CN108682875A - A kind of platinum controllable based on platinum carrying capacity-nano hollow carbon sphere catalyst and preparation method thereof - Google Patents
A kind of platinum controllable based on platinum carrying capacity-nano hollow carbon sphere catalyst and preparation method thereof Download PDFInfo
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- 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
- 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
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- 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 proposes a kind of platinum nano hollow carbon sphere catalyst controllable based on platinum carrying capacity and preparation method thereof, belongs to electrochemical field, and it is controllable and increase the technical problems such as the specific surface area of nano-platinum particle can to solve carrying capacity of the platinum in nano-hollow carbon ball.The polymer that the technical solution is grafted including the use of inorganic nanometer oxide nano grain surface is coordinated to form chloroplatinic acid root complex with chloroplatinic acid, it is formed simultaneously carbon and Pt nanoparticle during pyrolysis carbonization, inorganic nanometer oxide particle is removed by dissolving, forms the controllable platinum hollow carbon sphere catalyst of platinum carrying capacity.Catalyst provided by the invention and preparation method thereof can effectively improve the performance of platinum carbon elctro-catalyst, can be that the further commercial applications of fuel cell lay the foundation.
Description
Technical field
The invention belongs to electrochemical field more particularly to a kind of platinum controllable based on platinum carrying capacity-nano-hollow carbon ball catalysis
Agent and preparation method thereof.
Background technology
With the development of human society, environmental problem is more prominent, CO2 emission, haze, PM2.5, greenhouse effects
As social problems.The consequence that greenhouse gases largely discharge is persistently raised heat wave, arid, heavy rain and adjoint flood etc.
Climacteric disaster.And environmental crisis is not only pollution problem, behind is the energy problem for depending on conventional fossil fuel unduly,
Therefore, the need for finding new alternative energy source as national governments' reply energy crisis and environmental crisis are urgently asked.Due to hydrogen
High-energy-density is considered as replacing the ideal substitute of traditional fuel using hydrogen by the Hydrogen Energy of carrier；A master as Hydrogen Energy
Application approach is wanted, fuel cell, especially Proton Exchange Membrane Fuel Cells are because of its high-energy conversion efficiency, high-energy density, object
Exhaust emission etc. is got the attention.
The power generation process of fuel cell needs elctro-catalyst in anode-catalyzed oxidation of hydrogen and in cathode catalysis air
Oxygen reduction realize.Currently, platinum carbon catalyst is still fuel cell electricity because of its excellent electro catalytic activity and stability
The optimal selection of catalyst.However, platinum scarcity of resources, expensive so that the cost of fuel cell is high, constrains it
Wide popularization and application.Therefore, it is fuel cell to improve the performance of platinum carbon elctro-catalyst to reduce its dosage in a fuel cell
The key of further commercial applications.
Currently, the preparation of platinum carbon catalyst is focused primarily upon by being based in chloroplatinic acid and the mixed system of activated carbon part
Reduction reaction realizes load of the Pt nanoparticle on absorbent charcoal material, as patent application CN 103730668A disclose one kind
The preparation method of fuel cell platinum carbon catalyst goes back chloroplatinic acid in chloroplatinic acid-powdered carbon mixed system by polyalcohol
Original is prepared for the platinum carbon catalyst with larger electrochemical surface area；Patent application CN 105561986A disclose a kind of use
Stannous chloride prepares the technology of platinum carbon catalyst as reducing agent.The technology of preparing of existing platinum carbon catalyst is although urge platinum carbon
The active area of agent has some improvement, but due to being all made of activated carbon powder as carrier, improvement amplitude is difficult to obtain this
Promotion in matter；Meanwhile selection of the formation of Pt nanoparticle dependent on reduction system and reducing condition, grain diameter size
It is difficult to preferably be controlled with particle diameter distribution.
Compared to active carbon particle, nano hollow carbon ball has the specific surface area of bigger.It is urged using nano-hollow carbon ball as platinum
The carrier of agent is more advantageous to the gas transport dynamics in fuel cell, and then promotes the performance of fuel cell.However, realizing
Carrying capacity of the platinum in nano-hollow carbon ball is controllably and the specific surface area of increase nano-platinum particle is platinum-nano-hollow carbon ball electro-catalysis
The difficult point and key technology of agent exploitation.
