CN114695908A - Preparation and application of composite hollow graphene ball-loaded platinum-nickel nanoparticles - Google Patents
Preparation and application of composite hollow graphene ball-loaded platinum-nickel nanoparticles Download PDFInfo
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- CN114695908A CN114695908A CN202210424469.2A CN202210424469A CN114695908A CN 114695908 A CN114695908 A CN 114695908A CN 202210424469 A CN202210424469 A CN 202210424469A CN 114695908 A CN114695908 A CN 114695908A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 118
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- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 title claims abstract description 60
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
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- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 10
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 claims description 2
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 12
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite hollow graphene ball loaded platinum-nickel nano particle and a preparation method and application thereof, wherein different atmosphere radio frequency plasmas are used for treating an iron-cobalt bimetallic nitrogen doped hollow graphene ball as a conductive network, and platinum-nickel nano particles are loaded on the hollow graphene ball; the prepared modified iron-cobalt bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nano particles are applied to a methanol fuel cell multifunctional catalyst, can obviously enhance gas adsorption efficiency, improve oxygen reduction and methanol oxidation capacity, improve stability and conductivity in the reaction of catalyzing methanol fuel cells ORR and MOR, and have lower cost and good catalytic performance in the reaction of ORR and MOR.
Description
Technical Field
The invention belongs to the technical field of methanol fuel cell catalysts, and particularly relates to preparation of composite hollow graphene ball-loaded platinum-nickel nanoparticles and application of the composite hollow graphene ball-loaded platinum-nickel nanoparticles in a methanol fuel cell.
Background
Energy is the material basis of human social activities and the driving force for the development of the world economy. Non-renewable fossil energy sources such as coal, petroleum, natural gas and the like are the most main energy sources consumed globally at present. The energy crisis and environmental problems caused by traditional energy sources are the resistance of sustainable development of human society. The rising current situations of energy demand, depletion of fossil fuel reserves, environmental pollution, and the like have promoted human research into energy conversion devices having high efficiency and low emissions. Fuel cells powered by renewable small molecule substances (e.g., hydrogen, ethanol, formic acid, methanol, etc.) may have the potential to meet these requirements. Fuel Cells (FC) are a new power generation method that can directly convert chemical energy stored in Fuel into electrical energy through electrochemical reaction without using a heat engine to do work and without using a carnot cycle. Because it still has the advantage in aspects such as high power density and live time are long, consequently be honored as the fourth kind electric power technique beyond continuing thermoelectricity, water and electricity, nuclear power. Direct Methanol Fuel Cells (DMFCs) have attracted considerable interest in recent years due to their advantages of high power density, zero or low exhaust, ease of charging, simple structure, fast start-up at low temperatures, etc. However, DMFCs still have many obstacles in the way of commercialization, such as: the electrochemical oxidation kinetics process of the DMFC is slow at low temperature, and methanol easily permeates through a proton exchange membrane from an anode to a cathode to poison an oxygen electrode; electrocatalysts are susceptible to poisoning by intermediate products (CO) produced by the oxidation of methanol, and although considerable improvements have been achieved, DMFCs are still far from large-scale commercial use. Currently, platinum and its alloys are commonly used as bifunctional catalysts for oxygen reduction and Methanol Oxidation (MOR), and commercial oxygen reduction (ORR) catalysts are typically composed of platinum nanoparticles dispersed on high surface area carbon, which is costly and storage-limiting. The catalysis of oxygen reduction reactions at platinum surfaces is largely hindered by over-adsorbed oxygen-containing intermediates, particularly at low coordination surface sites. Pt is combined with transition metals (Fe, Co and Ni) with a 3d structure, so that the electronic structure of Pt is changed, the center of a d-band is reduced, the adsorption of oxygen-containing species is weakened, and the surface active sites are increased. Therefore, it is necessary to develop a catalyst with high Pt utilization rate, methanol resistance, uneasy poisoning, low cost and ORR/MOR dual-function catalysis.
Currently, carbon-based materials are widely used as nanoparticle carriers. The Fe-Co bimetallic nitrogen doped hollow graphene ball has the physicochemical characteristics of unique hollow structure, excellent electronic conductivity, high mechanical strength, higher specific surface area, good chemical stability and the like, and is considered to be an ideal electrocatalyst carrier material. However, the untreated composite hollow graphene spheres have low surface activity (inertness and hydrophobicity), are difficult to disperse in most organic or inorganic solvents, and thus are not easy to uniformly deposit platinum nickel nanoparticles with small size on the surface. In the field of electrocatalysis, there has been considerable progress in the research relating to the modification of materials by radio frequency plasma, such as etching, doping or other surface treatments. Platinum-nickel nano particles are uniformly loaded on the surface of the composite hollow graphene sphere through modification treatment of radio frequency plasma, and meanwhile, heteroatom doping can be carried out, so that the electronic structure, vibration mode, chemical activity, mechanical property and the like of the carbon substrate are changed, and therefore the key for improving the electrocatalytic performance and the utilization rate of Pt is to serve as a high-efficiency ORR/MOR bifunctional catalyst of a methanol fuel cell.
Disclosure of Invention
The invention aims to provide a preparation method of different-atmosphere radio frequency plasma treated iron-cobalt bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nanoparticles with high specific surface area, high Pt utilization rate and good catalytic performance and application of the nanoparticles in a methanol fuel cell electrode material.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
preparation method of composite hollow graphene ball loaded with platinum-nickel nanoparticles, wherein the composite hollow graphene ball is an iron-cobalt bimetallic nitrogen-doped hollow graphene ball (FeCo/N) which is doped with iron-cobalt bimetallic nitrogenxHGS) is a carrier, the platinum-nickel nano particles are a load, and the load is loaded on the carrier through radio frequency plasma treatment.
