CN107069049A - A kind of mesoporous polypyrrole nano-rings loaded Pt catalyst and preparation method thereof - Google Patents
A kind of mesoporous polypyrrole nano-rings loaded Pt catalyst and preparation method thereof Download PDFInfo
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- CN107069049A CN107069049A CN201710229425.3A CN201710229425A CN107069049A CN 107069049 A CN107069049 A CN 107069049A CN 201710229425 A CN201710229425 A CN 201710229425A CN 107069049 A CN107069049 A CN 107069049A
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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
- H01M4/9008—Organic or organo-metallic compounds
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- 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 present invention is a kind of mesoporous polypyrrole nano-rings loaded Pt catalyst and preparation method thereof.The composition of the catalyst includes the Pt nano particles of polypyrrole material and load, and Pt load quality percentage is 20% 50%；Wherein, described carrier polypyrrole material has hierarchical porous structure, i.e., be the meso-hole structure that aperture is 2 10nm in 200~500nm, the nanometer cyclic structure and hole wall that wall thickness is 30 60nm containing internal diameter.Present invention process is simple, and prepared polypyrrole material, which compares the polypyrrole prepared with electropolymerization method, has higher specific surface area, can be applied to such as gas sensing, catalysis, separation field.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous polypyrrole nano-rings supporting Pt nanoparticle catalyst, belong to Pt and urge
Agent technical field.
Background technology
As the mankind increasingly increase the demand of the energy, world energy sources crisis is also on the rise, and how fully to develop and profit
With cleaning new energy, mitigate and prevent the pollution of the environment and the destruction to ecology, it has also become the topic that the mankind pay close attention to.Direct first
Alcohol fuel battery (Direct Methanol Fuel Cell, DMFC), because of the easily transport of its fuel and storage, lightweight, volume
Small, energy density is big, transformation efficiency is high and the advantage such as pollution-free, in recent years the research heat as new energy field in the world
Point.Although recent decades DMFC research achieves significant progress, real large-scale commercial applications application is also not implemented.DMFC
It is to develop high performance, long-life catalyst to realize one of commercialized key technology.At present, platinum carbon catalyst is still to make
Use widest catalyst.However, in the long-time course of reaction of fuel cell, carbon carrier is easily corroded and causes structure
Cave in, thus cause the migration of Pt nano-particles, reunion, or even from catalyst system separate, influence catalyst activity and
Life-span.To solve the problems, such as carbon corrosion, people start the material more resistant to electrochemical corrosion sight steering, carried in this, as catalyst
Body, such as conducting metal oxide and conducting polymer.Wherein, polypyrrole has the advantages that high conductivity, synthesizes simple, is considered as
It is one of substitute of most promising catalyst carrier.
To improve Pt utilization rates, researcher is directed to developing new, and the polypyrrole material of nanostructured is urged as Pt
The backing material of agent.Nanometer ring-type polypyrrole material has high surface area-volume factor because of it, can provide more preferable biography
Matter passage, so as to improve the catalytic efficiency of the Pt catalyst of load thereon.However, the relatively low specific surface area of polypyrrole have impact on Pt
Disperseing for nano particle, reduces electro-catalysis effect.Meso-hole structure is added on the hole wall of polypyrrole nano-rings and forms multistage knot
Structure polypyrrole material, can be preferably applied for methanol fuel cell to a certain extent.The cyclic structure of this polypyrrole material
Resistance to mass tranfer can be effectively reduced, contributes to the diffusion of reactant and product, molecule can be made to be accessible to active sites, and is situated between
Pore structure can provide higher specific surface area and larger pore volume, so the polypyrrole material of this multilevel hierarchy can as carrier
So that catalyst has higher catalytic efficiency.
In view of mesoporous polypyrrole nano-rings possess huge prospect in terms of catalysis, the present invention provides a kind of new synthesis side
Method, is hard template using silicon dioxide microsphere, and one-step synthesis goes out the mesoporous polypyrrole nanometer ring material with high-specific surface area, born
Carry and the mesoporous polypyrrole nano-rings load with good stability, catalytic activity and mithridatism has been prepared after Pt nano particles
Pt catalyst.
