CN114735696A - Hollow bowl-shaped carbon carrier and preparation method thereof, platinum-based catalyst and membrane electrode - Google Patents

Hollow bowl-shaped carbon carrier and preparation method thereof, platinum-based catalyst and membrane electrode Download PDF

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CN114735696A
CN114735696A CN202210645705.3A CN202210645705A CN114735696A CN 114735696 A CN114735696 A CN 114735696A CN 202210645705 A CN202210645705 A CN 202210645705A CN 114735696 A CN114735696 A CN 114735696A
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bowl
platinum
hollow
carbon
based catalyst
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CN114735696B (en
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臧小刚
赵维
张泽鑫
孙海卫
柴茂荣
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Spic Hydrogen Energy Technology Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • 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 discloses a hollow bowl-shaped carbon carrier and a preparation method thereof, a platinum-based catalyst and a membrane electrode, wherein the preparation method of the hollow bowl-shaped carbon carrier comprises the following steps: a, adding tetraethoxysilane into a water-soluble dispersant and mixing; b, adding a first component and a second component into the solution obtained in the step a, filtering, washing and drying to obtain a solid product, wherein the first component is selected from one of m-aminophenol, phenol, cresol, xylenol, resorcinol, tert-butylphenol or bisphenol A, and the second component is selected from one of formaldehyde, acetaldehyde or furfural; c carbonizing the solid product of step b under inert atmosphere, and switchingActivating in an oxidizing atmosphere to obtain a sintered product; d, adding the sintered product obtained in the step c into hydrofluoric acid aqueous solution to remove SiO2And filtering, washing and drying to obtain the bowl-shaped carbon carrier. The preparation method can prepare the carbon carrier with a hollow bowl-shaped structure, and the platinum-based catalyst prepared by using the carbon carrier as the carrier can be applied to the field of electrocatalysis and can show excellent catalytic performance.

Description

Hollow bowl-shaped carbon carrier and preparation method thereof, platinum-based catalyst and membrane electrode
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a hollow bowl-shaped carbon carrier and a preparation method thereof, in particular to a platinum-based catalyst and a preparation method thereof, and more particularly to a membrane electrode.
Background
The proton exchange membrane fuel cell as an efficient energy conversion device has the advantages of high energy density, fast fuel supply, zero emission pollution and the like, and is a very promising technology. The catalyst is used as a key component of a membrane electrode in the proton exchange membrane fuel cell and plays an important role in the performance and durability of the cell. Platinum-based catalysts are one of the catalysts widely used in proton exchange membrane fuel cells. Generally, a carbon material is mostly used as a support carrier for the platinum-based catalyst, because the carbon material has a flexibly controllable structure, good electronic and mass transfer paths and excellent electrochemical stability.
Carbon materials such as carbon black, activated carbon, acetylene black and the like have been widely used as catalyst carriers, but the carbon carriers have the problems of uncontrollable micro-pore structure, unsatisfactory adsorption sites of active metals and the like, which leads to the unsatisfactory catalytic performance of the catalyst in devices. The hollow carbon sphere structure has a larger specific surface area and a microporous structure which is easy to regulate, the inner side and the outer side of the carbon wall can be simultaneously used as adsorption sites of catalytic active substances, the utilization rate of the catalytic active substances is improved, and the hollow carbon sphere structure has better application potential as a catalyst carrier.
However, there are still some problems to be solved when hollow carbon spheres are used as a catalyst support. The hollow carbon sphere is usually too large in its inner cavity, which can have some adverse effects: on one hand, the cavity structure occupies excessive space, so that the utilization rate of the electrode material is reduced; on the other hand, the larger cavity can increase the proton transmission distance, which is not favorable for proton conduction.
CN113106491A discloses a preparation method of a nitrogen-doped hollow mesoporous carbon sphere loaded platinum-cobalt oxide composite electrocatalytic material, which adopts SiO2The template method is characterized in that tetraethyl orthosilicate is used as a template agent, dopamine is used as a carbon source, hollow carbon spheres are prepared through the working procedures of coating, sintering, acid washing, drying and the like, and the hollow carbon spheres are subsequently mixed with a chemical activator and then sintered again, so that the purpose of forming holes on a carbon wall is achieved. The hollow spherical structure with rich mesopores on the carbon wall is obtained after acid washing and drying, then the platinum-cobalt oxide is loaded to prepare the composite electro-catalytic material, the material greatly reduces the loading capacity of platinum through the electron transfer and synergistic effect of platinum nano particles and cobaltosic oxide, and meanwhile, the material has more excellent hydrogen evolution activity. However, in this solution, the inner cavity of the hollow carbon sphere is relatively too large, so that some adverse effects may occur: on one hand, the cavity structure occupies too much space, which can greatly reduce the utilization rate of the electrode material; on the other hand, the larger cavity can lengthen the proton transmission distance, which is not favorable for the proton transmission. And in the pore-forming process, a chemical activation method needs secondary sintering and secondary washing, filtering and drying, so that the process is too complex and the pollution is large.
