CN108767280A - A kind of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material and preparation method thereof - Google Patents
A kind of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite materials and preparation method thereof.Pass through solvent thermal process on the basis of preparing hydroxyl carbon cerium mine nano-cluster/graphene composite material, using chloroplatinic acid as the presoma of platinum, platinum is restored from solution by oil bath after the pH value of adjustment reaction solution, so that platinum is dispersed in the surface of hydroxyl carbon cerium mine nano-cluster/graphene composite material, and is in close contact with hydroxyl carbon cerium mine nano particle.The thinking of the present invention is simply clear, prepared product remain platinum, hydroxyl carbon cerium mine and graphene structural intergrity, hydroxyl cerous carbonate adheres on the surface of graphene, while improving alcohol fuel battery, by the great specific surface area of graphene, conductive capability is improved, realize the close contact between each component, by the synergistic effect between each component, the activity and durability of the oxidation of platinum catalysis methanol can be effectively facilitated, is had broad application prospects.
Description
【Technical field】
The invention belongs to direct alcohol fuel cell fields, are related to a kind of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/stone
Black alkene composite material and preparation method.
【Background technology】
In recent decades, the high speed development of portable electronic device such as mobile phone, computer leads to the rapid increasing to energy demand
Add, new challenge also is proposed to existing battery technology.The short stand-by time of portable electronic device battery is currently associated skill
The outstanding problem in art field.In the research of numerous new battery technologies, direct alcohol fuel cell has high-energy density, high energy
The advantages that amount transfer efficiency, fuel are easily stored and convey and is environmentally friendly is the ideal energy supply of portable electronic device
Technology, it is of increased attention.
Compared to existing battery technology, though direct alcohol fuel cell has a huge advantage, its commercial applications by
Many restrictions.Wherein, the activity of noble metal catalyst is low and stability difference is to restrict the principal element of its commercial applications.With first
For alcohol, methanol oxygenolysis under the catalytic action of platinum, and carbon oxygen class intermediate product is generated, with ADSORPTION STATE carbon monoxy form
In the presence of, cause to continue with reaction, a large amount of platinum active sites are occupied by carbon monoxide, hinder new methanol molecules platinum live
The absorption and catalysis in property site, i.e., usually said Pt catalyst poisoning cause platinum catalyst activity and stability substantially
Loss.
In recent years, the design of platinum base multicomponent catalyst is considered as solving the most effective measure of Pt catalyst poisoning.It is logical
The addition for crossing other components forms cooperative interaction between platinum or influences the electronic structure of platinum, improves platinum catalysis methanol
Oxidation susceptibility.Wherein, the addition of metal hydroxides or metal hydroxy carbonate can be obviously improved the stability of platinum catalyst.Gold
Belonging to hydroxide usually has proliferative defect, and the dissociation of hydrone is contributed to form ADSORPTION STATE hydroxyl, based on Langmuir~
Hinshelwood mechanism, this ADSORPTION STATE hydroxyl react with the carbon monoxide for occupying platinum active site and generate carbon dioxide,
Platinum active site is promoted to expose again, so as to improve the stability of methanol oxidation reaction.Metal hydroxy carbonate also has cracking
Water is to generate the ability of ADSORPTION STATE hydroxyl, therefore, to the improvement result highly significant of the stability of methanol fuel cell.
As one kind in metal hydroxy carbonate, hydroxyl carbon cerium mine (chemical formula：Ce(CO3) OH) also have cracking aquatic
At the ability of ADSORPTION STATE hydroxyl.To be applied to Electrocatalytic Oxidation of Methanol field, it is also necessary to consider the following：1, nanometer
The technology of preparing of grade hydroxyl carbon cerium mine promotes the cracking ability to water to ensure to expose more surfaces；2, hydroxyl carbon cerium mine
Nano particle and Pt nanoparticle are in close contact to ensure that Langmuir~Hinshelwoo reacted is smoothed out；3, due to hydroxyl
The poorly conductive of base carbon cerium mine, and the high degree of dispersion of hydroxyl carbon cerium mine nano particle and Pt nanoparticle is needed, therefore, it is necessary to one
A electric conductivity is excellent and the carrier of large specific surface area.
Graphene has excellent electrology characteristic, and (carrier mobility is about 15000cm2/ (Vs), great specific surface
Product (up to 2630m2/ g), it is ideal carrier material.If hydroxyl carbon cerium mine nano particle and Pt nanoparticle are supported on stone
Black alkene surface can both solve the problems, such as conductive capability deficiency, additionally it is possible to ensure the high dispersion of nano particle.
【Invention content】
The purpose of the present invention is to provide a kind of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite materials
Preparation method.The technique can effectively control the close contact between hydroxyl carbon cerium mine nano particle and Pt nano particles, and
Even dispersion is on the surface of graphene.There is good synergistic effect between the composite material each component, Pt catalytic alcohols can be greatly improved
The activity and durability of oxidation, have a extensive future.