A preparation method of composite hollow graphene ball-loaded platinum-nickel nanoparticles comprises the following preparation steps:
step one, FeCo/NxPreparation of HGS: after Graphene Oxide (GO) and polystyrene spheres (PS spheres) are self-assembled, polyaniline is coated on the surface, melamine is added as a nitrogen source and a carbon source, then the polyaniline reacts with iron transition metal salt, cobalt transition metal salt and a reducing agent, and FeCo/N is obtained by calciningxHGS；
Step two, modifying FeCo/N by radio frequency plasmaxPreparation of HGS: miningThe iron-cobalt bimetallic nitrogen-doped hollow graphene ball prepared in the first step of surface treatment of the radio-frequency plasmas in different atmospheres is used for obtaining the radio-frequency plasma modified FeCo/NxHGS；
Step three, FeCo/N loaded with platinum-nickel nanoparticlesxPreparation of HGS: modifying FeCo/N by the radio frequency plasma prepared in the step twoxFeCo/N loaded with platinum-nickel nanoparticles obtained by combining HGS and platinum-nickel nanoparticlesxHGS。
Further, FeCo/N in the first stepxThe preparation steps of the HGS comprise:
(1) adding polystyrene spheres (PS spheres) into a hydrochloric acid solution, uniformly stirring, adding graphene oxide into water, performing ultrasonic treatment for 20-40 min, adding the graphene oxide into the polystyrene sphere solution, and performing magnetic stirring reaction at room temperature for 6-12 h;
(2) adding melamine into the solution (1), continuously carrying out magnetic stirring reaction at room temperature for a period of time, adding aniline, and keeping the temperature of the solution at 0 ℃ by adopting an ice-water bath; slowly adding an oxidant ammonium persulfate to promote the synthesis of polyaniline, simultaneously adding iron-cobalt transition metal salt, and reacting for 10-24 hours in a dark place to ensure that the polyaniline can be uniformly polymerized on the surface of the graphene;
(3) adding a reducing agent into the solution (2), refluxing at 90-120 ℃ to reduce graphene oxide into graphene, drying after reaction to obtain dark green graphene powder, mixing the graphene powder and melamine, dissolving in deionized water, mixing, magnetically stirring, reacting for a period of time, filtering and collecting a sample;
(4) annealing the solid sample obtained in the step (3) in a reducing atmosphere high-temperature tube furnace, heating the reaction device from room temperature to 380-450 ℃, staying for 2 hours, then heating to 750 ℃, continuing to calcine at high temperature for 1-3 hours, heating the prepared sample in 2M sulfuric acid solution at 80 ℃ for 4-10 hours to remove unstable and inactive substances of the sample, and fully washing with deionized water to obtain FeCo/NxHGS。
Further, the radio frequency plasma modified FeCo/NxPreparation of HGS: will be paired with FeCo/NxPutting HGS into a low-temperature radio frequency plasma machine device, and introducing different gasesAnd (5) performing surface treatment modification by line discharge.
Preferably, the different gas is one of argon, argon-hydrogen, argon-ammonia, nitrogen or oxygen.
Further, FeCo/N loaded with platinum-nickel nanoparticlesxThe preparation process of the HGS comprises the following steps: adding hydrated nickel acetylacetonate, 1, 2-tetradecanediol, oleic acid and oleylamine into a three-neck flask containing dioctyl ether, heating the solution to 60-90 ℃ under the protection of nitrogen, and keeping the temperature to remove crystal water; rapidly heating to 200 ℃, dissolving acetylacetone platinum in dichlorobenzene, and adding into a reaction bottle through an injector; preserving the heat for 1-3 h at 200 ℃, and cooling to room temperature; adding ethanol to obtain platinum nickel nanoparticles, centrifuging, collecting, washing with ethanol, and dispersing in n-hexane; ultrasonically dispersing a certain amount of modified iron-cobalt bimetallic nitrogen-doped hollow graphene balls in n-hexane for 15-30 min; meanwhile, the prepared platinum-nickel nanoparticles are also dispersed in n-hexane by ultrasonic waves for 15-30 min; then, mixing the nano particles with a substrate in a normal hexane solution, and carrying out ultrasonic dispersion for 0.5-1 h; the catalyst was then collected with a centrifuge and then completely dried overnight.
Preferably, in the step one, the amount of the polystyrene spheres, hydrochloric acid, graphene oxide, melamine, aniline, ammonium persulfate, iron transition metal salt, cobalt transition metal salt, ammonia water, hydrazine hydrate, hollow graphene spheres, melamine and sulfuric acid is 1500-2000mg, 80-100mL, 80-100mg, 2800-3000mg, 3-5mL, 12000-12500mg, 1000-1200mg, 2-3mL, 0.1-0.2mL, 100-110mg, 1000-1200mg and 30-50 mL.
Preferably, Co (NO) is used as the cobalt transition metal salt in the first step3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2、CoCl2、CoSO4·7H2O、CoSO4·H2One or more of O, Fe (NO) is adopted as the iron transition metal salt3)3·9H2O、FeCl3·6H2O、Fe(CH3COO)3、Fe2(SO4)3·6H2And one or more of O.
Preferably, the reducing atmosphere in the first step is Ar/H2(7％H2)；
Preferably, in the second step, the pressure, the discharge power and the processing time of the radio frequency plasma in different atmospheres in the tube are all 20Pa, 100W and 1 h.
Preferably, in the third step, the amounts of the hydrated nickel acetylacetonate, 1, 2-tetradecanediol, oleic acid, oleylamine, dioctyl ether, platinum acetylacetonate, dichlorobenzene, ethanol, hexane and modified composite hollow graphene spheres are 65-66mg, 69-70mg, 0.1-0.2mL, 10-12mL, 40-45mg, 0.5-0.8mL, 20-25mL and 66-70 mg.
An application of the modified composite hollow graphene ball-loaded platinum-nickel nano particle as a methanol fuel cell dual-function catalyst is used for catalyzing the reaction of an ORR (organic oxygen radical reactor) and an MOR (methanol fuel cell), the hollow graphene ball carbon-based material doped with the heteroatom has excellent electrocatalytic ORR performance, the doped heteroatom is rich in electrons or lack of electrons, can polarize and change the spin density of adjacent carbon atoms to generate new catalytic active sites and promote the chemical adsorption/desorption of an intermediate on the surface of the electrocatalyst, so that the catalytic activity of the ORR is improved, the radio frequency plasma etches and dopes the iron-cobalt bimetallic nitrogen doped hollow graphene ball to uniformly load the platinum-nickel nano particle on the surface of the composite hollow graphene ball, and simultaneously can dope the heteroatom to change the electronic structure, the vibration mode, the chemical activity, the mechanical performance and the like of the carbon substrate, thereby improving electrocatalytic performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) iron-cobalt-nitrogen doped hollow graphene ball (FeCo/N)xGHS) is used as a carrier, the carrier is superior to a common carbon-based material carrier due to the three-dimensional (3D) and porous structure, and the excellent conductivity of the graphene can be further improved by doping N hetero atoms and adjusting the electron orbital energy of adjacent carbon atoms, so that the electron transfer capacity is improved; the three-dimensional hollow structure with stretchability is not easy to deform and collapse, so that the stability of the composite material is remarkably improved; in the preparation of hollow graphene spheresThe polyaniline is coated on the outer surface, and nitrogen-doped carbide can be further formed in the roasting process, so that the collapse of spheres in the nano particle deposition process can be avoided; the combination of the hollow graphene spheres and the modified polyaniline can promote the interaction between the platinum-nickel nanoparticles and the iron-cobalt bimetallic nitrogen-doped hollow graphene spheres, and the electrochemical catalytic activity is improved; iron-cobalt alloy Nanoparticles (NPs) have better activity than their individual components; the alloy NPs coated by the carbon layer avoids the dissolution and corrosion of electrolytes to metals, and simultaneously prevents the aggregation of the NPs; the composite hollow graphene sphere has a porous structure, so that the composite hollow graphene sphere can better approach catalytic reaction, and charge is allowed to be rapidly transferred in the catalytic reaction; the non-uniform interface and strong coupling between the alloy NPs and the carbon shell helps to drive the fast reaction kinetics.
(2) The radio frequency plasma technology is based on a simple physical principle, energy supply is obtained, and the state of a substance is changed: changing from solid state to liquid state and then changing from liquid state to gas state; providing more energy to the gas, the gas will be ionized and enter a high-energy plasma state, which is the fourth state of the substance; the radio frequency plasma etches, dopes, reduces and increases defects on the iron-cobalt-nitrogen doped hollow graphene ball, so that the electronic structure, vibration mode, chemical activity, mechanical property and the like of the carbon substrate are changed, and conditions are created for the deposition of the platinum-nickel nano particles.