CN111215056A discloses a preparation method and application of a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst, which adopts triblock copolymer Pluronic cP123 as a soft template, adds a carbon source and a nitrogen source to prepare a hollow polymer sphere, and then prepares the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst through impregnation and calcination processes with a Pd source. The carbon source and the nitrogen source can promote the uniform dispersion of the Pd nano-particles due to rich oxygen-containing groups and nitrogen-containing groups. Thereby achieving higher electrocatalytic activity and atom utilization rate. The wall thickness of the hollow carbon sphere prepared by the technical scheme is 20-40 nm, and the wall thickness is too thick, so that the mass transfer process is not facilitated. In addition, materials such as PluronicP123 are relatively expensive and are difficult to mass produce.
Therefore, in order to solve the above problems, it is necessary to develop a technique with simple materials and processes to prepare a structurally optimized carbon material and to support a noble metal to use it as a fuel cell catalyst.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: hollow carbon spheres are commonly used Pt-based catalyst supports due to their large specific surface area, excellent conductivity and unique cavity structure. However, since the inner cavity of the hollow carbon sphere is too large, some adverse effects may occur: on one hand, the cavity structure occupies too much space, which can greatly reduce the utilization rate of the electrode material; on the other hand, the larger cavity can lengthen the proton transmission distance, which is not favorable for the proton transmission. And the related preparation method has the conditions that the carbon wall is too thick and the hole is not reached, so that the mass transfer is blocked and the catalyst loading rate is low. In addition, although the chemical activation pore-forming method is an effective pore-forming method, the method needs secondary sintering and secondary washing and filtering treatment, the process is too complex, and the environmental pollution is large.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a preparation method of a hollow bowl-shaped carbon carrier, the carbon carrier with a bowl-shaped structure is prepared by regulating and controlling the proportion of a template and a carbon source, gas activation pore-forming can be synchronously realized in the carbonization process, secondary sintering and acid washing are not needed, the method is simple, the pollution caused by chemical activation is reduced, and the prepared bowl-shaped carbon carrier can be used for preparing a catalyst, is applied to the field of electrocatalysis and can show excellent catalytic performance.
The preparation method of the hollow bowl-shaped carbon carrier comprises the following steps:
a. adding tetraethoxysilane into a water-soluble dispersant, and uniformly mixing;
b. adding a first component and a second component into the solution obtained in the step a, wherein the mass ratio of the first component to the second component to the tetraethoxysilane added in the step a is 1 (1-4) to (10-20), stirring, filtering, washing and drying a precipitate generated by reaction to obtain a solid product, wherein the first component is one of m-aminophenol, phenol, cresol, xylenol, resorcinol, tert-butylphenol or bisphenol A, and the second component is one of formaldehyde, acetaldehyde or furfural;
c. carbonizing the solid product dried in the step b in an inert atmosphere, and then switching to an oxidizing atmosphere for activation treatment to obtain a sintered product;
d. c, adding the sintered product obtained in the step c into hydrofluoric acid water solution, and stirring to remove SiO2And filtering, washing and drying to obtain the bowl-shaped carbon carrier.
The method of the embodiment of the invention prepares the bowl-shaped hollow carbon carrier material by controlling the adding proportion of the tetraethoxysilane, the first component and the second component, and the hollow bowl-shaped structure effectively improves the space utilization rate, shortens the ion transmission distance and improves the transmission capacity; 2. in the method of the embodiment of the invention, the adopted first component can be used as a carbon source and a nitrogen source at the same time, so that the use variety of medicines is reduced, the method is simple, the cost of the carbon raw material is low, and the method is beneficial to large-scale production and application; 3. according to the method, after carbonization, activation treatment is carried out in an oxidizing atmosphere, the carbon material subjected to gas activation treatment has a large specific surface area and a rich pore structure, and is beneficial to dispersion and anchoring of precious metals such as Pt and the like, Pt can be loaded on the outer wall surface and the inner surface of a cavity of a bowl-shaped hollow-structure carbon carrier at the same time, external Pt is beneficial to improving mass transfer characteristics, internal Pt is beneficial to improving dynamic activity, and a catalyst prepared by loading Pt on the hollow-bowl-shaped carbon carrier can show excellent ORR performance and MEA performance; 4. in the method of the embodiment of the invention, the pore-forming is carried out by adopting a gas activation mode, the pore-forming is carried out on the carbon wall by using a hollow spherical carbon material through a chemical pore-forming method, the hollow carbon sphere which is prepared in advance needs to be mixed with a chemical activating agent, and the hollow spherical carbon material is subjected to processes of sintering, washing, drying and the like again to obtain a hollow spherical structure with porous carbon wall.
In some embodiments, in the step a, the water-soluble dispersant includes ammonia, water and ethanol.
In some embodiments, in the step a, the volume ratio of the ammonia water to the ethanol is 1 (2-4) to (6-12).
In some embodiments, in step a, the mixing time is 1-4 h.
In some embodiments, in step b, the first component is m-aminophenol and the second component is formaldehyde.
In some embodiments, in step c, the dried solid product is ground to 0.15-5 microns before carbonization and activation.
In some embodiments, in step c, the gas used for the inert atmosphere comprises at least one of nitrogen or argon.
In some embodiments, in the step c, the carbonization temperature is 600-.
In some embodiments, in step c, the oxidizing atmosphere comprises at least one of air, oxygen, carbon dioxide, or water vapor.