Invention content
The present invention proposes a kind of platinum controllable based on platinum carrying capacity-nano hollow carbon sphere catalyst and preparation method thereof, realizes
Carrying capacity of the platinum in nano-hollow carbon ball is controllable and increases the specific surface area of nano-platinum particle, can further improve platinum carbon electricity
The performance of catalyst.
In order to achieve the above object, the present invention provides a kind of platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst
Preparation method is coordinated using the polymer of inorganic nanometer oxide nano grain surface grafting with chloroplatinic acid to form chloroplatinic acid root and match
Position object, carbon and Pt nanoparticle are formed simultaneously during pyrolysis carbonization, and inorganic nanometer oxide particle, shape are removed by dissolving
At the controllable platinum of platinum carrying capacity-hollow carbon sphere catalyst.
Preferably, specifically including following steps：
(1) preparation of nano carbon microsphere presoma：To the alkaline monomer of carbon-carbon double bonds and the N of radical initiator, N '-two
The inorganic nanometer oxide nano particle of modified by vinyl is added in methylformamide solution, ultrasonic disperse uniformly carries out freely afterwards
Base polymerisation is washed successively with deionized water, ethyl alcohol after the completion of reaction, solid product is collected by centrifugation, before obtaining nano carbon microsphere
Drive body；
(2) preparation of the chloroplatinic acid root complex of nano carbon microsphere presoma：By the nano carbon microsphere forerunner prepared by step (1)
Body is distributed in deionized water, and chloroplatinic acid aqueous solution is then added, and fully after reaction, centrifugation, separation, collection obtain nano carbon microsphere
The chloroplatinic acid root complex of presoma；
(3) preparation of platinum-nano carbon microsphere：By the chloroplatinic acid root complex of the nano carbon microsphere presoma prepared by step (2)
It is placed in reacting furnace, under nitrogen or argon gas protection, high temperature cabonization obtains platinum-nano carbon microsphere；
(4) preparation of platinum-nano hollow carbon sphere catalyst：Platinum-nano carbon microsphere prepared by step (3) is distributed to 48%
Hydrofluoric acid solution in fully react after, dissolve inorganic nanometer oxide nano particle, diluted with deionized water, is collected by centrifugation solid
Body obtains platinum-nano hollow carbon sphere catalyst after washing, freeze-drying.
Preferably, the inorganic nanometer oxide is in silica, titanium dioxide, zirconium dioxide and aluminium oxide
At least one, the grain size of the inorganic nanometer oxide particle are 10~100nm, the alkaline monomer be selected from vinyl imidazole,
The concentration of at least one of vinylpyridine and vinyl triazole, the alkaline monomer is not less than 0.1mol/L.
Preferably, the mass ratio of step (1) the neutral and alkali monomer and radical initiator is 20：1~5：1, it is described
The mass ratio of inorganic nanometer oxide nano particle and alkaline monomer is 3：97~50：50, polymerization reaction time is 1~12h.
Preferably, nano carbon microsphere presoma and the mass ratio of deionized water are 1 in the step (2)：10~1：50, institute
State a concentration of 1mg/ml~100mg/ml of chloroplatinic acid, the mass ratio of the nano carbon microsphere presoma and chloroplatinic acid is 1：0.01~
1：0.5, the reaction time is 1~12h.
Preferably, carburizing temperature is 800~1100 DEG C in the step (3), carbonization time is 1~4h.
Preferably, the ratio of platinum-nano carbon microsphere and hydrofluoric acid solution is 1g in the step (4):10mL~1g：
20mL, reaction time are 30min~4h.
Preferably, the radical initiator is azo-initiator or persulfide initiator.
The present invention also provides a kind of preparation method as described in any of the above-described technical solution be prepared based on platinum
The controllable platinum of carrying capacity-hollow carbon sphere catalyst.
