CN105702975B - The self-supporting palladium monofilm and its preparation method and purposes of a kind of hollow-core construction - Google Patents
The self-supporting palladium monofilm and its preparation method and purposes of a kind of hollow-core construction Download PDFInfo
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- CN105702975B CN105702975B CN201610022838.XA CN201610022838A CN105702975B CN 105702975 B CN105702975 B CN 105702975B CN 201610022838 A CN201610022838 A CN 201610022838A CN 105702975 B CN105702975 B CN 105702975B
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
A kind of self-supporting palladium monofilm of hollow-core construction, its size is in 25 cm2, palladium monofilm forms by palladium nano-hollow ball self assembly, and palladium hollow ball size is 18 25 nm.The self-supporting palladium monofilm of the hollow-core construction of the present invention has the characteristics that hollow-core construction and specific surface area are big.There is higher activity in ethanol electrocatalytic oxidation, in a fuel cell with potential application value.The invention discloses its preparation method.
Description
Technical field
The present invention relates to self-supporting palladium individual layer film catalyst of the hollow-core construction for fuel cell and preparation method thereof.
Background technology
The features such as Direct Ethanol Fuel Cell is due to its energy density height and low stain, before becoming a kind of great application
The portable and fixed power supply of scape.Palladium-based catalyst is opened up in the ethanol electrocatalysis oxidation reaction in Direct Ethanol Fuel Cell
Reveal excellent activity, Y.Su et al. and have studied catalytic performance of the palladium nanosphere in ethanol electrocatalysis oxidation reaction, achieve very
Good effect.The electro catalytic activity of palladium-based catalyst and its pattern and size are closely related, and palladium base catalysis material is with abundant
Pattern, such as nano wire, nanosphere, nano flower, this provides Research foundation for application of the palladium-based materials in this field.Such as
D.Ma etc. is studied the electrocatalytic properties of various different-shape palladium materials.
The research for preparing palladium-based materials achieves rapid development in recent years, and preparation method emerges in an endless stream, the system of Technique of Nano Pd
Preparation Method can totally be divided into two classes：A kind of is the vapour deposition process (PVD or CVD) based on solid-phase thermal sublimating technologe, passes through control
Reaction condition, such as reaction temperature, flow rate of carrier gas, carrier gas type, the different source material of selection or changes its composition, can prepare
The nanoscale palladium material of different-shape, but this kind of preparation process is required for high temperature and the instrument condition of complexity；It is prepared by another kind
Method is solution chemical method, increasingly abundanter with hydrothermal/solvent thermal technology and microwave synthesis, the development of ultrasonic synthetic technology
Palladium nanostructured prepared by solution chemical processes, compared with vapour deposition process, solution chemical method have mild condition,
The advantages that equipment is simple, thus as the very preparation method with application prospect.In these solution chemical methods, with nanometer
Grain is template, and porous hollow nanostructured, fresh understatement road are prepared by electrochemical displacement reaction.
We, using the silver nanoparticle crystalline substance with single-size as template, are successfully closed by a kind of green synthetic method
Into a kind of self-supporting palladium monofilm of hollow-core construction.Simple to operate because this method synthesis material is easy to get, no special installation will
Ask, it is had good application prospect in fuel cell field.
The content of the invention
It is an object of the invention to provide self-supporting palladium individual layer membrane material of a kind of hollow-core construction and its production and use.
Nanocrystalline for template with spherical silver, using simple electrochemical displacement method, prepared self-supporting palladium individual layer membrane material, which has, to be received
The features such as meter level hollow-core construction, specific surface area are big, electrocatalytic oxidation ethanol efficiency high.
The principle of the present invention is as follows：(PdCl4)2 -/ Pd normal reduction potentials are 0.62V, and AgCl/Ag normal reduction potentials are
0.22V, (PdCl4)2 -/ Pd normal reduction potentials are higher than AgCl/Ag normal reduction potentials, therefore Pd2+Pd can be reduced to by Ag,
Palladium ion in solution gradually replaces silver nanoparticle ball corrosion, ultimately forms Technique of Nano Pd hollow ball.Technique of Nano Pd hollow ball is in water-heptan
Single thin film is self-assembled on alcohol interface, after removing enanthol, the self-supporting palladium of hollow-core construction is finally formed on air-water interface
Monofilm, see Fig. 1.
Technical scheme is as follows：
A kind of self-supporting palladium monofilm of hollow-core construction, its size is in 2-5cm2, palladium monofilm by palladium nano-hollow ball from
Assemble, palladium hollow ball size is 18-25nm.
