CN115404513A - Carbon-coated heterostructure electrocatalyst and preparation and application thereof - Google Patents
Carbon-coated heterostructure electrocatalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a carbon-coated heterostructure electrocatalyst and preparation and application thereof, and belongs to the technical field of electrocatalysts. The carbon-coated heterostructure electrocatalyst comprises nanoparticles with a heterostructure and a carbon material coating the nanoparticles; the heterostructure is formed by mutually combining transition metal and phosphide thereof; the carbon material is a nitrogen and phosphorus heterogeneous element co-doped carbon material. The carbon-coated heterostructure electrocatalyst has unique structural advantages of a three-dimensional carbon material substrate containing a large number of defects, including large specific surface area, high conductivity and good chemical stability, enhances the transfer of electrons, effectively improves the activity of the hydrogen evolution reaction of electrolysis water, and has hydrogen evolution reaction activity in a full pH range superior to that of a carbon-supported platinum electrocatalyst.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a carbon-coated heterostructure electrocatalyst, and preparation and application thereof.
Background
Under the dual pressure of energy crisis and environmental pollution, the use of clean and sustainable energy sources, such as solar, wind and tidal energy, has been vigorously developed, and the commercialization of these new energy sources requires their conversion into chemical fuels that are easy to store, transport and handle. Among different energy carriers, hydrogen energy has great advantages compared with other energy sources due to high energy density and abundant natural resources, and the final product is only water, so that the emission of greenhouse gases and harmful gases can be greatly reduced by using the hydrogen energy. The excellent characteristics of high energy density, zero emission and sustainable recycling of hydrogen energy are one of the ideal energy sources recognized in the world. In order to meet the development requirements of world energy requirements, the development and development of efficient hydrogen production approaches become a great hot spot in the fields of current chemistry, materials, energy sources and the like.
The electrocatalytic water decomposition hydrogen analysis reaction provides an efficient and clean way for mass production of hydrogen energy. The electrochemical reactions generally take place at the electrode surface at the "electrode/solution" interface, and thus the electrode surface material is the dominant factor in achieving electrocatalytic processes, with activity, reaction kinetics and stability also varying with the intrinsic properties of the electrode surface and the actual electrochemical conditions. Electrochemical hydrogen evolution reactions are one of the simplest electrochemical reactions, the reaction steps of which include adsorption, reduction and desorption processes that occur on the electrode surface. Because the overpotential of the hydrogen evolution reaction is high, the hydrogen production efficiency is low, and the wide application of the electrochemical water decomposition technology is hindered, and in order to overcome the obstacles, an active catalyst needs to be introduced on the surface of an electrode, so that the cost of extra energy can be obviously reduced, and the conversion efficiency is improved. Hydrogen atoms are adsorbed to form hydrogen intermediates on the electrode surface catalyst in the hydrogen evolution reaction process, but the reaction rate can be reduced due to the over-strong or over-weak hydrogen bond formation, and the initial hydrogen adsorption process and the final hydrogen molecule desorption process of the electrode surface catalyst are respectively influenced. If the hydrogen bond formation is too weak, indicating that there is no strong interaction between the reactants and the catalyst, the reactants are difficult to complete into the product; if the hydrogen bond formation is too strong, it indicates that the interaction between the reactants and the catalyst is too strong, meaning that desorption of the product becomes exceptionally difficult. Therefore, the catalyst with neither too strong nor too weak adsorption strength with the reactant is the most efficient catalyst, and in order to improve the hydrogen production efficiency of the electrochemical water decomposition hydrogen analysis reaction as much as possible, the development of the high-performance water electrolysis hydrogen production catalyst has become one of the real-time hot spots in the world today.
