CN114122430B - Platinum-carbon catalyst and preparation method and application thereof - Google Patents

Platinum-carbon catalyst and preparation method and application thereof Download PDF

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CN114122430B
CN114122430B CN202010877417.1A CN202010877417A CN114122430B CN 114122430 B CN114122430 B CN 114122430B CN 202010877417 A CN202010877417 A CN 202010877417A CN 114122430 B CN114122430 B CN 114122430B
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platinum
carbon
catalyst
nitrogen
carbon material
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CN114122430A (en
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彭茜
荣峻峰
赵红
王厚朋
谢南宏
顾贤睿
张家康
张云阁
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to KR1020237010563A priority patent/KR20230058142A/en
Priority to EP21860474.2A priority patent/EP4207394A1/en
Priority to JP2023513711A priority patent/JP2023539876A/en
Priority to PCT/CN2021/114752 priority patent/WO2022042640A1/en
Priority to US18/043,310 priority patent/US20230369609A1/en
Priority to TW110131840A priority patent/TW202218746A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • 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 platinum-carbon catalyst, a preparation method and application thereof, and N analyzed by XPS of the platinum-carbon catalyst 1s In the spectrum peaks, except for the characteristic peaks between 399eV and 400.5eV, no other characteristic peaks exist between 395eV and 405 eV. The platinum-carbon catalyst has higher quality specific activity and stability when being used for oxygen reduction reaction.

Description

Platinum-carbon catalyst and preparation method and application thereof
Technical Field
The invention relates to a platinum-carbon catalyst and a preparation method and application thereof, in particular to a nitrogen-doped platinum-carbon catalyst and a preparation method and application thereof.
Background
Fuel cells are a power generation device that converts chemical energy into electrical energy by way of an electrochemical reaction, and are considered to be the most promising alternative to existing energy technologies on a large scale. Hydrogen fuel cells are currently the mainstream fuel cell technology, and catalysts and proton exchange membranes are the core of hydrogen fuel cell technology. In the development of hydrogen fuel cells, it has been a hot topic of scientific research to produce efficient and low-cost electrode catalysts, particularly cathode oxygen reduction electrode catalysts.
The nitrogen element can be doped into the carbon material in various structural forms, such as pyridine nitrogen, graphite nitrogen, pyrrole nitrogen, nitrogen oxide and the like, and the doping forms are different, so that the properties of the carbon material are different. Nitrogen-doped carbon materials have been reported more frequently as catalysts for alkaline fuel cells, but are far from industrial use. So far, no literature report that pyrrole nitrogen has an influence on the performance of the catalyst is found, and no literature report that pyrrole nitrogen has an influence on the performance of the platinum carbon catalyst is found.
The platinum carbon catalyst is the most mature hydrogen fuel cell catalyst at present, but the price of platinum is expensive, and the catalytic activity and the stability are not ideal. Factors influencing the catalytic activity and stability of the platinum-carbon catalyst are many and complicated, and some literatures believe that the quality specific activity and stability of the platinum-carbon catalyst are related to the particle size, morphology and structure of platinum, and the type, property and platinum loading of a carrier. In the prior art, the performance of the platinum-carbon catalyst is improved mainly by controlling the particle size, morphology and structure of platinum, the specific surface area and pore structure of a carrier; it has also been reported in the literature that modifying groups attached to the carbon surface improve the performance of platinum-carbon catalysts by modifying the carbon support.
Increasing the amount of platinum loading is beneficial for making thinner and better performing membrane electrodes, but in the prior art, increasing the amount of platinum loading by a large margin results in a significant decrease in catalytic performance in terms of platinum per unit mass.
The platinum loading of the platinum-carbon catalyst of the hydrogen fuel cell in practical application is at least more than 20wt%, and the manufacturing difficulty is much higher than that of the platinum-carbon catalyst for chemical engineering (the platinum loading is generally less than 5 wt%). The chemical reduction method is a commonly used method for preparing the platinum-carbon catalyst, and has the advantages of simple process and low utilization rate and catalytic activity of platinum. The reason for this may be that the platinum nanoparticles are not uniformly dispersed due to irregularities in the pore structure of the carbon support.
