CN107394222A - Cerium oxide/noble metal/graphene trielement composite material and its preparation method and application - Google Patents
Cerium oxide/noble metal/graphene trielement composite material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of cerium oxide/noble metal/graphene trielement composite material, it is layer structure, is made up of nanoscale cerium, noble metal and graphene, the formula of described trielement composite material is CeO2/ M/ graphenes, wherein M are Pd, Pt or Au.Cerium oxide and noble metal can be uniformly distributed and granularity is small due to the scattered and carrying effect of graphene in the composite, and form layer structure, can be effectively improved the catalytic performance of the trielement composite material, be can be used as lithium sky cell positive material.The invention also discloses a step low temperature preparation method of the composite, have that technique is simple, cost is low, the cycle is short, low power consumption and other advantages, be adapted to large-scale industrial production.
Description
Technical field
The present invention relates to lithium-empty battery field of compound material, and in particular to a kind of cerium oxide/noble metal/graphene three
First composite and its preparation method and application.
Background technology
Lithium-empty battery is a kind of using lithium metal as negative pole, and air (or oxygen) is positive pole, and lithium ion conductor is electrolyte
Novel energy storage apparatus.The theoretical energy density of lithium-empty battery is up to 11680Wh/kg (not including O2If including O2, then for
5200Wh/kg).In view of the weight of catalyst, electrolyte, battery packages etc., the reality of lithium-empty battery can obtain energy density about
For 1700Wh/kg, the value can be suitable with the energy density of gasoline, (general far above nickel-hydrogen (50Wh/kg), lithium ion<
200Wh/kg), lithium-sulphur (370Wh/kg), the energy density of zinc-sky (350Wh/kg) battery.Lithium-empty battery is due to its high energy
Metric density, there is important application prospect in fields such as the energy storage of Vehicular dynamic battery and power network.Just because of lithium-empty battery tool
There is very important application prospect, some leading companys and scientific research institution start the research of lithium sky battery in the world.Such as the U.S.
IBM Corporation starts that " Battery 500Project " projects, the final goal of the plan are that lithium-empty battery is used for into vapour
Car." 500 " represent each Rechargeable vehicle traveling 500 miles (800 kilometers) in the project.
It is many to influence the factor of lithium-empty battery performance, but the composition of catalyst and structure are key factors.Recently, it is various
New catalyst such as noble metal M (M=Ru, Au, Pd, Pt), PtAu, MnO2、MnO2/Ti、MnO2/ Pd, MoN/ graphenes,
MnCo2O4/ graphene etc. is developed.For catalyst component, relative to metal oxide (such as Fe2O3、MnO2) catalyst, your gold
Metal catalyst has its unique performance advantage, is lithium-extremely ideal catalyst of empty battery air.But noble metal catalyst
Cost is higher, therefore the usage amount for reducing noble metal is the trend of catalyst development from now on, wherein development of metallic oxide/expensive
Metal composite catalyst is one of effective means for solving the problem.In addition, noble metal on oxides dispersed and
Reduce one of method of its usage amount.And for Catalyst Design, composition and the structure of catalyst carrier are also important
One ring, comparatively ideal matrix material are carbon materials.In various carbon materials, graphene is because its high electrical conductivity, high machinery
Intensity, big specific surface area agent and porosity, are ideal matrix materials.
It is many that the report of composite is prepared using graphene as matrix material in the prior art, but is used as lithium-sky
The report of cell catalyst carrier is seldom, as a kind of for the empty electricity of lithium in disclosed in Chinese patent application CN201110405944.3
The graphene in pond-platinum nano-composite catalyst and preparation method thereof, the composite catalyst is made up of graphene and Pt nanoparticle,
Using solid platinum as target, using liquid-phase pulse laser ablation technology, nano-platinum particle is grown on graphene.The composite catalyzing material
Material has good catalytic performance, and under 100mA/g electric currents, reversible capacity reaches 4000mAh/g, and with less excessively electric
Pressure and good cyclical stability.Therefore, it is that composite catalyzing material has broad application prospects to develop graphene.But at present with stone
Black alkene is rarely reported for the ternary complex catalyst of carrier.