In order to achieve the above objectives, the present invention is achieved by the following scheme：
A kind of preparation method of hydroxyl carbon cerium mine nano-cluster/graphene composite material, includes the following steps：
1-1) mixed oxidization graphene solution and ethylene glycol solution obtain uniform mixed solution after supersound process；Stirring
Gained mixed solution, while cerous nitrate hexahydrate is added, continue to stir to get uniform suspended mixed liquor；
1-2) in step 1-1) urea is added in obtained suspended mixed liquor after adjustment pH value to 11~13, obtain mixture
System, mixed system is placed in autoclave and carries out hydro-thermal reaction, is quickly cooled down to obtain mixed solution after reaction；
1-3) centrifugal treating step 1-2) obtained mixed solution, collect sediment；With the mixing of ethyl alcohol and deionized water
Liquid washing precipitate several times, by the drying precipitate after washing, obtains hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Further improvement of the present invention is：
Preferably, step 1-1) in graphene oxide solution mass concentration be 1~10mg/ml, graphene oxide solution
Volume ratio with ethylene glycol solution is 1:(1~3)；Sonication treatment time is 50~70min；The cerous nitrate hexahydrate of addition
Ratio with graphene oxide solution is：(1~8) mg：2ml.
Preferably, step 1-2) in the urea and step 1~1 that are added) in the quality of cerous nitrate hexahydrate that is added
Than for (10~20)：(1~8)；The temperature of hydro-thermal reaction is 200 DEG C, the reaction time >=180min；By reaction kettle after hydro-thermal reaction
Into the water, mixed solution is made to be quickly cooled to room temperature.
Preferably, step 1-3) in volume ratio be 1：The ethyl alcohol and deionized water mixed liquor washing precipitate 4 of (2~5)
~6 times；The dry environment of sediment be vacuum or inert atmosphere, drying temperature be 60~80 DEG C, drying time be 12~for 24 hours.
A kind of hydroxyl carbon cerium mine nano-cluster/graphene composite material prepared by above-mentioned preparation method.
A kind of Pt nano particles based on above-mentioned hydroxyl carbon cerium mine nano-cluster/graphene composite material/hydroxyl carbon cerium mine is received
The preparation method of rice cluster/graphene composite material, includes the following steps：
2-1) grinding hydroxyl carbon cerium mine nano-cluster/graphene composite material obtains powder, and gained powder is put into ethylene glycol
In solution, after being ultrasonically treated the suspended mixed liquor of gained, the mixed of chloroplatinic acid and ethylene glycol is added during magnetic agitation solution
Liquid is closed, mixed solution is obtained；
2-2) set-up procedure 2-1) obtained mixed solution pH value is to 12~13, oil bath reflow treatment acquired solution；It will be molten
Liquid stirring is cooled to room temperature, and adjustment pH value to 2~3 obtains mixed solution after continuing stirring；
2-3) centrifugal treating step 2-2) obtained mixed solution, collect sediment；With the mixing of ethyl alcohol and deionized water
Liquid washs several times repeatedly, and it is multiple to obtain Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene for the sediment after dry cleaning
Condensation material.
Preferably, step 2-1) in use agate grinding hydroxyl carbon cerium mine nano-cluster/graphene composite material, the powder of addition
The ratio of end and ethylene glycol solution is (3~10) mg：4ml；The mass concentration of platinum is 5mg/ in chloroplatinic acid and ethylene glycol mixture
Ml, the chloroplatinic acid and ethylene glycol mixture of addition and the ratio of composite powder are (1~5) ml：(30~100) mg.
Preferably, step 2-2) in select saturation NaOH adjustment mixed solution pH to 12~13；Oil bath reflux temperature
For：100~200 DEG C, oil bath return time is 2~4h；Solution to the pH value of selection hydrochloric acid adjustment at room temperature stirs 5 after being 2~3
~30min, obtains mixed solution.
Preferably, step 2-3) in sediment ethyl alcohol and deionized water mixed liquor washing precipitate 4~6 times, ethyl alcohol and
The volume ratio of deionized water is 1：(2~5)；The dry environment of sediment is vacuum or inert atmosphere, and drying temperature is 60~80
DEG C, drying time be 12~for 24 hours.