The information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
It is an object of the present invention to provide a platinum-carbon catalyst which has superior quality and activity and stability to commercial catalysts. The second purpose of the invention is to provide a platinum-carbon catalyst with higher platinum loading amount on the basis of the first purpose. The invention also aims to improve the aqueous phase chemical reduction method for manufacturing the platinum-carbon catalyst and improve the quality specific activity and the stability of the platinum-carbon catalyst of the hydrogen fuel cell.
In order to achieve the above object, the present invention provides the following technical solutions.
1. A platinum-carbon catalyst characterized by N as analyzed by XPS 1s In the spectrum peaks, except for the characteristic peaks between 399eV and 400.5eV, no other characteristic peaks exist between 395eV and 405 eV.
2. The platinum-carbon catalyst according to any one of the above, characterized in that the mass fraction of platinum is 0.1% to 80%, preferably 20% to 70%, more preferably 40% to 70%, based on the mass of the catalyst.
3. The platinum-carbon catalyst according to any of the preceding claims, characterized in that the platinum-carbon catalyst has a resistivity of <10 Ω · m, preferably <2 Ω · m.
4. The platinum-carbon catalyst according to any one of the preceding claims, characterized in that the specific surface area of the platinum-carbon catalyst is 80m 2 /g～1500m 2 A/g, preferably of 100m 2 /g～200m 2 /g。
5. The platinum-carbon catalyst according to any one of the preceding claims, characterized in that the carrier of the platinum-carbon catalyst is nitrogen-doped conductive carbon black, nitrogen-doped graphene or nitrogen-doped carbon nanotubes.
6. The platinum-carbon catalyst according to 5, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP600JD, VXC72, black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B2.
7. A method of preparing a platinum-carbon catalyst, comprising: (1) impregnation of Nitrogen Source: mixing and soaking a carbon material and a nitrogen source aqueous solution to obtain a carbon material soaked with a nitrogen source; (2) a step of manufacturing a nitrogen-doped carbon material: heating the carbon material impregnated with the nitrogen source obtained in the step (1) to 1000-1500 ℃ at the speed of 8-15 ℃/min in inert gas, and then carrying out constant temperature treatment for 0.5-10 h to obtain a nitrogen-doped carbon material; (3) platinum-supporting step: and (3) taking the nitrogen-doped carbon material obtained in the step (1) as a carrier and loading platinum.
8. The production method according to any one of the preceding claims, characterized in that, in (2), the temperature of the constant temperature treatment is 1150 ℃ to 1450 ℃.
9. The preparation method according to any one of the preceding claims, characterized in that the duration of the isothermal treatment is between 1 and 5 hours, preferably between 2 and 4 hours.
10. The process according to any one of the preceding claims, characterized in that the nitrogen source is ammonia and/or urea.
11. The production method according to any one of the preceding claims, characterized in that the mass ratio of the carbon material to the nitrogen source is 30:1 to 1:2; preferably 25:1 to 1:1.5.
12. the production method according to any one of the preceding claims, characterized in that the carbon material is conductive carbon black, graphene or carbon nanotubes.
13. The method according to 12, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B2.
14. The production method according to any one of the preceding claims, characterized in that the carbon material has an oxygen mass fraction of more than 4%, preferably 4% to 15%, in XPS analysis.
15. A production method according to any one of the preceding claims, characterized in that the carbon material has a resistivity of <10 Ω · m, preferably <5 Ω · m, more preferably <2 Ω · m.
16. A production method according to any one of the preceding claims, characterized in that the carbon material has a specific surface area of 10m 2 /g～2000m 2 /g。
17. The production method according to any one of the preceding claims, characterized in that the step of supporting platinum comprises:
(a) Dispersing the nitrogen-doped carbon material obtained in the step (1) and a platinum precursor in a water phase, and adjusting the pH value to 8-12 (preferably, adjusting the pH value to 10 +/-0.5);
(b) Adding a reducing agent for reduction;
(c) Separating out solid, and post-treating to obtain the platinum-carbon catalyst.
18. The preparation method according to any one of the preceding claims, characterized in that the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.
