CN106345464A - Preparation method of carbon quantum dot/graphene loaded PtM alloy catalyst - Google Patents
Preparation method of carbon quantum dot/graphene loaded PtM alloy catalyst Download PDFInfo
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- CN106345464A CN106345464A CN201610601513.7A CN201610601513A CN106345464A CN 106345464 A CN106345464 A CN 106345464A CN 201610601513 A CN201610601513 A CN 201610601513A CN 106345464 A CN106345464 A CN 106345464A
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- graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 139
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 85
- 239000000956 alloy Substances 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000000151 deposition Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims description 36
- 239000002659 electrodeposit Substances 0.000 claims description 24
- 238000004070 electrodeposition Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 239000010953 base metal Substances 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 4
- 230000005518 electrochemistry Effects 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 2
- 241000521257 Hydrops Species 0.000 claims 2
- 206010030113 Oedema Diseases 0.000 claims 2
- 238000003475 lamination Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052697 platinum Inorganic materials 0.000 abstract description 15
- 239000002356 single layer Substances 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000002848 electrochemical method Methods 0.000 abstract description 3
- 229910001092 metal group alloy Inorganic materials 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 239000004575 stone Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B01J35/33—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a carbon quantum dot/graphene loaded PtM alloy catalyst which is used for catalyzing oxidation of methanol in a fuel battery. The catalyst comprises an active component, namely PtM alloy, and a carrier, namely a carbon quantum dot/graphene three-dimensional structure. The preparation method comprises the following steps: preparing carbon quantum dots; reducing graphene oxide in one step by an electrochemical method and depositing on the surface of an electrode to form single-layer graphene; electro-depositing one layer of carbon quantum dots on the surface of graphene; depositing a single-layer graphene film on the layer of the carbon quantum dots; and depositing PtM double-metal alloy on the synthesized carbon quantum dot/graphene three-dimensional structure carrier by taking a platinum-containing double-metal solution as depositing liquid so as to synthesize the carbon quantum point/graphene three-dimensional structure loaded PtM alloy catalyst. The preparation method has the advantages that the catalyst is simple to prepare, mild in reaction condition, efficient and environment-friendly. The catalyst prepared by the method has potential to serve as a direct alcohol fuel battery anode catalyst.
Description
Technical field
The invention belongs to catalyst preparation technical field and electrochemical energy technical field, particularly to a kind of carbon quantum
The preparation method of point/graphene-supported ptm alloy catalyst.
Background technology
Energy problem has become as one of factor of restriction today's society rapid economic development, development environment friendly clear
The clean energy is the problem of current urgent need to resolve.Energy density height, energy conversion rate height, work are had based on DMFC
Make the features such as temperature is low, pollutant discharge amount is few, structure is simple, it is extensively closed in clean reproducible energy research field
Note.But the commercialization of DMFC is still limited by various factors, one of maximum factor of impact is sun
Electrode catalyst lacks appropriate design, leads to the catalysis activity of catalyst low and easily lose activity.
In all transition metals, platinum has proved to be the catalysis of catalysis activity highest methanol fuel cell positive pole
Agent.But, the dynamic process of pure platinum catalysis methanol oxidation is slow and platinum nanoparticles are easily subject in methanol oxidation
Between product, such as co) poison, noble metal platinum is rare and expensive simultaneously, therefore greatly limit its commercial applications.Its
In, solving one of most efficient method of this problem is to make platinum and base metal (as ferrum, cobalt, nickel, copper, manganese, stannum etc.)
Form alloy.Platinum bimetallic alloy elctro-catalyst has caused the extensive concern of people in recent years, because it can not only
Enough reduce the consumption of noble metal additionally it is possible to significantly increase its co toleration and electro catalytic activity.This kind of catalyst activity
Raising owing to many factors, such as cooperative effect, d band Center shift, Lattice Contraction etc..
In order to improve the catalysis activity of platinum based catalyst further, reduce the consumption of noble metal simultaneously, metal load is arrived
Have on the carrier of large surface area and seem very necessary.Catalyst carrier affects dispersibility and the load capacity of catalyst, selects
Appropriate catalyst carrier is to improve the performance of catalyst and to improve the utilization rate of noble metal and can yet be regarded as a kind of good strategy.Base
In Graphene, there is huge theoretical specific surface area, good electric conductivity, very high electron mobility, superpower mechanical property etc.
