CN116706093A - Pt/porous carbon composite material for hydrogen fuel cell and preparation method thereof - Google Patents
Pt/porous carbon composite material for hydrogen fuel cell and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 68
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 6
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 6
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 3
- 239000001431 2-methylbenzaldehyde Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- SIXYIEWSUKAOEN-UHFFFAOYSA-N 3-aminobenzaldehyde Chemical compound NC1=CC=CC(C=O)=C1 SIXYIEWSUKAOEN-UHFFFAOYSA-N 0.000 claims description 2
- ZFBRJUBOJXNIQM-UHFFFAOYSA-N Atropaldehyde Chemical compound O=CC(=C)C1=CC=CC=C1 ZFBRJUBOJXNIQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- CJWLZBLADIYQOV-UHFFFAOYSA-L platinum(2+);dinitrite Chemical compound [Pt+2].[O-]N=O.[O-]N=O CJWLZBLADIYQOV-UHFFFAOYSA-L 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 8
- 239000002082 metal nanoparticle Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- -1 platinum metals Chemical class 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000666 effect on cation Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- VVKBUFYSWPMDNG-UHFFFAOYSA-N nitroxyl anion platinum(2+) Chemical compound N(=O)[Pt]N=O VVKBUFYSWPMDNG-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
Abstract
The invention relates to a Pt/porous carbon composite material for a hydrogen fuel cell and a preparation method thereof, and relates to the technical field of fuel cell catalysts. Firstly, carrying out polymerization reaction on azodiisobutyronitrile, styrene and a cross-linking agent, reacting a precursor material A obtained by the reaction with a Pt-based compound in an organic solvent, and drying to obtain a precursor material B; and then mixing the precursor material B with concentrated sulfuric acid, nickel nitrate and ammonium persulfate, oxidizing, washing and drying to obtain the Pt/porous carbon composite material. The preparation method can improve the dispersion degree of the noble metal Pt particles, effectively relieve the sintering growth of the Pt metal nano particles, and effectively improve the electrochemical performance of the catalyst.
Description
Technical Field
The invention relates to the technical field of fuel cell catalysts, in particular to a Pt/porous carbon composite material for a hydrogen fuel cell and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cell (PEMFC) is an acidic fuel cell, has the common characteristics of fuel cells, can be started and operated quickly at low temperature, has no electrolyte loss, long service life, high specific power and specific energy and other outstanding advantages, and is considered to be an optimal scheme for replacing an internal combustion engine as an automobile power source in the future, wherein H is used as a fuel source of the automobile 2 PEMFCs that are fuels are considered as the best alternative to internal combustion engines.
Carbon supportPlatinum-based catalysts are key materials for manufacturing PEMFC membrane electrodes, and are divided into anode catalysts and cathode catalysts. The anode catalyst widely used at present is mainly PtRu/C, and the cathode catalyst is mainly Pt/C. It is well known that platinum metals are rare noble metals, are limited in resources and are expensive, which requires that platinum particles must be highly dispersed on a nano-sized carbon support and that the platinum grain size be suitable to provide more active sites and stable catalytic activity. However, it is now H 2 The carbon-supported platinum-based catalyst for the PEMFC is used as fuel, and has the problems of low adsorption and desorption efficiency and low bearing capacity in the hydrogen preparation process, so that the carbon-supported platinum-based catalyst with excellent performance is provided to ensure the performance of the hydrogen fuel cell.
Disclosure of Invention
The invention aims to provide a Pt/porous carbon composite material for a hydrogen fuel cell and a preparation method thereof, and aims to solve the problems of low adsorption and desorption efficiency, low hydrogen production efficiency and low bearing capacity in the hydrogen production process.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a preparation method of a Pt/porous carbon composite material, which comprises the following steps:
step 1, performing polymerization reaction on azodiisobutyronitrile, styrene and a cross-linking agent to obtain a precursor material A;
step 2, reacting the precursor material A with a Pt-based compound in an organic solvent, and drying to obtain a precursor material B;
and 3, mixing the precursor material B with concentrated sulfuric acid, nickel nitrate and ammonium persulfate, oxidizing, washing and drying to obtain the Pt/porous carbon composite material.
Further, the mass ratio of the azodiisobutyronitrile to the styrene to the cross-linking agent is 100-500:100-500:10-50.
Further, the temperature of the polymerization reaction is 50-120 ℃, and the polymerization time is 1-6h.
Further, the cross-linking agent is one of 3-phenylpropionaldehyde, phenylacrylaldehyde, 4-methylbenzaldehyde, cinnamaldehyde and 3-aminobenzaldehyde.
Further, the mass ratio of the precursor material A to the organic solvent to the Pt-based compound is 100:500-1000:10-20.
Further, the temperature of the reaction in the step 2 is 100-150 ℃ and the time is 1-6h.
Further, the Pt-based compound is one of nitrous platinum, chloroplatinic acid, sodium chloroplatinate, platinum acetylacetonate, and diamido dinitroso platinum.
