CN106784900A - CNT of platinum base nano particle cladding tin ash covering and preparation method thereof - Google Patents
CNT of platinum base nano particle cladding tin ash covering and preparation method thereof Download PDFInfo
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- CN106784900A CN106784900A CN201611140644.6A CN201611140644A CN106784900A CN 106784900 A CN106784900 A CN 106784900A CN 201611140644 A CN201611140644 A CN 201611140644A CN 106784900 A CN106784900 A CN 106784900A
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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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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Abstract
CNT the present invention relates to a kind of cladding tin ash covering of platinum base nano particle and preparation method thereof, wherein, the CNT is multi-walled carbon nano-tubes, and one layer of tin ash is loaded on the carbon nanotubes, and one layer of platinum base metal is loaded on the tin dioxide layer.The platinum base metal exists in the form of nano particle, and connects into network structure.Catalyst of the invention, noble metal utilisation is high, the catalysis activity of catalyst, life-span and resisting CO poisoning performance are high, the activity of its catalysis oxidation methyl alcohol is more than 6.2 times of business Pt/C catalyst, and its hydrogen reduction mass activity in hydrogen scalar potential 0.9V is 9.6 times of business Pt/C catalyst.Its granularity preferably between 1.0 to 10.0nm, and preferably between 2.0 to 4.0nm.
Description
Technical field
The present invention relates to fuel-cell catalyst field, specifically refer to coat two for the platinum base nano particle of fuel cell
CNT of tin oxide covering and preparation method thereof.
Background technology
Fuel cell be it is a kind of the chemical energy of fuel directly can be transformed into efficiently and cleanly the device of electric energy, be
A kind of more satisfactory generation technology.Because fuel cell is at aspects such as vehicle power source, various portable power sources, Military Powers
Wide application prospect, therefore the research of fuel cell receives the great attention of various countries.
Run into some problems during current commercializing fuel cells, wherein it is the most prominent be catalyst price it is high,
Natural reserves are few, active low and short life.For the fuel cell with reformation gas as fuel, also there is catalyst and be easily poisoned mistake
Problem living.And these problems all have with the performance of catalyst and closely contact, therefore developmental research high-performance of new generation
Fuel-cell catalyst is for promoting the research and development of fuel cell significant.
Catalyst material as one of the most key material of fuel cell, its preparation method mainly have immersion reduction method,
Ion-exchange, the precipitation method, gas phase reduction process, microwave method, colloid method etc., but these methods can not control to urge well sometimes
The particle diameter of the active component of agent and the surface and interface structure of nano grain surface, it is difficult to which it is controllable to obtain surface and interface component, activearm
Divide high degree of dispersion, granularity small and disperse highly uniform platinum base nanocatalyst.
The applicant discloses a kind of CNT (Pt/ for being loaded with platinum base metal in patent CN105655607
MWCNTs).The mass activity of its catalysis oxidation methyl alcohol is 4.4 times of business platinum carbon (Johnson Matthey companies) catalyst.
Although above-mentioned catalyst improves in terms of stability and anti-poisoning capability relative to business platinum carbon.But its quality is lived
Property, stability and anti-poisoning capability are still not ideal enough, it is necessary to further improve its performance.
The content of the invention
Shortcoming and defect it is an object of the invention to overcome above-mentioned prior art, there is provided a kind of size tunable, surface and interface
Controllable, high dispersive and high activity, anti-poisoning capability are strong, and stability is high, the platinum base nanometer for fuel cell with low cost
CNT of grain cladding tin ash covering and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
A kind of CNT with two-layer load, it is characterised in that the CNT is multi-walled carbon nano-tubes, in institute
One layer of tin ash of load on CNT is stated, one layer of platinum base metal is loaded on the tin dioxide layer.
According to the present invention, the tin ash is tin oxide nano particles.Its granularity preferably 1.0 to 10.0nm it
Between, and preferably between 2.0 to 6.0nm.