A kind of Pt nano particles prepared by above-mentioned preparation method/hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Compared with prior art, the invention has the advantages that：
The invention discloses a kind of preparation methods of hydroxyl carbon cerium mine nano-cluster/graphene composite material.With graphite oxide
Presoma of the alkene solution as graphene, using cerous nitrate hexahydrate as the presoma of hydroxyl cerous carbonate, be added urea with
Carbonate is provided, using NaOH to provide OH-, generate Ce (CO jointly with cerous nitrate hexahydrate3)OH；This method passes through water
Hot method prepares hydroxyl carbon cerium mine nano particle, keeps its evenly dispersed on the surface of graphene, prepares hydroxyl carbon cerium mine nano-cluster/stone
Black alkene composite material.The hydroxyl carbon cerium mine nano-cluster prepared can promote the cracking ability to water in alcohol fuel battery,
The ADSORPTION STATE hydroxyl that hydrone is formed can be reacted with the CO for occupying noble metal active site generates CO2, make noble metal active position
Point exposes again, to improve the catalytic efficiency of alcohol fuel battery, and improves its stability, hydroxyl cerous carbonate is attached to graphite
, by the very big specific surface area of graphene, conductive capability is improved while improving alcohol fuel battery in alkene surface.The present invention is logical
Simple hydro-thermal method is crossed, composite material is prepared, raw materials used to be easy to get, production efficiency is high, is suitble to industrialized production.
The invention also discloses a kind of hydroxyl carbon cerium mine nano-cluster/graphene composite materials；The composite material is microcosmic
Under state, hydroxyl carbon cerium mine is nanocluster, and is uniformly distributed on the surface of graphene；The composite material have both hydroxyl cerous carbonate and
The excellent properties of both graphenes, the addition of hydroxyl cerous carbonate can be obviously improved the stability of noble metal catalyst, graphene tool
There is highly conductive ability.
The invention also discloses a kind of preparation sides of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
Method.By solvent thermal process on the basis of preparing hydroxyl carbon cerium mine nano-cluster/graphene composite material, using chloroplatinic acid as
The presoma of platinum adjusts and is restored platinum from solution by oil bath after the pH value of reaction solution, platinum is made to be dispersed in hydroxyl
The surface of base carbon cerium mine nano-cluster/graphene composite material, and be in close contact with hydroxyl carbon cerium mine nano particle；Agate mortar is hard
Degree is high, can ensure that the powder being ground is careful；The pH value of hydrochloric acid conditioning solution can ensure that Pt reduction is complete, and hydrochloric acid
Cl-With the Cl of chloroplatinic acid-, mixed solution is not polluted, prepares Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene
Composite material, the composite material prepared include three classes material, and hydroxyl carbon cerium mine nano-cluster can carry in alcohol fuel battery
The cracking ability to water is risen, the ADSORPTION STATE hydroxyl that hydrone is formed can be reacted with the CO for occupying Pt active sites generates CO2, make
Pt active sites expose again, provide more Adsorptions, there is higher catalytic efficiency, improve using Pt bases as catalyst alcohols
The stability of fuel cell, hydroxyl cerous carbonate adhere on the surface of graphene, while improving alcohol fuel battery, by graphite
The very big specific surface area of alkene improves conductive capability.Pt nano particles/graphene of hydroxyl carbon cerium mine nano-cluster is not added by comparison
Composite material and Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material discovery, the latter's composite material electro-catalysis
The stability of Oxidation of Methanol is substantially better than Pt nanoparticle/graphene composite material, and the resisting CO poison ability of the latter is also stronger.This
The thinking of invention is simply clear, prepared product both remained platinum, hydroxyl carbon cerium mine and graphene structural intergrity, it is also real
The close contact between each component is showed, by the synergistic effect between each component, the oxidation of platinum catalysis methanol can be effectively facilitated
Activity and durability, have broad application prospects.
The invention also discloses a kind of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite materials.Pass through comparison
The Pt nanoparticle/graphene composite materials discovery of cerous nitrate hexahydrate, the composite material that the present invention prepares are not added
It can be obviously improved the stability of platinum catalysis Oxidation of Methanol, and can more efficiently remove the CO of Pt adsorptions, that is, had excellent
Resisting CO poison effect.
【Description of the drawings】
Fig. 1 is the TEM figures that product morphology shown in cerous nitrate hexahydrate is not added for embodiment 1；
Fig. 2 is the XRD spectrum that product shown in cerous nitrate hexahydrate is added in embodiment 2；
Fig. 3 is the TEM figures that product morphology shown in cerous nitrate hexahydrate is added in embodiment 2；
Fig. 4 is embodiment 1, product Electrocatalytic Oxidation of Methanol mass activity figure shown in embodiment 2；
Fig. 5 is embodiment 1, product Electrocatalytic Oxidation of Methanol stability diagram shown in embodiment 2；
Fig. 6 is embodiment 1, product CO Stripping Voltammetry experimental result pictures shown in embodiment 2.