(3) The platinum-nickel nano particles enhance ORR activity, reduce Pt load and improve the utilization rate of Pt. However, catalyst structures using metal (alloy) nanoparticles on carbon supports suffer from serious drawbacks, including agglomeration and shedding of the alloy nanoparticles; in addition, carbon supports are susceptible to corrosion under typical direct methanol fuel cell operating conditions. The modified iron-cobalt-nitrogen-doped hollow graphene ball can improve the problems, not only can provide more electrochemical active sites, but also can obtain a rougher surface, and is beneficial to deposition of platinum-nickel nanoparticles.
(4) The Fe-Co bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nano particles treated by the radio frequency plasmas in different atmospheres can be directly used as an electrode material of a methanol fuel cell, and have the advantages of high Pt utilization rate, good stability and the like.
Drawings
Fig. 1 shows the microscopic morphology of the fe-co bimetallic n-doped hollow graphene spheres loaded with platinum-nickel nanoparticles under a Scanning Electron Microscope (SEM) and treated by the argon radio-frequency plasma;
FIG. 2 shows that the Fe-Co bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nanoparticle catalyst prepared by different-atmosphere radio frequency plasma treatment is in saturated O state20.1M KOH solution of Oxygen Reduction Reaction (ORR);
FIG. 3 shows that the Fe-Co bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nanoparticle catalyst prepared by different-atmosphere radio frequency plasma treatment is in saturated O state20.5M H2SO4Linear sweep voltammetric plots (LSV) of Oxygen Reduction Reactions (ORR) in solution.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention clearer, the present invention is described in detail below with reference to the accompanying drawings and the detailed description, the embodiments described in the present specification are only for explaining the present invention and are not intended to limit the present invention, and the parameters, proportions and the like of the embodiments can be selected according to circumstances without substantially affecting the results.
Example 1: a preparation method of composite hollow graphene ball-loaded platinum-nickel nanoparticles specifically comprises the following steps:
(1) synthesizing an iron-cobalt bimetallic nitrogen-doped hollow graphene ball:
2g of Polystyrene Spheres (PS)+) Add 100mL of 0.5M HCl solution and start stirring. Subjecting 100mg GO to ultrasound for 30min, adding the PS+In the solution, the reaction was magnetically stirred at room temperature for 12 h. Then add3g of melamine were added and the reaction was continued at room temperature for 12h with magnetic stirring. Thereafter, 5mL of aniline was added and the temperature of the solution was maintained at 0 ℃ using an ice water bath. Then slowly adding an oxidant ammonium persulfate to promote the synthesis of polyaniline (the adding amount of the ammonium persulfate is calculated by the same mole number as that of the aniline), and simultaneously adding 0.004mol of FeCl of transition metal salt3·6H2O，0.004mol Co(NO3)2·6H2And (O). And (5) reacting for 24 hours in a dark place, so that polyaniline can be uniformly polymerized on the surface of the graphene oxide. Then, a reducing agent (2mL of aqueous ammonia, 0.1mL of N) was added to the mixed solution2H4·H2O), then refluxed at 110 ℃ for 24h to reduce the graphene oxide to graphene (rGO). After that, the solution is dried in a forced air drying oven to obtain dark green powder, 100mg of the dark green powder sample prepared above and 1200mg of melamine are mixed and respectively dissolved in 25mL of distilled water, and the mixture is magnetically stirred and reacted for 12 hours. The obtained mixed solution sample was collected by filtration under reduced pressure. The solid sample was then placed in the center of the high temperature tube furnace reactor. Introducing Ar/H at one end2(7％H2) And (3) raising the temperature of the mixed gas in the reaction device from room temperature to 420 ℃ at the rate of 2 ℃/min, staying for 2 hours, then raising the temperature to 750 ℃ at the rate of 2 ℃/min, and continuing to calcine at high temperature for 1 hour. The sample prepared above was washed with 2M H2SO4Heating the solution at 80 deg.C for 8h to remove unstable and inactive substances in the sample, and washing with deionized water to obtain FeCo/NxHGS。
(2) Synthesizing an iron-cobalt bimetal nitrogen doped hollow graphene ball by argon radio-frequency plasma treatment:
putting the Fe-Co-N doped hollow graphene ball into a low-temperature radio-frequency plasma reaction device, introducing argon gas into the reaction device, controlling the air pressure in the tube to be 20Pa, the discharge power to be 100W and the treatment time to be 1h, carrying out radio-frequency plasma discharge surface modification treatment, and obtaining a sample recorded as Ar-FeCo/NxHGS。
(3) Synthesizing the Fe-Co bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nano particles treated by the argon radio-frequency plasma:
0.15mL of oleic acid, 0.15mL of oleylamine were added to a three-necked flask containing 10mL of dioctyl ether, andadding 69.1mg 1, 2-tetradecanediol, 65.78mg nickel acetylacetonate hydrate, introducing nitrogen for 30min, and removing air. The solution was heated to 80 ℃ under a stream of nitrogen and incubated for 30min to remove the water of crystallization. The temperature was raised to 200 ℃ over 20min, then 40mg of platinum acetylacetonate was dissolved in 0.5mL of dichlorobenzene and then added to the reaction flask in one portion through a syringe through the heat-insulating rubber. Incubate at 200 ℃ for 1h, then cool to room temperature. The nanoparticles were precipitated overnight by adding 20mL of ethanol, without removing the supernatant and without adding ethanol, and collected directly by centrifugation (8000rpm, 10min), and the nanoparticles were further washed with ethanol 3-4 times and then dispersed in 20mL of n-hexane. 66mg of Ar-FeCo/NxDispersing HGS into 20mL of normal hexane, performing ultrasonic dispersion for 15min, simultaneously performing ultrasonic dispersion on the nanoparticles in the normal hexane for 15min, and dropwise adding the nanoparticles into Ar-FeCo/N through a dropper in a stirring statexAnd (3) adding HGS (HGS) in n-hexane, performing ultrasonic treatment for 1h after dropwise addition is finished, then performing centrifugal separation (3000rpm for 5min) to collect the catalyst, and completely drying overnight. To remove the surfactant, the catalyst was heated in air at 180 ℃ for 1 hour. Then adding N at 180 DEG C2Blown into the furnace for 2 hours to remove O2Then Ar/H at 400 DEG C2(7％H2) Annealing for 4h in the mixed gas. The resulting sample was recorded as Pt1Ni2@Ar-FeCo-NxHGS。
Pt obtained in example 1 was subjected to Scanning Electron Microscopy (SEM)1Ni2@Ar-FeCo-NxThe morphology of the HGS material is analyzed, and the result is shown in FIG. 1, wherein FeCo/NxThe HGS has a stable structure, and the PtNi nanoparticles are uniformly loaded on the surface of the carrier.
Evaluation of bifunctional catalytic Performance:
all electrochemical tests were performed using an electrochemical workstation model CHI 760E equipped with a PINE rotating disk electrode test system and were performed at room temperature.