It is well known that platinum is the most effective catalyst for the electrolysis of water to produce hydrogen, which exhibits a unique catalytic capability for hydrogen evolution reactions. However, the high price of platinum greatly limits the wide application of platinum in the commercialization and industrialization fields, in order to reduce the cost of hydrogen production as much as possible, a novel catalyst with a specific structure is synthesized by adopting cheaper materials and a special preparation method, so that the novel catalyst has hydrogen evolution reaction activity superior to that of platinum, and a simpler and more convenient novel catalyst synthesis strategy is explored to reduce the energy loss and cost in the preparation process as much as possible, so as to facilitate the development of the commercialization and industrialization high-efficiency hydrogen production catalyst. Thus. Further researching and developing the catalyst for producing hydrogen by electrolyzing water with low cost and high efficiency has practical significance for meeting future energy demand in the world and the development of national energy strategy.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems of high preparation cost, low hydrogen production efficiency and the like of the electrocatalyst in the prior art.
In order to solve the technical problems, the invention provides a carbon-coated heterostructure electrocatalyst, and preparation and application thereof. The nano particles with the heterostructure of the electrocatalyst are embedded in a three-dimensional nitrogen and phosphorus co-doped carbon material containing a large number of defects to form a porous wrapping layer. The catalyst shows excellent activity and stability for the hydrogen evolution reaction of electrolyzed water and the hydrazine oxidation reaction in the full pH range, the performance of the hydrogen evolution reaction of electrolyzed water and the hydrazine oxidation reaction is superior to that of a carbon-supported platinum electrocatalyst, and the catalyst has the performance superior to that of the carbon-supported platinum electrocatalyst under the condition that the manufacturing cost is far lower than that of the carbon-supported platinum electrocatalyst.
A first object of the present invention is to provide a carbon-coated heterostructure electrocatalyst, comprising nanoparticles having a heterostructure, and a carbon material coating the nanoparticles; the heterostructure is formed by mutually combining transition metal and phosphide thereof; the carbon material is a nitrogen and phosphorus heterogeneous element co-doped carbon material.
In one embodiment of the invention, the nanoparticles have a particle size of 1-5nm.
In one embodiment of the invention, the transition metal is one or more of gold, silver, ruthenium, germanium, palladium, platinum, osmium, iridium, rhodium, platinum and cobalt.
A second object of the present invention is to provide a method for preparing the carbon-coated heterostructure electrocatalyst, comprising the steps of,
(1) Adding the mixed solution into the mixture of the transition metal salt, the phosphorus source and the carbon and nitrogen precursor, and performing ball milling and drying to obtain a powder mixture; the mixed solution is obtained by mixing a hydrochloric acid solution and ethanol;
(2) Pyrolyzing the powder mixture in the step (1) to obtain the carbon-coated heterostructure electrocatalyst; the pyrolysis is divided into 2 stages, namely a carbon pyrolysis stage and a metal ligand pyrolysis stage.
In one embodiment of the present invention, in step (1), the phosphorus source is one or more of glyphosate, triphenylphosphine oxide, phosphoric acid, phosphorus pentachloride and phosphorus oxychloride.
In one embodiment of the present invention, in the step (1), the carbon-nitrogen precursor is one or more of melamine, urea, dicyandiamide, cyanamide and aniline.
In one embodiment of the present invention, in step (1), the transition metal salt is a chloride salt and/or an acetate salt.
In one embodiment of the present invention, in the step (1), the mass ratio of the transition metal salt, the phosphorus source and the carbon-nitrogen precursor is 1:30-80:300-450.
Preferably, in the step (1), the mass ratio of the transition metal salt, the phosphorus source and the carbon-nitrogen precursor is 1:50-70:320-360.
In one embodiment of the present invention, in the step (1), the volume ratio of the hydrochloric acid solution to the ethanol in the mixed solution is 1:3-10.
In one embodiment of the present invention, in the step (1), the hydrochloric acid solution has a volume concentration of 30 to 44%.
In one embodiment of the invention, in the step (2), the temperature of the carbon pyrolysis stage is raised to 500-700 ℃ at the rate of 1-5 ℃/min, and the temperature is maintained for 60-180min.
In one embodiment of the invention, in the step (2), the metal ligand pyrolysis stage is to heat up to 700-900 ℃ at a rate of 1-5 ℃/min and keep the temperature for 30-180min.