【Specific implementation mode】
The present invention is described in further detail below in conjunction with the accompanying drawings：
The invention discloses a kind of preparation method of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material,
Include the following steps：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
1) graphene oxide solution and ethylene glycol solution of a concentration of 1~10mg/ml of mixing quality, graphene oxide solution
Volume ratio with ethylene glycol solution is 1:(1~3)；Acquired solution is ultrasonically treated, ultrasonic time is 50~70min, ultrasonic work(
Rate is 150W, obtains uniform mixed solution；
2) mixed solution that step 1) obtains is transferred on magnetic stirring apparatus, six water of cerous nitrate is added in whipping process
Object is closed, the cerous nitrate hexahydrate of addition and the ratio of graphene oxide solution are：(1~8) mg：2ml is obtained after lasting stirring
Obtain uniformly suspended mixed liquor；
3) urea, the urea of addition and the matter of cerous nitrate hexahydrate are added in the suspended mixed liquor that step 2) obtains
Amount is than being (10~20)：(1~8) then selects the NaOH solution of a concentration of 1~5mol/L to adjust pH value, and it is 11 to obtain pH value
~13 mixed system；
4) mixed system that step 3) obtains is put into the stainless steel autoclave that liner is 100ml polytetrafluoroethylene (PTFE)
In, sealing is placed into constant temperature oven, and hydro-thermal reaction, reaction time >=180min are carried out at 200 DEG C；It after reaction, will be anti-
It answers kettle to be quickly cooled to room temperature into the water, obtains mixed solution；
5) mixed solution that centrifugal treating step 4) obtains collects sediment, centrifugal speed 8000r/min；After centrifugation
The use of volume ratio is 1：The ethyl alcohol of (2~5) and the mixed liquor of deionized water wash mixed solution 4~6 times repeatedly；
6) sediment after cleaning is put into baking oven, dry under vacuum or inert gas, drying temperature is 60~80
DEG C, drying time be 12~for 24 hours, obtain hydroxyl carbon cerium mine nano-cluster/graphene composite material；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material.
7) it is lightly ground hydroxyl carbon cerium mine nano-cluster/graphene composite material that step 6) obtains with agate；It will be ground
Hydroxyl carbon cerium mine nano-cluster/graphene composite material be put into ethylene glycol solution, the ratio of composite material and ethylene glycol solution
For：(3~10) mg：4ml, supersound process obtain evenly dispersed suspended mixed liquor, ultrasonic power 150W, sonication treatment time
For 80~100min；
8) the suspended mixed liquor that step 7) obtains is transferred on magnetic stirring apparatus, the mixing of chloroplatinic acid and ethylene glycol is added
The mass concentration of platinum is 5mg/ml in liquid, chloroplatinic acid and ethylene glycol mixture, and magnetic agitation uniformly obtains mixed solution；It is added
The ratio of chloroplatinic acid and ethylene glycol mixture and composite material is (1~5) ml：(30~100) mg；
9) NaOH solution of saturation is added in the mixed solution that step 8) obtains with control ph, obtain pH value be 12~
13 mixed solutions.
10) mixed solution that the pH value that step 9) obtains is 12~13 is transferred in flask, in the present invention preferably
The three-neck flask of 100ml, 2~4h of oil bath heating reflux at 100~200 DEG C, and continue stirring until uniformly, it obtains mixing molten
Liquid.
11) it will stir and be cooled to room temperature in mixed solution fast transfer to beaker that step 10) obtains, hydrochloric acid is added and adjusts
PH obtains the solution that pH value is 2~3 to acidity after stirring evenly；A concentration of 1~5mol/ of preferred hydrochloric acid solution in the present invention
ml。
12) continue whipping step 11) centrifugal treating after obtained 5~30min of solution, centrifugal speed 8000r/min, so
It is washed repeatedly 4~6 times with ethyl alcohol and the mixed liquor of deionized water afterwards, finally obtains the sediment after cleaning, collect sediment；Second
Ethyl alcohol and deionized volume ratio are in alcohol and deionized water mixed liquor：1:(2~5).
13) it by the sediment merging baking oven after cleaning, dries in a vacuum or inert atmosphere, drying temperature is 60~80
DEG C, drying time be 12~for 24 hours, obtain Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material.
The present invention is further elaborated with reference to specific embodiments and the drawings：
Embodiment 1：Contrast test
20ml graphene oxide solutions and 20ml ethylene glycol solutions is taken to mix, ultrasound under conditions of ultrasonic power is 150W
60min, then mixed solution is transferred on magnetic stirring apparatus, it is controlled under stirring using 1mol/ml sodium hydroxide solutions
System pH is 12, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is placed into
180min is kept in constant temperature oven at 200 DEG C, after reaction, reaction kettle is quickly down to room temperature into the water, takes out mixing
Simultaneously sediment is collected by centrifugation in 8000r/min in solution, and ethyl alcohol/deionized water (1 is used in combination:2) mixed solution is centrifuged repeatedly washing 6
It is secondary, the sediment after washing is put into 60 DEG C of vacuum drying 12h in vacuum drying oven, for use；
The for use samples of 30mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, in the item that ultrasonic power is 150W
Ultrasound 90min, is then transferred on magnetic stirring apparatus under part, and it is molten that 1.5ml chloroplatinic acids/ethylene glycol is added under stirring
Liquid continues to stir 15min, and it is 12 that saturation sodium hydroxide solution control system pH value, which is added, and mixed liquor is transferred to tri- necks of 100ml
It in flask, is subsequently placed in oil bath, 2h is heated to reflux at 120 DEG C, it will be in mixed solution fast transfer to beaker after oil bath
Stirring is cooled to room temperature, and 1mol/ml hydrochloric acid regulation system pH value is added to 2, persistently stirs 30min, sediment is collected by centrifugation, uses
Ethyl alcohol/deionized water (1:2) mixed solution is centrifuged repeatedly washing 6 times, the sediment after washing be put into vacuum drying oven 60 DEG C it is true
The dry 12h of sky, obtains Pt nanoparticle/graphene composite material.