The content of the invention
The invention provides a kind of good stratiform knot of the chemical properties such as high power capacity, low overpotential, high circulation stability
Cerium oxide/noble metal/graphene trielement composite material of structure, additionally provide a kind of cerium oxide/noble metal/graphite of layer structure
The preparation method of alkene trielement composite material, this method technique is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production.
A kind of cerium oxide/noble metal/graphene trielement composite material, it is characterised in that by nanoscale cerium CeO2, it is expensive
Metal and graphene composition, wherein CeO2And noble metal forms layer structure, trielement composite material between graphene sheet layer
Formula be CeO2/ M/ graphenes, wherein noble metal M are Pt, Pd or Au.
Further, the weight percentage of graphene is 1%~20% in described trielement composite material, further excellent
Elect 6%~15% as.
Further, the weight percentage of noble metal is 1%~10% in described trielement composite material, further excellent
Elect 4%~8% as.
Excessive CeO2It is unfavorable for its uniform load on graphene and leaves space, very few CeO in interlayer2Meeting
Weaken concerted catalysis performance.Excessive bullion content can cause the reunion of particle and the increase of battery cost, your very few gold
Category can weaken concerted catalysis effect.Therefore, by CeO2Controlled with noble metal proper in above-mentioned level.
Further, the particle diameter of described nanoscale cerium is 5 nanometers~15 nanometers, of nanoscale precious metal
A diameter of 1 nanometer~5 nanometers of grain.
Cerium oxide particle diameter is smaller, more easily covers and is loaded on graphene, but particle is too small is unfavorable for reserving for bedding void
And the load of noble metal；The particle diameter of noble metal is smaller, is more easily carried on cerium oxide particle surface, but particle diameter crosses little particle
Easily reunite, therefore select above-mentioned particle diameter.
Further, described nanoscale cerium and noble metal nano particles are dispersed in graphene sheet layer, and
Graphene sheet layer forms layer structure, and makes to form space between layer, and the number of plies is less than 5 layers.
Different from traditional block structure, this structure is advantageous to the diffusion of oxygen and the transmission of lithium ion, and peroxide
Change the deposition of lithium, so as to improve the performance of lithium-empty battery.In addition, in this configuration, it is uniform due to being oxidized cerium nano particle
Load, disperse, it is suppressed that the reunion of noble metal nano particles, so as to improve its catalytic activity and persistence, and reduce it
Dosage, so as to reduce battery cost.
Further, described noble metal granule is carried on cerium oxide nanoparticles surface, is oxidized cerium nano particle
It is dispersed.
A kind of method for preparing cerium oxide/noble metal/graphene trielement composite material described in any of the above-described, including with
Lower step：
(1) trivalent Ce salt is dissolved in reproducibility organic solvent, obtains Ce3+Concentration be 0.01mol/L~0.1mol/L
Solution, add graphene oxide GO, mixed solution obtained through ultrasonic disperse；
Described GO addition is final product cerium oxide CeO2The 5%~50% of theoretical weight；More preferably
17%~47%；
(2) solution of step (1) is sealed, is warming up to 180 DEG C~220 DEG C, reaction cools down after 12 hours~48 hours, receives
Collect solid product, washed through deionized water and absolute ethyl alcohol alternate repetition, dry, obtain cerium oxide/graphene of layer structure
Composite；
(3) cerium oxide/graphene composite material obtained by step (2) is scattered in reproducibility organic solvent, adds and contain
The compound of noble metal, its addition are final product cerium oxide CeO2The 5%~25% of theoretical weight, it is close after ultrasonic disperse
Envelope, 100 DEG C~160 DEG C are warming up to, reaction cools down after 1 hour~6 hours, solid product is collected, through deionized water and anhydrous second
Alcohol alternate repetition washs, and dries, obtains cerium oxide/M/ graphene composite materials of layer structure, wherein M is Pd, Pt or Au.