The content of the invention
There is low, easy poisoning of activity etc. it is an object of the invention to the platinum carbon catalyst for commercial methanol fuel cell to lack
There is provided mesoporous polypyrrole nano-rings loaded Pt catalyst material that a kind of activity is high, antitoxin performance is good and preparation method thereof for point.Should
Material possesses the meso-hole structure on cyclic structure and hole wall.Meso-hole structure can strengthen Pt nano particles with increasing specific surface area
Dispersiveness, limit Pt nano particles growth and catalytic process in reunion, cyclic structure can be with mass transfer enhancement.Titanium dioxide
Silicon microballoon can not only be used for the guiding agent of cyclic structure, can make to gather with pyrroles's interaction in the polymerization process of pyrroles again
Pyrroles forms meso-hole structure on silicon dioxide sub-micron sphere surface.In preparation method, Gao Bibiao is prepared using chemical method polymerization
Area (>100m2g-1) polypyrrole material, using silicon dioxide microsphere (200-500nm) be template form mesoporous ring-type pattern,
By controlling the use of silica volume, to obtain a nanometer ring-shaped material.
The technical solution adopted by the present invention is：
A kind of mesoporous polypyrrole nano-rings loaded Pt catalyst, it is characterised in that the composition of the catalyst includes polypyrrole material
Material and the Pt nano particles of load, Pt load quality percentage is 20%-50%；Wherein, described carrier polypyrrole material
With hierarchical porous structure, i.e., it is 200~500nm containing internal diameter, wall thickness is aperture in 30-60nm nanometer cyclic structure and hole wall
For 2-10nm meso-hole structure.
The particle diameter of described Pt nano particles is less than 3.0nm；Preferably 1.5~2.5nm.
The preparation method of described mesoporous polypyrrole nano-rings loaded Pt catalyst, comprises the following steps：
(1) silicon dioxide microsphere colloidal sol is prepared：UtilizeMethod prepares monodispersed silicon dioxide microsphere, by titanium dioxide
Silicon microballoon is distributed in the aqueous solution, prepares the monodispersed silica spheres microballoon colloidal sol that mass fraction is 10%；
(2) mesoporous polypyrrole nanometer ring material is prepared：Pyrroles and sodium acetate dissolving are added in deionized water, then
The silicon dioxide microsphere colloidal sol that one step is prepared, is eventually adding 0.2M FeCl3The aqueous solution, in ice-water bath react 10~
15h, reaction is centrifuged after terminating, the once purged compound for obtaining polypyrrole and silica；Again by polypyrrole and
The compound of silica soaks 12-24h in HF solution, through over cleaning, obtains mesoporous polypyrrole nanometer ring material；
Wherein, 0.10-0.15g pyrroles and 0.1-0.3g sodium acetates, and 2-10mL are added in every 5-10mL deionized waters
Silicon dioxide microsphere colloidal sol and 10mL FeCl that previous step is prepared3The aqueous solution；
(3) mesoporous polypyrrole nano-rings loaded Pt catalyst is prepared：By mesoporous polypyrrole nanometer ring material obtained above
It is immersed in the ethanol solution of chloroplatinic acid；After ultrasonic disperse 10-15min, dry at room temperature；Then by hydrogen reducing, obtain
To mesoporous polypyrrole nano-rings loaded Pt catalyst；
Wherein, mass ratio is mesoporous polypyrrole nanometer ring material：Pt=1-4：1；The concentration of described platinum acid chloride solution is
45~55wt%.
In described step (3) is specially mixed gas of the product after drying in hydrogen and nitrogen by hydrogen reducing
Under, hydrogen volume content is 3~6%, 145~155 DEG C of 1~3h of reaction.
The sphere diameter of microballoon is 200~500nm in described monodispersed silicon dioxide microsphere colloidal sol.
The concentration of described HF solution is 5wt%.
Beneficial effects of the present invention are：
Two kinds of ducts (polypyrrole nanometer can be completed using a step template chemical polymerization using the preparation method of the present invention
It is mesoporous on the macropore and hole wall of ring structure) preparation, not only technique is simple but also prepared polypyrrole material is compared and voltolisation
Polypyrrole prepared by conjunction method has higher specific surface area (118.5m2g-1).This catalyst show as higher catalytic activity and
Good antitoxin performance.Compared with business platinum carbon catalyst, catalytic activity enhances 1.9 times, and antitoxin performance enhances 1.5 times.
Meanwhile, the polypyrrole with high electrocatalytic active can be prepared by supporting Pt nano particle and carry Pt catalyst.
In addition, the method can adjust the inner ring of mesoporous polypyrrole nano-rings by controlling the sphere diameter of silicon dioxide microsphere
Aperture.