Feature, has been used for catalyst carrier research field at present.Therefore, platino metal material is carried on permissible on Graphene carrier
Improve the dispersibility of metal nanoparticle, improve the catalytic performance of catalyst, improve platinum utilization, reduce the production of catalyst
Cost.
Although Graphene is had multiple advantages as catalyst carrier, stronger due to having between graphene sheet layer
Van der Waals force and π-π interact, be therefore susceptible to irreversible reunion, lead to its individual layer two-dimensional nano piece architectural characteristic
Lose.
Recently, carbon or non-carbon nanomaterial being combined with Graphene becomes a kind of effective way improving catalyst performance
Footpath.Mu reports a kind of graphene/carbon nanosphere/graphene composite material of sandwich structure, and is applied to catalysis combustion
The oxygen reduction reaction of material cell cathode, finds that this material shows preferable stability and higher catalysis activity.Zhang synthesizes
A kind of platinum/cesium dioxide/graphene composite nano material, finds that its catalysis activity significantly improves.Although in compound stone
A large amount of effort have been paid in mertenyl catalyst carrier field, a kind of novel Graphene carrier knot of design effective ways synthesis
Structure is still very necessary come the catalytic performance to improve catalyst.
On the other hand, now studies have reported that, carbon quantum dot has many excellent properties, as high water solublity, stronger change
Learn inertia, hypotoxicity, be easily functionalized, good biocompatibility etc., be widely used at present biomarker, biological become
The fields such as picture, medicine transmission.However, by carbon quantum dot be applied to electrochemical field research relatively fewer.
Content of the invention
In order to overcome above-mentioned deficiency, the present invention seeks to graphene/carbon quantum dot/graphite has been synthesized using electrodeposition process
The catalyst carrier of alkene three dimensional structure.Electrochemical process is a kind of green, environmental protection, simple, quick preparation method, can be by adjusting
Section external electric energy, to change the fermi level of the electrode surface material electronic state to change material, thus can be carried out to material
Controlled modification and reduction.In this graphene-based carrier system, conductive carbon quantum dot passes through chemical bond with graphene sheet layer
Close and form stable three dimensional structure.Due to the oxygen-containing functional group such as hydroxyl, carboxyl still being contained on redox graphene lamella, with
When carbon quantum dot on also contain the functional groups such as hydroxyl, carboxyl, dehydration can occur between the hydroxyl of bi-material and carboxyl, lead to
Cross chemical bonding and form stable three-dimensional carrier system (as shown in Figure 1).
The purpose of the present invention is for solving to there is noble metal in existing methanol fuel cell anode catalyzer preparation method
The problem that consumption is big, single noble metal nano catalyst is easily poisoned and catalyst carrier is easily reunited, and provide one kind
The preparation method of carbon quantum dot/graphene-supported ptm alloy catalyst, that is, pass through electrochemical method by graphene oxide one step also
Former and deposit to electrode surface formed single-layer graphene, then electro-deposition last layer carbon quantum dot on graphenic surface, then at
Single-layer graphene film is deposited on this layer of carbon quantum dot.Finally again with the bimetallic solution of platiniferous for depositing liquid, synthesized
Graphene/carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, has thus just synthesized carbon quantum dot/stone
Black alkene three dimensional structure loads ptm alloy catalyst.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of carbon quantum dot/graphene-supported ptm alloy catalyst, comprising:
Graphene；
It is supported on the carbon quantum dot layer on Graphene；
It is supported on the graphene layer on carbon quantum dot layer；
Be supported on above-mentioned Graphene, carbon quantum dot layer, graphene layer formed three dimensional structure carrier on ptm bimetallic close
Gold；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
Carried out with platinum bimetallic alloy using graphene/carbon quantum dot/special three dimensional structure of Graphene in the present invention
Combination effectively reduces committed step energy barrier in methanol oxidation, lifting reaction rate, can be under compared with low reaction temperatures and pressure
Obtain higher reactivity and target product selectivity.Meanwhile, the transition metal such as the ferrum of low cost, cobalt, copper can be with pt group
Become alloy, realize the surface enrichment in active center in crystal growth phase, so that ptm alloy is had close to or surmount urging of noble metal
Change performance.