19. The process according to any one of the preceding claims, wherein in (a), the pH of the aqueous phase is adjusted with an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide or aqueous ammonia.
20. The preparation method according to any one of the preceding claims, characterized in that in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 50-150 ℃, and preferably 60-90 ℃; the reduction time is 2 to 15 hours, preferably 8 to 12 hours.
21. The method of any one of the preceding claims, wherein said post-treatment comprises: washing, filtering and drying.
22. A platinum carbon catalyst, characterized in that the catalyst is prepared by any one of the methods of 7 to 21.
23. A hydrogen fuel cell, characterized in that any one of 1 to 6 and 22 of platinum-carbon catalysts is used in an anode and/or a cathode of the hydrogen fuel cell.
Compared with the prior art, the invention has the following beneficial technical effects.
1. The invention produces a new carbon carrier by doping nitrogen into carbon material, wherein nitrogen is doped on the surface of carbon material in the form of pyrrole nitrogen, the platinum carbon catalyst produced by the carbon carrier has higher half-wave potential, ECSA is 1.5-2 times of that of un-doped catalyst, and the quality specific activity and stability are improved obviously.
2. The platinum-carrying amount of the industrial hydrogen fuel cell platinum-carbon catalyst is generally more than 20wt%, and the difficulty in manufacturing the high-platinum-carrying-amount catalyst with excellent performance is very large. The chemical reduction method has simple process, but the stability of the prepared catalyst is still to be improved. However, when the nitrogen-doped carbon material produced by the present invention is used as a carrier, a high platinum-supported catalyst having good specific activity and stability can be easily produced by an aqueous chemical reduction method. Some carbon materials must be pretreated or used with an organic solvent as they are dispersed in water, however the nitrogen-doped carbon material of the present invention can be readily dispersed in water.
3. When the platinum carrying amount is similar, the performance of the catalyst of the invention is obviously superior to that of a commercial catalyst, even if the platinum carrying amount is far higher than that of the commercial catalyst, the performances of the catalyst of the invention, such as half-wave potential, ECSA, specific mass activity and the like, are still equivalent to that of the commercial catalyst, and the stability is still far higher than that of the commercial catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is an XPS spectrum of a nitrogen-doped carbon support of example 1.
Fig. 2 is an XPS spectrum of the nitrogen-doped carbon support of example 3.
Fig. 3 is an XPS spectrum of the platinum-carbon catalyst of example 5.
Fig. 4 is a polarization curve before and after 5000 circles of the platinum-carbon catalyst of example 5.
Fig. 5 is an XPS spectrum of the platinum-carbon catalyst of example 6.
Fig. 6 is an XPS spectrum of the platinum-carbon catalyst of example 7.
Fig. 7 is an XPS spectrum of the platinum carbon catalyst of example 8.
Fig. 8 is a polarization curve before and after 5000 cycles of the platinum-carbon catalyst of comparative example 3.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All of the features disclosed in this application can be combined in any combination which is understood to be disclosed or described in this application and which, unless clearly considered to be too irrational by a person skilled in the art, is to be considered as being specifically disclosed and described in this application. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.
Technical and scientific terms used herein are to be defined only in accordance with their definitions, and are to be understood as having ordinary meanings in the art without any definitions.
The "doping element" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine.
In the present invention, unless otherwise specified as "carbon material containing a doping element" according to the context or self-restriction, the other references to "carbon material" refer to a carbon material containing no doping element; so does the underlying concept of carbon material.
In the present invention, "carbon black" and "carbon black" are terms of art that can be substituted for each other.
The "inert gas" in the present invention means a gas that does not have any appreciable influence on the performance of the nitrogen-doped carbon material in the production method of the present invention.
In the present invention, other references to "pore volume" are intended to refer to P/P, except where the context or limitations may dictate 0 The maximum single point adsorption total pore volume.
The invention provides a platinum-carbon catalyst, N analyzed by XPS 1s In the spectrum peak, except that there is a characteristic peak between 399eV and 400.5eV, there is no characteristic peak between 395eV and 405eVHis characteristic peak.
The platinum-carbon catalyst according to the present invention does not contain doping elements other than nitrogen.
