CN105817240A - Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst - Google Patents
Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and preparation method of Pt doped phosphatizing cobalt bead catalyst Download PDFInfo
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- 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 Pt doped phosphatizing cobalt bead catalyst carried by methanol carbon dioxide and a preparation method of the Pt doped phosphatizing cobalt bead catalyst. The catalyst is Pt-CoP/C, and the preparation method mainly comprises the following steps: uniformly dispersing a carbon material to a solution of dehydrated alcohol and deionized water, adding cobalt salt and strong ammonia water, and through a heating reflow reaction, generating carbon-carrying cobalt complex compound solution; transmitting the solution into a polytetrafluoroethylene reaction kettle, and performing water heating so as to obtain a carbon-carrying cobaltosic oxide material; mixing the carbon-carrying cobaltosic oxide material with sodium hypophosphite, performing grinding so as to obtain a mixture, and transmitting the mixture to a high-temperature tuber furnace filled with protective gas; preforming heating treatment so as to obtain a CoP/C material, dispersing the CoP/C material to the mixed solution of ethanediol and the deionized water, adding a chloroplatinic acid solution, and then performing a heating reflow reaction so as to obtain a Pt-CoP/C catalyst. Compared with conventional business Pt/C, according to the prepared catalyst disclosed by the invention, the methanol oxidation activity and stability are significantly improved.
Description
Technical field
The invention belongs to the research of methanol fuel cell anode catalyzer, be specifically related to a kind of high efficiency methanol oxygen
Change carbon and carry Pt doping phosphatization cobalt granule catalyst and preparation method thereof.
Background technology
Since 21 century, due to the day by day exhaustion of the fossil energies such as oil, natural gas and coal, environment is dirty
Becoming increasingly conspicuous of the problems such as dye, so, development has the new energy technology of environmental protection and the feature such as renewable and draws
Play the extensive concern of people.For DMFC (DMFCs) relatively fossil energy be one more
The energy of cleaning, its specific energy reaches 6000Wh/Kg, far above the specific energy of accumulator, simultaneously
Its energy conversion rate can reach 60%-80%, secondly, for methanol is relative to other new forms of energy such as Hydrogen Energies,
There is the advantages such as abundance, accumulating convenience and low stain, thus paid close attention to widely.Directly first
Alcohol fuel battery is typically made up of anode, negative electrode, this three part of electrolyte.Anode part generation methanol oxygen
Changing reaction, the oxidizing process of methanol mainly includes following step: the absorption of (1) methanol；(2) first
Alcohol c h bond by activation and progressively deprotonation formation carbon containing intermedium；(3) absorption and the activation of water is formed
Activity oxygenated species OHads；(4) the carbon containing intermedium formed in methanol oxidation process is by OHadsOxidation,
Ultimately generate CO2.Generating proton in methanol oxidation process and provide free electron, electronics passes through dispatch from foreign news agency
Route anode movement, to negative electrode, provides electric energy for external circuit simultaneously.Owing to anode part methanol aoxidizes this
One process is relatively slower, and therefore, general employing catalyst improves methanol oxidation rate.Commercialization at present
Carbon supported platinum catalyst (Pt/C) be most widely used anode catalyst in current low-temperature fuel cell, but
Being in methanol oxidation process, series of intermediate products is easily caused Pt/C catalyst poisoning, ultimately results in
The cycle life of battery is shorter.Meanwhile, anode catalyst generally uses precious metals pt, and the storage of noble metal
Measuring the factor such as low causes catalyst cost high.This series of factors strongly limit the business of methanol fuel cell
Industryization develops.
Summary of the invention
For the problems referred to above, the present invention provides a kind of high efficiency methanol carbonoxide to carry Pt doping phosphatization cobalt granule and urges
Agent and preparation method thereof, in the hope of reaching to reduce the use of precious metals pt, improves the catalysis activity of catalyst
And stability.
A kind of high efficiency methanol carbonoxide that the present invention proposes carries Pt doping phosphatization cobalt granule catalyst
(Pt-CoP/C), it is by material with carbon element and cobalt salt, and heated backflow, hydrothermal oxidization, with sodium hypophosphite low temperature
After phosphatization, insert in the mixed solution of ethylene glycol and water, add platinum acid chloride solution and to be reduced into Pt mono-
Matter forms, in catalyst the mass percent of phosphatization cobalt, Pt and material with carbon element be followed successively by 30%-35%,
20%-25% and 40%-50%.