By above the characteristics of it can be seen from the obtained mesoporous polypyrrole nano-rings of the present invention except can supporting Pt nano particle
Applied to fuel cell field, such as gas sensing, catalysis, separation field are applied also for.
Brief description of the drawings
The adsorption/desorption isotherms and graph of pore diameter distribution (illustration) of mesoporous polypyrrole nano-rings prepared by Fig. 1 embodiments 1；
The SEM figures of mesoporous polypyrrole nano-rings prepared by Fig. 2 embodiments 2；
The TEM figures of mesoporous polypyrrole nano-rings prepared by Fig. 3 embodiments 3；
The SEM figures of polypyrrole material prepared by Fig. 4 embodiments 4；
The SEM figures of polypyrrole material prepared by Fig. 5 embodiments 5；
The TEM figures of the nano-rings loaded Pt catalyst of polypyrrole material prepared by Fig. 6 embodiments 6；
The thermogravimetric curve figure of mesoporous polypyrrole nano-rings loaded Pt catalyst prepared by Fig. 7 embodiments 7；
The XRD of mesoporous polypyrrole nano-rings loaded Pt catalyst prepared by Fig. 8 embodiments 8；
Mesoporous polypyrrole nano-rings loaded Pt catalyst and business platinum carbon catalyst prepared by Fig. 9 embodiments 8 is in 0.5M
H2SO4+1M CH3Cyclic voltammetry curve in OH solution；Sweep speed is 50mv s-1。
Embodiment
The method of the present invention is further described below in conjunction with example.These examples have further described and demonstrated this
Embodiment in invention scope.The purpose that the example provided is merely to illustrate, but this is not limited to, the present invention should not be constituted
It is any to limit, without departing from the spirit and scope of the present invention various changes can be carried out to it.
The silicon dioxide microsphere colloidal sol that is related to of present invention hair is known material, its preparation may refer to (W,et
al.Controlled growth of monodisperse silica spheres in the micron size
range.Journal of Colloid&Interface Science,1968,26(1):62-69)。
Embodiment 1
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step is as follows：
1) 9.0g deionized waters, 30.8mL ammoniacal liquor and 160mL absolute ethyl alcohols are well mixed under magnetic stirring stand-by.
2) ethanol solution for the tetraethyl orthosilicate (TEOS) that configuration 200mL contains 17.5g rapidly joins step 1) configuration
In solution.Magnetic agitation obtains white emulsion after reacting 12 hours at 25 DEG C.
3) by step 2) in obtained white emulsion silicon dioxide microsphere is obtained by way of centrifugation (sphere diameter is
350nm), silica spheres ultrasonic disperse is prepared into silica spheres colloidal sol, the matter of silicon dioxide microsphere into deionized water
Measure as the 10% of colloidal sol quality.
4) 0.13g pyrroles and 0.16g sodium acetates are added in 5mL water, step 3 is then added) silica for preparing is micro-
Ball colloidal sol 5mL, is eventually adding 0.2mol L-1FeCl3Aqueous solution 10mL reacts 12h as oxidant in ice-water bath.Will be anti-
Should after obtained black suspension is centrifuged, deionized water cleaning obtains the compound of polypyrrole and silica.
5) by step 4) compound of obtained polypyrrole and silica soaks 24h in 5wt% HF solution and removes
Silica template, is then cleaned multiple times product with ethanol and deionized water, finally obtains mesoporous polypyrrole nanometer ring material.
6) by the step 5 of certain mass) in obtained mesoporous polypyrrole nanometer ring material immersion chloroplatinic acid ethanol solution
(50wt%), wherein, polypyrrole material and Pt mass ratio are 1:1, then ultrasonic disperse 10-15min, and drying in the air at room temperature
It is dry.
7) hydrogen (percent by volume) and the mixed gas of 96% nitrogen by the sample after being dried in 6) step 4%
In, mesoporous polypyrrole nano-rings loaded Pt catalyst has just been obtained after reductase 12 h at 150 DEG C.
Fig. 1 show the adsorption/desorption isothermal curve of mesoporous polypyrrole nano-rings made from this example, and pore-size distribution
Curve (PSD) (illustration).Calculated from adsorption/desorption isothermal curve and obtain the BET specific surface areas of mesoporous polypyrrole nano-rings and be
118.5m2g-1, illustrate that mesoporous polypyrrole nano-rings possess larger specific surface area.From PSD it can be seen from the figure thats, this example is made
Standby polypyrrole material has meso-hole structure, and pore-size distribution is in 2-10nm.From the foregoing, it will be observed that polypyrrole material made from the present embodiment
Truly have meso-hole structure.