The reducing agents such as hydrazine hydrate, sodium borohydride need not be used in this method, in reproducibility solvent, graphene oxide can
By solvothermal into graphene, the compound containing noble metal is also reducible into noble metal.
Also without the poisonous oxygen original agent such as NaBH of use in this method4Or hydrazine hydrate, in step (1) ultrasonic disperse process
The O that middle trivalent Ce is easily dissolved in solution2Tetravalence Ce is oxidized to, but dissolved oxygen does not influence the reduction of graphene.
Further, described trivalent Ce salt is trivalent Ce fluoride, trivalent Ce chloride, trivalent Ce nitric acid
Salt, trivalent Ce sulfate, trivalent Ce oxalates, the hydrate of trivalent Ce acetate or any one salt；
The described compound containing noble metal includes H2PdCl4、Pd(NH3)4Cl2、Pd(NH3)2Cl2、Pd(NH3)4SO4、Pd
(NH3)4(NO3)2、H2PtCl6、H2PtCl4、K2PtCl6、(NH4)2PtCl6、K2PtCl4、(NH4)2PtCl4、HAuCl4、NaAuCl4、
KAuCl4Or the hydrate of any one compound.
Further, described reproducibility organic solvent is ethanol, glycerine, methanol, ethylene glycol, n-butyl alcohol, N, N- bis-
NMF, ethylenediamine or oleyl amine.
In step (2), cooled down after further preferably being reacted 20 hours~32 hours at 180 DEG C~220 DEG C；
In step (3), cooled down after further preferably being reacted 2 hours~4 hours at 110 DEG C~140 DEG C；
Reaction temperature is high, and time length, cerium oxide is easily formed, and graphene oxide is easily reduced into graphene, the change containing noble metal
Compound is easily reduced into noble metal, but too high temperature, long time easily cause growing up for cerium oxide and noble metal granule, and
The reunion of graphene, influence its catalytic effect.
The temperature of described cooling does not have strict restriction, based on adequate operation, can typically be cooled to 15 DEG C~30
DEG C environment temperature.
A kind of cerium oxide/noble metal/graphene trielement composite material described in any of the above-described is as lithium-empty anode
The application of material.
The present invention is compound by cerium oxide, noble metal and graphene, is acted on using their concerted catalysis to improve lithium sky battery
Chemical property, especially reduce overpotential.Its concerted catalysis mechanism is as follows, noble metal due to its high catalytic activity often into
To aoxidize the activated centre of original/evolution reaction, cerium oxide contains Ce due to it3+/Ce4+Redox couple serves the buffering of oxygen
Body, graphene are advantageous to lithium peroxide Li due to its high electrical conductivity and big specific surface area2O2Deposition, therefore three is answered
Close the performance for being advantageous to improve lithium-empty battery.
Compared with prior art, the invention has the advantages that：
1st, the present invention uses two step solvent-thermal methods in low temperature preparation cerium oxide/noble metal/graphene trielement composite material, tool
Have the advantages that technique is simple, cost is low, the cycle is short, energy consumption is low and suitable industrialized production.
2nd, due to the scattered and carrying effect of graphene, cerium oxide granularity is small in composite of the present invention, and diameter is about 5 to receive
Rice~15 nanometers, and be distributed than more uniform；Noble metal granule is small, and diameter is about 1 nanometer~5 nanometers, easily oxidized cerium it is scattered and
It is fixed.
3rd, ceria nanoparticles and noble metal granule are located in graphene sheet layer, and each graphene sheet layer forms stratiform knot
Structure, the structure are advantageous to the deposition of the transmission of oxygen, the diffusion of lithium ion and lithium peroxide, so as to improve lithium-empty battery electrification
Learn performance.
Brief description of the drawings
Fig. 1 is the gained CeO of embodiment 12The X ray diffracting spectrum of/Pt/ graphene composite materials；
Fig. 2 is the gained CeO of embodiment 12The transmission electron microscope photo of/Pt/ graphene composite materials；
Fig. 3 is the gained CeO of embodiment 12The stereoscan photograph of/Pt/ graphene composite materials；
Fig. 4 is the gained CeO of embodiment 12The chemical property figure of/Pt/ graphene composite materials.