Fig. 1 is the TEM photos of Pt nanoparticle/graphene composite material prepared by the embodiment of the present invention 1, can be with by Fig. 1
Find out, in the case where cerous nitrate hexahydrate is not added, the Pt nanoparticle size prepared by embodiment 1 is consistent, and
Even distribution is on the surface of graphene.
Embodiment 2：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 20ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
4mg/ml；Ultrasound 60min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
40mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 150mg urea, uses the NaOH solution of 1mol/ml
The pH value of adjustment system is 12, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 180min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:2) mixed solution is centrifuged repeatedly washing 6
It is secondary, then sediment is put into 60 DEG C of vacuum drying 12h in vacuum drying oven, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use sample for weighing 40mg, is put into after being lightly ground in 40ml ethylene glycol solutions, is in ultrasonic power by solution
Ultrasound 90min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 2ml chloroplatinic acids/ethylene glycol is added under stirring
Solution, after stirring evenly, it is 13 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred in 100ml three-neck flasks,
It is subsequently placed in oil bath, 2h is heated to reflux at 120 DEG C, will stir and cool down in mixed solution fast transfer to beaker after oil bath
To room temperature, 1mol/ml hydrochloric acid regulation system pH value is added to 3, persistently stirs 30min, sediment is collected by centrifugation, with ethyl alcohol/go
Ionized water (1:2) mixed solution is centrifuged repeatedly washing 6 times, 60 DEG C of vacuum drying in the sediment merging vacuum drying oven after washing
12h obtains Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material.
XRD and TEM points are carried out to 2 gained Pt nano particles of embodiment/hydroxyl carbon cerium mine nano-cluster/graphene composite material
Analysis, as a result as shown in Figures 2 and 3.
Fig. 2 is Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material prepared by the embodiment of the present invention 2
XRD spectrum, it can be seen that substance hydroxyl-removal carbon cerium mine characteristic peak (No.52~0352 JCPDS) prepared by embodiment 2 and platinum are special
Levy peak No.04~0802 JCPDS) outside, the appearance without other crystalline phase characteristic peaks shows that the composite material has high-purity characteristic,
20~35 ° of amorphous peak is the feature of graphene；
Fig. 3 is Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material prepared by the embodiment of the present invention 2
TEM photos, as seen from Figure 3, the hydroxyl carbon cerium mine prepared by embodiment 2 is nanocluster, and is evenly distributed on graphene
Surface, Pt nano particles are equally dispersed in entire graphene surface and are in close contact with hydroxyl carbon cerium mine nano particle.
Fig. 4 and Fig. 5 is the experiment knot that the composite material prepared to embodiment 1 and embodiment 2 carries out Electrocatalytic Oxidation of Methanol
Fruit.Fig. 4 is mass activity comparison diagram, it can be seen that Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster prepared by embodiment 2/
Graphene composite material Electrocatalytic Oxidation of Methanol activity is higher than the composite material prepared by embodiment 1；Fig. 5 is stability contrast
Figure, it can be seen that Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material electrocatalytic oxidation prepared by embodiment 2
The stability for changing methanol is substantially better than Pt nanoparticle/graphene composite material prepared by embodiment 1.The result shows that this hair
The Pt nano particles of bright preparation/hydroxyl carbon cerium mine nano-cluster/graphene composite material can be obviously improved platinum catalysis Oxidation of Methanol
Stability.
Fig. 6 is the experimental result that composite material prepared by embodiment 2 and embodiment 1 carries out resisting CO poison.As can be seen that real
Apply the oxidation peak starting spike potential of the CO of Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material prepared by example 2
In 0.345V, and the CO oxidation peaks of Pt nanoparticle/graphene composite material prepared by embodiment 1 starting spike potential exists
0.439V.The CO initial oxidations spike potential about 0.1V more early than embodiment 1 of embodiment 2, this illustrates that embodiment 2 can more efficiently be gone
Except the CO of Pt adsorptions, that is, there is excellent resisting CO poison effect.