Because the special absorption of graphene/carbon quantum dot of the present invention/special three dimensional structure of Graphene, carrier can improve
The load capacity of metal nano catalyst and dispersibility, therefore, in the present invention, the mass fraction of ptm alloy is up to catalyst gross mass
30～50%；When the mass fraction of ptm alloy is less than 30%, the nano metal of load is less, and catalytic efficiency is not good；When
When the mass fraction of ptm alloy is more than 50%, the dispersibility of bimetallic nano is not good, and catalyst conversion frequency declines, apparent work
Change and can reduce.Therefore, in the present invention, the mass fraction of preferred ptm alloy is 30～50%.
Preferably, described m is one of fe, co, ni, cu, mn or sn.
Present invention also offers a kind of graphene/carbon quantum dot/graphene three-dimensional structure carrier, comprising:
Graphene；
It is supported on the carbon quantum dot layer on Graphene；
It is supported on the graphene layer on carbon quantum dot layer；
In the middle of the present invention, carbon quantum dot is incorporated between graphene sheet layer and mainly has the advantage that
(1) carbon quantum dot embedded by can widen the space between graphene sheet layer, and it is conducive to the diffusion of reactant
And transmission.
(2) carbon quantum dot introducing can play " bridging " effect, and the electronics that can significantly improve between graphene sheet layer passes
Defeated speed.
(3) three dimensional structure that graphene sheet layer and carbon quantum dot cooperatively form can improve the load of metal nano catalyst
Amount and dispersibility, thus can improve the utilization rate of catalyst and improve the catalysis activity of catalyst.
Present invention also offers a kind of carbon quantum dot/graphene-supported ptm alloy electrode, comprising:
Basal electrode；
It is supported on the graphene layer on basal electrode；
It is supported on the carbon quantum dot layer on described graphene layer；
It is supported on the graphene layer on carbon quantum dot layer；
It is supported on the ptm bimetallic alloy on the three dimensional structure that graphene layer and graphene layer are constituted；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
Preferably, in described catalyst, the mass fraction of ptm alloy is 30～50%；
Preferably, described m is one of fe, co, ni, cu, mn or sn.
Present invention also offers a kind of electrochemical workstation, including arbitrary above-mentioned electrode.
Present invention also offers a kind of preparation method of carbon quantum dot/graphene-supported ptm alloy catalyst, comprising:
Deposit carbon quantum dot layer in graphene layer surface electrochemistry, obtain carbon quantum dot/Graphene；
Electrochemical deposition graphene layer on carbon quantum dot/Graphene, obtains the three-dimensional knot of graphene/carbon quantum dot/Graphene
Structure carrier；
In graphene/carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, obtain final product carbon quantum dot/
Graphene-supported ptm alloy catalyst；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
Preferably, in described catalyst, the mass percent of ptm bimetallic alloy is 30～50%；
Preferably, described m is one of fe, co, ni, cu, mn or sn；
Preferably, the concretely comprising the following steps of described electrochemical deposition carbon quantum dot layer: divided with the carbon quantum dot after supersound process
Dispersion liquid is electrodeposit liquid, and voltage set range is -1.5～3v, and the deposition number of turns is 10～20 circles；
Preferably, the concretely comprising the following steps of described electrochemical deposition graphene layer: with graphene oxide dispersion as electro-deposition
Liquid, voltage set range is -1.5～3v, and the deposition number of turns is 10～30 circles；
Preferably, the concretely comprising the following steps of described deposition ptm bimetallic alloy: with concentration as 0.03mol.l-1Ptm double
Metallic solution is electrodeposit liquid, in synthesized carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy,
Wherein voltage set range is -0.5～1.5v, and the deposition number of turns is 15～30 circles.