Embodiment
Embodiment 1
By CeCl3·6H2O is dissolved in ethylene glycol, is configured to 80 milliliters of Ce3+Concentration is 0.01mol/L solution, adds 65
Mixed solution is made in milligram GO, and now GO addition is final product cerium oxide CeO2The 47% of theoretical weight, through ultrasound point
Dissipate and obtain mixed solution, mixed solution is placed in the autoclave that capacity is 100 milliliters, compactedness is percent by volume 80%
In, reactor is sealed, is reacted 20 hours at 180 DEG C, naturally cools to room temperature；Solid reaction product is collected, product is passed through
Deionized water and the washing of absolute ethyl alcohol alternate repetition, dry, obtain cerium oxide/graphene composite material, then by above-mentioned composite wood
Material is scattered in ethylene glycol, then adds 15 milligrams of H2PtCl4, its addition is final product cerium oxide CeO2Theoretical weight
11%, sealed after ultrasonic disperse, be warming up to 110 DEG C, reaction cools down after 2 hours, solid product is collected, through deionized water and nothing
Water-ethanol alternate repetition washs, and dries, obtains 0.16g cerium oxide/Pt/ graphene composite materials, wherein, the weight hundred of graphene
It is 5% to divide the weight percentage that content is 15%, Pt.
X ray diffracting spectrum, transmission electron microscope photo and the stereoscan photograph difference of the composite of gained are as shown in Figure 1, Figure 2
And the diffraction maximum of X ray can be attributed to CeO in Fig. 3, Fig. 12, the diffraction maximum of graphene is cannot make out from X ray diffracting spectrum,
Illustrate graphene by CeO2Particle disperses.In addition, can not see the diffraction maximum of platinum from Fig. 1 X ray diffracting spectrum, this
It is because Pt comparision contents are low, from Fig. 2 transmission electron microscope it can be clearly seen that the composite of gained is CeO2/ Pt/ graphite
Alkene composite, wherein CeO2Particle size is in nanoscale, a diameter of 5 nanometers~15 nanometers, and is distributed than more uniform；Pt particles
Size be also nanoscale, a diameter of 1 nanometer~5 nanometers, be dispersed in CeO2Particle surface.From Fig. 3 stereoscan photographs
As can be seen that layer structure, i.e. CeO is presented in trielement composite material2And Pt nano particles are dispersed in each layer graphene lamella
In, the number of plies is less than 5 layers.
With CeO manufactured in the present embodiment2/ Pt/ graphenes trielement composite material is as lithium-empty anode, with lithium metal
For negative pole, polypropylene film (trade mark Celgard C480, Celgard companies of the U.S.) is barrier film, LiClO4Triethylene glycol two
Methyl ether TEGDME solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, enter
Row charge-discharge test, its cyclic curve are as shown in Figure 4.
According to capacity limit in 500mAh/g, current density 100mA/g, wherein voltage range 2V~4.5V, capacity and electricity
The constant volume charge-discharge test that current density is based on the gross weight of composite shows, in secondary charge and discharge process, the lithium-oxygen battery
Stable circulation can be kept.By 40 circulations, its charge and discharge stopping potential is kept at 3.95V and 2.28V or so,
Show relatively low polarization and preferable cyclical stability.