Embodiment 3：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 20ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
4mg/ml；Ultrasound 60min under conditions of ultrasonic power is 150W, mixed solution is transferred on magnetic stirring apparatus, is being stirred
80mg cerous nitrate hexahydrates are added in the process, are stirring evenly and then adding into 200mg urea, and molten using the NaOH of 1mol/ml
It is 13 that liquid, which adjusts system pH, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is put into constant temperature oven and keeps 180min that reaction kettle is quickly down to room temperature into the water after reaction at 200 DEG C, take out
Simultaneously sediment is collected by centrifugation in 8000r/min in mixed solution, and ethyl alcohol/deionized water (1 is used in combination:2) mixed solution, which is centrifuged repeatedly, washes
It washs 6 times, the sediment after washing is put into 60 DEG C of vacuum drying 12h in vacuum drying oven, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 100mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 90min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 5ml chloroplatinic acids/second two is added under stirring
Alcoholic solution, after stirring evenly, it is 13 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred to 100ml three-neck flasks
In, it is subsequently placed in oil bath, 2h is heated to reflux at 120 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It is cooled to room temperature, 1mol/ml hydrochloric acid regulation system pH value is added to 3, after persistently stirring 30min, sediment is collected by centrifugation, uses second
Alcohol/deionized water (1:2) mixed solution is centrifuged repeatedly washing 6 times, and the sediment after washing is put into 60 DEG C of vacuum in vacuum drying oven
Dry 12h, obtains Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Embodiment 4：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 40ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
1mg/ml；Ultrasound 50min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
10mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 100mg urea, uses the NaOH solution of 2mol/ml
The pH value of adjustment system is 11, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 220min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:3) mixed solution is centrifuged repeatedly washing 4
It is secondary, then sediment is put into 70 DEG C of vacuum drying 15h in vacuum drying oven, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 30mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 80min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 1ml chloroplatinic acids/second two is added under stirring
Alcoholic solution, after stirring evenly, it is 13 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred to 100ml three-neck flasks
In, it is subsequently placed in oil bath, 2h is heated to reflux at 100 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It is cooled to room temperature, 5mol/ml hydrochloric acid regulation system pH value is added to 2, after persistently stirring 5min, sediment is collected by centrifugation, uses second
Alcohol/deionized water (1:3) mixed solution is centrifuged repeatedly washing 6 times, and the sediment after washing is put into 60 DEG C of vacuum in vacuum drying oven
Drying for 24 hours, obtains Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Embodiment 5：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 80ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
10mg/ml；Ultrasound 50min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
80mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 100mg urea, uses the NaOH solution of 5mol/ml
The pH value of adjustment system is 12, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 200min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:4) mixed solution is centrifuged repeatedly washing 4
It is secondary, then sediment is put into the baking oven under Ar atmosphere 80 DEG C of dryings for 24 hours, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 100mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 85min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 1ml chloroplatinic acids/second two is added under stirring
Alcoholic solution, after stirring evenly, it is 12 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred to 100ml three-neck flasks
In, it is subsequently placed in oil bath, 3h is heated to reflux at 110 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It is cooled to room temperature, 5mol/ml hydrochloric acid regulation system pH value is added to 2, after persistently stirring 10min, sediment is collected by centrifugation, uses second
Alcohol/deionized water (1:4) mixed solution is centrifuged repeatedly washing 6 times, and the sediment after washing is put into 70 in the baking oven for being connected with Ar gas
It is DEG C dry for 24 hours, obtain Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Embodiment 6：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 60ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
6mg/ml；Ultrasound 70min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
60mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 100mg urea, uses the NaOH solution of 5mol/ml
The pH value of adjustment system is 11, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 230min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:5) mixed solution is centrifuged repeatedly washing 5
It is secondary, then sediment is put into 65 DEG C of vacuum drying 20h in vacuum drying oven, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 60mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 95min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 1ml chloroplatinic acids/second two is added under stirring
Alcoholic solution, after stirring evenly, it is 12 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred to 100ml three-neck flasks
In, it is subsequently placed in oil bath, 3h is heated to reflux at 105 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It is cooled to room temperature, 3mol/ml hydrochloric acid regulation system pH value is added to 3, after persistently stirring 15min, sediment is collected by centrifugation, uses second
Alcohol/deionized water (1:3) mixed solution is centrifuged repeatedly washing 4 times, and the sediment after washing is put into 70 in the baking oven for be passed through argon gas
DEG C dry 18h, obtains Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Embodiment 7：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 100ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
2mg/ml；Ultrasound 70min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
10mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 150mg urea, uses the NaOH solution of 3mol/ml
The pH value of adjustment system is 13, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 260min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:3) mixed solution is centrifuged repeatedly washing 5
It is secondary, then sediment is put into 75 DEG C of dry 18h in the baking oven for being connected with Ar gas, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 30mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 80min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 5ml chloroplatinic acids/second two is added under stirring