In some embodiments, in the step c, after the oxidizing atmosphere is switched, the activation treatment temperature is 600-1200 ℃, and the treatment time is 0.5-4 h.
In some embodiments, in step c, the carbonization and activation treatment is performed using a rotary sintering furnace.
In some embodiments, in the step c, after the oxidizing atmosphere is switched, the rotation function of the rotary sintering furnace is started, and the rotation speed is 10-50 rpm.
In some embodiments, in the step d, the hydrofluoric acid aqueous solution has a mass fraction of 5 to 15%.
In some embodiments, in the step d, the stirring time of the sintered product in the hydrofluoric acid aqueous solution is 10-36 h.
The embodiment of the invention also provides a hollow bowl-shaped carbon carrier which is prepared by the method of the embodiment of the invention. The hollow bowl-shaped carbon carrier provided by the embodiment of the invention is a carbon bowl-shaped particle, the inside of the hollow bowl-shaped carbon carrier is of a cavity structure, the thickness of the carbon wall is controllable, and the surface of the hollow bowl-shaped carbon carrier is distributed with abundant hierarchical pore structures, so that the hollow bowl-shaped carbon carrier has a large specific surface area and excellent conductivity; the hollow bowl-shaped structure of the carbon carrier of the embodiment of the invention effectively improves the space utilization rate, shortens the ion transmission distance and improves the transmission capability; in addition, the hollow bowl-shaped carbon carrier has larger specific surface area and rich pore structure, which is beneficial to the dispersion and anchoring of noble metals such as Pt and the like, Pt can be simultaneously loaded on the outer wall surface and the inner surface of the cavity of the carbon carrier with the bowl-shaped hollow structure, the external Pt is beneficial to improving mass transfer characteristics, the internal Pt is beneficial to improving kinetic activity, and a catalyst prepared by loading Pt on the carbon carrier with the hollow bowl-shaped structure can show excellent ORR performance and MEA performance
In some embodiments, the wall thickness of the hollow bowl-shaped carbon support is 10-20 nm.
In some embodiments, the specific surface area of the hollow bowl-shaped carbon support is 500-2/g。
The embodiment of the invention also provides a platinum-based catalyst which comprises the hollow bowl-shaped carbon carrier. In the catalyst of the embodiment of the present invention, the hollow bowl-shaped carbon carrier of the embodiment of the present invention is used as the carrier, and all advantages that can be brought by the hollow bowl-shaped carbon carrier of the embodiment of the present invention are provided, and are not described herein again.
In some embodiments, the platinum-based catalyst has a platinum loading ≧ 30%.
In some embodiments, the crystallite diameter of platinum in the platinum-based catalyst is from 2 to 5 nm.
The embodiment of the invention also provides a preparation method of the platinum-based catalyst, which comprises the steps of adding the hollow bowl-shaped carbon carrier into a dispersing agent for dispersion, then adding a platinum-containing precursor for continuous dispersion, adding a reducing agent for stirring, reacting, washing and drying to obtain the platinum-based catalyst. The method provided by the embodiment of the invention is simple in preparation method, and the prepared platinum-based catalyst is excellent in performance and can be applied to proton exchange membrane fuel cells.
In some embodiments, the dispersant comprises at least one of water, ethanol, ethylene glycol, isopropanol, or n-propanol; the platinum-containing precursor comprises at least one of chloroplatinic acid, platinum nitrate, platinum acetylacetonate, sodium chloroplatinate or potassium chloroplatinate; the reducing agent comprises at least one of ascorbic acid, methanol, ethylene glycol, ethanol, sodium borohydride, hydrazine hydrate, formaldehyde or formic acid.
Drawings
FIG. 1 is a scanning electron micrograph of a hollow bowl-shaped carbon support prepared in example 1 of the present invention;
FIG. 2 is a nitrogen adsorption/desorption curve of a hollow bowl-shaped carbon carrier produced in example 1 of the present invention;
fig. 3 is a pore size distribution diagram of the hollow bowl-shaped carbon support prepared in example 1 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The preparation method of the hollow bowl-shaped carbon carrier comprises the following steps:
a. adding tetraethoxysilane into a water-soluble dispersant, and uniformly mixing;
b. adding a first component and a second component into the solution obtained in the step a, wherein the mass ratio of the first component to the second component to the tetraethoxysilane added in the step a is 1 (1-4): 10-20, preferably 1 (1-4): 10-15, further preferably 1 (1-3): 10-14), stirring, filtering, washing and drying the precipitate generated in the reaction to obtain a solid product, wherein the first component is selected from one of m-aminophenol, phenol, cresol, xylenol, resorcinol, tert-butylphenol or bisphenol A, preferably m-aminophenol, and the second component is selected from one of formaldehyde, acetaldehyde or furfural, preferably formaldehyde;
c. carbonizing the solid product dried in the step b in an inert atmosphere, and then switching to an oxidizing atmosphere for activation treatment to obtain a sintered product;
d. c, adding the sintered product obtained in the step c into hydrofluoric acid water solution, and stirring to remove SiO2And filtering, washing and drying to obtain the bowl-shaped carbon carrier.