Embodiment 2
By Ce (NO3)3·6H2O is dissolved in ethylenediamine, is configured to 80 milliliters of Ce3+Total concentration is 0.05mol/L solution, then
Add 258 milligrams of GO and mixed solution is made, now GO addition is final product cerium oxide CeO2The 37% of theoretical weight, warp
Ultrasonic disperse obtains mixed solution, mixed solution is placed in the autoclave that capacity is 100 milliliters, its compactedness is volume
Percentage 80%, reactor is sealed, and is reacted 24 hours at 200 DEG C, is naturally cooled to room temperature；Collect solid reaction product,
Product is washed through deionized water and absolute ethyl alcohol alternate repetition, dries, obtains cerium oxide/graphene composite material, then will be upper
State composite to be scattered in ethylenediamine, then add 162 milligrams of H2PdCl4, its addition is final product cerium oxide CeO2Reason
By the 23% of weight, sealed after ultrasonic disperse, be warming up to 120 DEG C, reaction cools down after 4 hours, collects solid product, through go from
Sub- water and absolute ethyl alcohol alternate repetition washing, dries, obtains 0.85g cerium oxide/Pd/ graphene composite materials, wherein, graphene
Weight percentage be 12%, Pd weight percentage be 8%.
The composite of gained characterizes through X ray diffracting spectrum, transmission electron microscope photo and stereoscan photograph, it is determined that
CeO2/ Pd/ graphene trielement composite materials, wherein CeO2Particle size is in nanoscale, a diameter of 5 nanometers~15 nanometers, and is distributed
Than more uniform；The size of Pd particles is also nanoscale, a diameter of 1 nanometer~5 nanometers, is dispersed in CeO2Particle surface.Three
Layer structure, i.e. CeO is presented in first composite2And Pd nano particles are dispersed in the number of plies in each layer graphene lamella and are less than 5
Layer.
With CeO manufactured in the present embodiment2/ Pd/ graphenes trielement composite material is as lithium-empty anode, with lithium metal
For negative pole, polypropylene film (trade mark Celgard C480, Celgard companies of the U.S.) is barrier film, LiClO4Triethylene glycol two
Methyl ether TEGDME solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, enter
Row charge-discharge test.
According to capacity limit in 500mAh/g, current density 100mA/g, wherein voltage range 2V~4.5V, capacity and electricity
The constant volume charge-discharge test that current density is based on the gross weight of composite shows, in secondary charge and discharge process, the lithium-oxygen battery
Stable circulation can be kept.By 40 circulations, its charge and discharge stopping potential is kept at 3.98V and 2.32V or so,
Show relatively low polarization and preferable cyclical stability.
Embodiment 3
By Ce2(SO4)3·8H2O is dissolved in DMF, is configured to 80 milliliters of Ce3+Concentration is 0.1mol/L's
Solution, add 230 milligrams of GO and mixed solution is made, its addition is final product cerium oxide CeO2The 17% of theoretical weight,
Mixed solution is obtained through ultrasonic disperse；Mixed solution is placed in autoclave (compactedness 80%, the body that capacity is 100 milliliters
Product percentage) in, reactor is sealed, is reacted 32 hours at 220 DEG C, naturally cools to room temperature；Collect solid reaction product,
Product is washed through deionized water and absolute ethyl alcohol alternate repetition, dries, obtains cerium oxide/graphene composite material, then will be upper
State composite to be scattered in DMF, then add 117 milligrams of KAuCl4, its addition is final product oxygen
Change cerium CeO2The 8.5% of theoretical weight, is sealed after ultrasonic disperse, is warming up to 140 DEG C, and reaction cools down after 3 hours, collects solid
Product, washed through deionized water and absolute ethyl alcohol alternate repetition, dry, obtain 1.5g cerium oxide/Au/ graphene composite materials,
Wherein, the weight percentage that the weight percentage of graphene is 6%, Au is 4%.
The composite of gained characterizes through X ray diffracting spectrum, transmission electron microscope photo and stereoscan photograph, it is determined that
CeO2Au/ graphene trielement composite materials, wherein CeO2Particle size is in nanoscale, a diameter of 5 nanometers~15 nanometers, and is distributed
Than more uniform；The size of Au particles is also nanoscale, a diameter of 1 nanometer~5 nanometers, is dispersed in CeO2Particle surface.Three
Layer structure, i.e. CeO is presented in first composite2And Pd nano particles are dispersed in the number of plies in each layer graphene lamella and are less than 5
Layer.