Preparation of a working electrode: before using a Rotating Disk Electrode (RDE), i.e. a glassy carbon electrode (GCE, d ═ 0.4cm), Al was first used2O3Grinding the surface of the electrode on polishing cloth to a mirror surface by using powder, then washing the electrode with distilled water for several times, ultrasonically oscillating for 10s, and drying the electrode at room temperature for later use. Accurate weighing4mg of Pt obtained in example 11Ni2@Ar-FeCo-NxMixing HGS material, 282 mu L of isopropanol, 705 mu L of deionized water and 13 mu L of Nafion solution (5 wt.%), carrying out ultrasonic treatment on the mixture for 1h, and finally, uniformly dripping 10 mu L of prepared ink on the surface of GCE and naturally drying to obtain the working electrode for testing. The loading of the catalyst on the surface of the electrode is about 0.32mg cm-2. As a control experiment, a commercial 20 wt.% Pt/C catalyst was also prepared and tested using the same electrode preparation method.
And (3) electrochemical performance testing: in the testing process, a standard three-electrode electrochemical testing system is adopted, wherein the counter electrode is a Pt sheet, and the reference electrode is a Saturated Calomel Electrode (SCE) and the prepared working electrode.
Pt obtained in example 1 was tested using a Rotating Disk Electrode (RDE)1Ni2@Ar-FeCo-NxHGS samples at saturated O20.1M KOH and 0.5M H2SO4The results are shown in FIGS. 2 and 3 for an LSV curve at 1600rpm for the solution. Pt1Ni2@Ar-FeCo-NxThe HGS sample shows high ORR electrocatalytic activity, the initial potential and the half-wave potential under alkaline environment are respectively 0.95 and 0.84V vs. RHE, the initial potential and the half-wave potential under acidic environment are respectively 0.83 and 0.75V vs. RHE, and Pt1Ni2@Ar-FeCo-NxThe HGS samples exhibited high limiting current densities.
Comparative example 1: iron-cobalt bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nano particle (Pt)1Ni2@FeCo-NxHGS), comprising the following steps:
(1) iron-cobalt bimetal nitrogen-doped hollow graphene ball (FeCo/N)xHGS) synthesis:
2g of Polystyrene Spheres (PS)+) Add 100mL of 0.5M HCl solution and start stirring. Subjecting 100mg GO to ultrasound for 30min, adding the PS+In the solution, the reaction was magnetically stirred at room temperature for 12 h. 3g of melamine were then added and the reaction was continued at room temperature with magnetic stirring for 12 h. Thereafter, 5mL of aniline was added and the temperature of the solution was maintained at 0 ℃ using an ice water bath. Followed by slow addition of oxidationAmmonium persulfate is used as an agent to promote the synthesis of polyaniline (the adding amount of the ammonium persulfate is calculated by the same mole number as that of the aniline), and 0.004mol of FeCl of transition metal salt is also added3·6H2O，0.004mol Co(NO3)2·6H2And O. And (5) reacting for 24 hours in a dark place, so that the polyaniline can be uniformly polymerized on the surface of the graphene. Then, a reducing agent (2mL of ammonia water, 0.1mL of N) was added to the mixed solution2H4·H2O), then refluxed at 110 ℃ for 24h to reduce the graphene oxide to graphene (rGO). After that, the solution is dried in a forced air drying oven to obtain dark green powder, 100mg of the dark green powder sample prepared above and 1200mg of melamine are mixed and respectively dissolved in 25mL of distilled water, and the mixture is magnetically stirred and reacted for 12 hours. The obtained mixed solution sample was collected by filtration under reduced pressure. The solid sample was then placed in the center of the high temperature tube furnace reactor. Introducing Ar/H at one end2(7％H2) And (3) raising the temperature of the mixed gas in the reaction device from room temperature to 420 ℃ at the rate of 2 ℃/min, staying for 2 hours, then raising the temperature to 750 ℃ at the rate of 2 ℃/min, and continuing to calcine at high temperature for 1 hour. The sample prepared above was incubated at 2M H2SO4Heating the solution at 80 deg.C for 8h to remove unstable and inactive substances, and washing with deionized water to obtain FeCo/NxHGS。
(2) Synthesizing the platinum-nickel nano particles loaded on the iron-cobalt bimetallic nitrogen-doped hollow graphene spheres:
0.15mL of oleic acid and 0.15mL of oleylamine were added to a three-necked flask containing 10mL of dioctyl ether, and 69.1mg of 1, 2-tetradecanediol and 65.78mg of nickel acetylacetonate hydrate were added, nitrogen was introduced for 30min, and air was removed. The solution was heated to 80 ℃ under a stream of nitrogen and incubated for 30min to remove the water of crystallization. The temperature was raised to 200 ℃ over 20min, then 40mg of platinum acetylacetonate was dissolved in 0.5mL of dichlorobenzene and then added to the reaction flask in one portion through a syringe through the heat-insulating rubber. Incubate at 200 ℃ for 1h, then cool to room temperature. The nanoparticles were precipitated overnight by adding 20mL of ethanol, without removing the supernatant and without adding ethanol, directly collected by centrifugation (8000rpm, 10min), further washed with ethanol 3-4 times, and then dispersed in 20mL of n-hexane. 66mg FeCo/NxHGS is dispersed into 20mL of n-hexanePerforming ultrasonic treatment for 15min, simultaneously performing ultrasonic dispersion on the nanoparticles in N-hexane for 15min, and dropwise adding the nanoparticles to FeCo/N through a dropper under the stirring statexAnd (3) adding the mixture into an HGS (HGS) n-hexane solution, performing ultrasonic treatment for 1h after dropwise addition is finished, then performing centrifugal separation (3000rpm for 5min) to collect the catalyst, and completely drying overnight. To remove the surfactant, the catalyst was heated in air at 180 ℃ for 1 h. Then adding N at 180 DEG C2Blown into the furnace for 2 hours to remove O2Then Ar/H at 400 DEG C2(7％H2) Annealing for 4h in the mixed gas. The resulting sample was recorded as Pt1Ni2@FeCo-NxHGS。