The platinum-carbon catalyst according to the present invention does not contain other metal elements than platinum.
According to the platinum-carbon catalyst of the present invention, the mass fraction of platinum is 0.1% to 80%, preferably 20% to 70%, more preferably 40% to 70%, based on the mass of the catalyst.
According to the platinum-carbon catalyst of the present invention, the platinum-carbon catalyst has a resistivity of <10.0 Ω · m, preferably <2 Ω · m.
According to the platinum-carbon catalyst of the present invention, the specific surface area of the platinum-carbon catalyst is 80m 2 /g～1500m 2 A ratio of/g, preferably 100m 2 /g～200m 2 /g。
According to the platinum-carbon catalyst, the carrier is nitrogen-doped conductive carbon black, nitrogen-doped graphene or nitrogen-doped carbon nano tube.
According to the platinum carbon catalyst of the invention, the conductive carbon black can be one or more of Ketjen black series superconducting carbon black, cabot series conductive carbon black and series conductive carbon black produced by Wingda Gusai company; preferably, ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
A method of preparing a platinum carbon catalyst comprising: (1) impregnation of Nitrogen Source: mixing and soaking a carbon material and a nitrogen source aqueous solution to obtain a carbon material soaked with a nitrogen source; (2) a step of manufacturing a nitrogen-doped carbon material: heating the carbon material impregnated with the nitrogen source obtained in the step (1) to 1000-1500 ℃ at the speed of 8-15 ℃/min in inert gas, and then carrying out constant temperature treatment for 0.5-10 h to obtain a nitrogen-doped carbon material; (3) a step of loading platinum: and (3) taking the nitrogen-doped carbon material obtained in the step (2) as a carrier, and loading platinum.
According to the preparation method of the platinum-carbon catalyst, the constant treatment temperature can be 1000-1500 ℃, and preferably 1150-1450 ℃; the treatment time may be 0.5 to 10 hours, preferably 1 to 5 hours, and more preferably 2 to 4 hours.
According to the preparation method of the platinum-carbon catalyst, the nitrogen source can be ammonia water or urea.
According to the preparation method of the platinum-carbon catalyst, the mass ratio of the carbon material to the nitrogen source is 30:1 to 1:2; preferably 25:1 to 1:1.5.
according to the preparation method of the platinum-carbon catalyst, the carbon material can be conductive carbon black, graphene or carbon nanotubes.
According to the preparation method of the platinum carbon catalyst, the Conductive carbon black can be common Conductive carbon black (Conductive black), super Conductive carbon black (Super Conductive black) or special Conductive carbon black (Extra Conductive black), for example, the Conductive carbon black can be one or more of Ketjen black series superconducting carbon black, cabot series Conductive carbon black and series Conductive carbon black produced by Yingchuang Degussa; preferably, ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the preparation method of the platinum-carbon catalyst, the preparation method and the source of the conductive carbon black are not limited. The conductive carbon black may be acetylene black, furnace black, or the like.
I of the conductive carbon black according to the preparation method of the platinum-carbon catalyst of the present invention D /I G The value is generally from 0.8 to 5, preferably from 1 to 4. In the Raman spectrum, it is located at 1320cm -1 The nearby peak is the D peak and is located at 1580cm -1 The nearby peak is G peak, I D Represents the intensity of the D peak, I G Representing the intensity of the G peak.
According to the preparation method of the platinum-carbon catalyst, the graphene or the carbon nanotube can be graphene or carbon nanotube which is not subjected to oxidation treatment, and can also be graphene or carbon nanotube which is subjected to oxidation treatment.
According to the preparation method of the platinum-carbon catalyst, the carbon material has an oxygen mass fraction of more than 4%, preferably 4-15% in XPS analysis.
According to the method for producing a platinum-carbon catalyst of the present invention, the carbon material has a resistivity of <10 Ω · m, preferably <5 Ω · m, and more preferably <2 Ω · m.
According to the preparation method of the platinum-carbon catalyst of the present invention, the carbon material in (1) has a specific surface area of 10m 2 /g～2000m 2 (iv) g; the pore volume is 0.2mL/g to 6.0mL/g.