Present invention also offers a kind of preparation method of carbon quantum dot/graphene-supported ptm alloy electrode, comprising:
Electrochemical deposition graphene layer on basal electrode；
In the graphenic surface electrochemical deposition carbon quantum dot layer of electrode, obtain carbon quantum dot/Graphene electrodes；
Electrochemical deposition graphene layer in carbon quantum dot/Graphene electrodes, obtains graphene/carbon quantum dot/Graphene three
Three-dimensional structure carrier；
In graphene/carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, obtain final product ptm/ graphite
Alkene/carbon quantum dot/Graphene electrodes；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
Preferably, in described electrode, the quality of ptm bimetallic alloy is the 30～50% of electrode deposition gross mass；
Preferably, described m is one of fe, co, ni, cu, mn or sn；
Preferably, the concretely comprising the following steps of described electrochemical deposition carbon quantum dot layer: divided with the carbon quantum dot after supersound process
Dispersion liquid is electrodeposit liquid, and voltage set range is -1.5～3v, and the deposition number of turns is 10～20 circles；
Preferably, the concretely comprising the following steps of described electrochemical deposition graphene layer: with graphene oxide dispersion as electro-deposition
Liquid, voltage set range is -1.5～3v, and the deposition number of turns is 10～30 circles；
Preferably, the concretely comprising the following steps of described deposition ptm bimetallic alloy: with concentration as 0.03mol.l-1Ptm double
Metallic solution is electrodeposit liquid, in the double gold of synthesized graphene/carbon quantum dot/graphene three-dimensional structure deposited on supports ptm
Belong to alloy, wherein voltage set range is -0.5～1.5v, the deposition number of turns is 15～30 circles.
In the present invention, arbitrary described carbon quantum dot/graphene-supported ptm alloy catalyst, carbon quantum dot/Graphene are born
Carry ptm alloy electrode and electrochemical workstation all can be applicable to catalysis methanol oxidation or Electrochemical Detection, obtain preferably
Effect, has reached the requirement of concerned countries and international standard.
Beneficial effects of the present invention
(1) purpose of the present invention is for solving to there is noble metal in existing methanol fuel cell anode catalyzer preparation method
The problem that consumption is big, single noble metal nano catalyst is easily poisoned and catalyst carrier is easily reunited, and provide one kind
The preparation method of carbon quantum dot/graphene-supported ptm alloy catalyst, that is, pass through electrochemical method by graphene oxide one step also
Former and deposit to electrode surface formed single-layer graphene, then electro-deposition last layer carbon quantum dot on graphenic surface, then at
Single-layer graphene film is deposited on this layer of carbon quantum dot.Finally again with the bimetallic solution of platiniferous for depositing liquid, synthesized
Carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, has thus just synthesized carbon quantum dot/Graphene three
Dimension structural load ptm alloy catalyst.
(2) present invention is carried using the catalyst that electrodeposition process has synthesized graphene/carbon quantum dot/graphene three-dimensional structure
Body.Electrochemical process is a kind of green, environmental protection, simple, quick preparation method, can change electrode by adjusting external electric energy
The fermi level of surfacing, to change the electronic state of material, thus can carry out controlled modification and reduction to material.At this
In one graphene-based carrier system, conductive carbon quantum dot forms stable three-dimensional knot with graphene sheet layer by chemical bonding
Structure.Due to still containing the oxygen-containing functional group such as hydroxyl, carboxyl on redox graphene lamella, also contain in carbon quantum dot simultaneously
The functional groups such as hydroxyl, carboxyl, can occur dehydration between the hydroxyl of bi-material and carboxyl, formed stable by chemical bonding
Three-dimensional carrier system (as shown in Figure 1).
(3) preparation method of the present invention is simple, detection efficiency is high, practical it is easy to promote.
Brief description
Fig. 1 is catalyzed preparation principle figure for the present invention.
Fig. 2 is the tem picture of carbon quantum dot/graphene three-dimensional structure carrier.
The cyclic voltammetry curve that Fig. 3 aoxidizes for modified electrode catalysis methanol.
The time current curve that Fig. 4 aoxidizes for modified electrode catalysis methanol.
Specific embodiment
By the following examples feature of present invention and other correlated characteristic are described in further detail, in order to the same industry
The understanding of technical staff:
Embodiment 1:
(1) take the Radix Dauci Sativae juice that 60ml has squeezed and to add 0.7g beta-schardinger dextrin-in beaker, then magnetic force is carried out to it and stir
Mix 10min.This mixture is transferred in autoclave, and takes out after reaction 20h under the conditions of 180 DEG C and naturally cool to room
Temperature.Take supernatant after product is centrifuged and filtered with filter membrane, then filtrate be transferred in Rotary Evaporators, extremely burning to be evaporated
Pour 20ml acetone and ethanol in bottle during the obvious liquid of nothing successively into and continue to be evaporated in flask remaining a small amount of liquid.Gained is produced
Thing is transferred to and is centrifuged in centrifuge tube and is cleaned multiple times, and last gained precipitation is prepared carbon quantum dot, and it is dried naturally
Standby.