Pt was tested using a Rotating Disk Electrode (RDE)1Ni2@FeCo-NxHGS sample catalyst at saturated O20.1M KOH and 0.5M H2SO4The results are shown in FIGS. 2 and 3 for an LSV curve at 1600rpm for the solution. Pt1Ni2@FeCo-NxThe initial potential and the half-wave potential of the HGS sample are respectively 0.93V vs.RHE under the alkaline environment, and the initial potential and the half-wave potential are respectively 0.84V vs.RHE under the acidic environment;
example 2: a preparation method of composite hollow graphene ball-loaded platinum-nickel nanoparticles specifically comprises the following steps:
(1) synthesizing an iron-cobalt bimetallic nitrogen-doped hollow graphene ball:
2g of Polystyrene Spheres (PS)+) Add 100mL of 0.5M HCl solution and start stirring. Subjecting 100mg GO to ultrasound for 30min, adding the PS+In the solution, the reaction was magnetically stirred at room temperature for 12 h. 3g of melamine were then added and the reaction was continued at room temperature with magnetic stirring for 12 h. Thereafter, 5mL of aniline was added and the temperature of the solution was maintained at 0 ℃ using an ice-water bath. Then slowly adding an oxidant ammonium persulfate to promote the synthesis of polyaniline (the adding amount of the ammonium persulfate is calculated by the same mole number as that of the aniline), and simultaneously adding 0.004mol of FeCl of transition metal salt3·6H2O，0.004mol Co(NO3)2·6H2And O. And (5) reacting for 24 hours in a dark place, so that polyaniline can be uniformly polymerized on the surface of the graphene oxide. Then, a reducing agent (2mL of aqueous ammonia,0.1mL N2H4·H2o), then refluxed at 110 ℃ for 24h to reduce the graphene oxide to graphene (rGO). After that, the solution is dried in a forced air drying oven to obtain dark green powder, 100mg of the dark green powder sample prepared above and 1200mg of melamine are mixed and respectively dissolved in 25mL of distilled water, and the mixture is magnetically stirred and reacted for 12 hours. The obtained mixed solution sample was collected by filtration under reduced pressure. The solid sample was then placed in the center of the high temperature tube furnace reactor. Introducing Ar/H at one end2(7％H2) And (3) raising the temperature of the mixed gas in the reaction device from room temperature to 420 ℃ at the rate of 2 ℃/min, staying for 2 hours, then raising the temperature to 750 ℃ at the rate of 2 ℃/min, and continuing to calcine at high temperature for 1 hour. The sample prepared above was washed with 2M H2SO4Heating the solution at 80 deg.C for 8h to remove unstable and inactive substances, and washing with deionized water to obtain FeCo/NxHGS。
(2) Synthesizing an iron-cobalt bimetallic nitrogen doped hollow graphene ball by argon-ammonia radio-frequency plasma treatment:
putting the Fe-Co bimetallic nitrogen-doped hollow graphene ball into a low-temperature radio frequency plasma reaction device, and adding Ar/NH3(7％NH3) Introducing into a control tube, controlling the air pressure in the control tube to be 20Pa, the discharge power to be 100W and the treatment time to be 1h, carrying out radio frequency plasma discharge surface modification treatment, and recording the obtained sample as Ar/NH3-FeCo/NxHGS。
(3) Synthesizing the Fe-Co bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nano particles treated by the argon-ammonia radio-frequency plasma:
0.15mL of oleic acid and 0.15mL of oleylamine were added to a three-necked flask containing 10mL of dioctyl ether, and 69.1mg of 1, 2-tetradecanediol and 65.78mg of nickel acetylacetonate hydrate were added, nitrogen was introduced for 30min, and air was removed. The solution was heated to 80 ℃ under a stream of nitrogen and incubated for 30min to remove the water of crystallization. The temperature was raised to 200 ℃ over 20min, then 40mg of platinum acetylacetonate was dissolved in 0.5mL of dichlorobenzene and then added to the reaction flask in one portion through a syringe through the heat-insulating rubber. Incubate at 200 ℃ for 1h, then cool to room temperature. Adding 20ml ethanol overnight to precipitate nanoparticles, directly centrifuging without removing supernatant and ethanolThe nanoparticles were collected (8000rpm, 10min), further washed with ethanol 3-4 times, and then dispersed in 20mL of n-hexane. 66mg Ar/NH3-FeCo/NxDispersing HGS into 20mL of n-hexane, performing ultrasonic treatment for 15min, simultaneously performing ultrasonic dispersion on the nanoparticles in the n-hexane for 15min, and dropwise adding the mixture into Ar/NH through a dropper under the stirring state3-FeCo/NxAnd (3) adding HGS (HGS) in n-hexane, performing ultrasonic treatment for 1h after dropwise addition is finished, then performing centrifugal separation (3000rpm for 5min) to collect the catalyst, and completely drying overnight. To remove the surfactant, the catalyst was heated in air at 180 ℃ for 1 hour. Then adding N at 180 DEG C2Blowing into the furnace for 2 hours to remove O2Then Ar/H at 400 DEG C2(7％H2) Annealing for 4h in the mixed gas. The resulting sample was recorded as Pt1Ni2@Ar/NH3-FeCo-NxHGS。
Pt was tested using a Rotating Disk Electrode (RDE)1Ni2@Ar/NH3-FeCo-NxHGS sample catalyst at saturated O20.1MKOH and 0.5M H2SO4The results are shown in FIGS. 2 and 3 for an LSV curve at 1600rpm for the solution. Pt1Ni2@Ar/NH3-FeCo-NxThe HGS sample exhibited high ORR electrocatalytic activity, the initial potential and the half-wave potential in the alkaline environment being 0.96 and 0.85V vs. RHE, respectively, and the initial potential and the half-wave potential in the acidic environment being 0.86 and 0.78V vs. RHE, respectively, which exceeded the electrocatalytic activity of the Pt obtained in comparative example 1 tested under the same conditions1Ni2@FeCo-NxHGS catalyst (initial potential and half-wave potential of 0.93 and 0.83V vs. RHE under alkaline condition, initial potential and half-wave potential of 0.84 and 0.76V vs. RHE under acidic condition), Pt1Ni2@Ar/NH3-FeCo-NxThe HGS samples exhibited high limiting current densities. The above description of Pt1Ni2@Ar/NH3-FeCo-NxThe HGS material has faster reaction kinetics in the ORR electrocatalytic process.
