CN109256568B - Monodisperse Pt-rich nanocage material with accurately controllable wall thickness and preparation method and application thereof - Google Patents

Monodisperse Pt-rich nanocage material with accurately controllable wall thickness and preparation method and application thereof Download PDF

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CN109256568B
CN109256568B CN201810935758.2A CN201810935758A CN109256568B CN 109256568 B CN109256568 B CN 109256568B CN 201810935758 A CN201810935758 A CN 201810935758A CN 109256568 B CN109256568 B CN 109256568B
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wall thickness
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CN109256568A (en
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尹峰
张亚峰
杨智博
秦娟
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Shaanxi Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a monodisperse Pt-rich nano cage material with accurately controllable wall thickness, a preparation method and application thereof, wherein the Pt wall thickness of the Pt-rich nano cage material is increased by 3 layers corresponding to the number of single layers of the Pt wall when the thickness of the Pt wall is increased by about 0.7nm, the Pt-rich nano cage material with high dispersibility and high uniformity is synthesized by combining a one-pot solvothermal method and an acid etching treatment method, the preparation process is simple, the conditions are mild, the material has expansibility, short reaction period, high efficiency, good reproducibility and wide industrial application prospect, in addition, the invention firstly proposes that the monodispersity and the accurate controllable wall thickness are realized by controlling the reaction temperature, the wall thickness of the Pt-rich nano cage material is further adaptively controlled by different application environments and different requirements, and the catalytic activity and the stability of the Pt/C catalyst are far superior to those of commercial Pt/C catalysts.

Description

Monodisperse Pt-rich nanocage material with accurately controllable wall thickness and preparation method and application thereof
Technical Field
The invention relates to the field of fuel cell materials, in particular to a monodisperse Pt-rich nano cage material with accurately controllable wall thickness and a preparation method and application thereof.
Background
At present, while the traditional energy sources are accompanied with the vigorous development of the world economy, the corresponding environmental pollution and energy crisis also potentially destroy the ecological environment of the earth. Therefore, the search for new energy sources that can replace the traditional energy sources is a problem to be solved urgently in the economic and industrial development of the 21 st century. Fuel cells are receiving attention from researchers because of their advantages such as high energy conversion efficiency and low noise.
Although fuel cells are a new energy conversion technology, their commercial application still faces significant challenges, mainly due to the large amount of noble metal Pt catalyst still required for the cathode Oxygen Reduction Reaction (ORR). In order to reduce the amount of Pt and improve the catalytic performance and stability, a Pt-rich nanocage electrocatalyst attracts attention, and is characterized in that: 1. the consumption of Pt is reduced; 2. a larger specific surface area; 3. more three-dimensional accessible surfaces; 4. higher Pt atom utilization.
To date, several methods for preparing Pt-rich nanocages have been reported. Xia's group A series of groups consisting of (100) were prepared by first using Pd seed assisted growth methodPtOr {111}PtPd @ Pt nano particles surrounded by crystal faces are subjected to acid etching treatment to prepare the Pt-rich nano cage with determined Pt wall thickness. In addition, Li's group also uses Pd seed assisted growth method to prepare the seed crystal composed of {111}PtPd @ Pt nano particles surrounded by crystal faces are subjected to acid etching treatment to prepare the Pt-rich nano cage with determined Pt wall thickness. Although the method has the advantage of determining the Pt wall thickness, the method still has the defects of complicated process, low yield, incapability of accurately regulating and controlling the Pt wall thickness, inconvenience for batch preparation and the like.
However, the one-pot solvothermal method has attracted the interest of researchers due to its advantages of simplicity, feasibility, economy, effectiveness, and being beneficial to batch preparation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a monodisperse Pt-rich nano cage material with accurately controllable wall thickness, which has high dispersibility, high uniformity, high catalytic activity and accurately controllable wall thickness.
Meanwhile, the invention also provides a supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness, which is prepared by using the monodisperse Pt-rich nano cage material with accurately controllable wall thickness.
The technical scheme adopted by the invention is as follows:
the Pt-rich nano cage material is monodisperse and has accurately controllable wall thickness, and the number n of Pt wall layers of the Pt-rich nano cage material is 5.3-13.9; the distribution range of the wall thickness is 1.22 nm-3.20 nm, and the wall thickness can be accurately controlled.