Preferably, the platinum carrying capacity of the catalyst is 12wt%~78wt%, Pt nanoparticle 2~3.5nm of grain size is urged
4.5~87nm of agent aperture, 196~548m of specific surface area of catalyst2/ g, 60~90m of catalyst electrochemical surface area2/g。
Compared with prior art, the advantages and positive effects of the present invention are：
1, compared with existing activated carbon is as the catalyst of carrier, nano hollow carbon ball has the specific surface area of bigger,
Be conducive to the transmission of gas and the promotion of catalytic performance in catalysis reaction；
2, real by adjusting the coordination condition of the polymer of chloroplatinic acid and the grafting of inorganic nanometer oxide nano grain surface
Now platinum carrying capacity is controllable, and the preparation for the catalyst of different application environment provides optimize technique；
3, it is prepared due to the carbonization of catalyst carrier hollow carbon sphere and platinum nanometer is prepared by pyrolytic chloroplatinate
Grain is carried out at the same time, and can optimize the preparation process of catalyst accordingly, energy saving；
4, it is limited by the coordination of alkaline polymer, prepared Pt nanoparticle grain size is smaller, has bigger
Electrochemical surface area and electrocatalysis characteristic.
Description of the drawings
The preparation method for the platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst that Fig. 1 is provided by the embodiment of the present invention
Process schematic.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
An embodiment of the present invention provides a kind of preparation method of the platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst, profits
The polymer being grafted with inorganic nanometer oxide nano grain surface is coordinated to form chloroplatinic acid root complex with chloroplatinic acid, is being pyrolyzed
It is formed simultaneously carbon and Pt nanoparticle in carbonisation, inorganic nanometer oxide particle is removed by dissolving, forming platinum carrying capacity can
The platinum of control-hollow carbon sphere catalyst.
It, can be such as figure in order to realize that above-mentioned preparation method, the present invention in a preferred embodiment, specifically provide following steps
Shown in 1：
S1：The preparation of nano carbon microsphere presoma：To the alkaline monomer of carbon-carbon double bonds and the N of radical initiator, N '-two
The inorganic nanometer oxide nano particle of modified by vinyl is added in methylformamide solution, ultrasonic disperse uniformly carries out freely afterwards
Base polymerisation is washed successively with deionized water, ethyl alcohol after the completion of reaction, solid product is collected by centrifugation, before obtaining nano carbon microsphere
Drive body；
S2：The preparation of the chloroplatinic acid root complex of nano carbon microsphere presoma：By the nano carbon microsphere forerunner prepared by step (1)
Body is distributed in deionized water, and chloroplatinic acid aqueous solution is then added, and fully after reaction, centrifugation, separation, collection obtain nano carbon microsphere
The chloroplatinic acid root complex of presoma；
S3：The preparation of platinum-nano carbon microsphere：By the chloroplatinic acid root complex of the nano carbon microsphere presoma prepared by step (2)
It is placed in reacting furnace, under nitrogen or argon gas protection, high temperature cabonization obtains platinum-nano carbon microsphere；
S4：The preparation of platinum-nano hollow carbon sphere catalyst：Platinum-nano carbon microsphere prepared by step (3) is distributed to 48%
Hydrofluoric acid solution in fully react after, dissolve inorganic nanometer oxide nano particle, diluted with deionized water, is collected by centrifugation solid
Body obtains platinum-nano hollow carbon sphere catalyst after washing, freeze-drying.
The technical characteristics for the preparation method that above-described embodiment provides are：Cause free radical polymerization by surface in situ
The polymer precursor that can be coordinated with platinum ion is directly grafted to the surface of inorganic nanometer oxide template by reaction；It utilizes
The coordination of platinum ion and surface grafting polymerization object so that platinum ion and subsequent Pt nanoparticle are equal in carbon material
Even dispersion promotes its catalytic performance；It is heated up by a step, realizes that carbon material is synchronous with Pt nanoparticle and formed, be conducive to give birth to
Energy consumption is reduced in production and improves yield；Finally, inorganic oxide nanoparticles template is removed, the ratio of material can be further promoted
Surface area advantageously forms the transmission of more active sites and gas in material.