Correspondingly, the present invention proposes the preparation method of catalyst, comprises the steps:
(1) being joined by material with carbon element in the mixed solution of dehydrated alcohol and deionized water, ultrasonic Treatment makes
Material with carbon element is dispersed in this mixed solution；Add cobalt salt so that it is add quality after fully dissolving dense
Degree is the strong aqua ammonia of 28%, is heated to reflux 14-15h at 80-90 DEG C, obtains carbon and carries the complex solution of cobalt；
(2) proceed to this complex solution answer in still after 140-150 DEG C of hydro-thermal 2-4h to hydro-thermal, filter,
Washing removes other ion of residual, the driest in the vacuum drying oven of 60-80 DEG C, obtains carbon and carries
Cobalto-cobaltic oxide material；
(3) carbon is carried the ratio mixing with mass ratio as 1:5 of Cobalto-cobaltic oxide material and sodium hypophosphite, grinds
After being milled to uniform powder, transfer to be filled with in the high temperature process furnances of nitrogen or noble gas, be heated to
300-350 DEG C makes the abundant phosphatization of Cobalto-cobaltic oxide, obtains carbon and carries phosphatization cobalt material (CoP/C)；
(4) by described carbon load phosphatization cobalt material pass through ultrasonic Treatment so that it is be dispersed in ethylene glycol and go from
In the mixed solution of sub-water, and add platinum acid chloride solution, be heated to reflux 4-5h at 140-150 DEG C, make chlorine
Platinic acid is reduced into Pt simple substance, finally gives Pt-CoP/C catalyst, and wherein the size of phosphatization cobalt granule is
The size of 10-20nm, Pt granule is 2-3nm.
Preferential, described cobalt salt is four acetate hydrate cobalt or cabaltous nitrate hexahydrates.
Preferential, described material with carbon element is carbon black material.
Preferential, in step (1), dehydrated alcohol is 48:1 or pure anhydrous second with the volume ratio of deionized water
Alcoholic solution.
Preferential, in described step (2), noble gas is argon.
Preferential, in described step (3), the volume ratio of ethylene glycol and deionized water is 3:1 or pure second two
Alcoholic solution.
The present invention introduces a kind of promoter in the catalyst based on Pt so that anode catalyst exists
There is provided activity oxygen carrier with speed faster under more negative potential, can also be modified by electronic action simultaneously
The Electronic Performance of Pt, thus affect absorption and the deprotonation process of methanol, weaken intermediate product at metal watch
The adsorption strength in face is near and weakens the poisoning of catalyst, also improves while improving catalyst stability
The activity of catalyst, and the usage amount of the Pt of noble metal can be reduced to a certain extent.
Catalyst obtained by the present invention, can produce in a large number, relative to existing commercialization Pt/C catalyst
For, electro catalytic activity and the stability of carbon load Pt doping CoP beaded catalyst catalysis methanol oxidation have
Improve greatly, reduce the production cost of fuel cell to a certain extent.Test result indicate that, this
The catalyst that invention prepares has obvious catalytic effect to catalysis methanol oxidation, and has good methanol tolerance
Intermediate oxidation product poisoning performance, therefore pole is hopeful to be applied in methanol fuel cell.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of the catalyst prepared by embodiment 1；
Fig. 2 is the catalyst (solid line) prepared by embodiment 1 and existing commercialization Pt/C catalyst (void
Line) at 0.5M H2SO4Cyclic voltammetry curve in solution；
Fig. 3 be existing commercialization Pt/C catalyst (dotted line 1) and embodiment 2,3,4 (solid line 2,3,
4) the linear sweep voltammetry curve chart of the catalyst prepared by；
Fig. 4 is the catalyst (solid line) prepared by embodiment 1 and existing commercialization Pt/C catalyst (void
Line) timing ampere curve.
Detailed description of the invention
For making the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and
Embodiment, is further elaborated to the present invention.It should be noted that the invention is not restricted to following
Embodiment, any in the technical scope that the invention discloses, by changing trickle operation or experiment ginseng
Number, all should contain within the scope of the present invention.
Data in order to make electro-chemical test obtain have comparability, and following instance is all in Shanghai occasion China instrument
Electro-chemical test is carried out on the CHI 750D electrochemical workstation of company limited.Test condition is as follows: platinum
Silk is as to electrode, and saturated calomel electrode is as reference electrode, after the catalyst preparation of preparation is become solution
Take 0.014mg and drop on the glass-carbon electrode of a diameter of 0.3mm, as work after air dries naturally
Make electrode, form three electrode test systems.