Further limiting, the particle size range of the Pt-rich nanocage material is 15.6 nm-20.8 nm.
Further, the Pt wall thickness of the Pt-rich nanocage material is in direct proportion to the number of Pt monolayers under a certain condition.
Further limiting, in a certain raw material proportioning range, the number of layers of the corresponding Pt single layer is increased by 3 layers when the wall thickness of the Pt-rich nano cage material is increased by about 0.7 nm.
A supported monodisperse Pt-rich nanocage electrocatalyst with precisely controllable wall thickness, comprising a carrier and an active component supported on the carrier, wherein the active component is the monodisperse Pt-rich nanocage material with precisely controllable wall thickness as claimed in claim 1.
Further limiting, the percentage of the active component in the total mass of the catalyst is 5-10%.
Further limiting, the highest mass activity of the supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness in catalyzing oxygen reduction reaction is 1.17A/mgPtAnd the highest specific activity of the area is 4.17mA/cm2。
The preparation method of the monodisperse Pt-rich nanocage material with accurately controllable wall thickness comprises the following steps:
1) preparation of Pd @ Pt core @ shell nano material
Weighing acetylacetone platinum, acetylacetone palladium, a surfactant and a reducing aid, adding the materials into dimethylformamide, performing ultrasonic treatment and stirring dispersion, adding the solution into a polytetrafluoroethylene stainless steel reaction kettle, putting the polytetrafluoroethylene stainless steel reaction kettle into a common drying box, controlling the thickness of a shell layer by regulating and controlling the drying temperature to achieve a set thickness, naturally cooling to room temperature after the reaction is finished, centrifuging and washing the obtained product by using absolute ethyl alcohol, and dispersing the obtained product in deionized water for later use;
2) preparation of Pt-rich nanocage material
Weighing iron halide, a surfactant and potassium halide according to the mass ratio: mixing the raw materials in a ratio of 1-8: 2-5: 17-30, adding the mixture into an inorganic solvent, and adding a certain amount of acid solution after the mixture is completely dissolved; mixing the materials, heating the materials to 55-100 ℃ from room temperature in an oil bath kettle under the state of magnetic stirring, then adding the product obtained in the step 1), preserving the heat at 55-100 ℃ for 1-3 h, naturally cooling the solution to room temperature after the reaction is finished, centrifuging and washing the obtained product by using absolute ethyl alcohol, and keeping the obtained product in a drying oven at 80 ℃ for 12h to obtain the monodisperse Pt-rich nano cage material with accurately controllable wall thickness.
Further limiting, in the step 1), the thickness of the shell layer is controlled by regulating and controlling the drying temperature so as to reach a set thickness, and specifically, the method comprises the following steps: when the reaction temperature is increased by 10 ℃, the Pt wall thickness of the Pt-rich nano cage material is sequentially increased by about 0.7nm, and the number of corresponding Pt single layers is increased by 3 layers.
The monodisperse Pt-rich nanocage material with accurately controllable wall thickness is applied to the cathode oxygen reduction reaction of the fuel cell as an active component.
The monodisperse Pt-rich nano cage material with accurately controllable wall thickness is mainly prepared by combining a one-pot solvothermal method and an acid etching treatment method, has high dispersibility and high uniformity, and can accurately control the wall thickness.
Drawings
FIG. 1(a, b, c, d) are Transmission Electron Microscope (TEM) photographs of Pt-rich nanocages prepared at reaction temperatures from 150 ℃ to 180 ℃, respectively; (e, f, g, h) are the corresponding Pt wall thickness distribution histograms, respectively.
FIG. 2 is a graph of reaction temperature versus the number of Pt monolayers.
FIG. 3 shows PtnLORR stability test column for catalysis of/C and commercial Pt/C catalystsA drawing; test conditions were O2Saturated 0.1M HClO4The scanning voltage range of the solution is 0.05-1.1V vs. RHE (relative to a reversible hydrogen electrode), the scanning speed is 10mV/s, and the rotating speed is 1600 r/min.
Detailed Description
The technical solution of the present invention will be further explained with reference to the drawings and examples, but the present invention is not limited to the following implementation cases.