Embodiment 2
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step be the same as Example 1, except that step
2) TEOS amount is 8.5g in, and the sphere diameter of prepared silicon dioxide microsphere is 280nm.
Fig. 2 show the SEM pictures of mesoporous polypyrrole nano-rings made from this example, and as can be seen from the figure sample has very
Good cyclic structure, and it is dispersed.Sample annular diameters can be measured from illustration for 280nm, wall thickness 60nm.Nano-rings
Internal diameter size is consistent with the sphere diameter of silicon dioxide microsphere in silica template.
Embodiment 3
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step be the same as Example 1, except that step
2) TEOS amount is 21.5g in, and the sphere diameter of prepared silicon dioxide microsphere is 450nm.
Fig. 3 show the TEM pictures of mesoporous polypyrrole nano-rings made from this example, and as can be seen from the figure sample has very
Good cyclic structure, and it is dispersed.Can be seen that hole wall from the enlarged drawing of the single polypyrrole nano-rings in illustration has mesoporous
Structure is present.
Embodiment 4
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step be the same as Example 1, except that step
4) addition of silicon dioxide microsphere is 3mL in.
Fig. 4 is the SEM pictures of polypyrrole material made from the present embodiment.It can be seen that due to adding titanium dioxide
The amount of silicon microballoon is reduced so that polypyrrole has largely been wrapped in silicon dioxide microsphere surface, forms aggregating state, this reunion
Polypyrrole be not easy to disperse, be unfavorable for electrochemical applications.
Embodiment 5
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step be the same as Example 1, except that step
4) addition of silicon dioxide microsphere is 7mL in.
Fig. 5 is the SEM pictures of polypyrrole material made from the present embodiment.It can be seen that due to adding titanium dioxide
The amount of silicon microballoon increases, polypyrrole can not fully wrapped around silicon dioxide microsphere surface, cause polypyrrole in HF etching processes
Fracture, formed semicircular.Therefore the present invention preferably silica addition is 5mL.
Embodiment 6
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step be the same as Example 1, except that step
6) carbon material and Pt mass ratioes are 2 in:1.
Fig. 6 is mesoporous polypyrrole nano-rings loaded Pt catalyst made from the present embodiment (load capacity is about 33wt%)
TEM pictures, as can be seen from the figure the structure of pyrroles's nano-rings is still still high-visible after supporting Pt nano particle, and this is conducive to
The quick diffusion of catalyst reactant and product in catalytic process.
Embodiment 7
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step be the same as Example 1, except that step
6) carbon material and Pt mass ratioes are 3 in:1.Fig. 7 is the thermal gravimetric analysis curve of mesoporous polypyrrole nano-rings supporting Pt material.Can be with
Find out, polypyrrole material starts to decompose at 200 DEG C, is decomposed completely to 600 DEG C, in the process about weightlessness 75wt%, explanation
Pt content is about 25wt%, it was demonstrated that chloroplatinic acid is reduced into Pt completely in hydrogen reduction, does not almost lose.
Embodiment 8
The preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst, step be the same as Example 1, except that step
6) carbon material and Pt mass ratioes are 4 in:1.Fig. 8 is mesoporous polypyrrole nano-rings loaded Pt catalyst (Pt made from the present embodiment
Load capacity is 20wt%) X ray diffracting spectrum (XRD).The XRD spectrum of sample has a broad peak between 20 degree to 30 degree, this
It is the characteristic peak of polypyrrole.In addition, occur obvious Pt (111) in XRD spectrum, Pt (200), Pt (220) and Pt (311) four
Characteristic peak, illustrates that the chloroplatinic acid of polypyrrole carrier surface absorption has been reduced sufficiently as the intact Pt particles of crystallinity.From figure
The Pt grains size that the half-peak breadth in middle Pt (220) face can calculate loaded Pt catalyst is 2.2nm, the formation of little crystal grain
It is due to the mesoporous growth for limiting Pt particles.XRD diffraction patterns contain the characteristic peak of polypyrrole, it may have Pt characteristic peak,
Illustrate material manufactured in the present embodiment not only comprising polypyrrole material but also comprising Pt nano particles.Fig. 9 urges to be manufactured in the present embodiment
Agent and business platinum carbon catalyst (Johnson Matthey companies, model：HiSPEC 3000) in 0.5M H2SO4+1M