Alcoholic solution, after stirring evenly, it is 12 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred to 100ml three-neck flasks
In, it is subsequently placed in oil bath, 3h is heated to reflux at 115 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It is cooled to room temperature, 3mol/ml hydrochloric acid regulation system pH value is added to 3, after persistently stirring 20min, sediment is collected by centrifugation, uses second
Alcohol/deionized water (1:5) mixed solution is centrifuged repeatedly washing 4 times, and the sediment after washing is put into 80 in the baking oven for be passed through argon gas
DEG C dry 16h, obtains Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Embodiment 8：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 40ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
8mg/ml；Ultrasound 55min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
80mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 150mg urea, uses the NaOH solution of 4mol/ml
The pH value of adjustment system is 12, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 280min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:2) mixed solution is centrifuged repeatedly washing 6
It is secondary, then sediment is put into 80 DEG C of dry 22h in the baking oven for being connected with Ar gas, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 60mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 100min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 5ml chloroplatinic acids/second is added under stirring
Glycol solution, after stirring evenly, it is 13 that saturation NaOH solution control solution ph, which is added, and mixed liquor, which is transferred to tri- necks of 100ml, to be burnt
In bottle, it is subsequently placed in oil bath, 4h is heated to reflux at 120 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It mixes and is cooled to room temperature, 2mol/ml hydrochloric acid regulation system pH value is added to 2, after persistently stirring 25min, sediment is collected by centrifugation, uses
Ethyl alcohol/deionized water (1:4) mixed solution is centrifuged repeatedly washing 5 times, the sediment after washing be put into vacuum drying oven 80 DEG C it is true
The dry 20h of sky, obtains Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Embodiment 9：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 20ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
3mg/ml；Ultrasound 65min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
10mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 200mg urea, uses the NaOH solution of 2mol/ml
The pH value of adjustment system is 11, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 300min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:3) mixed solution is centrifuged repeatedly washing 5
It is secondary, then sediment is put into 62 DEG C of vacuum drying 17h in vacuum drying oven, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 30mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 90min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 3ml chloroplatinic acids/second two is added under stirring
Alcoholic solution, after stirring evenly, it is 13 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred to 100ml three-neck flasks
In, it is subsequently placed in oil bath, 4h is heated to reflux at 100 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It is cooled to room temperature, 4mol/ml hydrochloric acid regulation system pH value is added to 2, after persistently stirring 5min, sediment is collected by centrifugation, uses second
Alcohol/deionized water (1:3) mixed solution is centrifuged repeatedly washing 5 times, and the sediment after washing is put into 70 DEG C of vacuum in vacuum drying oven
Dry 22h, obtains Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
Embodiment 10：
The first step：Prepare hydroxyl carbon cerium mine nano-cluster/graphene composite material
20ml graphene oxide solutions and 100ml ethylene glycol solutions is taken to mix, the mass concentration of graphene oxide solution is
5mg/ml；Ultrasound 70min under conditions of ultrasonic power is 150W；Mixed solution is transferred on magnetic stirring apparatus, is being stirred
30mg cerous nitrate hexahydrates are added in the process, is stirring evenly and then adding into 200mg urea, uses the NaOH solution of 3mol/ml
The pH value of adjustment system is 13, is then transferred to mixed solution in the reaction kettle for the polytetrafluoroethylene (PTFE) that liner is 100ml, sealing is simultaneously
It is placed in constant temperature oven and keeps 320min at 200 DEG C, reaction kettle is quickly down to room temperature into the water after reaction, take out mixed
It closes solution and sediment is collected by centrifugation in 8000r/min, ethyl alcohol/deionized water (1 is used in combination:5) mixed solution is centrifuged repeatedly washing 4
It is secondary, then sediment is put into 75 DEG C of vacuum drying 23h in vacuum drying oven, for use；
Second step：Prepare Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite material
The for use samples of 100mg are weighed, are put into after being lightly ground in 40ml ethylene glycol solutions, are in ultrasonic power by solution
Ultrasound 85min, is then transferred on magnetic stirring apparatus under conditions of 150W, and 3ml chloroplatinic acids/second two is added under stirring
Alcoholic solution, after stirring evenly, it is 12 that saturation NaOH solution control solution ph, which is added, and mixed liquor is transferred to 100ml three-neck flasks
In, it is subsequently placed in oil bath, 4h is heated to reflux at 110 DEG C, will be stirred in mixed solution fast transfer to beaker after oil bath
It is cooled to room temperature, 4mol/ml hydrochloric acid regulation system pH value is added to 3, after persistently stirring 20min, sediment is collected by centrifugation, uses second
Alcohol/deionized water (1:5) mixed solution is centrifuged repeatedly washing 4 times, and the sediment after washing is put into 80 in the baking oven for be passed through argon gas
DEG C dry 14h, obtains Pt nanoparticle~hydroxyl carbon cerium mine nano-cluster/graphene composite material.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of preparation method of hydroxyl carbon cerium mine nano-cluster/graphene composite material, it is characterised in that：Include the following steps：
1-1) mixed oxidization graphene solution and ethylene glycol solution obtain uniform mixed solution after supersound process；Stirring gained
Mixed solution, while cerous nitrate hexahydrate is added, continue to stir to get uniform suspended mixed liquor；
1-2) in step 1-1) urea is added in obtained suspended mixed liquor after adjustment pH value to 11~13, obtain mixed system,
Mixed system is placed in autoclave and carries out hydro-thermal reaction, is quickly cooled down to obtain mixed solution after reaction；
1-3) centrifugal treating step 1-2) obtained mixed solution, collect sediment；It is washed with the mixed liquor of ethyl alcohol and deionized water
It washs sediment several times, by the drying precipitate after washing, obtains hydroxyl carbon cerium mine nano-cluster/graphene composite material.