The Pt-rich nano cage material is of a nano cage structure with Pt as a wall material, and the number n of Pt wall layers is 5.3-13.9; the wall thickness distribution range is 1.22 nm-3.20 nm, the average size of the particle size is 15.6 nm-20.8 nm, the wall thickness of the Pt-rich nanocage material can be accurately controlled within the particle size range, and the thickness of the Pt wall layer is in direct proportion to the number of the Pt monolayer layers, namely, the number of the Pt monolayer layers is increased by 3 for each increase of the thickness of the Pt wall layer by about 0.7 nm.
The Pt-rich nanocage material has high dispersibility and high uniformity, and can also be used as an active component in the cathode oxygen reduction reaction of a fuel cell. In order to further improve the catalytic efficiency of the Pt-rich nanocage material which is monodisperse and has accurately controllable wall thickness, the Pt-rich nanocage material can be used as an active component to be loaded on an active carbon carrier, and the active component accounts for 5-10% of the total weight.
Through detection, the maximum mass activity of the Pt-rich nano cage material which is monodisperse and has accurately controllable wall thickness after being loaded on the activated carbon carrier reaches 1.17A/mgPtAnd the highest area specific activity reaches 4.17mA/cm2。
Example 1: preparation of Pt-richnLcatalyst/C (n ═ 5.3)
1) Preparation of nanoparticle Dispersion
Weighing 200mg of phenol, adding the phenol into 2mL of dimethylformamide, and marking the obtained solution as A; 31mg of platinum acetylacetonate, 12mg of palladium acetylacetonate and 92mg of polyvinylpyrrolidone (PVP, number average molecular weight 58000) were weighed and added to 10mL of dimethylformamide, and the resulting solution was labeled B; adding the solution A into the solution B, carrying out ultrasonic treatment for 5 minutes, stirring for 10 minutes, adding the solution C into a polytetrafluoroethylene stainless steel reaction kettle, heating to 150 ℃ from room temperature in a drying box, keeping for 8 hours, cooling to room temperature, centrifuging, washing with ethanol for 3-5 times, and dispersing the obtained black product into 2mL of deionized water to obtain a nanoparticle dispersion liquid for later use.
2) Preparation of Pt-rich nanocage material
170mg of potassium bromide (KBr), 20mg of polyvinylpyrrolidone (PVP) and 10mg of ferric chloride (FeCl) were weighed out separately3) Adding the mixture into deionized water (5mL), and after the mixture is completely dissolved, transferring 0.05mL of hydrochloric acid (HCl) by using a micro liquid transfer gun; and then heating the mixed solution to 55 ℃ from room temperature in an oil bath kettle under the state of magnetic stirring, then adding 0.2mL of the nanoparticle dispersion liquid obtained in the step 1) and keeping the solution at 55 ℃ for 1h, after the reaction is finished, naturally cooling the solution to room temperature, centrifuging and washing the obtained product by using absolute ethyl alcohol for 3-5 times, and keeping the solution in a drying oven at 80 ℃ for 12h to obtain black powder which is the Pt-rich nanocage.
Through detection, the particle size of the Pt-rich nanocage material in the embodiment is 19.20 +/-1.94 nm, the average size of the Pt wall thickness is 1.22nm, and the number n of Pt single-layer layers is 5.3.
3) Preparation of Pt-richnLcatalyst/C
Weighing 2mg of the Pt-rich nanocage material obtained in the step 2), ultrasonically dispersing the Pt-rich nanocage material in 9mL of absolute ethyl alcohol, then adding 1mL of cyclohexane, and marking the obtained black dispersion liquid as D; weighing 18mg of carbon black, dispersing the carbon black in 5mL of absolute ethyl alcohol, marking the obtained black dispersion liquid as F, adding the solution F into the solution D, carrying out ultrasonic treatment for 2 hours, centrifuging the obtained product, washing the product for 2 times by using the absolute ethyl alcohol, keeping the obtained product in a drying oven at 80 ℃ for 12 hours, and obtaining black powder, namely the supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness.