According to the present invention, the platinum base metal exists in the form of nano particle.Its granularity is preferably in 1.0 to 10.0nm
Between, and preferably between 2.0 to 4.0nm.The platinum base metal nanoparticle links together, and forms platinum base metal nano
Grain network structure.According to the present invention, the platinum base metal is Pt or platinum base alloy, and the platinum base alloy is Pt and one or more
The alloy that other metals are formed, described other metals can be one or more in Rh, Ru, Ir, Cu, Ni.The platinum base metal
Can also be a kind of core shell structure, kernel is platinum base alloy, and shell is that platinum or platinum and other metals for being insoluble in acid are formed
Alloy.
In another preferred embodiment of the invention, the platinum base metal can be closed for Pt, Pt-Rh alloy, Pt-Ru
Gold, Pt-Cu alloys, Pt-Ru-Cu alloys, Pt-Ru-Rh-Ni alloys, Pt-Cu@Pt (kernel is Pt-Cu alloys, and shell is platinum).
Present invention also offers a kind of preparation method of the above-mentioned CNT with two-layer load, including：
(1) multi-walled carbon nano-tubes is dispersed in concentrated nitric acid, reaction obtains many walls of functionalization (hydroxylating and carboxylated)
CNT；
(2) the function multi-walled carbon nano-tube mixing that will be obtained in stannous chloride, water, urea and step (1), reaction is obtained
The multi-walled carbon nano-tubes of tin oxide nano particles covering；
(3) many wall carbon of the tin oxide nano particles covering that will be obtained in corresponding platinum base metal precursor, step (2)
Nanotube and solvent mix, and obtain mixture；
(4) (a) mixes formic acid with step (3) gained mixture, and reaction obtains the covering of platinum base metallic cover tin ash
CNT.Or, the mixed liquor of step (3) gained mixture NaOH and alcohol is adjusted to alkalescence by (b), is being heated back
Stream obtains the CNT of platinum base metallic cover tin ash covering.
According to the present invention, in the step (1), multi-walled carbon nano-tubes back flow reaction in concentrated nitric acid, the backflow
Temperature is, for example, 120-200 DEG C, preferably 140-180 DEG C.
According to the present invention, in the step (2), the temperature of the reaction is preferably 60-100 DEG C, more preferably 90-100
DEG C, for example, 95 DEG C.The reaction time is preferably 8-16 hours.Preferably, by stannous chloride, water, in urea and step (1)
The function multi-walled carbon nano-tube mixing ultrasound for obtaining, is then refluxed for being reacted, and reflux temperature is, for example, 95 DEG C, return time
For example, 12 hours.Reaction carries out cold filtration after terminating.
According to the present invention, in the step (3), the platinum base metal precursor is platinum base slaine, such as chlorate, sulphur
Hydrochlorate, nitrate etc., by taking Pt as an example, its presoma can be H2PtCl6·6H2O；By taking Pt-Cu alloys as an example, its presoma can be
H2PtCl6·6H2O and CuSO4·5H2O.The solvent can be ethylene glycol, water etc..
According to the present invention, in step (3), the mol ratio of the platinum base metal precursor is adjusted in required ratio and carrying capacity
Control.
According to the present invention, in the step (4) (a), the reaction is carried out in a solvent, the solvent can for water, methyl alcohol,
Ethanol etc..The reaction temperature is preferably 60-130 DEG C, preferably 90-120 DEG C.The reaction is carried out in a nitrogen atmosphere.It is preferred that
, step (3) gained mixture is heated to 90 DEG C, the mixed liquor of formic acid and ethylene glycol is added dropwise, stirred back in nitrogen atmosphere
Stream obtains the CNT of the platinum base metallic cover tin ash covering after a period of time.
According to the present invention, in the step (4) (b), the alcohol is ethylene glycol, glycerine etc..The heating-up temperature is 150
More than DEG C, preferably 160-250 DEG C, the heating can be oil bath heating, or heating using microwave.It is described to be heated to reflux in nitrogen
Carried out in gas atmosphere.For example, the mixed liquor of step (3) gained mixture NaOH and ethylene glycol is adjusted to alkalescence, 160
Flowed back more than DEG C and in nitrogen atmosphere and obtain the CNT of the platinum base metallic cover tin ash covering.