According to the preparation method of the hollow bowl-shaped carbon carrier, the bowl-shaped hollow carbon carrier material is prepared by controlling the adding proportion of the ethyl orthosilicate, the first component and the second component, the hollow bowl-shaped structure effectively improves the space utilization rate, shortens the ion transmission distance and improves the transmission capacity; in the method of the embodiment of the invention, the adopted first component can be used as a carbon source and a nitrogen source at the same time, so that the use types of medicines are reduced, the method is simple, the cost of the carbon raw material is low, and the method is beneficial to large-scale production and application; according to the method, after carbonization, activation treatment is carried out in an oxidizing atmosphere, the carbon material subjected to gas activation treatment has a large specific surface area and a rich pore structure, and is beneficial to dispersion and anchoring of precious metals such as Pt and the like, Pt can be loaded on the outer wall surface and the inner surface of a cavity of a bowl-shaped hollow-structure carbon carrier at the same time, external Pt is beneficial to improving mass transfer characteristics, internal Pt is beneficial to improving dynamic activity, and a catalyst prepared by loading Pt on the hollow-bowl-shaped carbon carrier can show excellent ORR performance and MEA performance; in the method of the embodiment of the invention, the pore-forming is carried out by adopting a gas activation mode, the pore-forming is carried out on the carbon wall by using a hollow spherical carbon material through a chemical pore-forming method, the hollow carbon sphere which is prepared in advance needs to be mixed with a chemical activating agent, and the hollow spherical carbon material is subjected to processes of sintering, washing, drying and the like again to obtain a hollow spherical structure with porous carbon wall.
In some embodiments, in the step a, the water-soluble dispersant comprises ammonia water, water and ethanol, preferably, the volume ratio of the ammonia water to the ethanol is 1 (2-4) to (6-12), and the mixing time is 1-4 h. In the embodiment of the invention, a water-soluble dispersant is preferably selected, which is beneficial to the dispersion of tetraethoxysilane.
In some embodiments, in step c, the dried solid product is ground to 0.15-5 microns before carbonization and activation. In the embodiment of the invention, the dried solid is subjected to grinding treatment before carbonization and activation, so that the solid is in full contact with an oxidizing atmosphere during activation treatment.
In some embodiments, in step c, the gas used in the inert atmosphere includes at least one of nitrogen or argon, preferably, the carbonization temperature is 600-; the oxidizing atmosphere comprises at least one of air, oxygen, carbon dioxide, or water vapor; after the oxidizing atmosphere is switched, the activation treatment temperature is preferably 600-1200 ℃, and the treatment time is 0.5-4 h. In the embodiment of the invention, the temperature of activation treatment is optimized, the temperature is too low to reach the reaction temperature of oxidizing atmosphere and carbon material, the reaction rate is low, and the pore-forming effect is influenced; too high temperature can cause the reaction rate to be too fast, and the carbon material is easy to be excessively decomposed, so that the reaction process is uncontrollable. In addition, the template SiO2The crystallinity is increased at high temperature, the carbon material is not easy to be dissolved out by acid, and SiO is easy to be left in the carbon material2Impurities, which affect the product performance. In the embodiment of the invention, the carbonization atmosphere is switched into the oxidizing atmosphere after the carbonization is finished, the carbonization and the activation can be realized in the same equipment, the process is simple, the process conditions of the carbonization and the activation treatment are optimized, and the carbonization process of the carbon carrier and the formation of rich hierarchical pore structures are facilitated.
In some embodiments, in the step c, the carbonization and activation treatment is completed by using a rotary sintering furnace, and preferably, after the oxidizing atmosphere is switched to, the rotation function of the rotary sintering furnace is started, and the rotation speed is 10-50 rpm. In the embodiment of the invention, a rotary sintering furnace is preferably adopted as the heat treatment equipment for sintering and activating, and the rotary function is started in the activation treatment stage, so that more ideal carbonization and pore-forming functions are realized.
In some embodiments, in the step d, the mass fraction of the hydrofluoric acid aqueous solution is 5-15%, and the sintered product is in the hydrofluoric acid aqueous solutionThe stirring time in the solution is 10-36 h. In the embodiment of the invention, the process condition of cleaning by adopting hydrofluoric acid is optimized, which is beneficial to SiO2Is effectively removed.