The third purpose of the invention is to provide the application of the carbon-coated heterostructure electrocatalyst in the electrolytic hydrogen evolution reaction and the hydrazine oxidation reaction.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The carbon-coated heterostructure electrocatalyst provided by the invention has the advantages that the nano particles with the heterostructure are embedded in a three-dimensional nitrogen and phosphorus co-doped carbon material containing a large number of defects to form a porous wrapping layer, and the three-dimensional carbon material substrate containing a large number of defects has unique structural advantages, so that the material has a large specific surface area, and a large number of gaps are formed in the material, thereby being beneficial to the transfer of electrons and protons and the adsorption and desorption capabilities of gas, and further enhancing the hydrogen production rate and efficiency of the electrolytic water hydrogen evolution reaction, and having good corrosion resistance.
(2) The carbon-coated heterostructure electrocatalyst provided by the invention has the advantages that the nano particles are uniformly distributed, and the particle density is extremely high, so that the carbon-coated heterostructure electrocatalyst has a large number of active sites, and the efficiency of the electrolytic water hydrogen evolution reaction is enhanced.
(3) The unique heterogeneous interface structure of the nano particles in the carbon-coated heterostructure electrocatalyst effectively adjusts the electronic structure of the surface of the catalyst, optimizes the adsorption/desorption effect of a reaction intermediate in the reaction process, thereby improving the speed of the hydrogen evolution reaction of electrolysis water and the hydrazine oxidation reaction, and ensuring that the activity of the catalyst in the hydrogen evolution reaction in the full pH range and the hydrazine oxidation reaction under the alkaline condition is superior to that of a commercial carbon-supported platinum electrocatalyst.
(4) The preparation method of the carbon-coated heterostructure electrocatalyst adopts a ball milling method to fully and uniformly mix and mill the precursor, and then carries out high-temperature pyrolysis, and the integral synthesis method is simple and convenient, is easy to prepare and can be used for large-scale production.
Drawings
In order that the manner in which the present invention is more fully understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, wherein:
FIG. 1 is an SEM image of a rhodium on carbon/rhodium diphosphide heterostructure electrocatalyst of example 1 of the present invention.
FIG. 2 is a bright field TEM image of a rhodium on carbon/rhodium diphosphide heterostructure electrocatalyst of example 1 of the invention.
FIG. 3 is a representation of a rhodium on carbon/rhodium diphosphide heterostructure electrocatalyst according to example 1 of the invention; wherein, the upper left is a dark field TEM image, the lower left is an EDS full spectrogram, and the rest is an EDS image of the marked elements.
FIG. 4 is an XRD pattern of a rhodium on carbon/rhodium diphosphide heterostructure electrocatalyst of example 1 of the invention.
FIG. 5 is a BET plot of the carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst of example 1 of the present invention.
FIG. 6 is a graph of hydrogen evolution reaction electrochemical polarization for a rhodium on carbon/rhodium diphosphide heterostructure electrocatalyst and a 20% platinum on carbon electrocatalyst according to example 1 of the present invention.
FIG. 7 is a polarization diagram of electrochemical hydrazine oxidation reaction for a carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst and a 20% carbon supported platinum electrocatalyst according to example 1 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
In the present invention, unless otherwise specified, the concentrated hydrochloric acid has a volume concentration of 34%.
Example 1
A carbon-coated heterostructure electrocatalyst and a preparation method thereof specifically comprise the following steps:
(1) 25mg of rhodium chloride, 1.4g of glyphosate and 8g of melamine are accurately weighed, mixed together, ground for 5min and then placed into an oven to be fully dried.
(2) And (3) putting the fully dried powder mixture into a ball milling tank, carrying out ball milling treatment for 1.5h by using a planetary ball mill, then adding 15mL of mixed solution (1).
(3) Putting the fully dried mixture into a ball mill, ball-milling for 30min, grinding the mixture into powder, putting the powder into a sealed quartz boat, then transferring the quartz boat into a tubular calcining furnace, heating to 650 ℃ at the speed of 2.5 ℃/min in an inert atmosphere, and preserving heat for 2h; then adding the mixture into the reactor at a speed of 2 ℃/min to 850 ℃, and preserving the heat for 1.5 hours to obtain the carbon-supported rhodium/diphosphoridinium heterostructure electrocatalyst.