According to the present invention, in the step (4), step (3) gained mixture is heated under stirring and nitrogen protection, so
Naturally cool to room temperature again afterwards.
According to the present invention, in the step (4), the mixture suction filtration of room temperature will be naturally cooled to, washed, dried, obtained
The catalyst.It is preferred that washing with water.Preferably, it is dried under vacuum, then cools down again, grind, obtains the catalyst.
The further preferred preparation method of the present invention is as follows：
A kind of preparation method of the CNT with two-layer load, including：
(1) multi-walled carbon nano-tubes is mixed with concentrated nitric acid, is flowed back, obtain many wall carbon of functionalization (hydroxylating and carboxylated)
Nanotube；
(2) by stannous chloride, water, the function multi-walled carbon nano-tube mixing ultrasound obtained in urea and step (1), then
Cold filtration after being refluxed 12 hours at 95 DEG C, obtains the multi-walled carbon nano-tubes of tin oxide nano particles covering；
(3) many wall carbon of the tin oxide nano particles covering that will be obtained in corresponding platinum base metal precursor, step (2)
Nanotube and ethylene glycol mix, ultrasound, obtain mixture, and the mol ratio and carrying capacity of platinum base metal precursor are in required ratio
Regulation and control；
(4) under nitrogen protection, step (3) gained mixture is mixed with the mixed liquor of formic acid and ethylene glycol, is heated back
Stream more than 10 hours, temperature control is between 90 to 100 degrees Celsius；Then cooling, suction filtration, washing, drying, obtains the platinum base
The CNT of nano particle cladding tin ash covering.
The present invention still further provides the purposes of the above-mentioned CNT with two-layer load, and it is used for fuel cell.
The present invention has loaded tin dioxide layer and platinum base nano-particle layer and in platinum base from inside to outside on the carbon nanotubes
In nano-particle layer, network structure is connected between the platinum base metal nanoparticle, therefore, on the one hand received by platinum base metal
The quality catalysis activity of active component platinum and the catalytic stability of platinum are improved in interface between rice grain, on the other hand by described
Improve the catalytic stability of active component platinum and an anti-oxidation in interface between tin oxide nano particles and platinum base nano particle
Carbon poisoning capability.
The present invention compared with prior art, at least has the following advantages that and beneficial effect：
(1) catalyst of the CNT covered the invention provides class platinum base nano particle cladding tin ash, its
Catalysis activity, the life-span of platinum can not only be improved；Simultaneously also by connecing between platinum base nano particle and tin oxide nano particles
Contacting surface collaboration improves the catalytic life and anti-poisoning capability of platinum.The peak current density of the catalyst Oxidation of Methanol is
6.2 times of the high-performance Pt/C catalyst of Johnson Matthey companies.Oxygen reduction activity is business in hydrogen scalar potential 0.9V
9.6 times of Pt/C catalyst
(2) formic acid low-temperature reduction or heating alcohol reducing process are used, active component particles degree can be obtained in 2.0 to 4.0nm
Between high activated catalyst, the distribution of particle sizes of active component is extremely uniform, effectively increases the utilization rate of noble metal.
(3) CNT of the platinum base nano particle cladding tin ash covering of synthesis, platinum base nano particle is in one-dimensional more
Hole platinum base Specific surface area, platinum base nano particle is coated on the surface of tin oxide nano particles, effectively increases urging for platinum
Change life-span and resisting CO poisoning ability.
(4) catalyst is prepared using formic acid reducing process or heating alcohol reducing process, process is simple is environment-friendly, is reclaimed
Rate is high, reduces catalyst cost.
Brief description of the drawings
Fig. 1 is MWCNTs@SnO prepared by embodiment 12The XRD spectra of@Pt catalyst, MWCNTs is many walls of functionalization
The English abbreviation of CNT；
Fig. 2 is MWCNTs@SnO prepared by embodiment 12The ESEM and transmission electron microscope of the building-up process of@Pt catalyst
Picture.A, b are MWCNTs, and c, d are MWCNTs@SnO2, e, f are MWCNTs@SnO2@Pt, illustration is respective electron diffraction diagram；
Fig. 3 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst and business Pt/C catalyst are in 0.5mol/L H2SO4
+0.5mol/L CH3Cyclic voltammetry spectrum in OH solution；
Fig. 4 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst and business Pt/C catalyst are in 0.5mol/L H2SO4
Carbon monoxide cycle voltammogram in solution.