Example 2: preparation of Pt-richnLcatalyst/C (n ═ 8.2)
1) Preparation of nanoparticle Dispersion
Weighing 200mg of benzoic acid, adding the benzoic acid into 2mL of dimethylformamide, and marking the obtained solution as A; 31mg of platinum acetylacetonate, 12mg of palladium acetylacetonate and 92mg of polyvinylpyrrolidone (PVP, number average molecular weight 58000) were weighed and added to 10mL of dimethylformamide, and the resulting solution was labeled B; adding the solution A into the solution B, carrying out ultrasonic treatment for 5 minutes, stirring for 10 minutes, adding the solution C into a polytetrafluoroethylene stainless steel reaction kettle, heating the solution in a drying box from room temperature to 160 ℃, keeping the temperature for 8 hours, cooling the solution to room temperature, centrifuging the solution, washing the solution with ethanol for 3-5 times, and dispersing the obtained black product into 2mL of deionized water to obtain a nanoparticle dispersion liquid for later use.
2) Preparation of Pt-rich nanocage material
300mg of potassium bromide (KBr), 50mg of sodium dodecylbenzenesulfonate and 40mg of ferric chloride (FeCl) were weighed out separately3) Adding the mixture into deionized water (5mL), and after the mixture is completely dissolved, transferring 0.3mL of hydrochloric acid (HCl) by using a micro liquid transfer gun; and then heating the mixed solution to 100 ℃ from room temperature in an oil bath kettle under the state of magnetic stirring, then adding 0.2mL of the nanoparticle dispersion liquid obtained in the step 1) and keeping the solution at 100 ℃ for 3h, after the reaction is finished, naturally cooling the solution to room temperature, centrifuging and washing the obtained product for 3-5 times by using absolute ethyl alcohol, and keeping the solution in a drying oven at 80 ℃ for 12h to obtain black powder which is the Pt-rich nanocage.
Through detection, the particle size of the Pt-rich nanocage material in the embodiment is 17.40 +/-2.2 nm, the average size of the Pt wall thickness is 1.90nm, and the number n of Pt single-layer layers is 8.2.
3) Preparation of Pt-richnLcatalyst/C
Weighing 2mg of the Pt-rich nanocage material obtained in the step 2), ultrasonically dispersing the Pt-rich nanocage material in 9mL of absolute ethyl alcohol, then adding 1mL of cyclohexane, and marking the obtained black dispersion liquid as D; weighing 22mg of carbon black, dispersing the carbon black in 5mL of cyclohexane, marking the obtained black dispersion liquid as F, adding the solution F into the solution D, carrying out ultrasonic treatment for 2 hours, centrifuging the obtained product, washing the product with absolute ethyl alcohol for 2 times, keeping the obtained product in a drying oven at 80 ℃ for 12 hours, and obtaining black powder, namely the supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness.
Example 3: preparation of Pt-richnLcatalyst/C (n ═ 11.0)
1) Preparation of nanoparticle Dispersion
Weighing 200mg of glucose, adding the glucose into 2mL of dimethylacetamide, and marking the obtained solution as A; weighing 31mg of platinum acetylacetonate, 12mg of palladium acetylacetonate and 92mg of sodium dodecylbenzene sulfonate, adding the materials into 10mL of dimethylacetamide, and marking the obtained solution as B; adding the solution A into the solution B, carrying out ultrasonic treatment for 5 minutes, stirring for 10 minutes, adding the solution C into a polytetrafluoroethylene stainless steel reaction kettle, heating to 170 ℃ from room temperature in a drying box, keeping for 8 hours, cooling to room temperature, centrifuging, washing with ethanol for 3-5 times, and dispersing the obtained black product into 2mL of deionized water to obtain a nanoparticle dispersion liquid for later use.
2) Preparation of Pt-rich nanocage material
300mg of potassium bromide (KBr), 50mg of sodium dodecyl sulfate and 80mg of ferric chloride (FeCl) were weighed out separately3) Adding the mixture into deionized water (5mL), and after the mixture is completely dissolved, transferring 0.5mL of hydrochloric acid (HCl) by using a micro liquid transfer gun; heating the mixed solution to 100 ℃ from room temperature in an oil bath kettle under the state of magnetic stirring, then adding 0.1mL of the nanoparticle dispersion liquid obtained in the step 1) and keeping the solution at 100 ℃ for 3h, after the reaction is finished, naturally cooling the solution to room temperature, centrifuging and washing the obtained product for 3-5 times by using absolute ethyl alcohol, and keeping the solution in a drying oven at 80 ℃ for 12h to obtain black powder which is a Pt-rich nanocage;
through detection, the particle size of the Pt-rich nanocage material in the embodiment is 15.6 +/-2.7 nm, the average size of the Pt wall thickness is 2.52nm, and the number n of Pt single-layer layers is 11.0.