In a preferred embodiment, the inorganic nanometer oxide is selected from silica, titanium dioxide, zirconium dioxide and oxygen
Change at least one of aluminium, the grain size of the inorganic nanometer oxide particle is 10~100nm, and the alkaline monomer is selected from ethylene
The concentration of at least one of base imidazoles, vinylpyridine and vinyl triazole, the alkaline monomer is not less than 0.1mol/L.This
In embodiment, alternative inorganic nanometer oxide and its Particle size requirements, alkaline monomer and its concentration are shown in particular
It is applicable in it is required that those skilled in the art can carry out selection according to real reaction condition, it is to be understood that inorganic nanometer oxide
The grain size of particle can also be any other point value in 20,30,40,50,60,70,80,90nm and above range, and alkalinity is single
The concentration of body is in order to meet the progress of reaction, it is desirable that is not less than 0.1mol/L.But it is environmental-friendly in view of saving raw material,
The concentration of the alkaline monomer can be not higher than 2.0mol/L.It should be noted that the selected of above-mentioned component is not limited to this implementation
It is cited in example, it can also be what those skilled in the art thought rationally to replace according to reaction principle.
In a preferred embodiment, the mass ratio of step (1) the neutral and alkali monomer and radical initiator is 20：1~
5：1, the mass ratio of the inorganic nanometer oxide nano particle and alkaline monomer is 3：97~50：50, polymerization reaction time 1
~12h.Alkaline monomer and azodiisobutyronitrile and inorganic nanometer oxide nano particle and alkalinity are defined in the present embodiment
The mass ratio of monomer is conducive to the grafting efficiency for improving inorganic nanometer oxide nano particle, so as to utmostly in this way
Acquisition nano carbon microsphere presoma.It is understood that the mass ratio of alkaline monomer and azodiisobutyronitrile can also be 15:1、
10:1 or above range in arbitrary point value ratio, the mass ratio of inorganic nanometer oxide nano particle and alkaline monomer can also be
10:90、15:85、20:80、25:75、30:70、35:65、40:60 or above range in arbitrary point value ratio, art technology
Personnel can be adjusted according to real reaction situation.
In a preferred embodiment, nano carbon microsphere presoma and the mass ratio of deionized water are 1 in the step (2)：10
~1：50, a concentration of 1mg/ml~100mg/ml of the chloroplatinic acid, the mass ratio of the nano carbon microsphere presoma and chloroplatinic acid
It is 1：0.01~1：0.5, the reaction time is 1~12h.Nano carbon microsphere presoma and deionized water are specifically defined in the present embodiment
Ratio, the concentration of chloroplatinic acid, nano carbon microsphere presoma and chloroplatinic acid ratio and reaction time, primarily to can make
Nano carbon microsphere presoma is fully reacted with chloroplatinic acid root complex, to obtain expected chloroplatinic acid root complex.It is appreciated that
, the ratio of nano carbon microsphere presoma and deionized water can also be 1:15、1:20、1:25、1:30、1:35、1:40、1:45 or
Arbitrary point value ratio in above range, the concentration of chloroplatinic acid can also be 5,10,20,30,40,50,60,70,80,90mg/ml or
The ratio of arbitrary point value in above range, nano carbon microsphere presoma and chloroplatinic acid can also be 1:0.05、1:0.1、1:0.2、1:
0.3、1:0.4 or above range in arbitrary point value ratio, the reaction time can also be 2,3,4,5,6,7,8,9,10,11h or above-mentioned
Arbitrary point value in range, those skilled in the art can be adjusted according to real reaction situation.
In a preferred embodiment, carburizing temperature is 800~1100 DEG C in the step (3), and carbonization time is 1~4h.
Carburizing temperature and carbonization time have first specifically been pushed up in the present embodiment, in the temperature and nano carbon microsphere presoma can be made in the reaction time
The carbonization of chloroplatinic acid root complex it is complete, respectively obtain carbon and Pt nanoparticle.It is understood that carburizing temperature can also be
900, the arbitrary point value in 1000 DEG C or above range, carbonization time can also be 2,2.5,3, it is arbitrary in 3.5h or above range
Point value, those skilled in the art can be adjusted according to real reaction situation.It should be noted that used in carbonisation
Reacting furnace can be tube furnace, Muffle furnace etc..