The embodiment of the invention also provides a hollow bowl-shaped carbon carrier which is prepared by adopting the method of the embodiment of the invention, preferably, the wall thickness of the hollow bowl-shaped carbon carrier is 10-20nm, the specific surface area is 500-1800m2(ii) in terms of/g. In the embodiment of the invention, the wall thickness of the carbon carrier is optimized, the stability of the structure is insufficient when the wall thickness is too thin, the structure is easy to be damaged by mechanical impact in the catalyst pulping process, the bowl shape collapses, the cavity is blocked, the transmission of protons and oxygen is influenced, the catalytic activity and the MEA performance are further influenced, and the long-term operation of the fuel cell in a severe environment is not facilitated; the excessive thickness of the wall is not beneficial to the formation of a bowl-shaped structure, and the thicker wall thickness is not beneficial to the loading of the noble metal on the inner wall of the cavity, so that the dynamic activity of the catalyst is influenced. The hollow bowl-shaped carbon carrier provided by the embodiment of the invention is a carbon bowl-shaped particle, the inside of the hollow bowl-shaped carbon carrier is of a cavity structure, the thickness of the carbon wall is controllable, and the surface of the hollow bowl-shaped carbon carrier is distributed with abundant hierarchical pore structures, so that the hollow bowl-shaped carbon carrier has a large specific surface area and excellent conductivity; the hollow bowl-shaped structure of the carbon carrier of the embodiment of the invention effectively improves the space utilization rate, shortens the ion transmission distance and improves the transmission capacity; in addition, the hollow bowl-shaped carbon carrier has larger specific surface area and rich pore structure, which is beneficial to the dispersion and anchoring of noble metals such as Pt and the like, Pt can be simultaneously loaded on the outer wall surface and the inner surface of the cavity of the carbon carrier with the bowl-shaped hollow structure, the external Pt is beneficial to improving mass transfer characteristics, the internal Pt is beneficial to improving kinetic activity, and a catalyst prepared by loading Pt on the carbon carrier with the hollow bowl-shaped structure can show excellent ORR performance and MEA performance
The embodiment of the invention also provides a platinum-based catalyst which comprises the hollow bowl-shaped carbon carrier, preferably, the platinum loading capacity of the platinum-based catalyst is more than or equal to 30%, and the crystallite diameter of platinum in the platinum-based catalyst is 2-5 nm. In the catalyst of the embodiment of the present invention, the hollow bowl-shaped carbon carrier of the embodiment of the present invention is used as the carrier, and all advantages that can be brought by the hollow bowl-shaped carbon carrier of the embodiment of the present invention are provided, and are not described herein again.
The embodiment of the invention also provides a preparation method of the platinum-based catalyst, which comprises the steps of adding the hollow bowl-shaped carbon carrier into a dispersing agent for dispersion, then adding a platinum-containing precursor for continuous dispersion, adding a reducing agent for stirring, reacting, washing and drying to obtain the platinum-based catalyst. Preferably, the dispersant comprises at least one of water, ethanol, ethylene glycol, isopropanol, or n-propanol; the platinum-containing precursor comprises at least one of chloroplatinic acid, platinum nitrate, platinum acetylacetonate, sodium chloroplatinate or potassium chloroplatinate; the reducing agent comprises at least one of ascorbic acid, methanol, ethylene glycol, ethanol, sodium borohydride, hydrazine hydrate, formaldehyde or formic acid. The method provided by the embodiment of the invention is simple in preparation method, and the prepared platinum-based catalyst is excellent in performance and can be applied to proton exchange membrane fuel cells.
The present invention will be described in detail below with reference to examples and the accompanying drawings.
Example 1
Preparation of carbon carrier
5.5g of tetraethoxysilane is dissolved in 20mL of ethanol, and then the mixture is dripped into a mixed solution consisting of 70 mL of ethanol, 10mL of ammonia water and 30 mL of water, and the mixture is uniformly stirred for 1.5 h. Then 0.5 g resorcinol and 0.6 g formaldehyde, i.e. resorcinol: formaldehyde: the mass ratio of the ethyl orthosilicate is 1:1.2:11, stirring at room temperature, centrifuging, collecting precipitates, and repeatedly washing the precipitates with ethanol and deionized water for multiple times. And drying the washed product overnight, then sending the product into a rotary tube type sintering furnace, heating at a rate of 5 ℃/min, carbonizing at a constant temperature of 700 ℃ for 5h in a nitrogen atmosphere, switching to carbon dioxide gas, heating to 950 ℃ at a heating rate of 10 ℃/min, carrying out constant temperature treatment for 0.5h, starting a rotating function after ventilation, and rotating at a speed of 15 rpm. Finally, the product after heat treatment is put into 10 wt% HF aqueous solution to be stirred for 18h, and SiO is removed2And washing, filtering and drying to obtain the nitrogen-doped hollow porous bowl-shaped carbon carrier material.
Preparation of catalyst
0.1 g of the carbon material was added to 100mL of ultrapure water, heated to 80 ℃ and stirred well for 2h, after which 20mL of platinum-containing 0.1 g of platinum nitrate was added and stirring was continued for 4 h. And then adding an ascorbic acid aqueous solution into the mixed solution, fully stirring for 1h, repeatedly washing and filtering the obtained dispersion liquid after stirring to enable the filtrate to be neutral, and drying the filter cake in vacuum to obtain the nitrogen-doped hollow bowl-shaped carbon carrier Pt-based catalyst with the platinum loading of 50%.
The scanning electron micrograph of the hollow bowl-shaped carbon carrier prepared in this example is shown in fig. 1, the nitrogen adsorption and desorption curve is shown in fig. 2, the pore diameter distribution diagram is shown in fig. 3, the physical property parameters are shown in table 1, and the properties of the prepared platinum-based catalyst are shown in table 2.