Embodiment 1, comprises the steps:
50mg carbon black material is joined 48mL dehydrated alcohol and the mixed solution of 1mL deionized water
In, ultrasonic Treatment makes carbon black material fully dispersed in the solution；83mg tetra-is added in above-mentioned solution
Acetate hydrate cobalt, stirring adds, after making it be substantially dissolved in solution, the dense ammonia that 1mL mass concentration is 28% again
Water, is heated to reflux 14h at 80 DEG C, obtains carbon and carries the complex solution of cobalt；This solution is proceeded to hydro-thermal
Answer in still after 140 DEG C of hydro-thermals 2h, filter, wash other ion removing residual, in the vacuum of 60 DEG C
Drying baker is fully dried to obtain carbon and carries Cobalto-cobaltic oxide material；Itself and sodium hypophosphite are mixed with the ratio of 1:5
Close, be ground to uniform powder after, transfer to be filled with in the high temperature process furnances of nitrogen, be heated to 300 DEG C and make
Cobalto-cobaltic oxide, fully by phosphatization, obtains CoP/C material；CoP/C is made its point by ultrasonic Treatment
It is dispersed in the mixed solution of 45mL ethylene glycol and 15mL deionized water, and to add 1mL concentration be 53.1
mg mL-1Platinum acid chloride solution, under the conditions of 140 DEG C, be then heated to reflux 4h make chloroplatinic acid be reduced into
Pt simple substance, finally gives Pt-CoP/C catalyst, and wherein the size of CoP granule is 10nm, Pt granule
The mass percent that size is 2nm, CoP be 30%, the mass percent of Pt is 20%, carbon black
Mass percent is 50%.
Understand the CoP granule the catalyst of example 1 preparation from the scanning electron microscope (SEM) photograph of Fig. 1 and Pt granule is uniform
It is dispersed in carbon black support.Take the catalyst of certain mass, at 0.5M H2SO4In solution, with 50mV
s-1Sweep speed to its be circulated volt-ampere test, test result as shown in Figure 2, hydrogen adsorption be desorbed district
In the range of territory, the electrochemistry liberation of hydrogen dehydrogenation area of Pt-CoP/C catalyst prepared by the present invention is significantly greater than existing
There is business-like Pt/C, illustrate that the electro-chemical activity of Pt-CoP/C catalyst is better than existing business-like Pt/C.
At 0.5M H2SO4+1M CH3In OH solution, with 50mV s-1Sweep speed above-mentioned material is counted
Shi Anpei tests, and as shown in Figure 4, the stability of Pt-CoP/C catalyst is obvious for stability test result
Higher than existing business-like Pt/C.
Embodiment 2, comprises the steps:
50mg carbon black material is joined 48mL dehydrated alcohol and the mixed solution of 1mL deionized water
In, ultrasonic Treatment makes carbon black material fully dispersed in the solution；97mg six is added in above-mentioned solution
Nitric hydrate cobalt, stirring adds, after making it fully dissolve, the strong aqua ammonia that 1mL mass concentration is 28% again,
80 DEG C are heated to reflux 14h, obtain carbon and carry the complex solution of cobalt；Proceed to this solution to hydro-thermal answer in still
After 140 DEG C of hydro-thermals 2h, filter, wash other ion removing residual, at the vacuum drying oven of 60 DEG C
In be fully dried to obtain carbon carry Cobalto-cobaltic oxide material；It is mixed with sodium hypophosphite with the ratio of 1:5, grind
After being milled to uniform powder, transfer to be filled with in the high temperature process furnances of nitrogen, be heated to 300 DEG C and make four oxidations
Three cobalts, fully by phosphatization, obtain carbon and carry phosphatization cobalt material C oP/C；CoP/C is made by ultrasonic Treatment
It is dispersed in the mixed solution of 45mL ethylene glycol and 15mL deionized water, and adds 1mL concentration
For 53.1mg mL-1Platinum acid chloride solution, under the conditions of 140 DEG C, be then heated to reflux 4h make chloroplatinic acid also
Former one-tenth Pt simple substance, finally gives Pt-CoP/C catalyst, and wherein the size of CoP granule is 10nm, Pt
The size of granule be the mass percent of 2nm, CoP be 30%, the mass percent of Pt is 20%, carbon
Black mass percent is 50%.
Take the catalyst of certain mass, at 0.5M H2SO4+1M CH3In OH solution, with 50mV s-1
Sweep speed it is carried out linear sweep voltammetry test.Test result as shown in the curve 2 in accompanying drawing 3,
The electric current density of Pt-CoP/C catalyst methanol oxidation is apparently higher than existing business-like Pt/C.