(2) take graphene oxide and each 8mg of carbon quantum dot, with secondary water respectively compound concentration be 1mg/ml graphite oxide
The carbon quantum dot solution of alkene solution and 1mg/ml, and will be standby for solution supersound process 30min.
(3) with the graphene oxide dispersion after supersound process as electrodeposit liquid, using circulation in electrochemical workstation
Voltammetry directly prepares graphene film in electrode surface, and wherein voltage set range is -1.5～3v, and the deposition number of turns is 10 circles.
(4) with the carbon quantum dot dispersion liquid after supersound process as electrodeposit liquid, on graphenic surface described in (3), electricity is heavy
Long-pending one layer of carbon quantum dot, wherein voltage set range are -1.5～3v, and the deposition number of turns is 10 circles.
(5) with graphene oxide dispersion as electrodeposit liquid, then at the upper monolayer stone of the deposition of carbon quantum dot outer layer described in (4)
Black alkene thin film, wherein voltage set range are -1.5～3v, and the deposition number of turns is 10 circles.
(6) with concentration as 0.03mol.l-1Ptco bimetallic solution be electrodeposit liquid, in synthesized carbon quantum dot/stone
Black alkene three dimensional structure deposited on supports ptco bimetallic alloy, wherein voltage set range are -0.5～1.5v, and the deposition number of turns is
20 circles.
(7) with this modified electrode as working electrode, investigate its performance to methanol catalytic oxidation in electrochemical workstation.
During measurement, reference electrode is saturated calomel electrode, is platinum filament to electrode, and electrolyte is 0.5mol.l-1(c2h5oh+h2so4) mix
Close solution.Tested using cyclic voltammetry, wherein voltage is set to -0.2v～1.2v, sweep speed and be set to 50mv/s, observed
The take-off potential of methanol oxidation and peak current, to analyze catalytic action and the anti-poisoning to co that modified electrode aoxidizes to methanol
Property, referring to Fig. 3.Voltage is set to 0.6v, set of time is 3600s, scans the current-time curvel of above-mentioned solution, observes
Beginning size of current and current attenuation trend, to judge the stability of modified electrode, referring to Fig. 4.
Wherein, in ptco bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 2:
(1) take the Radix Dauci Sativae juice that 60ml has squeezed and to add 0.7g beta-schardinger dextrin-in beaker, then magnetic force is carried out to it and stir
Mix 10min.This mixture is transferred in autoclave, takes out after reaction 20h under the conditions of 180 DEG C and naturally cool to room
Temperature.Take supernatant after product is centrifuged and filtered with filter membrane, then filtrate be transferred in Rotary Evaporators, extremely burning to be evaporated
Pour 20ml acetone and ethanol in bottle during the obvious liquid of nothing successively into and continue to be evaporated in flask remaining a small amount of liquid.Gained is produced
Thing is transferred to and is centrifuged in centrifuge tube and is cleaned multiple times, and last gained precipitation is prepared carbon quantum dot, and it is dried naturally
Standby.
(2) take graphene oxide and each 8mg of carbon quantum dot, with secondary water respectively compound concentration be 1mg/ml graphite oxide
The carbon quantum dot solution of alkene solution and 1mg/ml, and will be standby for solution supersound process 30min.
(3) with the graphene oxide dispersion after supersound process as electrodeposit liquid, using circulation in electrochemical workstation
Voltammetry directly prepares graphene film in electrode surface, and wherein voltage set range is -1.5～3v, and the deposition number of turns is 20 circles.
(4) with the carbon quantum dot dispersion liquid after supersound process as electrodeposit liquid, on graphenic surface described in (3), electricity is heavy
Long-pending one layer of carbon quantum dot, wherein voltage set range are -1.5～3v, and the deposition number of turns is 15 circles.
(5) with graphene oxide dispersion as electrodeposit liquid, deposit mono-layer graphite then at carbon quantum dot outer layer described in (4)
Alkene thin film, wherein voltage set range are -1.5～3v, and the deposition number of turns is 20 circles.
(6) with concentration as 0.03mol.l-1Ptco bimetallic solution be electrodeposit liquid, in synthesized carbon quantum dot/stone
Black alkene three dimensional structure deposited on supports ptco bimetallic alloy, wherein voltage set range are -0.5～1.5v, and the deposition number of turns is
20 circles.