Example 2
A carbon-coated heterostructure electrocatalyst and a preparation method thereof specifically comprise the following steps:
(1) 20mg of rhodium chloride, 1.6g of glyphosate and 8.5g of melamine are accurately weighed, mixed together, ground for 5min and then placed into an oven for full drying.
(2) And (3) putting the fully dried powder mixture into a ball milling tank, carrying out ball milling treatment for 1.5h by using a planetary ball mill, then adding 15mL of mixed solution (1).
(3) Putting the fully dried mixture into a ball mill, performing ball milling for 30min, grinding the mixture into powder, putting the powder into a sealed quartz boat, then transferring the quartz boat into a tubular calcining furnace, heating to 650 ℃ at the speed of 2.5 ℃/min in an inert atmosphere, and preserving heat for 2h; then adding the mixture into the reactor at a speed of 2 ℃/min to 850 ℃, and preserving the temperature for 1.5h to obtain the carbon-supported rhodium/diphosphorization rhodium heterostructure electrocatalyst.
Example 3
A carbon-coated heterostructure electrocatalyst and a preparation method thereof specifically comprise the following steps:
(1) 30mg of rhodium chloride, 1.5g of glyphosate and 9g of melamine are accurately weighed, mixed together, ground for 5min and then placed into an oven to be fully dried.
(2) And (3) putting the powder mixture subjected to full drying treatment into a ball milling tank, carrying out ball milling treatment for 1.5h by using a planetary ball mill, then adding 20mL of mixed solution (1).
(3) Putting the fully dried mixture into a ball mill, performing ball milling for 30min, grinding the mixture into powder, putting the powder into a sealed quartz boat, then transferring the quartz boat into a tubular calcining furnace, heating to 650 ℃ at the speed of 2.5 ℃/min in an inert atmosphere, and preserving heat for 2h; then adding the mixture into the reactor at a speed of 2 ℃/min to 850 ℃, and preserving the temperature for 1.5h to obtain the carbon-supported rhodium/diphosphorization rhodium heterostructure electrocatalyst.
Example 4
A carbon-coated heterostructure electrocatalyst and a preparation method thereof specifically comprise the following steps:
(1) 30mg of ruthenium chloride, 1.5g of glyphosate and 9g of melamine are accurately weighed, mixed together, ground for 5min and then placed into an oven to be fully dried.
(2) And (3) putting the fully dried powder mixture into a ball milling tank, carrying out ball milling treatment for 1.5h by using a planetary ball mill, then adding 20mL of mixed solution (1) of concentrated hydrochloric acid and ethanol, carrying out ball milling treatment for 10min by using the ball mill, and finally putting into an oven for fully drying.
(3) Putting the fully dried mixture into a ball mill, ball-milling for 30min, grinding the mixture into powder, putting the powder into a sealed quartz boat, then transferring the quartz boat into a tubular calcining furnace, heating to 650 ℃ at the speed of 2.5 ℃/min in an inert atmosphere, and preserving heat for 2h; then adding the mixture into the reactor at the speed of 2 ℃/min to 900 ℃, and preserving the temperature for 1h to obtain the carbon-supported ruthenium/ruthenium diphosphinate heterostructure electrocatalyst.
Example 5
A carbon-coated heterostructure electrocatalyst and a preparation method thereof specifically comprise the following steps:
(1) 30mg of iridium chloride, 1.5g of glyphosate and 9g of melamine are accurately weighed, mixed together, ground for 5min and then placed into an oven to be fully dried.
(2) And (3) putting the fully dried powder mixture into a ball milling tank, carrying out ball milling treatment for 1.5h by using a planetary ball mill, then adding 20mL of mixed solution (1) of concentrated hydrochloric acid and ethanol, carrying out ball milling treatment for 10min by using the ball mill, and finally putting into an oven for fully drying.