Example 3: a preparation method of composite hollow graphene ball loaded platinum-nickel nanoparticles specifically comprises the following steps:
(1) synthesizing an iron-cobalt bimetallic nitrogen-doped hollow graphene ball:
2g of Polystyrene Spheres (PS)+) Add 100mL of 0.5M HCl solution and start stirring. Subjecting 100mg GO to ultrasound for 30min, adding the PS+In the solution, the reaction was magnetically stirred at room temperature for 12 h. 3g of melamine were then added and the reaction was continued at room temperature with magnetic stirring for 12 h. Thereafter, 5mL of aniline was added and the temperature of the solution was maintained at 0 ℃ using an ice water bath. Then slowly adding an oxidant ammonium persulfate to promote the synthesis of polyaniline (the adding amount of the ammonium persulfate is calculated by the same mole number as that of the aniline), and simultaneously adding 0.004mol of FeCl of transition metal salt3·6H2O，0.004mol Co(NO3)2·6H2And (O). And (5) reacting for 24 hours in a dark place, so that polyaniline can be uniformly polymerized on the surface of the graphene oxide. Then, a reducing agent (2mL of aqueous ammonia, 0.1mL of N) was added to the mixed solution2H4·H2O), then refluxed at 110 ℃ for 24h to reduce the graphene oxide to graphene (rGO). After that, the solution is dried in a forced air drying oven to obtain dark green powder, 100mg of the dark green powder sample prepared above and 1200mg of melamine are mixed and respectively dissolved in 25mL of distilled water, and the mixture is magnetically stirred and reacted for 12 hours. The obtained mixed solution sample was collected by filtration under reduced pressure. The solid sample was then placed in the center of the high temperature tube furnace reactor. Introduction of Ar/H at one end2(7％H2) And (3) raising the temperature of the mixed gas in the reaction device from room temperature to 420 ℃ at the rate of 2 ℃/min, staying for 2 hours, then raising the temperature to 750 ℃ at the rate of 2 ℃/min, and continuing to calcine at high temperature for 1 hour. The sample prepared above was washed with 2M H2SO4Heating the solution at 80 deg.C for 8h to remove unstable and inactive substances, and washing with deionized water to obtain FeCo/NxHGS。
(2) Synthesizing an iron-cobalt bimetallic nitrogen doped hollow graphene ball by oxygen radio frequency plasma treatment:
putting the Fe-Co bimetallic nitrogen-doped hollow graphene ball into a low-temperature radio-frequency plasma reaction device, introducing oxygen into the reaction device, controlling the air pressure in the tube to be 20Pa, the discharge power to be 100W and the treatment time to be 1h, carrying out radio-frequency plasma discharge surface modification treatment, and obtaining a sample recorded as O2-FeCo/NxHGS。
(3) Synthesizing iron-cobalt bimetallic nitrogen-doped hollow graphene ball-loaded platinum-nickel nanoparticles treated by oxygen radio-frequency plasma:
0.15mL of oleic acid and 0.15mL of oleylamine were added to a three-necked flask containing 10mL of dioctyl ether, and 69.1mg of 1, 2-tetradecanediol and 65.78mg of nickel acetylacetonate hydrate were added, nitrogen was introduced for 30min, and air was removed. The solution was heated to 80 ℃ under a stream of nitrogen and incubated for 30min to remove the water of crystallization. The temperature was raised to 200 ℃ over 20min, then 40mg of platinum acetylacetonate was dissolved in 0.5mL of dichlorobenzene and then added to the reaction flask in one portion through a syringe through the heat-insulating rubber. Incubate at 200 ℃ for 1h, then cool to room temperature. The nanoparticles were precipitated overnight by adding 20mL of ethanol, without removing the supernatant and without adding ethanol, and collected directly by centrifugation (8000rpm, 10min), and the nanoparticles were further washed with ethanol 3-4 times and then dispersed in 20mL of n-hexane. 66mg of O2-FeCo/NxDispersing HGS into 20mL of n-hexane, performing ultrasonic treatment for 15min, simultaneously performing ultrasonic dispersion on the nanoparticles in the n-hexane for 15min, and dropwise adding the mixture into O through a dropper in a stirring state2-FeCo/NxAnd (3) adding HGS (HGS) in n-hexane, performing ultrasonic treatment for 1h after dropwise addition is finished, then performing centrifugal separation (3000rpm for 5min) to collect the catalyst, and completely drying overnight. To remove the surfactant, the catalyst was heated in air at 180 ℃ for 1 hour. Then adding N at 180 DEG C2Blown into the furnace for 2 hours to remove O2Then Ar/H at 400 DEG C2(7％H2) Annealing for 4h in the mixed gas. The resulting sample was recorded as Pt1Ni2@O2-FeCo-NxHGS。
Pt was tested using a Rotating Disk Electrode (RDE)1Ni2@O2-FeCo-NxHGS sample catalyst at saturated O20.1M KOH and 0.5M H2SO4The results are shown in FIGS. 2 and 3 for the LSV curve at 1600rpm for the solution. Pt1Ni2@O2-FeCo-NxThe initial potential and the half-wave potential of the HGS in an alkaline environment are respectively 0.93 and 0.82V vs. RHE, and the initial potential and the half-wave potential in an acidic environment are respectively 0.81 and 0.73V vs. RHE.
Example 4: the preparation method of the composite hollow graphene ball loaded platinum-nickel nano particles specifically comprises the following steps:
(1) synthesizing an iron-cobalt bimetallic nitrogen-doped hollow graphene ball:
2g of Polystyrene Spheres (PS)+) Add 100mL of 0.5M HCl solution and start stirring. Subjecting 100mg GO to ultrasound for 30min, adding the PS+In the solution, the reaction was magnetically stirred at room temperature for 12 h. 3g of melamine were then added and the reaction was continued at room temperature with magnetic stirring for 12 h. Thereafter, 5mL of aniline was added and the temperature of the solution was maintained at 0 ℃ using an ice water bath. Then slowly adding an oxidant ammonium persulfate to promote the synthesis of polyaniline (the adding amount of the ammonium persulfate is calculated by the same mole number as that of the aniline), and simultaneously adding 0.004mol of FeCl of transition metal salt3·6H2O，0.004mol Co(NO3)2·6H2And O. And (5) reacting for 24 hours in a dark place, so that polyaniline can be uniformly polymerized on the surface of the graphene oxide. Then, a reducing agent (2mL of aqueous ammonia, 0.1mL of N) was added to the mixed solution2H4·H2O), then refluxed at 110 ℃ for 24h to reduce the graphene oxide to graphene (rGO). After that, the solution is dried in a forced air drying oven to obtain dark green powder, 100mg of the dark green powder sample prepared above and 1200mg of melamine are mixed and respectively dissolved in 25mL of distilled water, and the mixture is magnetically stirred and reacted for 12 hours. The obtained mixed solution sample was collected by filtration under reduced pressure. The solid sample was then placed in the center of the high temperature tube furnace reactor. Introducing Ar/H at one end2(7％H2) And (3) raising the temperature of the mixed gas in the reaction device from room temperature to 420 ℃ at the rate of 2 ℃/min, staying for 2 hours, then raising the temperature to 750 ℃ at the rate of 2 ℃/min, and continuing to calcine at high temperature for 1 hour. The sample prepared above was washed with 2M H2SO4Heating the solution at 80 deg.C for 8h to remove unstable and inactive substances, and washing with deionized water to obtain FeCo/NxHGS。
(2) Synthesizing an iron-cobalt bimetallic nitrogen-doped hollow graphene ball by nitrogen radio-frequency plasma treatment:
putting the Fe-Co bimetallic nitrogen-doped hollow graphene ball into low-temperature radio frequency plasmaA body reaction device, nitrogen is led into the body reaction device, the air pressure in the control tube is 20Pa, the discharge power is 100W, the processing time is 1h, the radio frequency plasma discharge surface modification treatment is carried out, the obtained sample is marked as N2-FeCo/NxHGS。
(3) Synthesizing the iron-cobalt bimetal nitrogen-doped hollow graphene ball loaded platinum-nickel nano particles treated by the nitrogen radio-frequency plasma:
0.15mL of oleic acid and 0.15mL of oleylamine were added to a three-necked flask containing 10mL of dioctyl ether, and 69.1mg of 1, 2-tetradecanediol and 65.78mg of nickel acetylacetonate hydrate were added, nitrogen was introduced for 30min, and air was removed. The solution was heated to 80 ℃ under a stream of nitrogen and incubated for 30min to remove the water of crystallization. The temperature was raised to 200 ℃ over 20min, then 40mg of platinum acetylacetonate was dissolved in 0.5mL of dichlorobenzene and then added to the reaction flask in one portion through a syringe through the heat-insulating rubber. Incubate at 200 ℃ for 1h, then cool to room temperature. The nanoparticles were precipitated overnight by adding 20mL of ethanol, without removing the supernatant and without adding ethanol, and collected directly by centrifugation (8000rpm, 10min), and the nanoparticles were further washed with ethanol 3-4 times and then dispersed in 20mL of n-hexane. 66mg N2-FeCo/NxDispersing HGS into 20mL of N-hexane, performing ultrasonic treatment for 15min, simultaneously performing ultrasonic dispersion on the nanoparticles in the N-hexane for 15min, and dropwise adding the mixture into N through a dropper in a stirring state2-FeCo/NxAnd (3) adding HGS (HGS) in n-hexane, performing ultrasonic treatment for 1h after dropwise addition is finished, then performing centrifugal separation (3000rpm for 5min) to collect the catalyst, and completely drying overnight. To remove the surfactant, the catalyst platinum nickel nanoparticles were heated in air at 180 ℃ for 1 hour. Then adding N at 180 DEG C2Blown into the furnace for 2 hours to remove O2Then Ar/H at 400 DEG C2(7％H2) Annealing for 4h in the mixed gas. The resulting sample was recorded as Pt1Ni2@N2-FeCo-NxHGS。
Pt was tested using a Rotating Disk Electrode (RDE)1Ni2@N2-FeCo-NxHGS sample catalyst at saturated O20.1M KOH and 0.5M H2SO4The results are shown in FIGS. 2 and 3 for an LSV curve at 1600rpm for the solution. Pt1Ni2@N2-FeCo-NxThe HGS has an initial potential and a half-wave potential of 0.94 and 0.84V vs. RHE respectively under an alkaline environment, and the initial potential and the half-wave potential of 0.82 and 0.75V vs. RHE respectively under an acidic environment.