According to the preparation method of the platinum-carbon catalyst, in an embodiment of manufacturing the nitrogen-doped carbon material, a carbon material and a nitrogen source aqueous solution are mixed, dipped (generally for 12-72 h), dried (generally for 70-120 ℃), then placed in a tubular furnace, the tubular furnace is heated (the heating rate can be 8-15 ℃/min), and then treated at a high temperature (1000-1500 ℃, preferably 1150-1450 ℃) for a period of time (0.5-10 h, generally for 1-5 h), so as to obtain the nitrogen-doped carbon material.
According to the preparation method of the platinum-carbon catalyst, the nitrogen-doped carbon material prepared in the step (2) can be easily dispersed in the water phase. However, it is difficult to directly disperse the carbon material in the aqueous phase, such as ketjen black.
According to the preparation method of the platinum-carbon catalyst of the present invention, the step of supporting platinum comprises:
(a) Dispersing the nitrogen-doped carbon material obtained in the step (2) and a platinum precursor in a water phase, and adjusting the pH value to 8-12 (preferably, adjusting the pH value to 10 +/-0.5);
(b) Adding a reducing agent for reduction;
(c) Separating out solid, and carrying out post-treatment to obtain the platinum-carbon catalyst.
According to the preparation method of the platinum-carbon catalyst, the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.
According to the preparation method of the platinum-carbon catalyst of the present invention, in (a), the pH of the aqueous phase is adjusted with an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, or aqueous ammonia.
According to the preparation method of the platinum-carbon catalyst, in the step (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol.
According to the method for preparing a platinum-carbon catalyst of the present invention, in the step (b), the molar ratio of the reducing agent to platinum is 2 to 100.
According to the preparation method of the platinum-carbon catalyst, in the step (b), the reduction temperature is 50-150 ℃, and preferably 60-90 ℃; the reduction time is 4 to 15 hours, preferably 8 to 12 hours.
According to the preparation method of the platinum-carbon catalyst, the post-treatment comprises the following steps: washing, filtering and drying.
A platinum carbon catalyst prepared by any one of the methods described above.
A hydrogen fuel cell comprising an anode and/or a cathode, wherein any one of the platinum-carbon catalysts described above is used.
The invention adopts a simple method to dope nitrogen on the surface of the carbon material in the form of pyrrole nitrogen, thereby manufacturing the platinum-carbon electrode catalyst for hydrogen fuel cell anode hydrogen oxidation reaction or cathode oxygen reduction reaction, compared with the catalyst with the same carbon material and platinum-carrying amount, the catalyst has higher half-wave potential, and in particular, the ECSA and quality specific activity and the stability of the catalyst are obviously improved.
The platinum-carbon catalyst according to the present invention, when used in an oxygen reduction reaction, in some embodiments, ECSA>55m 2 g -1 Pt, e.g. at 55m 2 g -1 -Pt～140m 2 g -1 -Pt。
According to the platinum-carbon catalyst of the present invention, when used in an oxygen reduction reaction, in some examples, the specific mass activity decreased by <10% after 5000 cycles.
The platinum-carbon catalyst according to the present invention, when used in an oxygen reduction reaction, in some embodiments, has a half-wave potential >0.88V, such as 0.88V to 0.92V.
The platinum-carbon catalyst according to the present invention, when used in an oxygen reduction reaction, may, in some examples, have a specific mass activity>0.11A mg -1 Pt, e.g. 0.11A mg -1 -Pt～0.44A mg -1 -Pt。
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The analytical tests in the invention are all carried out by the following instruments and methods.
The invention detects elements on the surface of the material by an X-ray photoelectron spectrum analyzer (XPS). The adopted X-ray photoelectron spectrum analyzer is an ESCALb 220i-XL type ray photoelectron analyzer which is produced by VG scientific company and is provided with Avantage V5.926 software, and the X-ray photoelectron spectrum analysis test conditions are as follows: the excitation source is monochromatized A1K alpha X-ray, the power is 330W, and the basic vacuum is 3 multiplied by 10 during analysis and test -9 mbar. In addition, the electron binding energy was corrected with the C1s peak (284.3 eV) of elemental carbon, and the late-stage peak-splitting software was XPSPEAK.