Embodiment 3, comprises the steps:
Being joined by 40mg carbon black material in 49mL ethanol solution, ultrasonic Treatment makes carbon black material
Expect fully dispersed in the solution；Adding 113mg cabaltous nitrate hexahydrate in above-mentioned solution, stirring makes it fill
Divide and add, after dissolving, the strong aqua ammonia that 1.2mL mass concentration is 28% again, be heated to reflux 15h at 90 DEG C,
The complex solution of cobalt is carried to carbon；Proceed to this solution answer in still after 150 DEG C of hydro-thermals 4h to hydro-thermal, filter,
Washing removes other ion of residual, is fully dried to obtain carbon and carries four oxidations in the vacuum drying oven of 80 DEG C
Three cobalt materials；After it being mixed with sodium hypophosphite with the ratio of 1:5, be ground to uniform powder, transfer to fill
Have in the high temperature process furnances of argon, be heated to 350 DEG C and make Cobalto-cobaltic oxide fully by phosphatization, obtain CoP/C
Material；It is made to be dispersed in 45mL ethylene glycol and 15mL deionized water by ultrasonic Treatment CoP/C
Mixed solution in, and to add 1.25mL concentration be 53.1mg mL-1Platinum acid chloride solution, then exist
Being heated to reflux 5h under the conditions of 150 DEG C makes chloroplatinic acid be reduced into Pt simple substance, finally gives Pt-CoP/C catalysis
Agent, wherein the size of CoP granule is the percent mass that size is 2nm, CoP of 20nm, Pt granule
Ratio is 35%, and the mass percent of Pt is 25%, and the mass percent of carbon black is 40%.
Take the catalyst of certain mass, at 0.5M H2SO4+1M CH3In OH solution, with 50mV s-1
Sweep speed it is carried out linear sweep voltammetry test.As shown in Figure 3, carbon black material disperses test result
The catalysis methanol oxidation of the Pt-CoP/C catalyst (curve 3) of preparation in the dehydrated alcohol not added water
Electric current density is dispersed in the mixed solution of second alcohol and water the Pt-CoP/C catalyst (curve of preparation less than it
2)。
Embodiment 4, comprises the steps:
40mg carbon black material is joined in the mixed solution of 48mL ethanol and 1mL deionized water, super
Sonicated makes carbon black material fully dispersed in the solution；In above-mentioned solution, add 113mg six be hydrated nitre
Acid cobalt, stirring adds the strong aqua ammonia that 1.2mL mass concentration is 28%, again at 90 DEG C after making it fully dissolve
It is heated to reflux 15h, obtains carbon and carry the complex solution of cobalt；Proceed to this solution to hydro-thermal answer in still 150 DEG C
After hydro-thermal 4h, filter, wash other ion removing residual, in the vacuum drying oven of 80 DEG C fully
It is dried to obtain carbon and carries Cobalto-cobaltic oxide material；After it is mixed with sodium hypophosphite, is ground to uniform powder,
Transfer to be filled with in the high temperature process furnances of argon, be heated to 350 DEG C and make Cobalto-cobaltic oxide fully by phosphatization,
Obtain CoP/C material；It is made to be dispersed in 60mL ethylene glycol by ultrasonic Treatment CoP/C material molten
In liquid, and to add 1.25mL concentration be 53.1mg mL-1Platinum acid chloride solution, then add at 150 DEG C
Hot reflux 5h makes chloroplatinic acid be reduced into Pt simple substance, finally gives Pt-CoP/C catalyst, wherein CoP
The mass percent that size is 3nm, CoP that size is 20nm, Pt granule of grain is 35%, Pt's
Mass percent is 25%, and the mass percent of carbon black is 40%.
Take the catalyst of certain mass, at 0.5M H2SO4+1M CH3In OH solution, with 50mV s-1
Sweep speed it is carried out linear sweep voltammetry test, test result as shown in Figure 3, is made with pure ethylene glycol
The catalysis methanol oxidate current of the Pt-CoP/C catalyst (curve 4) prepared for reducing agent less than with
The Pt-CoP/C catalyst (curve 2) that ethylene glycol and water mixed solution are prepared as reducing agent.
In catalyst prepared by above example, example 3 and example 4 are by changing the nothing in reaction condition
Catalyst prepared by the ratio of water-ethanol and the ratio of water and ethylene glycol and water, the oxidation of its catalysis methanol
Electric current density is inferior to the performance of the catalyst of example 2 preparation.Meanwhile, the institute of preparation in present example
Having in catalyst, electric current density and the stability of the oxidation of catalyst methanol are substantially better than existing business
The Pt/C catalyst of industry.
