaction condition of an ice water bath (0 ℃), heating to room temperature after reacting for 4 hours, continuously stirring and reacting for 24 hours, then carrying out suction filtration on the reaction solution after the reaction is finished, washing the obtained filter residue to be neutral, then washing the filter residue for several times by using an organic solvent, and then carrying out vacuum drying at 70 ℃ for 10 hours to obtain dark green FeW/N, P-a C precursor.
(2) Preparation of FeW/N, P-C composite material
And (2) taking 50mg of the FeW/N, P-C precursor obtained in the step (a) according to a mass ratio of 1. Wherein: the temperature of the primary annealing is 950 ℃, the time of the primary annealing is 1h, the heating rate is 3 ℃/min, and the annealing process is carried out under the protection of argon in inert atmosphere; the pickling process specifically comprises the following steps: dispersing the intermediate product after primary annealing in H with the concentration of 0.5M 2 SO 4 Stirring the solution at 50 ℃ for 12h, then carrying out suction filtration to obtain filter residues, washing the filter residues to be neutral, washing the filter residues with an organic solvent for a plurality of times, and then carrying out vacuum drying at 50 ℃ for 10h; the temperature of the secondary annealing is 950 ℃, the annealing time is 1h, the heating rate of the secondary annealing is 5 ℃/min, and the annealing process is carried out under the inert atmosphere of argon.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (8)
1. The preparation method of the nitrogen-phosphorus co-doped FeW/N, P-C composite material derived from phytic acid is characterized by comprising the following steps of:
(a) Taking an acidic solution A containing aniline, phytic acid and a tungsten source and an acidic solution B containing ammonium persulfate and an iron source, dropwise adding the acidic solution B into the acidic solution A for reaction, and carrying out post-treatment to obtain a FeW/N, P-C precursor;
(b) Uniformly mixing the FeW/N, P-C precursor obtained in the step (a) with NaCl and KCl, and sequentially carrying out primary annealing, acid washing and secondary annealing to obtain a FeW/N, P-C composite material, wherein the FeW/N, P-C composite material is of a porous lamellar structure and comprises a nitrogen-phosphorus co-doped carbon carrier and Fe and W which are loaded on the carbon carrier and exist in a highly dispersed atomic form;
in the step (a), the acidic solution A is prepared from H with the concentration of 0.5M 2 SO 4 The solution and the ultrapure water are prepared according to the volume ratio of 1 (0.5-1), and the solution contains aniline, phytic acid and a tungsten source;
the acid solution B is prepared from H with the concentration of 0.5M 2 SO 4 Prepared with ultrapure water according to the volume ratio of 1 (0.5-1), and contains ammonium persulfate and iron source;
in the step (a), phosphotungstic acid is used as a tungsten source, and ferric acetylacetonate is used as an iron source;
the mol ratio of the aniline, the phytic acid, the ammonium persulfate and the iron source is (1-2): (0.1-0.3): (0.5-1): 0.01-0.1), and the mol ratio of the iron source to the tungsten source is (20-40): 1.
2. The preparation method of the nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid according to claim 1, wherein in the step (a), the initial temperature of the reaction is 0-5 ℃, the temperature is increased to room temperature after the reaction is carried out for 1-4 hours at a low temperature, the reaction is continued for 20-24 hours, and stirring is carried out while the reaction is carried out.
3. The method for preparing the nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid according to claim 1, wherein in the step (a), the post-treatment process specifically comprises the following steps: and (3) carrying out suction filtration on the reaction solution after the reaction is finished, washing the obtained filter residue to be neutral by water, then washing the filter residue for a plurality of times by using an organic solvent, and then carrying out vacuum drying at the drying temperature of 50-70 ℃ for 10-12h.
4. The method for preparing the nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from the phytic acid as claimed in claim 1, wherein in the step (b), the mass ratio of the FeW/N, P-C precursor to NaCl to KCl is 1 (5-20) to (5-20).
5. The preparation method of the nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid according to claim 1, wherein in the step (b), the temperature of primary annealing is 800-950 ℃, the time of the primary annealing is 1-4h, the annealing process is carried out in an inert atmosphere, and then the composite material is naturally cooled to room temperature;
in the step (b), the temperature of the secondary annealing is 800-950 ℃, the time of the secondary annealing is 1-4h, the annealing process is carried out in an inert atmosphere, and then the annealing is naturally cooled to room temperature.
6. The preparation method of the nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid according to claim 1, wherein in the step (b), the acid washing process specifically comprises the following steps: dispersing the intermediate product after primary annealing in H with the concentration of 0.5M 2 SO 4 Stirring the solution at 50-80 deg.C for 10-12h, vacuum filtering to obtain filter residue, washing the filter residue with water to neutral, washing with organic solvent for several times, and vacuum drying at 50-70 deg.C for 10-12h.
7. The nitrogen-phosphorus-codoped FeW/N, P-C composite material derived from phytic acid and prepared by the preparation method according to any one of claims 1 to 6, wherein the FeW/N, P-C composite material is in a porous lamellar structure.
8. Use of the nitrogen and phosphorus co-doped FeW/N, P-C composite material derived from phytic acid according to claim 7 in a fuel cell.
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