With CeO manufactured in the present embodiment2/ Au/ graphenes trielement composite material is as lithium-empty anode, with lithium metal
For negative pole, polypropylene film (trade mark Celgard C480, Celgard companies of the U.S.) is barrier film, LiClO4Triethylene glycol two
Methyl ether TEGDME solution is electrolyte, and battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, enter
Row charge-discharge test.
According to capacity limit in 500mAh/g, current density 100mA/g, wherein voltage range 2V~4.5V, capacity and electricity
The constant volume charge-discharge test that current density is based on the gross weight of composite shows, in secondary charge and discharge process, the lithium-oxygen battery
Stable circulation can be kept.By 40 circulations, its charge and discharge stopping potential is kept at 4.02V and 2.21V or so,
Show relatively low polarization and preferable cyclical stability.
Claims (10)
1. a kind of cerium oxide/noble metal/graphene trielement composite material, it is characterised in that by nanoscale cerium CeO2, your gold
Category and graphene composition, wherein CeO2And noble metal forms layer structure between graphene sheet layer, trielement composite material
Formula is CeO2/ M/ graphenes, wherein noble metal M are Pt, Pd or Au.
2. cerium oxide/noble metal/graphene trielement composite material according to claim 1, it is characterised in that described three
The weight percentage of graphene is 1%~20%, more preferably 6%~15% in first composite.
3. cerium oxide/noble metal/graphene trielement composite material according to claim 1, it is characterised in that described three
The weight percentage of noble metal is 1%~10%, more preferably 4%~8% in first composite.
4. cerium oxide/noble metal/graphene trielement composite material according to claim 1, it is characterised in that described receives
The particle diameter of meter level cerium oxide is 5 nanometers~15 nanometers, and the particle diameter of nanoscale precious metal is 1 nanometer~5 nanometers.
5. cerium oxide/noble metal/graphene trielement composite material according to claim 1, it is characterised in that described receives
Meter level cerium oxide and noble metal nano particles are dispersed in graphene sheet layer, and graphene sheet layer forms layer structure, and
Make to form space between layer, the number of plies is less than 5 layers.
6. cerium oxide/noble metal/graphene trielement composite material according to claim 5, it is characterised in that described is expensive
Metallic particles is carried on cerium oxide nanoparticles surface, and it is dispersed to be oxidized cerium nano particle.
7. a kind of method for preparing cerium oxide/noble metal/graphene trielement composite material described in any one of claim 1~6,
Comprise the following steps：
(1) trivalent Ce salt is dissolved in reproducibility organic solvent, obtains Ce3+Concentration be 0.01mol/L~0.1mol/L it is molten
Liquid, adds graphene oxide GO, and mixed solution is obtained through ultrasonic disperse；
Described GO addition is final product cerium oxide CeO2The 5%~50% of theoretical weight；More preferably 17%~
47%；
(2) solution of step (1) is sealed, is warming up to 180 DEG C~220 DEG C, reaction cools down after 12 hours~48 hours, collects solid
Body product, wash, dry through deionized water and absolute ethyl alcohol alternate repetition, the cerium oxide/graphene for obtaining layer structure is compound
Material；
(3) cerium oxide/graphene composite material obtained by step (2) is scattered in reproducibility organic solvent, added containing your gold
The compound of category, its addition are final product cerium oxide CeO2The 5%~25% of theoretical weight, is sealed after ultrasonic disperse,
100 DEG C~160 DEG C are warming up to, reaction cools down after 1 hour~6 hours, collects solid product, is handed over through deionized water and absolute ethyl alcohol
For washing repeatedly, dry, obtain cerium oxide/M/ graphene composite materials of layer structure, wherein M is Pd, Pt or Au.
8. preparation method according to claim 7, it is characterised in that described trivalent Ce salt be trivalent Ce fluoride,
Trivalent Ce chloride, trivalent Ce nitrate, trivalent Ce sulfate, trivalent Ce oxalates, trivalent Ce acetate or
The hydrate of any one salt；
The described compound containing noble metal includes H2PdCl4、Pd(NH3)4Cl2、Pd(NH3)2Cl2、Pd(NH3)4SO4、Pd(NH3)4
(NO3)2、H2PtCl6、H2PtCl4、K2PtCl6、(NH4)2PtCl6、K2PtCl4、(NH4)2PtCl4、HAuCl4、NaAuCl4、
KAuCl4Or the hydrate of any one compound.