Apparatus and method of elemental analysis, conditions: an element analyzer (Vario EL Cube), the reaction temperature is 1150 ℃, 5mg of the sample is weighed, the reduction temperature is 850 ℃, the flow rate of carrier gas helium is 200mL/min, the flow rate of oxygen is 30mL/min, and the oxygen introducing time is 70s.
The instrument, the method and the conditions for testing the mass fraction of platinum in the platinum-carbon catalyst are as follows: and (3) adding 30mL of aqua regia into 30mg of the prepared Pt/C catalyst, condensing and refluxing for 12h at 120 ℃, cooling to room temperature, taking supernatant liquid for dilution, and testing the Pt content in the supernatant liquid by using ICP-AES (inductively coupled plasma-atomic emission Spectrometry).
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Nippon electronics Co., ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV. The particle size of the nanoparticles in the sample is measured by an electron microscope picture.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
The Raman detection of the invention adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer produced by HORIBA company of Japan, and the laser wavelength is 532nm.
Electrochemical performance test, instrument Model Solartron analytical energy lab and Princeton Applied Research (Model 636A), methods and test conditions: polarization curve LSV of catalyst at 1600rpm 2 Saturated 0.1M HClO 4 Test in (1), CV Curve under Ar atmosphere 0.1M HClO 4 To calculate the electrochemically active area ECSA. At O in the stability test 2 Saturated 0.1M HClO 4 After 5000 cycles of scanning in the range of 0.6V to 0.95V, LSV and ECSA were tested as described above. During the test, the catalyst is prepared into evenly dispersed slurry and coated on a glassy carbon electrode with the diameter of 5mm, and the platinum content of the catalyst on the electrode is 3-4 mu g.
Resistivity test four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure is 3.9 plus or minus 0.03MPa, and the current is 500 plus or minus 0.1mA.
VXC72 (Vulcan XC72, produced by Kaborde, USA) was purchased from Suzhou winging sandiske energy science and technology Co., ltd. The results of the tests by the instrument method show that: specific surface area 258m 2 Per g, pore volume 0.388mL/g, oxygen mass fraction 8.72%, I D /I G 1.02, and a resistivity of 1.22. Omega. M.
Ketjenblack ECP600JD (manufactured by Lion corporation, japan) is purchased from tsuzhou wingong sandisk energy science and technology limited. The results of the tests by the instrument method show that: specific surface area 1362m 2 G, pore volume 2.29mL/g, oxygen mass fraction 6.9%, I D /I G 1.25, and resistivity of 1.31. Omega. M.
A commercial platinum-carbon catalyst (trade designation HISPEC4000, from Johnson Matthey corporation) was purchased from Alfa Aesar. And (3) testing results: the mass fraction of platinum was 40.2%.
Example 1
This example illustrates the preparation of a nitrogen-doped carbon support according to the present invention.
Immersing 1g of Vulcan XC72 in 20mL of 2.5wt% ammonia solution for 24h; drying in an oven at 100 ℃; then placing the tube furnace into a tube furnace, heating the tube furnace to 1100 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3h; and naturally cooling to obtain the nitrogen-doped carbon carrier, which is numbered as carbon carrier A.
Sample characterization and testing
The nitrogen mass fraction by XPS analysis was 1.43%; the oxygen mass fraction by XPS analysis was 9.31%; the specific surface area is 239m 2 (ii)/g; the resistivity was 1.28. Omega. M.
Fig. 1 is an XPS spectrum of the carbon support a of example 1.
Example 2
This example illustrates the preparation of a nitrogen-doped carbon support according to the present invention.
Immersing 1g of Vulcan XC72 in 15mL of 0.7wt% urea aqueous solution for 24h; drying in an oven at 100 ℃; then placing the tube furnace into a tube furnace, heating the tube furnace to 1200 ℃ at the speed of 10 ℃/min, and carrying out constant temperature treatment for 3h; and naturally cooling to obtain the nitrogen-doped carbon carrier, which is numbered as carbon carrier B.