(7) with this modified electrode as working electrode, investigate its performance to methanol catalytic oxidation in electrochemical workstation.
During measurement, reference electrode is saturated calomel electrode, is platinum filament to electrode, and electrolyte is 0.5mol.l-1(c2h5oh+h2so4) mix
Close solution.Tested using cyclic voltammetry, wherein voltage is set to -0.2v～1.2v, sweep speed and be set to 50mv/s, observed
The take-off potential of methanol oxidation and peak current, to analyze catalytic action and the anti-poisoning to co that modified electrode aoxidizes to methanol
Property.Voltage is set to 0.6v, set of time is 3600s, scans the current-time curvel of above-mentioned solution, observes initial current big
Little and current attenuation trend, to judge the stability of modified electrode.
Wherein, in ptco bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 3:
(1) take the Radix Dauci Sativae juice that 60ml has squeezed and to add 0.7g beta-schardinger dextrin-in beaker, then magnetic force is carried out to it and stir
Mix 10min.This mixture is transferred in autoclave, takes out after reaction 20h under the conditions of 180 DEG C and naturally cool to room
Temperature.Take supernatant after product is centrifuged and filtered with filter membrane, then filtrate be transferred in Rotary Evaporators, extremely burning to be evaporated
Pour 20ml acetone and ethanol in bottle during the obvious liquid of nothing successively into and continue to be evaporated in flask remaining a small amount of liquid.Gained is produced
Thing is transferred to and is centrifuged in centrifuge tube and is cleaned multiple times, and last gained precipitation is prepared carbon quantum dot, and it is dried naturally
Standby.
(2) take graphene oxide and each 8mg of carbon quantum dot, with secondary water respectively compound concentration be 1mg/ml graphite oxide
The carbon quantum dot solution of alkene solution and 1mg/ml, and will be standby for solution supersound process 30min.
(3) with the graphene oxide dispersion after supersound process as electrodeposit liquid, using circulation in electrochemical workstation
Voltammetry directly prepares graphene film in electrode surface, and wherein voltage set range is -1.5～3v, and the deposition number of turns is 20 circles.
(4) with the carbon quantum dot dispersion liquid after supersound process as electrodeposit liquid, on graphenic surface described in (3), electricity is heavy
Long-pending one layer of carbon quantum dot, wherein voltage set range are -1.5～3v, and the deposition number of turns is 10 circles.
(5) with graphene oxide dispersion as electrodeposit liquid, then at the upper monolayer stone of the deposition of carbon quantum dot outer layer described in (4)
Black alkene thin film, wherein voltage set range are -1.5～3v, and the deposition number of turns is 20 circles.
(6) with concentration as 0.03mol.l-1Ptco bimetallic solution be electrodeposit liquid, in synthesized carbon quantum dot/stone
Black alkene three dimensional structure deposited on supports ptco bimetallic alloy, wherein voltage set range are -0.5～1.5v, and the deposition number of turns is
20 circles.
(7) with this modified electrode as working electrode, investigate its performance to methanol catalytic oxidation in electrochemical workstation.
During measurement, reference electrode is saturated calomel electrode, is platinum filament to electrode, and electrolyte is 0.5mol.l-1(c2h5oh+h2so4) mix
Close solution.Tested using cyclic voltammetry, wherein voltage is set to -0.2v～1.2v, sweep speed and be set to 50mv/s, observed
The take-off potential of methanol oxidation and peak current, to analyze catalytic action and the anti-poisoning to co that modified electrode aoxidizes to methanol
Property.Voltage is set to 0.6v, set of time is 3600s, scans the current-time curvel of above-mentioned solution, observes initial current big
Little and current attenuation trend, to judge the stability of modified electrode.
Wherein, in ptco bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 4:
(1) take the Radix Dauci Sativae juice that 60ml has squeezed and to add 0.7g beta-schardinger dextrin-in beaker, then magnetic force is carried out to it and stir
Mix 10min.This mixture is transferred in autoclave, takes out after reaction 20h under the conditions of 180 DEG C and naturally cool to room
Temperature.Take supernatant after product is centrifuged and filtered with filter membrane, then filtrate be transferred in Rotary Evaporators, extremely burning to be evaporated
Pour 20ml acetone and ethanol in bottle during the obvious liquid of nothing successively into and continue to be evaporated in flask remaining a small amount of liquid.Gained is produced
Thing is transferred to and is centrifuged in centrifuge tube and is cleaned multiple times, and last gained precipitation is prepared carbon quantum dot, and it is dried naturally
Standby.