In a preferred embodiment, the ratio of platinum-nano carbon microsphere and hydrofluoric acid solution is 1g in the step (4):10mL
~1g：20mL, reaction time are 30min~4h.The ratio of platinum-nano carbon microsphere and hydrofluoric acid solution is specifically defined in the present embodiment
Example and reaction time, it can ensure that preparation-obtained platinum-nano hollow carbon sphere catalyst is expected in the condition and range
And the catalyst with excellent properties.It is understood that the ratio of platinum-nano carbon microsphere and hydrofluoric acid solution can also be 1g:
12mL、1g:14mL、1g:15mL、1g:16mL、1g:Arbitrary point value in 18mL or above range, the reaction time can also be 1,
1.5, the arbitrary point value in 2,2.5,3,3.5h or above range, those skilled in the art can adjust according to real reaction situation
It is whole.
In a preferred embodiment, the radical initiator is azo-initiator or persulfide initiator.It needs
It is noted that the selection for radical initiator can be not limited to defined in the present embodiment, ability can also be
It can rationally be replaced known to field technique personnel.
The embodiment of the present invention additionally provides a kind of base that the preparation method as described in any of the above-described embodiment is prepared
In the controllable platinum of platinum carrying capacity-hollow carbon sphere catalyst.
In a preferred embodiment, the platinum carrying capacity of the catalyst be 12wt%~78wt%, Pt nanoparticle grain size 2~
3.5nm, 4.5~87nm of catalyst aperture, 196~548m of specific surface area of catalyst2/ g, catalyst electrochemical surface area 60~
90m2/g。
The catalyst that above-described embodiment provides is more advantageous to gas in catalysis reaction due to the specific surface area with bigger
The transmission of body and the promotion of catalytic performance, and due to the polymer of chloroplatinic acid and the grafting of inorganic nanometer oxide nano grain surface
Coordination condition it is adjustable, it is achieved that the Modulatory character of platinum carrying capacity, is its preparation in the catalyst of different application environment
It lays the foundation, further, due to being limited by the coordination of alkaline polymer in the catalyst, prepared platinum
Nano particle diameter is smaller, can be with the electrochemical surface area and electrocatalysis characteristic of bigger.
In order to become apparent from the platinum-hollow carbon sphere controllable based on platinum carrying capacity that the embodiment of the present invention is provided is introduced in detail urge
The preparation method of agent, is described below in conjunction with specific embodiment.
Embodiment 1
The preparation method of the platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst provided in this embodiment includes following step
Suddenly：
The preparation of nano carbon microsphere presoma：To the N, N '-of the vinyl imidazole (0.95g) of a concentration of 0.1mol/L of 100mL
The dioxy that the grain size of azodiisobutyronitrile and 0.95g modified by vinyl that 0.19g is added in dimethyl formamide solution is 10nm
SiClx nano particle is heated to 60 DEG C of ± 5 DEG C of progress free radical polymerization 12h, reaction under protection of argon gas after ultrasonic disperse 30min
Using deionized water, ethyl alcohol successively after the completion, respectively washing three times, is collected by centrifugation solid product, obtains nano carbon microsphere presoma 1.68g.
The preparation of the chloroplatinic acid root complex of nano carbon microsphere presoma：By the nano carbon microsphere presoma prepared by step (1)
0.5g is distributed in 25mL deionized waters, and the chloroplatinic acid aqueous solution of the 100mg/mL of 5mL is then added, and is centrifuged after reacting 12h, point
The chloroplatinic acid root complex of 0.57g nano carbon microsphere presomas is obtained from collecting.
The preparation of platinum-nano carbon microsphere：By the chloroplatinic acid root complex of the 0.4g nano carbon microsphere presomas prepared by step (2)
It is placed in tube furnace, under protection of argon gas, is warming up to 1100 DEG C of carbonization 2h, obtains 0.23g platinum-nano carbon microsphere.