2. a kind of preparation method of hydroxyl carbon cerium mine nano-cluster/graphene composite material according to claim 1, feature
It is：Step 1-1) in the mass concentration of graphene oxide solution be 1~10mg/ml, graphene oxide solution is molten with ethylene glycol
The volume ratio of liquid is 1:(1~3)；Sonication treatment time is 50~70min；The cerous nitrate hexahydrate and graphite oxide of addition
The ratio of alkene solution is：(1~8) mg：2ml.
3. a kind of preparation method of hydroxyl carbon cerium mine nano-cluster/graphene composite material according to claim 1, feature
It is：Step 1-2) in the urea and step 1~1 that are added) in the mass ratio of cerous nitrate hexahydrate that is added be (10~
20)：(1~8)；The temperature of hydro-thermal reaction is 200 DEG C, the reaction time >=180min；After hydro-thermal reaction into the water by reaction kettle,
Mixed solution is set to be quickly cooled to room temperature.
4. a kind of preparation method of hydroxyl carbon cerium mine nano-cluster/graphene composite material according to claim 1, feature
It is：Step 1-3) in volume ratio be 1：The ethyl alcohol of (2~5) and deionized water mixed liquor washing precipitate 4~6 times；Precipitation
The dry environment of object be vacuum or inert atmosphere, drying temperature be 60~80 DEG C, drying time be 12~for 24 hours.
5. a kind of hydroxyl carbon cerium mine nano-cluster/graphene that the preparation method described in claim 1-4 any one is prepared is multiple
Condensation material.
6. a kind of Pt nano particles/hydroxyl carbon based on hydroxyl carbon cerium mine nano-cluster/graphene composite material described in claim 5
The preparation method of cerium mine nano-cluster/graphene composite material, which is characterized in that include the following steps：
2-1) grinding hydroxyl carbon cerium mine nano-cluster/graphene composite material obtains powder, and gained powder is put into ethylene glycol solution
In, after being ultrasonically treated the suspended mixed liquor of gained, the mixed liquor of chloroplatinic acid and ethylene glycol is added during magnetic agitation solution,
Obtain mixed solution；
2-2) set-up procedure 2-1) obtained mixed solution pH value is to 12~13, oil bath reflow treatment acquired solution；Solution is stirred
It mixes and is cooled to room temperature, adjustment pH value to 2~3 obtains mixed solution after continuing stirring；
2-3) centrifugal treating step 2-2) obtained mixed solution, collect sediment；Mixed liquor with ethyl alcohol and deionized water is anti-
After backwashing is washed several times, and the sediment after dry cleaning obtains Pt nano particles/hydroxyl carbon cerium mine nano-cluster/graphene composite wood
Material.
7. the preparation side of Pt nano particles according to claim 6/hydroxyl carbon cerium mine nano-cluster/graphene composite material
Method, which is characterized in that step 2-1) in use agate grinding hydroxyl carbon cerium mine nano-cluster/graphene composite material, the powder of addition
The ratio of end and ethylene glycol solution is (3~10) mg：4ml；The mass concentration of platinum is 5mg/ in chloroplatinic acid and ethylene glycol mixture
Ml, the chloroplatinic acid and ethylene glycol mixture of addition and the ratio of composite powder are (1~5) ml：(30~100) mg.
8. the preparation side of Pt nano particles according to claim 6/hydroxyl carbon cerium mine nano-cluster/graphene composite material
Method, which is characterized in that step 2-2) in select saturation NaOH adjustment mixed solution pH to 12~13；Oil bath reflux temperature
For：100~200 DEG C, oil bath return time is 2~4h；Solution to the pH value of selection hydrochloric acid adjustment at room temperature stirs 5 after being 2~3
~30min, obtains mixed solution.
9. the preparation side of Pt nano particles according to claim 6/hydroxyl carbon cerium mine nano-cluster/graphene composite material
Method, which is characterized in that step 2-3) in sediment ethyl alcohol and deionized water mixed liquor washing precipitate 4~6 times, ethyl alcohol and go
The volume ratio of ionized water is 1：(2~5)；The dry environment of sediment is vacuum or inert atmosphere, and drying temperature is 60~80 DEG C,
Drying time be 12~for 24 hours.
10. a kind of Pt nano particles that the preparation method described in claim 6-9 any one is prepared/hydroxyl carbon cerium mine nanometer
Cluster/graphene composite material.
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