Fig. 5 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst is in 0.5mol/L H2SO4+0.5mol/L CH3OH
Cyclic voltammetric stabilization collection of illustrative plates in solution
Fig. 6 is business Pt/C catalyst in 0.5mol/L H2SO4+0.5mol/L CH3Cyclic voltammetric stabilization in OH solution
Collection of illustrative plates.
Fig. 7 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst and business Pt/C catalyst are in 0.1mol/L HClO4
Linear scan collection of illustrative plates in solution under oxygen-saturated conditions.
Fig. 8 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst and business Pt/C catalyst are in 0.1mol/L HClO4
In solution under oxygen-saturated conditions by the linear scan collection of illustrative plates after 10000 stable circulations.
Fig. 9 is business Pt/C catalyst in 0.1mol/L HClO4Followed by 10000 times under oxygen-saturated conditions in solution
Linear scan collection of illustrative plates after ring stabilization.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.Any those skilled in the art, a little change and modification done on the basis of technical scheme,
So as to form new inventive technique scheme, still fall within the range of technical solution of the present invention.
Embodiment 1：CNT (the MWCNTs@SnO of platinum base nano particle cladding tin ash covering2@Pt, platinum in platinum,
Percentage by weight in tin ash and multi-walled carbon nano-tubes is preparation 86%)
(1) multi-walled carbon nano-tubes (MWCNTs) is dispersed in concentrated nitric acid, is reacted 10 hours in 140 degrees Celsius of oil bath
More than after cold filtration, dry after grinding obtain functionalization multi-walled carbon nano-tubes it is standby；
(2) by SnCl2·2H2O, urea, multi-walled carbon nano-tubes and the water of the functionalization of step (1) are stirred at room temperature 30
Make its fully dispersed more than minute, and continue ultrasound, obtain the solution shape mixed liquor of high degree of dispersion.Then in 90 degrees Celsius of oil
Cold filtration after 10 hours is refluxed in bath.Obtain the material that tin ash covers CNT.
(3) H2PtCl6·6H2O and the multi-walled carbon nano-tubes of step (2) gained tin ash covering are distributed to ethylene glycol
Ultrasound, leads to nitrogen deoxygenation, while logical upper condensed water, and stir 30 minutes；H2PtCl6·6H2The also commercial weight of O is more in tin ash
Accounting is 86% in the weight of wall carbon nano tube and Pt；
(4) mixed liquor of formic acid and ethylene glycol is added drop-wise in step (3) resulting solution, and is stirred at reflux at 90 degrees Celsius
More than 10 hours, then naturally cool to room temperature；
(5) by step (4) gained mixed solution vacuum filtration, filter cake redistilled water washes clean, and it is dry in vacuum
Dried in dry case 10 hours, cooling, grinding, so as to obtain the CNT of platinum base nano particle cladding tin ash covering
(MWCNTs@SnO2@Pt), this catalyst is the nanocatalyst with network loose structure.
MWCNTs@SnO manufactured in the present embodiment2The X-ray powder diffraction spectrogram of@Pt and business Pt/C catalyst is shown in Fig. 1；
It can be seen that platinum is pure phase in the material prepared in the present embodiment.
MWCNTs@SnO manufactured in the present embodiment2The ESEM and transmission electron microscope of@Pt catalyst synthesis processes are shown in Fig. 2,
Wherein a), b) be multi-walled carbon nano-tubes (MWCNTs), c), d) for tin ash covering multi-walled carbon nano-tubes (MWCNTs@
SnO2), it is e), f) CNT (the MWCNTs@SnO of platinum base nano particle cladding tin ash covering2@Pt)；Can be with from figure
Find out, Pt nanoparticle is evenly distributed in the material prepared in the present embodiment, and good crystallinity, Pt nanoparticle is all coated on dioxy
Change on tin, form the Pt nanoparticle network for interconnecting.