The preparation of platinum-nano hollow carbon sphere catalyst：0.2g platinum-nano carbon microsphere prepared by step (3) is distributed to 2mL
48% hydrofluoric acid solution in, reaction 30min dissolve inorganic nano zinc oxide-silicon dioxide, solid is collected by centrifugation, deionization is used in combination
Water washing three times, after freeze-drying, obtains 0.06g platinum-nano hollow carbon sphere catalyst.
Embodiment 2
Preparation method is same as Example 1, the difference is that inorganic nanometer oxide nano particle used in step (1)
The titania nanoparticles for being 100nm for 0.95g grain sizes, polymerization reaction time 6h.
Embodiment 3
Preparation method is same as Example 1, the difference is that nano carbon microsphere presoma 1.0g is distributed in step (2)
In 10mL deionized waters, the amount of chloroplatinic acid used is 10mL, a concentration of 1mg/mL, reaction time 1h.
Embodiment 4
Preparation method is same as Example 1, the difference is that the Carbonization Conditions in step (3) are 800 DEG C of carbonization 4h, step
Suddenly 0.2g platinum-nano carbon microsphere is distributed in 48% hydrofluoric acid solution of 4mL in (4), reacts 4h.
Embodiment 5
The preparation method of the platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst provided in this embodiment includes following step
Suddenly：
The preparation of nano carbon microsphere presoma：Two isobutyl of azo of 0.98g is added into the vinylpyridine (19.5g) of 20mL
The grain size of nitrile and 0.60g modified by vinyl is the nano SiO 2 particle of 30nm, under protection of argon gas after ultrasonic disperse 30min
60 DEG C of ± 5 DEG C of progress free radical polymerization 1h are heated to, are respectively washed with deionized water, methanol, acetone, ethyl alcohol successively after the completion of reaction
Three times, solid product is collected by centrifugation, obtains nano carbon microsphere presoma 1.17g.
The preparation of the chloroplatinic acid root complex of nano carbon microsphere presoma：By the nano carbon microsphere presoma prepared by step (1)
1.0g is distributed in 10mL deionized waters, and the chloroplatinic acid aqueous solution of the 50mg/mL of 10mL is then added, and is centrifuged after reacting 8h, point
The chloroplatinic acid root complex of 1.22g nano carbon microsphere presomas is obtained from collecting.
The preparation of platinum-nano carbon microsphere：By the chloroplatinic acid root complex of the 1.0g nano carbon microsphere presomas prepared by step (2)
It is placed in tube furnace, under protection of argon gas, is warming up to 1000 DEG C of carbonization 2h to get to 0.73g platinum-nano carbon microsphere.
The preparation of platinum-nano hollow carbon sphere catalyst：0.5g platinum-nano carbon microsphere prepared by step (3) is distributed to
In 48% hydrofluoric acid solution of 40mL, reaction 1h dissolves inorganic nano zinc oxide-silicon dioxide, and solid is collected by centrifugation, deionization is used in combination
Water washing three times, 0.16g platinum-nano hollow carbon sphere catalyst is obtained after freeze-drying.
Embodiment 6
Preparation method is same as Example 5, the difference is that the inorganic nanometer oxide nanometer used in step (1)
Particle is the aluminum oxide micro-sphere of 50nm.
Embodiment 7
Preparation method is same as Example 5, the difference is that the carburizing temperature used in step (3) is 900 DEG C, carbon
The change time is 3h.
Embodiment 8
The preparation method of the platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst provided in this embodiment includes following step
Suddenly：
The preparation of nano carbon microsphere presoma：To the N, N '-of the vinyl triazole (4.75g) of a concentration of 0.5mol/L of 100mL
The dioxy that the grain size of azodiisobutyronitrile and 2.4g modified by vinyl that 0.475g is added in dimethyl formamide solution is 30nm
SiClx nano particle, is heated to 60 DEG C of ± 5 DEG C of progress free radical polymerization 6h under protection of argon gas after ultrasonic disperse 1h, reaction is completed
Using deionized water, ethyl alcohol successively afterwards, respectively washing three times, is collected by centrifugation solid product, obtains nano carbon microsphere presoma 3.74g.