CH3Cyclic voltammetry curve in OH solution；Sweep speed is 50mv s-1.This experiment utilizes the glass-carbon electrode for having loaded catalyst
For working electrode, Ag/AgCl (saturated potassium chloride solution) is reference electrode, and platinized platinum is the three-electrode system constituted to electrode.From
It can be seen that the peak current density at 0.69V is 286.8mA mg in Fig. 9-1, it is the peak current density of business platinum carbon catalyst
(148.7mA mg-1) 1.9 times, illustrate that there is the double mesoporous carbon-loaded Pt catalyst of prepared three-dimensional order higher methanol to urge
Change oxidation activity.Also, the peak current density I of forward potential scanningfWith the peak current density I of negative sense electric potential scanningbRatio be
1.23 (this numerical value represents the higher anti-CO of explanation of the oxidized degree of the intermediate product CO produced in methanol oxidation process, i.e. numerical value
The performance of poisoning is better), show prepared catalyst and business platinum carbon catalyst (If/Ib=0.84) compare, resist with higher
Toxicity energy.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. a kind of mesoporous polypyrrole nano-rings loaded Pt catalyst, it is characterised in that the composition of the catalyst includes polypyrrole material
With the Pt nano particles of load, Pt load quality percentage is 20%-50%；Wherein, described carrier polypyrrole material tool
There is hierarchical porous structure, i.e., be that aperture is in 200~500nm, the nanometer cyclic structure and hole wall that wall thickness is 30-60nm containing internal diameter
2-10nm meso-hole structure；
The particle diameter of described Pt nano particles is less than 3.0nm.
2. mesoporous polypyrrole nano-rings loaded Pt catalyst as claimed in claim 1, it is characterised in that described Pt nanometers
The particle diameter of grain is preferably 1.5~2.5nm.
3. the preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst as claimed in claim 1, it is characterized in that including with
Lower step：
(1) silicon dioxide microsphere colloidal sol is prepared：UtilizeMethod prepares monodispersed silicon dioxide microsphere, and silica is micro-
Ball is distributed in the aqueous solution, prepares the monodispersed silica spheres microballoon colloidal sol that mass fraction is 10%；
(2) mesoporous polypyrrole nanometer ring material is prepared：By pyrroles and sodium acetate dissolving in deionized water, previous step is then added
Suddenly the silicon dioxide microsphere colloidal sol prepared, is eventually adding 0.2M FeCl3The aqueous solution, reacts 10~15h, instead in ice-water bath
It is centrifuged after should terminating, the once purged compound for obtaining polypyrrole and silica；Again by polypyrrole and titanium dioxide
The compound of silicon soaks 12-24h in HF solution, through over cleaning, obtains mesoporous polypyrrole nanometer ring material；
Wherein, 0.10-0.15g pyrroles and 0.1-0.3g sodium acetates, and 2-10mL upper one are added in every 5-10mL deionized waters
Silicon dioxide microsphere colloidal sol and 10mL FeCl that step is prepared3The aqueous solution；
(3) mesoporous polypyrrole nano-rings loaded Pt catalyst is prepared：By mesoporous polypyrrole nanometer ring material immersion obtained above
Into the ethanol solution of chloroplatinic acid；After ultrasonic disperse 10-15min, dry at room temperature；Then by hydrogen reducing, it is situated between
Hole polypyrrole nano-rings loaded Pt catalyst；
Wherein, mass ratio is mesoporous polypyrrole nanometer ring material：Pt=1-4：1；The concentration of described platinum acid chloride solution be 45~
55wt%.
4. the preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst as claimed in claim 3, it is characterized in that described
In step (3) by hydrogen reducing be specially product after drying under the mixed gas of hydrogen and nitrogen, hydrogen volume contains
Measure as 3~6%, 145~155 DEG C of 1~3h of reaction.
5. the preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst as claimed in claim 3, it is characterized in that described
The sphere diameter of microballoon is 200~500nm in monodispersed silicon dioxide microsphere colloidal sol.
6. the preparation method of mesoporous polypyrrole nano-rings loaded Pt catalyst as claimed in claim 3, it is characterized in that described
The concentration of HF solution is 5wt%.
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| CN110350142A (en) * | 2019-06-28 | 2019-10-18 | 浙江大学 | The sodium electrode of integrated Porous Polypyrrole load and the preparation method of sulfur electrode |
| CN108992419B (en) * | 2018-06-27 | 2021-05-04 | 南京师范大学 | Mesoporous-macroporous nano motor and preparation method and application thereof |
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