Further, the MWCNTs@SnO for being prepared to the present embodiment2The catalytic performance of@Pt catalyst is examined
Survey, also compared with business Pt/C catalyst (weight content is 20%), by comparing it can be seen that in the present embodiment
Catalyst has more preferable catalytic performance, and testing result is referring to Fig. 3-Fig. 7.
Fig. 3 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst and business Pt/C catalyst are in 0.5mol/L H2SO4
+0.5mol/L CH3Cyclic voltammetry spectrum in OH solution；It can be seen that the material catalysis oxidation prepared in the present embodiment
The mass activity of methyl alcohol is greatly improved, and is 6.2 times of business Pt/C.And the property of business Pt/C (20%) catalysis oxidation methyl alcohol
Can be relatively low, this is and the Pt nanoparticle in the catalyst that the present embodiment is obtained because Pt nanoparticle is single isolated presence
Network structure is formed, the contact mask between Pt nanoparticle and between Pt nanoparticle and tin oxide nano particles
There is the performance of good catalysis oxidation methyl alcohol.
Fig. 4 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst and business Pt/C catalyst are in 0.5mol/L H2SO4
Carbon monoxide cycle voltammogram in solution.Although it can be seen that the material load capacity prepared in the present embodiment is up to
86%, but the spike potential that rises of its CO catalytic oxidation is substantially reduced, only -400 millivolts, and business platinum carbon catalyst is 0 millivolt.
This is the platinum because Pt nanoparticle is evenly distributed on the tin ash for be coated with CNT in the material that the present embodiment synthesizes
Nano particle and tin oxide nano particles form good interracial contact, and Pt nanoparticle connects into network structure.
Fig. 5 is the Pt/MWCNTs catalyst of the preparation of embodiment 1 in 0.5mol/L H2SO4+0.5mol/LCH3In OH solution
Cyclic voltammetric stabilization collection of illustrative plates.It can be seen that the stability of the material catalysis oxidation methyl alcohol prepared in the present embodiment is obtained
To considerable degree of raising.After 10000 circulate, the mass activity of its catalysis oxidation methyl alcohol is also up to initial mass work
The 71% of property.
Fig. 6 is business Pt/C catalyst by after 6000 circulations, the mass activity of its catalysis oxidation methyl alcohol only has starting
The 39% of mass activity, the speed ratio material manufactured in the present embodiment of its performance degradation is much faster.
Fig. 7 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst and business Pt/C catalyst are in 0.1mol/L HClO4
Linear scan figure in solution under conditions of oxygen saturation.Although it can be seen that the material prepared in the present embodiment is born
Carrying capacity is up to 86%, but its hydrogen reduction mass activity in 0.9V hydrogen scalar potentials is 9.6 times of business platinum carbon catalyst.
Fig. 8 is MWCNTs@SnO prepared by embodiment 12@Pt catalyst is in 0.1mol/L HClO4Oxygen saturation in solution
Under the conditions of by the linear scan figure after 10000 cyclic voltammetrics.It can be seen that the material prepared in the present embodiment exists
By after the cyclic voltammetric of 10000 times, its half wave potential essentially unchangedization.This is because platinum is received in the material that the present embodiment synthesizes
Rice grain is evenly distributed on the tin ash for be coated with CNT, and Pt nanoparticle and tin oxide nano particles are formd
Good interracial contact, and Pt nanoparticle connects into network structure.
Fig. 9 is business Pt/C catalyst in 0.1mol/L HClO4By 10000 times under conditions of oxygen saturation in solution
Linear scan figure after cyclic voltammetric.The half wave potential of Pt/C catalyst is negative to move 20mV.