The preparation of the chloroplatinic acid root complex of nano carbon microsphere presoma：By the nano carbon microsphere presoma prepared by step (1)
1.0g is distributed in 30mL deionized waters, and the chloroplatinic acid aqueous solution of the 80mg/mL of 10mL is then added, and is centrifuged after reacting 6h, point
The chloroplatinic acid root complex of 1.44g nano carbon microsphere presomas is obtained from collecting.
The preparation of platinum-nano carbon microsphere：By the chloroplatinic acid root complex of the 1.0g nano carbon microsphere presomas prepared by step (2)
It is placed in tube furnace, under protection of argon gas, is warming up to 1000 DEG C of carbonization 1.5h to get to 0.61g platinum-nano carbon microsphere.
The preparation of platinum-nano hollow carbon sphere catalyst：0.5g platinum-nano carbon microsphere prepared by step (3) is distributed to 5mL
48% hydrofluoric acid solution in, reaction 1h dissolve inorganic nano zinc oxide-silicon dioxide, solid is collected by centrifugation, and be washed with deionized water
It washs three times, 0.25g platinum-nano hollow carbon sphere catalyst is obtained after freeze-drying.
Embodiment 9
Preparation method is same as Example 8, the difference is that inorganic nanometer oxide nanometer used in step (1)
Grain is the zirconium oxide microballoons of 30nm；Radical initiator used is ammonium persulfate.
Embodiment 10
Preparation method is same as Example 8, the difference is that the amount of chloroplatinic acid used is 10mL, concentration in step (2)
For 1mg/mL, reaction time 30min.
Comparative example 1
The preparation of nano carbon microsphere presoma：To the N, N '-two of the vinyl imidazole (0.6g) of a concentration of 0.15mol/L of 50mL
The silica that the grain size of azodiisobutyronitrile and 0.6g modified by vinyl that 0.2g is added in methylformamide solution is 10nm
Nano particle, is heated to 60 DEG C of ± 5 DEG C of progress free radical polymerization 12h under protection of argon gas after ultrasonic disperse 30min, reaction is completed
Using deionized water, ethyl alcohol successively afterwards, respectively washing three times, is collected by centrifugation solid product, obtains nano carbon microsphere presoma 0.94g.
The preparation of the chloroplatinic acid root complex of nano carbon microsphere presoma：By the nano carbon microsphere presoma prepared by step (1)
0.5g is distributed in 25mL deionized waters, and the chloroplatinic acid aqueous solution of the 100mg/mL of 5mL is then added, and is centrifuged after reacting 12h, point
The chloroplatinic acid root complex of 0.62g nano carbon microsphere presomas is obtained from collecting.
The preparation of platinum-nano carbon microsphere：By the chloroplatinic acid root complex of the 0.5g nano carbon microsphere presomas prepared by step (2)
It is placed in tube furnace, under protection of argon gas, is warming up to 1100 DEG C of carbonization 2h, obtains 0.31g platinum-nanocarbon catalyst.
Comparative example 2
0.2g commercializations activated carbon XC-72 is distributed in 25mL ethylene glycol solvents, is then added the 100mg/mL's of 5mL
Chloroplatinic acid ethylene glycol solution is warming up to 80 DEG C, is centrifuged after reacting 12h, and spent glycol, deionized water, ethyl alcohol wash three times successively,
Centrifugation product is freeze-dried, 0.28g platinum carbon catalyst is obtained.
Performance test
Characterization test, institute's measured data result such as table 1 are carried out to the various embodiments described above and the obtained catalyst of comparative example
It is shown：
1 each embodiment of table and comparative example characterize test result
In above-described embodiment and comparative example, we are prepared for conventional platinum-activated-carbon catalyst respectively and platinum-is non-hollow receives
Rice carbon ball catalyst, from test result as can be seen that the specific surface area of the catalyst material prepared by the embodiment of the present invention is long-range
In the specific surface area of comparative example.Correspondingly, the electrochemical surface area directly related with specific surface area is also above in comparative example
Electrochemical surface area.Therefore, the electrochemical catalyst prepared by preparation method provided by the present invention has preferably catalysis
Activity.