3) Preparation of Pt-richnLcatalyst/C
Weighing 2mg of the Pt-rich nanocage material obtained in the step 2), ultrasonically dispersing the Pt-rich nanocage material in 9mL of absolute ethyl alcohol, then adding 1mL of cyclohexane, and marking the obtained black dispersion liquid as D; weighing 31mg of carbon black, dispersing the carbon black in 5mL of absolute ethyl alcohol, marking the obtained black dispersion liquid as F, adding the solution F into the solution D, carrying out ultrasonic treatment for 2 hours, centrifuging the obtained product, washing the product with absolute ethyl alcohol for 2 times, keeping the obtained product in a drying oven at 80 ℃ for 12 hours, and obtaining black powder, namely the supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness.
Example 4:preparation of Pt-richnLcatalyst/C (n ═ 13.9)
1) Preparation of nanoparticle Dispersion
Weighing 200mg of ascorbic acid, adding the ascorbic acid into 2mL of dimethylpropionamide, and marking the obtained solution as A; 31mg of platinum acetylacetonate, 12mg of palladium acetylacetonate and 92mg of polyvinylpyrrolidone (PVP, number average molecular weight 58000) were weighed and added to 10mL of dimethylpropionamide, and the resulting solution was labeled B; adding the solution A into the solution B, carrying out ultrasonic treatment for 5 minutes, stirring for 10 minutes, adding the solution C into a polytetrafluoroethylene stainless steel reaction kettle, heating the solution in a drying box from room temperature to 180 ℃, keeping the temperature for 8 hours, cooling the solution to room temperature, centrifuging the solution, washing the solution with ethanol for 3-5 times, and dispersing the obtained black product into 2mL of deionized water to obtain a nanoparticle dispersion solution for later use.
2) Preparation of Pt-rich nanocage material
200mg of potassium bromide (KBr), 30mg of sodium dodecyl sulfate and 50mg of ferric chloride (FeCl) were weighed out separately3) Adding the mixture into deionized water (5mL), and after the mixture is completely dissolved, transferring 0.5mL of hydrochloric acid (HCl) by using a micro liquid transfer gun; heating the mixed solution to 100 ℃ from room temperature in an oil bath kettle under the state of magnetic stirring, then adding 0.1mL of the nanoparticle dispersion liquid obtained in the step 1) and keeping the solution at 100 ℃ for 3h, after the reaction is finished, naturally cooling the solution to room temperature, centrifuging and washing the obtained product for 3-5 times by using absolute ethyl alcohol, and keeping the solution in a drying oven at 80 ℃ for 12h to obtain black powder which is a Pt-rich nanocage;
through detection, the particle size of the Pt-rich nanocage material in the embodiment is 20.80 +/-2.0 nm, the average size of the Pt wall thickness is 3.20nm, and the number n of Pt single-layer layers is 13.9.
3) Preparation of Pt-richnLcatalyst/C
Weighing 2mg of the Pt-rich nanocage material obtained in the step 2), ultrasonically dispersing the Pt-rich nanocage material in 9mL of absolute ethyl alcohol, then adding 1mL of cyclohexane, and marking the obtained black dispersion liquid as D; weighing 38mg of carbon black, dispersing the carbon black in 5mL of absolute ethyl alcohol, marking the obtained black dispersion liquid as F, adding the solution F into the solution D, carrying out ultrasonic treatment for 2 hours, centrifuging the obtained product, washing the product for 2 times by using the absolute ethyl alcohol, keeping the obtained product in a drying oven at 80 ℃ for 12 hours, and obtaining black powder, namely the supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness.