Embodiment 2：CNT (the MWCNTs@SnO of platinoid Core-shell Structure Nanoparticles cladding tin ash covering2@
Pt-Cu@Pt) preparation
(1) by H2PtCl6·6H2O、CuSO4·5H2O, the multi-walled carbon nano-tubes of tin ash covering and ethylene glycol are in room temperature
Lower stirring makes its fully dispersed in 30 minutes.The mol ratio of Pt and Cu is 1 in mixed solution：3；
(2) step (1) gained mixed solution alternating is stirred and ultrasonically treated, then uses NaOH ethylene glycol solution
It is 10 to adjust its pH value；
(3) step (2) gained mixed solution is continued that ultrasound and stirring is used alternatingly, until forming the dispersion of solution shape
Liquid；
(4) step (3) gained mixed solution is put into microwave reactor, leads to nitrogen deoxygenation, while logical upper condensed water, and
Stirring 30 minutes；
(5) step (4) resulting solution heating using microwave more than 3 minutes (more than 160 degree), room temperature is then naturally cooled to；
(6) by step (5) gained mixed solution vacuum filtration, filter cake redistilled water washes clean, and it is dry in vacuum
90 degrees Celsius of 10 hours of drying in dry case, cooling, grinding obtains sample MWCNTs@SnO2@Pt-Cu；
(7) step (6) gained sample is placed on after being stirred 30 minutes in 0.3M nitric acid, preservation more than 2 days, then ultrasound 30
More than minute；
(8) by step (7) gained acid dispersion vacuum filtration, filter cake redistilled water washes clean, and in vacuum
Dried in drying box 10 hours, cooling, grinding, so as to obtain the cladding tin ash covering of platinoid Core-shell Structure Nanoparticles
CNT (MWCNTs@SnO2@Pt-Cu@Pt)。
As described above, the present invention can be better realized.
Claims (9)
1. it is a kind of with two-layer load CNT, it is characterised in that the CNT be multi-walled carbon nano-tubes, described
One layer of tin ash is loaded on CNT, one layer of platinum base metal is loaded on the tin dioxide layer.
2. it is according to claim 1 with two-layer load CNT, wherein, the tin ash be titanium dioxide sijna
Rice grain, its granularity preferably between 1.0 to 10.0nm, and preferably between 2.0 to 6.0nm.
3. it is according to claim 1 with two-layer load CNT, wherein, the platinum base metal is with nano particle
Form is present；Its granularity preferably between 1.0 to 10.0nm, and preferably between 2.0 to 4.0nm.
4. the CNT with two-layer load according to claim 1, wherein, the platinum base metal is that Pt or platinum base are closed
Gold, the platinum base alloy is the alloy that Pt is formed with one or more other metal, described other metals can be Rh, Ru, Ir,
One or more in Cu, Ni.The platinum base metal can also be a kind of core shell structure, and kernel is platinum base alloy, and shell is
Platinum or platinum are insoluble in the metal of acid with other；Preferably, the platinum base metal is Pt, Pt-Rh alloy, Pt-Ru alloys, Pt-Cu
Alloy, Pt-Ru-Cu alloys, Pt-Ru-Rh-Ni alloys, Pt-Cu@Pt (kernel is Pt-Cu alloys, and shell is platinum).
5. described in any one of claim 1-4 with two-layer load CNT preparation method, including：
(1) multi-walled carbon nano-tubes is dispersed in concentrated nitric acid, many wall carbon that reaction obtains functionalization (hydroxylating and carboxylated) are received
Mitron；
(2) by stannous chloride, water, the function multi-walled carbon nano-tube mixing obtained in urea and step (1), reaction obtains dioxy
Change the multi-walled carbon nano-tubes of tin nanoparticles covering；
(3) multi-wall carbon nano-tube of the tin oxide nano particles covering that will be obtained in corresponding platinum base metal precursor, step (2)
Pipe and solvent mixing, obtain mixture；
(4) (a) mixes formic acid with step (3) gained mixture, reacts, and obtains the carbon of platinum base metallic cover tin ash covering
Nanotube.Or, the mixed liquor of step (3) gained mixture NaOH and alcohol is adjusted to alkalescence by (b), is being heated to reflux
To the CNT of platinum base metallic cover tin ash covering.