(3) Putting the fully dried mixture into a ball mill, ball-milling for 30min, grinding the mixture into powder, putting the powder into a sealed quartz boat, then transferring the quartz boat into a tubular calcining furnace, heating to 650 ℃ at the speed of 2.5 ℃/min in an inert atmosphere, and preserving heat for 2h; then adding the mixture into the reactor at the speed of 2 ℃/min to 900 ℃, and preserving the temperature for 1h to obtain the carbon-supported iridium/iridium diphosphide heterostructure electrocatalyst.
Example 6
A carbon-coated heterostructure electrocatalyst and a preparation method thereof specifically comprise the following steps:
(1) 30mg of cobalt chloride, 1.5g of glyphosate and 9g of melamine are accurately weighed, mixed together, ground for 5min and then placed into an oven to be fully dried.
(2) And (3) putting the powder mixture subjected to full drying treatment into a ball milling tank, carrying out ball milling treatment for 1.5h by using a planetary ball mill, then adding 20mL of mixed solution (1).
(3) Putting the fully dried mixture into a ball mill, performing ball milling for 30min, grinding the mixture into powder, putting the powder into a sealed quartz boat, then transferring the quartz boat into a tubular calcining furnace, heating to 650 ℃ at the speed of 2.5 ℃/min in an inert atmosphere, and preserving heat for 2h; then adding the mixture into the reactor at the temperature of 900 ℃ at the speed of 2 ℃/min, and preserving the temperature for 1h to obtain the carbon-supported cobalt/cobalt diphosphide heterostructure electrocatalyst.
Test example 1
(1) Scanning Electron Microscope (SEM)
Scanning Electron Microscope (SEM) characterization was performed on the carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst prepared in example 1, and as shown in fig. 1, it can be seen from fig. 1 that a large number of pore defects are contained in the three-dimensional graphene substrate.
(2) Transmission Electron Microscope (TEM)
Transmission Electron Microscopy (TEM) characterization of the carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst prepared in example 1 resulted in the average size of the nanoparticles formed by the rhodium/rhodium diphosphide heterostructures in the carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst, as shown in FIG. 2, which is evident from FIG. 2, being about 2.59nm.
(3)EDS-Mapping
EDS-Mapping analysis of the carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst prepared in example 1 is carried out, and the result is shown in FIG. 3. From FIG. 3, it can be seen that the main elements of the carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst are carbon, nitrogen, phosphorus and rhodium which are uniformly dispersed.
(4) X-ray diffraction (XRD)
The carbon-supported rhodium/rhodium diphosphide heterostructure electrocatalyst prepared in example 1 was subjected to X-ray diffraction (XRD) analysis, and as a result, as shown in fig. 4, characteristic diffraction peaks attributed to rhodium and characteristic diffraction peaks attributed to rhodium diphosphide were clearly seen from fig. 4.
(5) Specific surface area
The specific surface area test (BET) was carried out on the carbon-supported rhodium/rhodium diphosphide heterostructure electrocatalyst prepared in example 1, and as a result, as shown in FIG. 5, it can be seen from FIG. 5 that the specific surface area of the carbon-supported rhodium/rhodium diphosphide heterostructure electrocatalyst was 913.38cm -2 。
Test example 2
(1) Electrolytic water hydrogen evolution reaction
The carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst prepared in the example 1 and 20% of carbon supported platinum electrocatalyst were subjected to an electrolytic water hydrogen evolution reaction test, which specifically included the following steps:
5mg of the sample was mixed with 0.49mL of isopropanol, 0.49mL of deionized water, 0.02mL of a solution in L nafion (5 wt.%, CAS No. 31175-20-9), and then sonicated for 2h to mix well. And dripping 6 microliters of the prepared mixed solution on a glassy carbon electrode (with the diameter of 5 mm), and naturally drying to obtain the working electrode. After the material is prepared into a working electrode, the working electrode is prepared at normal timesAt room temperature, 0.5M H respectively 2 SO 4 The water electrolysis hydrogen evolution reaction is carried out in (a), 0.5M PBS (b) and 0.1M KOH (c), the linear sweep voltammetry diagram is shown in figure 6, and it can be seen from figure 6 that the water electrolysis hydrogen evolution reaction activity of the carbon-supported rhodium/diphosphorium heterostructure electrocatalyst is better than that of the carbon-supported platinum catalyst under three environmental conditions.