The mass of the raw materials, such as the palladium precursor, the platinum precursor, the surfactant, and the co-reducing agent, in the above embodiments can be properly adjusted by referring to the mixture ratio in the above embodiments, for example, the mass ratio of the palladium precursor, the platinum precursor, the surfactant, and the co-reducing agent is properly adjusted within a range of 1: 2 to 3: 5 to 8: 16 to 17, which is not limited to the above embodiments. The Pt wall thickness of different raw material mass ratios can be changed, but the regulation and control method can realize accurate wall thickness control within the range of the raw material mass ratio.
It can be seen from the above embodiments that the thickness of the Pt-rich nanocage material of the present invention is proportional to the number of layers, and 3 layers are added for every 0.7nm increase in the thickness of the Pt-rich nanocage material, so that monodispersion and precise and controllable shell thickness of the Pt-rich nanocage material can be achieved, and the specific thickness control method is to control the wall thickness of the nanocage to a set thickness by adjusting and controlling the temperature, specifically: when the proportion of the reaction raw materials is in a certain range, the average size of the Pt wall thickness of the Pt-rich nano cage material is increased by about 0.7nm when the reaction temperature is increased by 10 ℃, and the number of corresponding Pt single layers is increased by 3 layers.
The phenol as the co-reducing agent in embodiments 1 to 4 can be optionally selected from benzoic acid, sodium benzoate, glucose, citric acid, sodium citrate and ascorbic acid. The surfactant can be one of polyvinylpyrrolidone, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; the reducing agent can be any one selected from dimethylformamide, dimethylacetamide and dimethylpropionamide.
The catalytic performance and stability of the Pt-rich nanocage material are further verified through the following experiments, which are as follows:
1. determining the relationship between the reaction temperature and the number of Pt wall layers by controlling an experimental method, as shown in FIG. 1, wherein (a) - (d) in FIG. 1 are Transmission Electron Microscope (TEM) photographs of nanocages in the Pt-rich nanocage electrocatalyst prepared at the reaction temperature of 150-180 ℃; in fig. 1, (e) to (h) are histograms of the Pt wall thickness distribution.
As can be seen from (a) to (d) in fig. 1, the nanocages in the Pt-rich nanocage electrocatalyst according to the present invention have high dispersibility and high uniformity; and the average size distribution range of the nano-cages in the Pt-rich nano-cage electro-catalysts prepared in the embodiments 1 to 4 of the invention is calculated to be 15.6 +/-2.7-20.8 +/-2.0 nm. As can be seen from the comparison of (e) to (h) in fig. 1, the Pt wall thickness of the nanocages in the Pt-rich nanocage electrocatalyst increases with the increase of the reaction temperature; the statistical wall thickness distribution range is 1.22 +/-0.25-3.20 +/-0.96 nm, and the corresponding distribution range of the number of the Pt wall single layers is 5.3 +/-1.1-13.9 +/-4.2.
FIG. 2 is a graph of the Pt wall monolayer number of the nanocages in the Pt-rich nanocage electrocatalyst obtained according to FIG. 1 versus the reaction temperature, it can be seen that the Pt wall thickness of the nanocages in the Pt-rich nanocage electrocatalyst can be accurately controlled by the reaction temperature; when the reaction temperature is increased by 10 ℃ in sequence, the Pt wall thickness of the Pt nano cage rich in Pt as the active component is increased by about 0.7nm in sequence, and the number of corresponding Pt wall monolayers is increased by about 3 monolayers in sequence.
2. Pt-rich nanocage electrocatalysts (Pt) prepared in examples 1-4 of the present inventionnL/C) and commercial Pt/C catalysts catalyze ORR stability test histograms.
And (3) testing conditions are as follows: is O2Saturated 0.1M HClO4The scanning voltage range of the solution is 0.05-1.1V vs. RHE (relative to a reversible hydrogen electrode), the scanning speed is 10mV/s, and the rotating speed is 1600 r/min.