(2) take graphene oxide and each 8mg of carbon quantum dot, with secondary water respectively compound concentration be 1mg/ml graphite oxide
The carbon quantum dot solution of alkene solution and 1mg/ml, and will be standby for solution supersound process 30min.
(3) with the graphene oxide dispersion after supersound process as electrodeposit liquid, using circulation in electrochemical workstation
Voltammetry directly prepares graphene film in electrode surface, and wherein voltage set range is -1.5～3v, and the deposition number of turns is 20 circles.
(4) with the carbon quantum dot dispersion liquid after supersound process as electrodeposit liquid, on graphenic surface described in (3), electricity is heavy
Long-pending one layer of carbon quantum dot, wherein voltage set range are -1.5～3v, and the deposition number of turns is 15 circles.
(5) with graphene oxide dispersion as electrodeposit liquid, then at the upper monolayer stone of the deposition of carbon quantum dot outer layer described in (4)
Black alkene thin film, wherein voltage set range are -1.5～3v, and the deposition number of turns is 20 circles.
(6) with concentration as 0.03mol.l-1Ptco bimetallic solution be electrodeposit liquid, in synthesized carbon quantum dot/stone
Black alkene three dimensional structure deposited on supports ptco bimetallic alloy, wherein voltage set range are -0.5～1.5v, and the deposition number of turns is
30 circles.
(7) with this modified electrode as working electrode, investigate its performance to methanol catalytic oxidation in electrochemical workstation.
During measurement, reference electrode is saturated calomel electrode, is platinum filament to electrode, and electrolyte is 0.5mol.l-1(c2h5oh+h2so4) mix
Close solution.Tested using cyclic voltammetry, wherein voltage is set to -0.2v～1.2v, sweep speed and be set to 50mv/s, observed
The take-off potential of methanol oxidation and peak current, to analyze catalytic action and the anti-poisoning to co that modified electrode aoxidizes to methanol
Property.Voltage is set to 0.6v, set of time is 3600s, scans the current-time curvel of above-mentioned solution, observes initial current big
Little and current attenuation trend, to judge the stability of modified electrode.
Wherein, in ptco bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 5
Preparation method is with embodiment 1 difference, substitutes ptco bimetallic alloy using ptfe bimetallic alloy,
In ptfe bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 6
Preparation method is with embodiment 1 difference, substitutes ptco bimetallic alloy using ptni bimetallic alloy,
In ptni bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 7
Preparation method is with embodiment 1 difference, substitutes ptco bimetallic alloy using ptcu bimetallic alloy,
In ptcu bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 8
Preparation method is with embodiment 1 difference, substitutes ptco bimetallic alloy using ptmn bimetallic alloy,
In ptmn bimetallic alloy, pt mass fraction is 10%～50%.
Embodiment 9
Preparation method is with embodiment 1 difference, substitutes ptco bimetallic alloy using ptsn bimetallic alloy,
In ptsn bimetallic alloy, pt mass fraction is 10%～50%.
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to this
Bright, although being described in detail to the present invention with reference to the foregoing embodiments, for a person skilled in the art, it is still
Technical scheme described in previous embodiment can be modified, or to wherein partly carrying out equivalent.All at this
Within bright spirit and principle, any modification, equivalent substitution and improvement made etc., should be included in protection scope of the present invention
Within.Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to the scope of the present invention
Restriction, one of ordinary skill in the art should be understood that, on the basis of technical scheme, those skilled in the art are not required to
Various modifications that creative work to be paid can be made or deformation are still within protection scope of the present invention.
Claims (10)
1. a kind of carbon quantum dot/graphene-supported ptm alloy catalyst is it is characterised in that include:
Graphene；
It is supported on the carbon quantum dot layer on Graphene；
It is supported on the graphene layer on carbon quantum dot layer；
Be supported on Graphene, carbon quantum dot, graphene layer constitute three dimensional structure carrier on ptm bimetallic alloy；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
2. catalyst as claimed in claim 1 it is characterised in that in described catalyst ptm alloy mass fraction be 30～
50%；
Or described m is one of fe, co, ni, cu, mn or sn.