9. preparation method according to claim 7, it is characterised in that described reproducibility organic solvent is ethanol, the third three
Alcohol, methanol, ethylene glycol, n-butyl alcohol, N,N-dimethylformamide, ethylenediamine or oleyl amine.
10. cerium oxide/noble metal/graphene trielement composite material described in a kind of any one of claim 1-6 is as lithium-sky electricity
The application of pond positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710557159.7A CN107394222B (en) | 2017-07-10 | 2017-07-10 | Cerium oxide/precious metal/graphene ternary composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710557159.7A CN107394222B (en) | 2017-07-10 | 2017-07-10 | Cerium oxide/precious metal/graphene ternary composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107394222A true CN107394222A (en) | 2017-11-24 |
| CN107394222B CN107394222B (en) | 2020-05-12 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878897A (en) * | 2018-06-22 | 2018-11-23 | 西安交通大学 | A kind of one-dimensional nano line hydroxyl cerous carbonate/graphene composite material and preparation method thereof |
| CN109082329A (en) * | 2018-07-23 | 2018-12-25 | 江苏大学 | A kind of ternary nano self-lubricating composite and preparation method thereof |
| CN110629266A (en) * | 2019-10-30 | 2019-12-31 | 贵州民族大学 | Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic |
| CN111180745A (en) * | 2019-12-30 | 2020-05-19 | 浙江工业大学 | CeO (CeO)xPreparation method and application of/MC nanosheet material |
| CN113231061A (en) * | 2021-03-04 | 2021-08-10 | 广东工业大学 | Cerium dioxide nanorod supported catalyst and preparation method and application thereof |
| WO2021181085A1 (en) * | 2020-03-10 | 2021-09-16 | Amalyst Limited | Catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102716734A (en) * | 2012-06-15 | 2012-10-10 | 浙江师范大学 | Preparation method for cerium oxide/graphene oxide nanocomposite |
| CN106457210A (en) * | 2014-03-18 | 2017-02-22 | 巴斯夫欧洲公司 | A process for the production of a carbon supported catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102716734A (en) * | 2012-06-15 | 2012-10-10 | 浙江师范大学 | Preparation method for cerium oxide/graphene oxide nanocomposite |
| CN106457210A (en) * | 2014-03-18 | 2017-02-22 | 巴斯夫欧洲公司 | A process for the production of a carbon supported catalyst |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108878897A (en) * | 2018-06-22 | 2018-11-23 | 西安交通大学 | A kind of one-dimensional nano line hydroxyl cerous carbonate/graphene composite material and preparation method thereof |
| CN109082329A (en) * | 2018-07-23 | 2018-12-25 | 江苏大学 | A kind of ternary nano self-lubricating composite and preparation method thereof |
| CN109082329B (en) * | 2018-07-23 | 2021-04-20 | 江苏大学 | Ternary nano self-lubricating composite material and preparation method thereof |
| CN110629266A (en) * | 2019-10-30 | 2019-12-31 | 贵州民族大学 | Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic |
| CN110629266B (en) * | 2019-10-30 | 2020-10-16 | 贵州民族大学 | Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic |
| CN111180745A (en) * | 2019-12-30 | 2020-05-19 | 浙江工业大学 | CeO (CeO)xPreparation method and application of/MC nanosheet material |
| CN111180745B (en) * | 2019-12-30 | 2021-11-23 | 浙江工业大学 | CeO (CeO)xPreparation method and application of/MC nanosheet material |
| WO2021181085A1 (en) * | 2020-03-10 | 2021-09-16 | Amalyst Limited | Catalyst |
| CN113231061A (en) * | 2021-03-04 | 2021-08-10 | 广东工业大学 | Cerium dioxide nanorod supported catalyst and preparation method and application thereof |
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