Sample characterization and testing
The nitrogen mass fraction by XPS analysis was 0.68%; the oxygen mass fraction by XPS analysis was 8.92%; the resistivity was 1.25. Omega. M.
Example 3
This example illustrates the preparation of a nitrogen-doped carbon support according to the present invention.
Adding 10mL of absolute ethanol into 1g of Ketjenblack ECP600JD, and then adding 25mL of 10wt% ammonia water solution for soaking for 24 hours; drying in an oven at 100 ℃; then placing the tube furnace into the tube furnace, heating the tube furnace to 1100 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3h; and naturally cooling to obtain the nitrogen-doped carbon carrier, which is numbered as carbon carrier C.
Sample characterization and testing
The nitrogen mass fraction by XPS analysis was 1.48%; the oxygen mass fraction by XPS analysis was 11.22%; specific surface area of 1369m 2 (ii) a resistivity of 1.36. Omega. M.
Fig. 2 is an XPS spectrum of the carbon support C of example 3.
Example 4
This example illustrates the preparation of a nitrogen-doped carbon support according to the invention.
Adding 10mL of absolute ethanol into 1g of Ketjenblack ECP600JD, and then adding 20mL of 1wt% aqueous urea solution for soaking for 24 hours; drying in an oven at 100 ℃; then placing the tube furnace into the tube furnace, heating the tube furnace to 1300 ℃ at the speed of 10 ℃/min, and carrying out constant temperature treatment for 3h; and naturally cooling to obtain the nitrogen-doped carbon carrier, which is numbered as carbon carrier D.
Sample characterization and testing
The nitrogen mass fraction by XPS analysis was 1.31%; the oxygen mass fraction by XPS analysis was 9.54%; the resistivity was 1.34. Omega. M.
Example 5
This example illustrates the preparation of a platinum carbon catalyst according to the invention.
Dispersing a carbon carrier A into deionized water according to the proportion that 250mL of water is used for each gram of carbon carrier, adding 3.4mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of sodium carbonate aqueous solution to ensure that the pH value of the system is 10; heating the suspension to 80 ℃, adding formic acid while stirring for reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50; and filtering the reacted mixture, washing the mixture by deionized water until the pH value of the filtrate is neutral, filtering the mixture, and drying the filtrate at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 39.7%.
Fig. 3 is an XPS spectrum of the platinum-carbon catalyst of example 5.
Fig. 4 is a polarization curve before and after 5000 circles of the platinum-carbon catalyst of example 5.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Example 6
This example illustrates the preparation of a platinum carbon catalyst.
A platinum carbon catalyst was prepared according to the method of example 5, except that: using the carbon support B prepared in example 2, 1.3mmol of chloroplatinic acid per gram of carbon support was added.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 20.1%.
Fig. 5 is an XPS spectrum of the platinum-carbon catalyst of example 6.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Example 7
This example illustrates the preparation of a platinum carbon catalyst according to the invention.
Dispersing a carbon carrier C in deionized water according to the proportion that 250mL of water is used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of potassium hydroxide aqueous solution to adjust the pH value of the system to 10; heating the suspension to 80 ℃, adding sodium borohydride while stirring for reduction reaction, wherein the molar ratio of the reducing agent to the platinum precursor is 5:1, and maintaining the reaction for 12 hours; and filtering the reacted mixture, washing until the pH value of the solution is neutral, and drying at 100 ℃ to obtain the carbon-supported platinum catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 70.0%.
Fig. 6 is an XPS spectrum of the platinum carbon catalyst of example 7.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Example 8
This example illustrates the preparation of a platinum carbon catalyst.
A platinum carbon catalyst was prepared according to the method of example 7, except that: using the carbon support D prepared in example 4, 1.3mmol of chloroplatinic acid was added per gram of carbon support.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 20.1%.
Fig. 7 is an XPS spectrum of the platinum-carbon catalyst of example 8.
The results of the platinum carbon catalyst performance test are shown in Table 1.