(2) Hydrazine oxidation reaction
The carbon supported rhodium/rhodium diphosphide heterostructure electrocatalyst prepared in example 1 and 20% carbon supported platinum electrocatalyst were subjected to hydrazine oxidation reaction test, specifically comprising the following steps:
after the material is prepared into a working electrode, hydrazine oxidation reaction is carried out in a mixed solution of 1M KOH and 0.1M hydrazine at the optimal working temperature, a linear scanning voltammetry diagram of the material is shown in figure 7, and figure 7 shows that the activity of the hydrazine oxidation reaction of the carbon-supported rhodium/rhodium diphosphide heterostructure electrocatalyst is superior to that of the carbon-supported platinum electrocatalyst under the environmental condition, which shows that the carbon-supported rhodium/rhodium diphosphide heterostructure electrocatalyst is also a bifunctional catalyst with excellent activity.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Various other modifications and alterations will occur to those skilled in the art upon reading the foregoing description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A carbon-coated heterostructure electrocatalyst, comprising nanoparticles having a heterostructure, and a carbon material coating the nanoparticles; the heterostructure is formed by mutually combining transition metal and phosphide thereof; the carbon material is a nitrogen and phosphorus heterogeneous element co-doped carbon material.
2. The carbon-coated heterostructure electrocatalyst according to claim 1, wherein the nanoparticles have a particle size of 1-5nm.
3. The carbon-coated heterostructure electrocatalyst according to claim 1, wherein the transition metal is one or more of gold, silver, ruthenium, germanium, palladium, platinum, osmium, iridium, rhodium, platinum, and cobalt.
4. The method of preparing a carbon-coated heterostructure electrocatalyst according to any one of claims 1-3, comprising the steps of,
(1) Adding the mixed solution into the mixture of the transition metal salt, the phosphorus source and the carbon and nitrogen precursor, and performing ball milling and drying to obtain a powder mixture; the mixed solution is obtained by mixing a hydrochloric acid solution and ethanol;
(2) Pyrolyzing the powder mixture in the step (1) to obtain the carbon-coated heterostructure electrocatalyst; the pyrolysis is divided into 2 stages, namely a carbon pyrolysis stage and a metal ligand pyrolysis stage.
5. The method for preparing the carbon-coated heterostructure electrocatalyst according to claim 4, wherein in step (1), the phosphorus source is one or more of glyphosate, triphenylphosphine oxide, phosphoric acid, phosphorus pentachloride, and phosphorus oxychloride; the carbon-nitrogen precursor is one or more of melamine, urea, dicyandiamide, cyanamide and aniline.
6. The method for preparing a carbon-coated heterostructure electrocatalyst according to claim 4, wherein in step (1), the mass ratio of the transition metal salt, the phosphorus source and the carbon-nitrogen precursor is 1:30-80:300-450.
7. The method for preparing a carbon-coated heterostructure electrocatalyst according to claim 4, wherein in step (1), the volume ratio of the hydrochloric acid solution to ethanol in the mixed solution is 1:3-10.
8. The method for preparing a carbon-coated heterostructure electrocatalyst according to claim 4, wherein in step (2), the carbon pyrolysis stage is performed by raising the temperature to 500-700 ℃ at a rate of 1-5 ℃/min and holding the temperature for 60-180min.
9. The method for preparing the carbon-coated heterostructure electrocatalyst according to claim 4, wherein in the step (2), the metal ligand pyrolysis stage is to heat up to 700-900 ℃ at a rate of 1-5 ℃/min and to keep the temperature for 30-180min.
10. Use of the carbon-coated heterostructure electrocatalyst of any one of claims 1-3 in the hydrogen evolution reaction from electrolysis water and in the hydrazine oxidation reaction.
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CN116759594B (en) * | 2023-07-24 | 2024-02-27 | 武汉纺织大学 | Carbon-supported rhodium phosphide/platinum heterojunction nano composite catalyst and preparation method and application thereof |
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