Example 5: the preparation method of the composite hollow graphene ball loaded platinum-nickel nano particles specifically comprises the following steps:
(1) synthesizing an iron-cobalt bimetallic nitrogen-doped hollow graphene ball:
2g of Polystyrene Spheres (PS)+) Add 100mL of 0.5M HCl solution and start stirring. Subjecting 100mg GO to ultrasound for 30min, adding the PS+In the solution, the reaction was magnetically stirred at room temperature for 12 h. 3g of melamine were then added and the reaction was continued at room temperature with magnetic stirring for 12 h. Thereafter, 5mL of aniline was added and the temperature of the solution was maintained at 0 ℃ using an ice water bath. Then slowly adding an oxidant ammonium persulfate to promote the synthesis of polyaniline (the adding amount of the ammonium persulfate is calculated by the same mole number as that of the aniline), and simultaneously adding 0.004mol of FeCl of transition metal salt3·6H2O，0.004mol Co(NO3)2·6H2And O. And (5) reacting for 24 hours in a dark place, so that polyaniline can be uniformly polymerized on the surface of the graphene oxide. Then, a reducing agent (2mL of aqueous ammonia, 0.1mL of N) was added to the mixed solution2H4·H2O), then refluxed at 110 ℃ for 24h to reduce the graphene oxide to graphene (rGO). After that, the solution is dried in a forced air drying oven to obtain dark green powder, 100mg of the dark green powder sample prepared above and 1200mg of melamine are mixed and respectively dissolved in 25mL of distilled water, and the mixture is magnetically stirred and reacted for 12 hours. The obtained mixed solution sample was collected by filtration under reduced pressure. The solid sample was then placed in the center of the high temperature tube furnace reactor. Introduction of Ar/H at one end2(7％H2) And (3) raising the temperature of the mixed gas in the reaction device from room temperature to 420 ℃ at the rate of 2 ℃/min, staying for 2 hours, then raising the temperature to 750 ℃ at the rate of 2 ℃/min, and continuing to calcine at high temperature for 1 hour. The sample prepared above was washed with 2M H2SO4Heating the solution at 80 deg.C for 8h to remove unstable and inactive substances in the sample, and washing with deionized water to obtain FeCo/NxHGS。
(2) Synthesizing an iron-cobalt bimetallic nitrogen-doped hollow graphene ball by argon-hydrogen radio-frequency plasma treatment:
putting the Fe-Co bimetallic nitrogen-doped hollow graphene ball into a low-temperature radio frequency plasma reaction device, and adding Ar/H2(7％H2) Introducing into a control tube, controlling the air pressure in the control tube to be 20Pa, the discharge power to be 100W and the treatment time to be 1H, carrying out radio frequency plasma discharge surface modification treatment, and recording the obtained sample as Ar/H2-FeCo/NxHGS。
(2) Synthesizing the Fe-Co bimetallic nitrogen-doped hollow graphene ball loaded platinum-nickel nano particles treated by the argon-hydrogen radio-frequency plasma:
0.15mL of oleic acid and 0.15mL of oleylamine were added to a three-necked flask containing 10mL of dioctyl ether, and 69.1mg of 1, 2-tetradecanediol and 65.78mg of nickel acetylacetonate hydrate were added, nitrogen was introduced for 30min, and air was removed. The solution was heated to 80 ℃ under a stream of nitrogen and incubated for 30min to remove the water of crystallization. The temperature was raised to 200 ℃ over 20min, then 40mg of platinum acetylacetonate was dissolved in 0.5mL of dichlorobenzene and then added to the reaction flask in one portion through a syringe through the heat-insulating rubber. Incubate at 200 ℃ for 1h, then cool to room temperature. The nanoparticles were precipitated overnight by adding 20mL of ethanol, without removing the supernatant and without adding ethanol, and collected directly by centrifugation (8000rpm, 10min), and the nanoparticles were further washed with ethanol 3-4 times and then dispersed in 20mL of n-hexane. 66mg Ar/H2-FeCo/NxDispersing HGS into 20mL of n-hexane, performing ultrasonic treatment for 15min, simultaneously performing ultrasonic dispersion on the nanoparticles in the n-hexane for 15min, and dropwise adding the mixture into Ar/H through a dropper in a stirring state2-FeCo/NxAnd (3) adding HGS (HGS) in n-hexane, performing ultrasonic treatment for 1h after dropwise addition is finished, then performing centrifugal separation (3000rpm for 5min) to collect the catalyst, and completely drying overnight. To remove the surfactant, the catalyst was heated in air at 180 ℃ for 1 hour. Then adding N at 180 DEG C2Blown into the furnace for 2 hours to remove O2Then Ar/H at 400 DEG C2(7％H2) The mixed gas is further annealed for 4 hours. The resulting sample was recorded as Pt1Ni2@Ar/H2-FeCo-NxHGS。
Pt was tested using a Rotating Disk Electrode (RDE)1Ni2@Ar/H2-FeCo-NxHGS sample catalyst at saturated O20.1MKOH and 0.5M H2SO4The results are shown in FIGS. 2 and 3 for an LSV curve at 1600rpm for the solution. Pt1Ni2@Ar/H2-FeCo-NxThe HGS samples exhibited high ORR electrocatalytic activity with an initial potential and half-wave potential of 0.94 and 0.84V vs. rhe, respectively, in alkaline environments and an initial potential and half-wave potential of 0.83 and 0.74V vs. rhe, respectively, in acidic environments.