Comparative example 1
A platinum carbon catalyst was prepared according to the method of example 5, except that: the vector was Vulcan XC72.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 40.1%.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Comparative example 2
A platinum-carbon catalyst was produced and tested in the same manner as in example 7, except that: the carbon support was Ketjenblack ECP600JD, and was dispersed with 200mL water and 50mL ethanol per gram of carbon support when Pt was supported.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 69.7%.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Comparative example 3
The platinum carbon catalyst was a commercial catalyst purchased under the designation HISPEC4000.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 40.2%.
Fig. 8 is a polarization curve before and after 5000 circles of the platinum-carbon catalyst of comparative example 3.
The results of the platinum carbon catalyst performance tests are shown in table 1.
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Claims (14)

1. A platinum-carbon catalyst for hydrogen fuel cell anode hydrogen oxidation reaction or cathode oxygen reduction reaction, characterized by N analyzed in XPS thereof 1s In the spectrum peaks, except that characteristic peaks exist between 399ev and 400.5ev, other characteristic peaks do not exist between 395ev and 405 ev; the carrier of the platinum carbon catalyst is nitrogen-doped conductive carbon black; taking the mass of the catalyst as a reference, the mass fraction of platinum is 20-70%;
the nitrogen-doped conductive carbon black is prepared by the following method:
(1) A step of dipping a nitrogen source: mixing and soaking a carbon material and a nitrogen source aqueous solution to obtain a nitrogen source-soaked carbon material; the carbon material is conductive carbon black; the nitrogen source is ammonia water;
(2) The step of manufacturing the nitrogen-doped carbon material comprises the following steps: and (3) heating the carbon material impregnated with the nitrogen source obtained in the step (1) to 1150-1500 ℃ at the speed of 8-15 ℃/min in inert gas, and then carrying out constant temperature treatment for 0.5-10 h to obtain the nitrogen-doped carbon material.
2. The platinum-carbon catalyst according to claim 1, wherein the mass fraction of platinum is 40% to 70% based on the mass of the catalyst.
3. Platinum-carbon catalyst according to claim 1, characterized in that it has a resistivity <10 Ω -m.
4. A platinum-carbon catalyst according to claim 1, wherein said conductive carbon Black is EC-300J, EC-600JD, ECP600JD, VXC72, black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or hilblaxk 40B2.
5. A method for preparing the platinum-carbon catalyst of claim 1, comprising:
(1) A step of dipping a nitrogen source: mixing and soaking a carbon material and a nitrogen source aqueous solution to obtain a nitrogen source-soaked carbon material; the carbon material is conductive carbon black; the nitrogen source is ammonia water;
(2) The step of manufacturing the nitrogen-doped carbon material comprises: heating the carbon material impregnated with the nitrogen source obtained in the step (1) to 1150-1500 ℃ at the speed of 8-15 ℃/min in inert gas, and then carrying out constant temperature treatment for 0.5-10 h to obtain a nitrogen-doped carbon material;
(3) A step of loading platinum, comprising: (a) Dispersing the nitrogen-doped carbon material obtained in the step (2) and a platinum precursor in a water phase, and adjusting the pH value to 8-12; (b) adding a reducing agent for reduction; (c) Separating out solid, and post-treating to obtain the platinum-carbon catalyst.
6. The production method according to claim 5, wherein in (2), the temperature of the constant temperature treatment is 1150 ℃ to 1450 ℃.
7. The method according to claim 5, wherein the mass ratio of the carbon material to the nitrogen source is 30:1 to 1:2.
8. the process according to claim 5, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
9. The production method according to claim 5, wherein the carbon material has an oxygen mass fraction of more than 4% in XPS analysis.
10. The method according to claim 5, wherein the carbon material has an electrical resistivity of <10 Ω -m.
11. The preparation method according to claim 5, wherein the platinum precursor is chloroplatinic acid, potassium chloroplatinate, or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.
12. The method according to claim 5, wherein in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 50-150 ℃; the reduction time is 2-15 h.
13. A platinum carbon catalyst for hydrogen fuel cell anode hydrogen oxidation reaction or cathode oxygen reduction reaction, characterized in that the catalyst is prepared by any one of the methods of claims 5 to 12.
14. A hydrogen fuel cell characterized in that the platinum-carbon catalyst according to any one of claims 1 to 4 and 13 is used in an anode and/or a cathode of the hydrogen fuel cell.
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