Example 2
Preparation of carbon carrier
10 g of tetraethoxysilane is dissolved in 50mL of ethanol, and then the mixture is dropwise added into a mixed solution consisting of 105 mL of ethanol, 15 mL of ammonia water and 60 mL of water, and the mixture is uniformly stirred for 2 hours. Then 0.8g of m-aminophenol and 1.2g of formaldehyde, i.e. m-aminophenol: formaldehyde: the mass ratio of the ethyl orthosilicate is 1:1.5:12.5, stirring at room temperature, centrifuging, collecting precipitate, and repeatedly washing the precipitate with ethanol and deionized water for multiple times. Drying the washed product overnight, then sending the product into a rotary tube type sintering furnace, heating at a rate of 3 ℃/min, carbonizing at a constant temperature of 800 ℃ for 4h under a nitrogen atmosphere, switching carbon dioxide gas, heating to 1000 ℃ at a heating rate of 10 ℃/min, carrying out constant temperature treatment for 1h, starting a rotation function after ventilation, and rotating at a speed of 30 rpm. Finally, the heat-treated product is put into 10 wt% HF aqueous solution to be stirred for 20 hours, and SiO is removed2And washing, filtering and drying to obtain the nitrogen-doped hollow porous bowl-shaped carbon material.
Preparation of catalyst
0.2 g of the carbon material was added to 200mL of the aqueous solution and heated to 80 ℃ and stirred well for 2h, after which 0.2 g of platinic chloride containing platinum was added and stirring was continued for 4 h. And then adding a sodium borohydride aqueous solution into the mixed solution, fully stirring for 1h, repeatedly washing and filtering the obtained dispersion liquid after stirring to enable the filtrate to be neutral, and drying the filter cake in vacuum to obtain the nitrogen-doped hollow bowl-shaped carbon carrier Pt-based catalyst with the platinum loading of 50%.
The physical parameters of the hollow bowl-shaped carbon carrier prepared in this example are shown in table 1, and the properties of the platinum-based catalyst prepared in this example are shown in table 2.
Example 3
Preparation of carbon carrier
2.6 g of tetraethoxysilane is dissolved in 10mL of ethanol, and then dropwise added into a mixed solution consisting of 30 mL of ethanol, 5 mL of ammonia water and 10mL of water to be uniformly stirred for 30 min. Then 0.2 g phenol and 0.4 g acetaldehyde, i.e. phenol: acetaldehyde: stirring the ethyl orthosilicate at room temperature and the ethyl orthosilicate at a mass ratio of 1:2:13, centrifuging and collecting precipitates, and repeatedly washing the precipitates with ethanol and deionized water for multiple times. Drying the washed product at 60 ℃ overnight, then sending the product into a rotary tube type sintering furnace, heating at a rate of 2 ℃/min, carbonizing at 800 ℃ for 4h under a nitrogen atmosphere, switching carbon dioxide gas, heating to 1000 ℃ at a heating rate of 10 ℃/min, carrying out constant temperature treatment for 2h, starting a rotation function after ventilation, and rotating at a speed of 15 rpm. Finally, the heat-treated product is put into 10 wt% HF aqueous solution to be stirred for 10 hours, and SiO is removed2And washing, filtering and drying to obtain the nitrogen-doped hollow porous bowl-shaped carbon material.
Preparation of catalyst
0.1 g of the carbon material was added to 100mL of ultrapure water, heated to 80 ℃ and stirred well for 2h, after which 0.1 g of platinic chloride containing platinum was added and stirring was continued for 4 h. And then adding ethylene glycol into the mixed solution, fully stirring for 1h, repeatedly washing and filtering the obtained dispersion liquid after stirring to enable the filtrate to be neutral, and drying the filter cake in vacuum to obtain the nitrogen-doped hollow bowl-shaped carbon carrier Pt-based catalyst with the platinum loading capacity of 50%.
The physical properties of the hollow bowl-shaped carbon support obtained in this example are shown in Table 1, and the properties of the platinum-based catalyst obtained are shown in Table 2.
Example 4
The carbon support was prepared in the same manner as in example 2.
Preparation of the catalyst
0.7 g of the carbon material was added to 200mL of the aqueous solution and heated to 80 ℃ and stirred well for 2h, after which 0.3 g of platinum nitrate containing platinum was added and stirring was continued for 4 h. And then adding a sodium borohydride aqueous solution into the mixed solution, fully stirring for 1h, repeatedly washing and filtering the obtained dispersion liquid after stirring to enable the filtrate to be neutral, and drying the filter cake in vacuum to obtain the nitrogen-doped hollow bowl-shaped carbon carrier Pt-based catalyst with the platinum loading of 30%.
The properties of the platinum-based catalyst prepared in this example are shown in Table 2.
Example 5
The carbon support was prepared as in example 2.
Preparation of the catalyst
0.3 g of the carbon material was added to 200mL of the aqueous solution and heated to 80 ℃ and stirred well for 2h, after which 0.2 g of platinum nitrate containing platinum was added and stirring was continued for 4 h. And then adding a sodium borohydride aqueous solution into the mixed solution, fully stirring for 1h, repeatedly washing and filtering the obtained dispersion liquid after stirring to enable the filtrate to be neutral, and drying the filter cake in vacuum to obtain the nitrogen-doped hollow bowl-shaped carbon carrier Pt-based catalyst with the platinum loading of 40%.
The properties of the platinum-based catalyst prepared in this example are shown in Table 2.
Example 6
The carbon support was prepared in the same manner as in example 2.