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention,
Not in order to limit the present invention, all made within the spirit and principles in the present invention any amendment, equivalent
Replacement and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a methanol carbonoxide carries Pt doping phosphatization cobalt granule catalyst, it is characterised in that wherein phosphatization
The mass percent of cobalt, Pt and material with carbon element is followed successively by 30%-35%, 20%-25% and 40%-50%.
Catalyst the most according to claim 1, it is characterised in that carbon material surface high degree of dispersion is born
Carry phosphatization cobalt granule and the Pt granule of 2-3nm of 10-20nm.
Catalyst the most according to claim 1 and 2, it is characterised in that it is by material with carbon element and cobalt salt,
After heated backflow, hydrothermal oxidization, with sodium hypophosphite low temperature phosphor, the mixing inserting ethylene glycol and water is molten
In liquid, add platinum acid chloride solution and be reduced into Pt simple substance and form.
The preparation method of catalyst the most according to claim 1 or claim 2, it is characterised in that described material with carbon element
It it is carbon black material.
Catalyst the most according to claim 1 and 2, it is characterised in that described cobalt salt is four water
Close cobalt acetate or cabaltous nitrate hexahydrate.
6. a methanol carbonoxide carries Pt doping phosphatization cobalt granule method for preparing catalyst, it is characterised in that
Comprise the steps:
(1) it is heated to reflux: material with carbon element is joined in the mixed solution of dehydrated alcohol and deionized water, super
Sonicated makes material with carbon element be dispersed in this mixed solution；Add cobalt salt so that it is after fully dissolving again
Adding mass concentration is the strong aqua ammonia of 28%, is heated to reflux 14-15h at 80-90 DEG C, obtains carbon and carries cobalt
Complex solution；
(2) hydrothermal oxidization: proceed to this complex solution to hydro-thermal answer 140-150 DEG C of hydro-thermal 2-4h in still
After, filter, wash other ion removing residual, the driest in the vacuum drying oven of 60-80 DEG C,
Obtain carbon and carry Cobalto-cobaltic oxide material；
(3) low temperature phosphor: carbon is carried Cobalto-cobaltic oxide material and the sodium hypophosphite ratio with mass ratio as 1:5
Example mixing, be ground to uniform powder after, transfer to be filled with in the high temperature process furnances of nitrogen or noble gas,
It is heated to 300-350 DEG C, makes the abundant phosphatization of Cobalto-cobaltic oxide, obtain CoP/C material；
(4) reduction of ethylene glycol: described CoP/C material is passed through ultrasonic Treatment so that it is be dispersed in second two
In the mixed solution of alcohol and deionized water, and add platinum acid chloride solution, be heated to reflux 4-5 at 140-150 DEG C
H, makes chloroplatinic acid be reduced into Pt simple substance, finally gives Pt-CoP/C catalyst.
The preparation method of catalyst the most according to claim 6, it is characterised in that nothing in step (1)
Water-ethanol is 48:1 or pure ethanol solution with the volume ratio of deionized water.
The preparation method of catalyst the most according to claim 6, it is characterised in that lazy in step (3)
Property gas is argon.
The preparation method of catalyst the most according to claim 6, it is characterised in that second in step (4)
The volume ratio of glycol and deionized water is 3:1 or pure ethylene glycol solution.
The preparation method of catalyst the most according to claim 6, it is characterised in that described material with carbon element is
Carbon black material.
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| CN106450305A (en) * | 2016-11-15 | 2017-02-22 | 哈尔滨工程大学 | Preparation method of lithium ion battery cathode material CoP/C |
| CN108598511A (en) * | 2018-05-15 | 2018-09-28 | 西南大学 | A kind of load type palladium cobalt phosphorus nano material and its preparation method and application |
| CN109301267A (en) * | 2018-10-29 | 2019-02-01 | 广东工业大学 | A kind of phosphide nanocatalyst and preparation method thereof |
| CN110560064A (en) * | 2019-09-20 | 2019-12-13 | 武汉轻工大学 | Preparation method and application of magnetic carbon sphere loaded cobaltosic oxide catalyst |
| CN110890558A (en) * | 2019-11-05 | 2020-03-17 | 中新国际联合研究院 | Supported platinum-based core-shell catalyst and preparation method thereof |
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| CN113249739A (en) * | 2021-06-04 | 2021-08-13 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN113373345A (en) * | 2021-06-07 | 2021-09-10 | 中氢新能(北京)新能源技术研究院有限公司 | Supported superfine PtCoP ternary alloy nanoparticle for electrocatalytic methanol oxidation and preparation method thereof |
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