3. a kind of carbon quantum dot/graphene-supported ptm alloy electrode is it is characterised in that include:
Basal electrode；
It is supported on the graphene layer on basal electrode；
It is supported on the carbon quantum dot layer on described graphene layer；
It is supported on the graphene layer on carbon quantum dot layer；
It is supported on the ptm bimetallic alloy on the three dimensional structure that graphene layer and graphene layer are constituted；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
4. electrode as claimed in claim 3 it is characterised in that in described catalyst ptm alloy mass fraction be 30～
50%；
Or described m is one of fe, co, ni, cu, mn or sn.
5. a kind of graphene/carbon quantum dot/graphene three-dimensional structure carrier is it is characterised in that include:
Graphene；
It is supported on the carbon quantum dot layer on Graphene；
It is supported on the graphene layer on carbon quantum dot layer.
6. a kind of preparation method of carbon quantum dot/graphene-supported ptm alloy catalyst is it is characterised in that include:
In graphenic surface electrochemical deposition carbon quantum dot layer, obtain carbon quantum dot/Graphene；
Electrochemical deposition graphene layer on carbon quantum dot/Graphene, obtains graphene/carbon quantum dot/graphene three-dimensional structure and carries
Body；
In graphene/carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, obtain final product ptm/ graphene/carbon
Quantum dot/graphen catalyst；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
7. method as claimed in claim 6 it is characterised in that in described catalyst ptm bimetallic alloy mass percent
For 30～50%；
Or described m is one of fe, co, ni, cu, mn or sn；
Or the concretely comprising the following steps of described electrochemical deposition carbon quantum dot layer: it is that electricity is heavy with the carbon quantum dot dispersion liquid after supersound process
Hydrops, voltage set range is -1.5～3v, and the deposition number of turns is 10～20 circles；
Or the concretely comprising the following steps of described electrochemical deposition graphene layer: with graphene oxide dispersion as electrodeposit liquid, voltage sets
Putting scope is -1.5～3v, and the deposition number of turns is 10～30 circles；
Or the concretely comprising the following steps of described deposition ptm bimetallic alloy: with concentration as 0.03mol.l-1Ptm bimetallic solution be
Electrodeposit liquid, in synthesized carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, wherein voltage sets
Putting scope is -0.5～1.5v, and the deposition number of turns is 15～30 circles.
8. the preparation method of a kind of carbon quantum dot/graphene-supported ptm alloy electrode, comprising:
Deposit carbon quantum dot layer in Graphene electrodes surface electrochemistry, obtain carbon quantum dot/Graphene electrodes；
Electrochemical deposition graphene layer in carbon quantum dot/Graphene electrodes, obtains the three-dimensional knot of graphene/carbon quantum dot/Graphene
Structure carrier；
In graphene/carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, obtain final product ptm/ graphene/carbon
Quantum dot/Graphene electrodes；
Wherein, m is base metal；In described ptm bimetallic alloy, pt mass fraction is 10%～50%.
9. electrode as claimed in claim 8 it is characterised in that in described electrode ptm bimetallic alloy quality for electrode sink
The 30～50% of lamination gross mass；
Or described m is one of fe, co, ni, cu, mn or sn；
Or the concretely comprising the following steps of described electrochemical deposition carbon quantum dot layer: it is that electricity is heavy with the carbon quantum dot dispersion liquid after supersound process
Hydrops, voltage set range is -1.5～3v, and the deposition number of turns is 10～20 circles；
Or the concretely comprising the following steps of described electrochemical deposition graphene layer: with graphene oxide dispersion as electrodeposit liquid, voltage sets
Putting scope is -1.5～3v, and the deposition number of turns is 10～30 circles；
Or the concretely comprising the following steps of described deposition ptm bimetallic alloy: with concentration as 0.03mol.l-1Ptm bimetallic solution be
Electrodeposit liquid, in synthesized carbon quantum dot/graphene three-dimensional structure deposited on supports ptm bimetallic alloy, wherein voltage sets
Putting scope is -0.5～1.5v, and the deposition number of turns is 15～30 circles.
10. the catalyst described in claim 1 or 2, the electrode described in claim 3 or 4 are in catalysis methanol oxidation or electrochemistry
Application in detection.
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