Preparation of the catalyst
0.4 g of the carbon material was added to 200mL of the aqueous solution and heated to 80 ℃ and stirred well for 2h, after which 0.6 g of platinum nitrate containing platinum was added and stirring was continued for 4 h. And then adding a sodium borohydride aqueous solution into the mixed solution, fully stirring for 1h, repeatedly washing and filtering the obtained dispersion liquid after stirring to enable the filtrate to be neutral, and drying the filter cake in vacuum to obtain the nitrogen-doped hollow bowl-shaped carbon carrier Pt-based catalyst with the platinum loading capacity of 60%.
The properties of the platinum-based catalyst prepared in this example are shown in Table 2.
Example 7
The same preparation method as in example 1 was conducted except that the tube furnace did not start the rotation function after switching the carbon dioxide gas.
This example prepared a nitrogen-doped hollow bowl-shaped carbon support Pt-based catalyst with a platinum loading of 50%.
The physical properties of the carbon support obtained in this example are shown in Table 1, and the properties of the platinum-based catalyst obtained in this example are shown in Table 2.
Comparative example 1
The same procedure as in example 1 was followed, except that the carbon dioxide activation treatment stage was not performed.
Comparative example 1a nitrogen doped hollow bowl carbon support Pt-based catalyst with a platinum loading of 45% was prepared.
Physical properties of the carbon support prepared in comparative example 1 are shown in table 1, and properties of the platinum-based catalyst prepared are shown in table 2.
Comparative example 2
The same preparation method as in example 1 was conducted except that the carbon dioxide treatment time was extended to 5 hours.
Comparative example 2 a nitrogen doped hollow bowl carbon support Pt-based catalyst with 50% platinum loading was prepared.
Physical properties of the carbon support prepared in comparative example 2 are shown in table 1, and properties of the platinum-based catalyst prepared are shown in table 2.
Comparative example 3
The same preparation method as in example 1 was conducted except that resorcinol was added in an amount of 0.8g and formaldehyde was added in an amount of 1.2g, that is, resorcinol: formaldehyde: the mass ratio of the ethyl orthosilicate is 1:1.5: 5.875.
Comparative example 3 a nitrogen doped hollow bowl carbon support Pt-based catalyst with 50% platinum loading was prepared.
Physical properties of the carbon support prepared in comparative example 3 are shown in table 1, and properties of the platinum-based catalyst prepared are shown in table 2.
TABLE 1
Specific surface area Carbon wall thickness Average pore diameter
Example 1 721m2/g 19±2 nm 3.8 nm
Example 2 1082m2/g 14±2 nm 5.2 nm
Example 3 1560m2/g 11±2 nm 4.3 nm
Example 4 1082m2/g 14±2 nm 5.2 nm
Example 5 1082m2/g 14±2 nm 5.2 nm
Example 6 1082m2/g 14±2 nm 5.2 nm
Example 7 647m2/g 21±3 nm 3.0 nm
Comparative example 1 435m2/g 25±2 nm 2.6 nm
Comparative example 2 2031m2/g — 2.3 nm
Comparative example 3 975 m2/g 35±2 nm 3.2 nm
TABLE 2
Diameter of platinum crystallite Electrochemical active area Specific mass activity MEA Performance
Commercial platinum carbon 3.4 nm 58 m2/g 0.23A/mg Pt 1.00W/[email protected]
Example 1 3.2 nm 65m2/g 0.37A/mg Pt 1.23W/[email protected]
Example 2 3.0 nm 74 m2/g 0.38A/mg Pt 1.40W/[email protected]
Example 3 2.7 nm 77 m2/g 0.35A/mg Pt 1.15W/[email protected]
Example 4 2.6 nm 75 m2/g 0.30A/mg Pt 1.08W/[email protected]
Example 5 2.9 nm 72 m2/g 0.33A/mg Pt 1.16W/[email protected]
Example 6 3.4 nm 70 m2/g 0.34A/mg Pt 1.42W/[email protected]
Example 7 3.3 nm 61 m2/g 0.30 A/mg Pt 1.07W/[email protected]
Comparative example 1 3.6 nm 60 m2/g 0.22 A/mg Pt 0.72W/[email protected]
Comparative example 2 2.0 nm 85 m2/g 0.34 A/mg Pt 0.58W/[email protected]
Comparative example 3 3.1 nm 73 m2/g 0.35 A/mg Pt 0.54W/[email protected]
As can be seen from table 2, the catalysts of examples 1 to 7 all had more excellent oxygen reduction activity and MEA performance than commercial platinum carbon. In comparative example 1, since the stage of the oxidizing atmosphere activation treatment was not performed, the specific surface and pore structure of the prepared carbon support were not developed, resulting in poor platinum supporting ability, and thus the electrochemical performance and MEA performance of the prepared catalyst were relatively low. In comparative example 2, since the carbon dioxide treatment time was prolonged, the wall thickness of the carbon material was too thin, which resulted in structural damage, channel collapse, and mass transfer inhibition, resulting in unsatisfactory MEA performance. In comparative example 3, the content of carbon source was increased, resulting in excessive wall thickness of the material, and finally hollow carbon spheres were formed, which were inferior in mass transfer performance to the bowl-shaped structure due to excessive cavity size, and also resulted in poor MEA performance. In example 7, the specific surface area and the average pore diameter are reduced compared with example 1 due to the fact that the rotating function of the tubular furnace is not started, and the carbon wall thickness is not uniform compared with example 1, but the performance of the prepared catalyst is still better than that of commercial platinum carbon, which shows that the carbon support material is subjected to more uniform gas activation treatment by adopting a starting rotation mode in the activation process, and a richer hierarchical pore structure is obtained.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (23)

1. A preparation method of a hollow bowl-shaped carbon carrier is characterized by comprising the following steps:
a. adding tetraethoxysilane into a water-soluble dispersant, and uniformly mixing;
b. adding a first component and a second component into the solution obtained in the step a, wherein the mass ratio of the first component to the second component to the tetraethoxysilane added in the step a is 1 (1-4) to (10-20), stirring, filtering, washing and drying a precipitate generated by reaction to obtain a solid product, wherein the first component is one of m-aminophenol, phenol, cresol, xylenol, resorcinol, tert-butylphenol or bisphenol A, and the second component is one of formaldehyde, acetaldehyde or furfural;
c. carbonizing the solid product dried in the step b in an inert atmosphere, and then switching to an oxidizing atmosphere for activation treatment to obtain a sintered product;
d. c, adding the sintered product obtained in the step c into hydrofluoric acid water solution, and stirring to remove SiO2And filtering, washing and drying to obtain the bowl-shaped carbon carrier.