Finally, it should also be mentioned that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the composite hollow graphene ball loaded with the platinum-nickel nanoparticles is characterized in that the composite hollow graphene ball is an iron-cobalt bimetallic nitrogen-doped hollow graphene ball (FeCo/N) which is doped with iron-cobalt bimetallic nitrogenxHGS) is a carrier, the platinum nickel nano particles are a load, and the load is loaded on the carrier through radio frequency plasma treatment.
2. The preparation method of the composite hollow graphene sphere-loaded platinum-nickel nanoparticle according to claim 1, wherein the preparation method specifically comprises the following steps:
step one, FeCo/NxPreparation of HGS: after Graphene Oxide (GO) and polystyrene spheres (PS spheres) are self-assembled, polyaniline is coated on the surface, melamine is added as a nitrogen source and a carbon source, then the polyaniline reacts with iron transition metal salt, cobalt transition metal salt and a reducing agent, and FeCo/N is obtained by calciningxHGS；
Step two, radio frequency plasmaDaughter-modified FeCo/NxPreparation of HGS: the method comprises the step of processing the surfaces of the radio frequency plasmas in different atmospheres by adopting the iron-cobalt bimetallic nitrogen doped hollow graphene ball prepared in the step I to obtain the radio frequency plasma modified FeCo/NxHGS；
Step three, FeCo/N loaded with platinum-nickel nano particlesxPreparation of HGS: modifying FeCo/N by the radio frequency plasma prepared in the step twoxFeCo/N loaded with platinum-nickel nanoparticles obtained by combining HGS and platinum-nickel nanoparticlesxHGS。
3. The method for preparing platinum-nickel nanoparticles loaded on composite hollow graphene spheres according to claim 2, wherein FeCo/N is adopted in the first stepxThe preparation steps of the HGS comprise:
(1) adding polystyrene spheres (PS spheres) into a hydrochloric acid solution, uniformly stirring, adding graphene oxide into water, performing ultrasonic treatment for 20-40 min, adding the graphene oxide into the polystyrene sphere solution, and performing magnetic stirring reaction at room temperature for 6-12 h;
(2) adding melamine into the solution (1), continuously carrying out magnetic stirring reaction at room temperature for a period of time, adding aniline, and keeping the temperature of the solution at 0 ℃ by adopting an ice-water bath; slowly adding an oxidant ammonium persulfate to promote the synthesis of polyaniline, simultaneously adding iron-cobalt transition metal salt, and reacting for 10-24 hours in a dark place to ensure that the polyaniline can be uniformly polymerized on the surface of the graphene;
(3) adding a reducing agent into the solution (2), refluxing at 90-120 ℃ to reduce graphene oxide into graphene, drying after reaction to obtain dark green graphene powder, mixing the graphene powder and melamine, dissolving in deionized water, mixing, magnetically stirring, reacting for a period of time, filtering and collecting a sample;
(4) annealing the solid sample obtained in the step (3) in a reducing atmosphere high-temperature tube furnace, heating the reaction device from room temperature to 380-450 ℃, preserving heat for 2h, then heating to 750 ℃, continuing to calcine at high temperature for 1-3 h, cooling to room temperature, heating the prepared sample in 2M sulfuric acid solution at 80 ℃ for 4-10 h to remove unstable and inactive substances in the sample, and fully washing with deionized water to obtain FeCo/NxHGS。
4. The method for preparing composite hollow graphene sphere loaded platinum-nickel nanoparticles according to claim 2, wherein the radio frequency plasma modified FeCo/NxPreparation of HGS: FeCo/NxPutting the HGS into a low-temperature radio frequency plasma machine device, and introducing different gases to carry out discharge surface treatment modification.
5. The method for preparing the composite hollow graphene sphere-loaded platinum-nickel nanoparticle according to claim 4, wherein the different gas is one of argon, argon-hydrogen, argon-ammonia, nitrogen or oxygen.
6. The method for preparing the composite hollow graphene sphere loaded platinum-nickel nanoparticle as claimed in claim 2, wherein the platinum-nickel nanoparticle loaded FeCo/N isxThe preparation process of the HGS comprises the following steps: adding hydrated nickel acetylacetonate, 1, 2-tetradecanediol, oleic acid and oleylamine into a three-neck flask containing dioctyl ether, heating the solution to 60-90 ℃ under the protection of nitrogen, and keeping the temperature to remove crystal water; rapidly heating to 200 ℃, dissolving acetylacetone platinum in dichlorobenzene, adding into a reaction bottle through an injector, preserving heat for 1-3 h at 200 ℃, and cooling to room temperature; adding ethanol to obtain platinum nickel nanoparticles, centrifuging, collecting, washing with ethanol, and dispersing in n-hexane; ultrasonically dispersing a certain amount of modified iron-cobalt bimetallic nitrogen doped hollow graphene balls in n-hexane for 15-30 min, and ultrasonically dispersing the prepared platinum-nickel nanoparticles in the n-hexane for 15-30 min; and mixing the nano particles with the substrate in a normal hexane solution, carrying out ultrasonic dispersion for 0.5-1 h, collecting the catalyst by using a centrifugal machine, and drying.
7. The method for preparing the composite hollow graphene ball-loaded platinum nickel nanoparticle as claimed in claim 3, wherein in the first step, the amounts of the polystyrene ball, the hydrochloric acid, the oxidized graphene, the melamine, the aniline, the ammonium persulfate, the iron transition metal salt, the cobalt transition metal salt, the ammonia water, the hydrazine hydrate, the hollow graphene ball, the melamine and the sulfuric acid are 1500-2000mg, 80-100mL, 80-100mg, 2800-3000mg, 3-5mL, 12000-12500mg, 1000-1200mg, 2-3mL, 0.1-0.2mL, 100-110mg, 1000-1200mg and 30-50mL respectively.
8. The method for preparing composite hollow graphene sphere loaded platinum-nickel nanoparticles according to claim 7, wherein the cobalt transition metal salt in the first step is Co (NO)3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2、CoCl2、CoSO4·7H2O、CoSO4·H2One or more of O, Fe (NO) is adopted as the iron transition metal salt3)3·9H2O、FeCl3·6H2O、Fe(CH3COO)3、Fe2(SO4)3·6H2And one or more of O.
9. The method for preparing the platinum-nickel nanoparticle loaded on the composite hollow graphene sphere according to claim 6, wherein the amounts of the hydrated nickel acetylacetonate, 1, 2-tetradecanediol, oleic acid, oleylamine, dioctyl ether, platinum acetylacetonate, dichlorobenzene, ethanol, n-hexane and the modified composite hollow graphene sphere are 65-66mg, 69-70mg, 0.1-0.2mL, 10-12mL, 40-45mg, 0.5-0.8mL, 20-25mL and 66-70mg, respectively.
10. The application of the modified composite hollow graphene ball-loaded platinum-nickel nanoparticles is characterized in that the modified composite hollow graphene ball-loaded platinum-nickel nanoparticles are used as a bifunctional catalyst of a methanol fuel cell and applied to catalyzing ORR and MOR reactions of the methanol fuel cell, have excellent electrocatalysis ORR performance, can promote chemical adsorption/desorption of an intermediate on the surface of the electrocatalysis, and improve catalytic activity of ORR.
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