Claims (10)
1. a kind of preparation method of the platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst, which is characterized in that utilize inorganic nano
The polymer of oxide nanoparticle surface grafting is coordinated to form chloroplatinic acid root complex with chloroplatinic acid, during being pyrolyzed carbonization
It is formed simultaneously carbon and Pt nanoparticle, inorganic nanometer oxide particle is removed by dissolving, it is hollow to form the controllable platinum-of platinum carrying capacity
Carbon ball catalyst.
2. preparation method according to claim 1, which is characterized in that specifically include following steps：
(1) preparation of nano carbon microsphere presoma：To the alkaline monomer of carbon-carbon double bonds and the N of radical initiator, N '-dimethyl
The inorganic nanometer oxide nano particle of modified by vinyl is added in formamide solution, ultrasonic disperse uniformly carries out radical polymerization afterwards
Reaction is closed, is washed successively with deionized water, ethyl alcohol after the completion of reaction, solid product is collected by centrifugation, obtains nano carbon microsphere presoma；
The radical initiator is azo-initiator or persulfide initiator；
(2) preparation of the chloroplatinic acid root complex of nano carbon microsphere presoma：By the nano carbon microsphere presoma prepared by step (1) point
It is scattered in deionized water, chloroplatinic acid aqueous solution is then added, fully after reaction, centrifugation, separation, collection obtain nano carbon microsphere forerunner
The chloroplatinic acid root complex of body；
(3) preparation of platinum-nano carbon microsphere：The chloroplatinic acid root complex of nano carbon microsphere presoma prepared by step (2) is placed in
In reacting furnace, under nitrogen or argon gas protection, high temperature cabonization obtains platinum-nano carbon microsphere；
(4) preparation of platinum-nano hollow carbon sphere catalyst：Platinum-nano carbon microsphere prepared by step (3) is distributed to 48% hydrogen
After fully being reacted in fluorspar acid solution, inorganic nanometer oxide nano particle is dissolved, is diluted with deionized water, solid is collected by centrifugation,
After washing, freeze-drying, platinum-nano hollow carbon sphere catalyst is obtained.
3. preparation method according to claim 2, which is characterized in that the inorganic nanometer oxide be selected from silica,
At least one of titanium dioxide, zirconium dioxide and aluminium oxide, the grain size of the inorganic nanometer oxide particle is 10~
100nm, the alkaline monomer are selected from least one of vinyl imidazole, vinylpyridine and vinyl triazole, the alkalinity
The concentration of monomer is not less than 0.1mol/L.
4. preparation method according to claim 2, which is characterized in that step (1) the neutral and alkali monomer draws with free radical
The mass ratio for sending out agent is 20：1~5：1, the mass ratio of the inorganic nanometer oxide nano particle and alkaline monomer is 3：97~
50：50, polymerization reaction time is 1~12h.
5. preparation method according to claim 2, which is characterized in that in the step (2) nano carbon microsphere presoma with go
The mass ratio of ionized water is 1：10~1：50, a concentration of 1mg/ml~100mg/ml of the chloroplatinic acid, before the nano carbon microsphere
The mass ratio for driving body and chloroplatinic acid is 1：0.01~1：0.5, the reaction time is 1~12h.
6. preparation method according to claim 2, which is characterized in that carburizing temperature is 800~1100 in the step (3)
DEG C, carbonization time is 1~4h.
7. preparation method according to claim 2, which is characterized in that platinum-nano carbon microsphere and hydrofluoric acid in the step (4)
The ratio of solution is 1g:10mL~1g：20mL, reaction time are 30min~4h.
8. preparation method according to claim 2, which is characterized in that the radical initiator be azo-initiator or
Person's persulfide initiator.
9. the hollow carbon of the platinum-controllable based on platinum carrying capacity being prepared according to claim 1-8 any one of them preparation methods
Sphere catalyst.
10. the platinum controllable based on platinum carrying capacity-hollow carbon sphere catalyst according to claim 9, which is characterized in that described to urge
The platinum carrying capacity of agent is 12wt%~78wt%, Pt nanoparticle 2~3.5nm of grain size, 4.5~87nm of catalyst aperture, catalysis
196~548m of agent specific surface area2/ g, 60~90m of catalyst electrochemical surface area2/g。
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