Further, the mass ratio of the precursor material B to the concentrated sulfuric acid to the nickel nitrate to the ammonium persulfate is 10-100:10-50:100:200-300; the oxidation temperature in the step 3 is 250-350 ℃ and the time is 1-6h.
The invention also provides the Pt/porous carbon composite material prepared by the preparation method.
The Pt/porous carbon composite material prepared by the invention is composed of Pt and nickel doped porous carbon, wherein the mass ratio of the Pt to the nickel doped porous carbon is calculated to be 100%, the content of the Pt is 3.5-6.9wt% and the content of the nickel is 6.4-10.3wt%.
The invention doped with nickel element can improve the catalytic activity, the specific surface area of the material and the hydrogen production rate of the material.
The invention further provides application of the Pt/porous carbon composite material in a hydrogen fuel cell, and the application is specifically an anode catalyst.
The invention discloses the following technical effects:
according to the invention, the azodiisobutyronitrile, the styrene and the cross-linking agent are used for forming holes through cross-linking, so that the bearing capacity of the material is improved.
Under the treatment condition of 250-350 ℃, the platinum compound can be reduced into platinum metal nano particles, polystyrene can be pyrolyzed to form amorphous carbon, and the amorphous carbon formed by pyrolysis can serve as a physical barrier to limit the platinum metal nano particles to be heated and migrate, so that the agglomeration and growth of the platinum metal nano particles are effectively prevented.
The azodiisobutyronitrile contains nitrogen element, a carbon-nitrogen layer is formed on the surface of the original carbon carrier after pyrolysis, and the conductivity of the carbon carrier is enhanced to a certain extent, so that the activity of the catalyst is effectively promoted. In addition, the porous carbon has good adsorption effect on cations, and can provide more adsorption sites for platinum cations through surface modification of nitrogen atoms, so that the adsorption and dispersion of the platinum cations are promoted.
According to the invention, the catalytic effect and catalytic efficiency of the composite material are improved by doping platinum and nickel in the porous carbon, and meanwhile, the frame structure of the porous carbon plays a role in dispersing metal platinum and improves the activity and stability of the material. The preparation method can improve the dispersion degree of the noble metal Pt particles, effectively relieve the sintering growth of the Pt metal nano particles, and obviously improve the electrochemical performance of the prepared catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a Pt/porous carbon composite material prepared in example 1 of the present invention;
fig. 2 is a high resolution electron microscope image of the Pt/porous carbon composite material prepared in example 1 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
Step S1: 300g of styrene is added into 300g of azodiisobutyronitrile, 30g of 3-phenylpropionaldehyde is added, and polymerization reaction is carried out for 3 hours at the temperature of 80 ℃ to obtain a precursor material A;
step S2: 100g of precursor material A is taken and added into 800g of carbon tetrachloride organic solvent to be uniformly dispersed, 15g of platinum nitrate is added, and the mixture is magnetically stirred and reacts for 3 hours at the temperature of 120 ℃ to obtain precursor material B;
step S3: and then 50g of precursor material B, 30g of concentrated sulfuric acid, 100g of nickel nitrate and 250g of ammonium persulfate are mixed, oxidized for 3 hours at the temperature of 300 ℃, washed, and dried in vacuum at the temperature of 80 ℃ for 24 hours to obtain the Pt/porous carbon composite material (Pt/C catalyst).
Example 2
Step S1: adding 100g of styrene into 100g of azodiisobutyronitrile, adding 10g of phenylacrylic aldehyde, and carrying out polymerization reaction at 50 ℃ for 6 hours to obtain a precursor material A;
step S2: 100g of precursor material A is taken and added into 500g N-methyl pyrrolidone organic solvent to be dispersed uniformly, then 10g of sodium chloroplatinate is added, and the reaction is carried out for 6 hours at the temperature of 100 ℃ through magnetic stirring, and the precursor material B is obtained through spray drying;
step S3: 10g of precursor material B, 10g of concentrated sulfuric acid, 100g of nickel nitrate and 200g of ammonium persulfate are mixed, oxidized for 6 hours at the temperature of 250 ℃, washed and dried in vacuum at the temperature of 80 ℃ for 24 hours, and the Pt/porous carbon composite material (Pt/C catalyst) is obtained.
Example 3
Step S1: 500g of styrene is added into 500g of azodiisobutyronitrile, 50g of 4-methylbenzaldehyde is added, and polymerization reaction is carried out for 1h at the temperature of 120 ℃ to obtain a precursor material A;
step S2: 100g of precursor material A is added into 1000g of N-methyl pyrrolidone organic solvent to be uniformly dispersed, then 20g of platinum acetylacetonate is added, and the reaction is carried out for 1h at 150 ℃ through magnetic stirring, and the precursor material B is obtained through spray drying;
step S3: 100g of precursor material B, 50g of concentrated sulfuric acid, 100g of nickel nitrate and 300g of ammonium persulfate are mixed, oxidized for 1h at the temperature of 350 ℃, washed, and dried in vacuum at 80 ℃ for 24h to obtain the Pt/porous carbon composite material (Pt/C catalyst). Comparative example 1:
step S1: adding 100g of porous carbon into 800g of carbon tetrachloride organic solvent, dispersing uniformly, adding 15g of platinum nitrate, reacting for 3 hours at 120 ℃ through magnetic stirring, and spray drying to obtain a precursor material B;
step S2: and then 50g of precursor material B, 30g of concentrated sulfuric acid, 100g of nickel nitrate and 250g of ammonium persulfate are mixed, oxidized for 3 hours at the temperature of 300 ℃, washed, and dried in vacuum at the temperature of 80 ℃ for 24 hours to obtain the Pt/porous carbon composite material (Pt/C catalyst).