As can be seen from FIG. 3, Pt compares to the commercial Pt/C electrocatalystnLthe/C (n ═ 5.3, 8.2, 11.0, 13.9) catalysts exhibit very superior catalytic performance. RHE (relative to reversible hydrogen electrode) at 0.9V vs. PtnLthe/C (n ═ 8.2) nanocage catalyst catalyzes the Oxygen Reduction Reaction (ORR) with the highest Mass Activity (MA) reaching 1.17A/mgPtIs a commercial Pt/C catalyst (0.18A/mg)Pt) 6.5 times of the total weight of the powder. PtnLThe specific area activity (SA) of the/C (n-13.9) catalyst was the highest, reaching 4.17mA/cm2Is a commercial Pt/C catalyst (0.29 mA/cm)2) 14 (c) of4 times. Pt after 8000(8K) stability testsnLthe/C (n ═ 5.3, 8.2, 11.0, 13.9) catalysts showed very good stability compared to the commercial Pt/C catalysts.

Claims (7)

1. A monodisperse Pt-rich nano cage material with accurately controllable wall thickness is characterized in that: the number n of Pt wall layers of the Pt-rich nano cage material is 5.3-13.9; the distribution range of the wall thickness is 1.22 nm-3.20 nm, and the wall thickness can be accurately controlled; in a given raw material ratio, the number of layers of the corresponding Pt single layer is increased by 3 layers when the wall thickness of the Pt-rich nano cage material is increased by 0.7 nm;
the preparation method of the monodisperse Pt-rich nanocage material with accurately controllable wall thickness comprises the following steps:
1) preparation of Pd @ Pt core @ shell nano material
Weighing acetylacetone platinum, acetylacetone palladium, a surfactant and a co-reducing agent, adding the materials into dimethylformamide, performing ultrasonic treatment and stirring dispersion, adding the solution into a polytetrafluoroethylene stainless steel reaction kettle, putting the polytetrafluoroethylene stainless steel reaction kettle into a common drying box, controlling the thickness of a shell layer by regulating and controlling the drying temperature to achieve a set thickness, regulating and controlling the temperature of the drying box to be 150-180 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging and washing the obtained product by using absolute ethyl alcohol, and dispersing the obtained product in deionized water for later use;
2) preparation of Pt-rich nanocage material
Weighing iron halide, a surfactant and potassium halide according to the mass ratio: mixing the raw materials in a ratio of 1-8: 2-5: 17-30, adding the mixture into an inorganic solvent, and adding a certain amount of acid solution after the mixture is completely dissolved; mixing the materials, heating the materials to 55-100 ℃ from room temperature in an oil bath kettle under the state of magnetic stirring, then adding the product obtained in the step 1), preserving the heat at 55-100 ℃ for 1-3 h, naturally cooling the solution to room temperature after the reaction is finished, centrifuging and washing the obtained product by using absolute ethyl alcohol, and keeping the obtained product in a drying oven at 80 ℃ for 12h to obtain the monodisperse Pt-rich nano cage material with accurately controllable wall thickness.
2. The monodisperse, precisely controllable wall thickness Pt-rich nanocage material of claim 1, wherein: the particle size range of the Pt-rich nano cage material is 15.6 nm-20.8 nm.
3. The monodisperse, precisely controllable wall thickness Pt-rich nanocage material of claim 2, wherein: the thickness of the Pt layer of the Pt-rich nano cage material is in direct proportion to the number of the Pt single layers under a certain condition.
4. The monodisperse, precisely controllable wall thickness Pt-rich nanocage material of claim 1, wherein: the method is characterized in that: step 1) controlling the thickness of a shell layer by regulating and controlling the drying temperature to achieve a set thickness, which specifically comprises the following steps: when the reaction temperature is increased by 10 ℃, the Pt wall thickness of the Pt-rich nano cage material is sequentially increased by 0.7nm, and the number of corresponding Pt single layers is increased by 3 layers.
5. A supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness is characterized in that: the supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness comprises a carrier and an active component supported on the carrier, wherein the active component is the monodisperse Pt-rich nano cage material with accurately controllable wall thickness as claimed in claim 1.
6. The supported monodisperse, precisely controllable wall thickness Pt-rich nanocage electrocatalyst according to claim 5, wherein: the percentage of the active component in the total mass of the catalyst is 5-10%.
7. The supported monodisperse, precisely controllable wall thickness Pt-rich nanocage electrocatalyst according to claim 5, wherein: the highest mass activity of the supported monodisperse Pt-rich nano cage electrocatalyst with accurately controllable wall thickness in the catalytic oxygen reduction reaction is 1.17A/mgPtAnd the highest area specific activity is 4.17mA/cm2。
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