6. the preparation method described in claim 5, wherein, in the step (1), the multi-walled carbon nano-tubes is returned in concentrated nitric acid
Stream reaction, the reflux temperature is 120-200 DEG C, preferably 140-180 DEG C；
Preferably, in the step (2), the temperature of the reaction is preferably 60-100 DEG C, more preferably 90-100 DEG C, for example,
95℃；
Preferably, in the step (4) (a), the reaction is carried out in a solvent, and the solvent can be water, methyl alcohol, ethanol etc.；
The reaction temperature is preferably 60-130 DEG C, preferably 90-120 DEG C.The reaction is carried out in a nitrogen atmosphere；
Preferably, in the step (4) (b), the alcohol is ethylene glycol, glycerine etc.；The heating-up temperature is more than 150 DEG C,
It is preferably 160-250 DEG C, described to be heated to reflux being carried out in nitrogen atmosphere.
7. the preparation method described in claim 5, wherein, in the step (3), the platinum base metal precursor is platinum base metal
Salt, such as chlorate, sulfate, nitrate etc., by taking Pt as an example, its presoma can be H2PtCl6·6H2O；It is with Pt-Cu alloys
Example, its presoma can be H2PtCl6·6H2O and CuSO4·5H2O；The solvent can be ethylene glycol, water etc..
8. the preparation method described in claim 5, wherein, the preparation method includes：
(1) multi-walled carbon nano-tubes is mixed with concentrated nitric acid, is flowed back, obtain the multi-wall carbon nano-tube of functionalization (hydroxylating and carboxylated)
Pipe；
(2) by stannous chloride, water, the function multi-walled carbon nano-tube mixing ultrasound obtained in urea and step (1), then 95
DEG C cold filtration after 12 hours is refluxed, obtains the multi-walled carbon nano-tubes of tin oxide nano particles covering；
(3) multi-wall carbon nano-tube of the tin oxide nano particles covering that will be obtained in corresponding platinum base metal precursor, step (2)
Pipe and ethylene glycol mixing, ultrasound, obtain mixture, and the mol ratio and carrying capacity of platinum base metal precursor are adjusted in required ratio
Control；
(4) under nitrogen protection, step (3) gained mixture is mixed with the mixed liquor of formic acid and ethylene glycol, is heated to reflux 10
More than hour, temperature control is between 90 to 100 degrees Celsius；Then cooling, suction filtration, washing, drying, obtains the platinum base nanometer
The CNT of particles coat tin ash covering.
9. described in any one of claim 1-4 with two-layer load CNT purposes, it is used for fuel cell.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110323442A (en) * | 2019-07-17 | 2019-10-11 | 中国科学院福建物质结构研究所 | A kind of carbon coating Fe3O4Composite material and preparation method and application |
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| CN114864974A (en) * | 2022-05-17 | 2022-08-05 | 华中科技大学 | Catalyst loaded with platinum particles by cable structure and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110858652A (en) * | 2018-08-23 | 2020-03-03 | 现代摩比斯株式会社 | Electrode catalyst for fuel cell and method for manufacturing the same |
| CN110323442A (en) * | 2019-07-17 | 2019-10-11 | 中国科学院福建物质结构研究所 | A kind of carbon coating Fe3O4Composite material and preparation method and application |
| CN112736260A (en) * | 2020-12-09 | 2021-04-30 | 中国科学院福建物质结构研究所 | Composite material and preparation method and application thereof |
| CN113113624A (en) * | 2021-04-06 | 2021-07-13 | 南京工业大学 | Nano platinum catalyst with carbon nano tube as carrier and preparation method thereof |
| CN113903933A (en) * | 2021-09-29 | 2022-01-07 | 清华大学深圳国际研究生院 | Carbon-supported platinum-tin nano catalyst for long-life proton exchange membrane fuel cell and preparation method thereof |
| CN114864974A (en) * | 2022-05-17 | 2022-08-05 | 华中科技大学 | Catalyst loaded with platinum particles by cable structure and preparation method thereof |
| CN114864974B (en) * | 2022-05-17 | 2024-05-14 | 华中科技大学 | Catalyst loaded with platinum particles by cable structure and preparation method thereof |
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