2. The method for preparing a hollow carbon carrier bowl according to claim 1, wherein in the step a, the water-soluble dispersant includes ammonia water, water and ethanol.
3. The method for preparing a hollow carbon carrier bowl as claimed in claim 2, wherein in the step a, the volume ratio of the ammonia water, the water and the ethanol is 1 (2-4) to (6-12).
4. The method for preparing a hollow bowl-shaped carbon carrier according to claim 1, wherein the mixing time in the step a is 1-4 h.
5. The method for preparing a hollow carbon bowl as claimed in claim 1, wherein in the step b, the first component is m-aminophenol and the second component is formaldehyde.
6. The method for preparing a hollow carbon support bowl according to claim 1, wherein the dried solid product is ground to 0.15 to 5 μm before carbonization and activation in the step c.
7. The method for preparing a hollow carbon bowl according to claim 1, wherein in the step c, the inert atmosphere is provided with a gas comprising at least one of nitrogen or argon.
8. The method for preparing a hollow carbon carrier bowl as claimed in claim 1, wherein in the step c, the carbonization temperature is 600-.
9. The method for preparing a hollow carbon bowl according to claim 1, wherein in the step c, the oxidizing atmosphere comprises at least one of air, oxygen, carbon dioxide or water vapor.
10. The method as claimed in claim 1 or 9, wherein the activating temperature is 600-1200 ℃ and the treating time is 0.5-4h after the oxidizing atmosphere is switched to step c.
11. The method for producing a hollow bowl-shaped carbon carrier according to claim 1, wherein in the step c, the carbonization and activation treatment is performed by using a rotary sintering furnace.
12. The method for producing a hollow carbon bowl-shaped carrier according to claim 11, wherein the rotation function of the rotary sintering furnace is started at a rotation speed of 10 to 50rpm after the oxidizing atmosphere is switched to the step c.
13. The method for preparing a hollow carbon bowl according to claim 1, wherein the hydrofluoric acid aqueous solution is 5 to 15% by mass in the step d.
14. The method for preparing a hollow carbon bowl as claimed in claim 1, wherein the stirring time of the sintered product in the hydrofluoric acid aqueous solution in the step d is 10-36 h.
15. A hollow bowl-shaped carbon support, characterized in that it is obtained by the process according to any one of claims 1 to 14.
16. The hollow bowl-shaped carbon support of claim 15, wherein the wall thickness of the hollow bowl-shaped carbon support is 10-20 nm.
17. The hollow carbon bowl as claimed in claim 15, wherein the specific surface area of the hollow carbon bowl is 500-1800m2/g。
18. A platinum-based catalyst comprising the hollow bowl-shaped carbon support of any one of claims 15 to 17.
19. The platinum-based catalyst of claim 18, wherein the platinum loading of the platinum-based catalyst is greater than or equal to 30%.
20. Platinum-based catalyst according to claim 18, characterized in that the crystallite diameter of the platinum in the platinum-based catalyst is between 2 and 5 nm.
21. A method for preparing a platinum-based catalyst according to any one of claims 18 to 20, comprising the steps of adding the hollow bowl-shaped carbon carrier into a dispersing agent for dispersion, then adding a platinum-containing precursor for continuous dispersion, adding a reducing agent for stirring, reacting, washing and drying to obtain the platinum-based catalyst.
22. The method of preparing a platinum-based catalyst according to claim 21, wherein the dispersant comprises at least one of water, ethanol, ethylene glycol, isopropanol, or n-propanol; the platinum-containing precursor comprises at least one of chloroplatinic acid, platinum nitrate, platinum acetylacetonate, sodium chloroplatinate or potassium chloroplatinate; the reducing agent comprises at least one of ascorbic acid, methanol, ethylene glycol, ethanol, sodium borohydride, hydrazine hydrate, formaldehyde or formic acid.
23. A membrane electrode comprising a platinum-based catalyst according to any one of claims 18 to 20 or a platinum-based catalyst obtainable by a process according to claims 21 to 22.
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