The Pt/porous carbon composite material prepared in example 1 of the present invention was subjected to X-ray diffraction, and the XRD pattern of fig. 1 is shown. As can be seen from fig. 1, there is a broad diffraction peak around 2θ=25°, which is attributed to the (111), (200) and (220) diffraction characteristic peaks of the Pt face-centered cubic (fcc) crystal form, respectively, with a diffraction peak at the crystal plane of the carbon support (200) and a peak occurring near the 2θ of 39.8 °,46.2 °,67.5 °. Observations find that: the characteristic peak-to-peak intensity of the platinum is stronger, which indicates that the particle size of the sample particles is larger and the crystal form is complete.
The Pt/porous carbon composite material prepared in example 1 of the present invention was subjected to electron microscopy, and fig. 2 is a high resolution electron microscopy image thereof. The electron microscope analysis result shows that platinum and nickel catalyst particles are loaded on the surface of a carbon carrier, are uniformly distributed, have similar particle sizes (about 5nm average particle size), have obvious petal shapes, and are distributed around large metal particles.
The Pt/porous carbon composite material prepared by the method has the advantages of high platinum loading capacity, high catalytic activity, high chemical stability, good dispersibility and the like, and can promote the further development of fuel cells.
Performance test:
the testing method comprises the following steps:
electrochemically active area: electrochemical performance testing was performed using an IM6e electrochemical analyzer from ZAHNER company, cyclic voltammetry was performed, 1g of the Pt/porous carbon composites prepared in examples 1-3 and comparative example 1 were added to 500g of deionized water, respectively, and a three-electrode system electrolytic cell was used for the test, and the electrochemical active areas were qualitatively compared by applying the same voltage.
Hydrogen production rate: 1g of the catalysts prepared in examples 1 to 3 according to the present invention and comparative example 1 was added to 500mL of 5wt% sodium hydroxide solution at a test temperature of 25℃to determine the hydrogen production rate. Details are shown in Table 1.
Meanwhile, the mass contents of nickel element and Pt element of the materials prepared in examples 1-3 and comparative example 1 are tested by EDS, and the test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the materials prepared in the examples of the present invention have high electrochemically active areas and hydrogen production rates.
The material of the embodiment of the invention has high specific surface area, high material bearing capacity and excellent hydrogen production efficiency and absorption and desorption efficiency.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The preparation method of the Pt/porous carbon composite material is characterized by comprising the following steps of:
step 1, performing polymerization reaction on azodiisobutyronitrile, styrene and a cross-linking agent to obtain a precursor material A;
step 2, reacting the precursor material A with a Pt-based compound in an organic solvent, and drying to obtain a precursor material B;
and 3, mixing the precursor material B with concentrated sulfuric acid, nickel nitrate and ammonium persulfate, oxidizing, washing and drying to obtain the Pt/porous carbon composite material.
2. The preparation method according to claim 1, wherein the mass ratio of the azobisisobutyronitrile, the styrene and the crosslinking agent is 100-500:100-500:10-50.
3. The process according to claim 1, wherein the polymerization reaction temperature is 50 to 120 ℃.
4. The method according to claim 1, wherein the crosslinking agent is one of 3-phenylpropionaldehyde, phenylacrylaldehyde, 4-methylbenzaldehyde, cinnamaldehyde, and 3-aminobenzaldehyde.
5. The preparation method according to claim 1, wherein the mass ratio of the precursor material a, the organic solvent and the Pt-based compound is 100:500-1000:10-20.
6. The process according to claim 1, wherein the reaction in step 2 is carried out at a temperature of 100 to 150 ℃ for a time of 1 to 6 hours.
7. The method according to claim 1, wherein the Pt-based compound is one of platinum nitrite, chloroplatinic acid, sodium chloroplatinate, platinum acetylacetonate, and diamidodinitroso platinum.
8. The preparation method according to claim 1, wherein the mass ratio of the precursor material B, the concentrated sulfuric acid, the nickel nitrate and the ammonium persulfate is 10-100:10-50:100:200-300; the temperature of the oxidation in step 3 is 250-350 ℃.
9. A Pt/porous carbon composite material prepared by the method of any one of claims 1 to 8.
10. Use of the Pt/porous carbon composite as claimed in claim 8 in a hydrogen fuel cell.
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