A kind of method for the self-supporting palladium monofilm for preparing above-mentioned hollow-core construction, it is by sodium citrate aqueous solution
(1wt%), silver nitrate aqueous solution (1wt%), aqueous sodium bromide (20mmolL-1) and copper nitrate aqueous solution (10mmolL-1) mix at room temperature, the amount ratio of each material is：Sodium citrate aqueous solution (1wt%):Silver nitrate aqueous solution
(1wt%):Aqueous sodium bromide (20mmolL-1):Copper nitrate aqueous solution (10mmolL-1)=1mL:0.25mL:50μL:
0-100μL.At room temperature after aging 5min, by mixed liquor be expelled to 47.5mL boiling aqueous ascorbic acid (AA,
0.1mmol·L-1), seethe with excitement 1h under stirring, obtains silver nanoparticle crystalline substance solution.Under magnetic stirring, with syringe pump with 100 μ
L·min-1Speed is by 5mL tetrachloro-palladium acids sodium water solution (125 μm of olL-1) be expelled in 50mL silver nanoparticle crystalline substance solution.Weighing
In bottle, the 5mL mixed liquors, 15mL water and the mixing of 5mL enanthol are taken, ethanol is added dropwise dropwise, after removing enanthol, by measuring cup at 48 DEG C
Water-bath 3h, the self-supporting palladium monofilm of hollow-core construction is finally formed on air-water interface.
Catalyst of the self-supporting palladium monofilm of the hollow-core construction of the present invention as electrocatalytic oxidation ethanol, has higher
The catalytic efficiency of electrocatalytic oxidation ethanol.
The self-supporting palladium monofilm of the present invention has the spies such as nano-scale hollow structure, specific surface area are big and electro catalytic activity is high
Point.The preparation self-supporting palladium individual layer film method of the present invention, simple to operate because raw material is cheap and easily-available, equipment requirement is not high, makes it
There is good potential application foreground in alcohol fuel cell field.
The advantages of preparation method of the present invention：
1. method is easy, equipment is simple, and pollution is few；
2. gained self-supporting palladium monofilm has nano-scale hollow structure, specific surface area is big, electro-catalysis efficiency high.
Brief description of the drawings
Fig. 1 is the preparation process schematic diagram of hollow-core construction self-supporting palladium monofilm.
Fig. 2 is the TEM results and ultraviolet-visible spectrogram of the Ag nanometer crystal templates prepared：(a) it is 0 μ L nitric acid copper waters of addition
Solution (10mmolL-1) nanocrystalline for the Ag of adjuvant preparation, (b) is 37.5 μ L copper nitrate aqueous solutions (10mmolL of addition-1) nanocrystalline for the Ag of adjuvant preparation, (c) is 87.5 μ L copper nitrate aqueous solutions (10mmolL of addition-1) prepared for adjuvant
Ag it is nanocrystalline, (d) is that above-mentioned addition different volumes copper nitrate aqueous solution is nanocrystalline ultraviolet of three kinds of Ag prepared by adjuvant
Visible ray spectrogram：0 μ L (d1 curves), 37.5 μ L (d2 curves), 87.5 μ L (d3 curves).
Fig. 3 is the optical photograph and TEM results of the self-supporting palladium monofilm of the hollow-core construction prepared：(a) it is hollow-core construction
Self-supporting palladium monofilm optical photograph, (b) be hollow-core construction self-supporting palladium monofilm low power TEM results, (c) for sky
The high power TEM results of the self-supporting palladium monofilm of core structure.
Fig. 4 is the self-supporting palladium monofilm of hollow-core construction and the electrocatalytic oxidation of commercial palladium carbon (Pd/C) catalyst of the present invention
Change ethanol Activity Results：(a) the cyclic voltammetry curve figure of the self-supporting palladium monofilm for hollow-core construction and commercial Pd/C catalyst,
(b) the current potential cyclical stability curve map of the self-supporting palladium monofilm for hollow-core construction and commercial Pd/C catalyst.
Embodiment
Preparation of the embodiment 1. without using copper nitrate for the Ag nanometer crystal templates of adjuvant
1mL sodium citrate aqueous solutions (1wt%), 0.25mL silver nitrate aqueous solutions (1wt%) and 50 μ L sodium bromides are water-soluble
Liquid (20mmolL-1) mix at room temperature, at room temperature after aging 5min, mixed liquor is expelled to 47.5mL boilings
Aqueous ascorbic acid (AA, 0.1mmolL-1), seethe with excitement 1h under stirring, obtains silver nanoparticle crystalline substance solution, its TEM and purple
Outer visible spectrum measurement result is shown in Fig. 2.
Preparation of the embodiment 2. using 37.5 μ L copper nitrates as the Ag nanometer crystal templates of adjuvant
By 1mL sodium citrate aqueous solutions (1wt%), 0.25mL silver nitrate aqueous solutions (1wt%), 50 μ L aqueous sodium bromides
(20mmol·L-1) and 37.5 μ L copper nitrate aqueous solutions (10mmolL-1) mix at room temperature, aging at room temperature
After 5min, mixed liquor is expelled to aqueous ascorbic acid (AA, the 0.1mmolL of 47.5mL boilings-1), under stirring
Seethe with excitement 1h, obtains silver nanoparticle crystalline substance solution, its TEM and uv-vis spectra measurement result are shown in Fig. 2.
Preparation of the embodiment 3. using 87.5 μ L copper nitrates as the Ag nanometer crystal templates of adjuvant
By 1mL sodium citrate aqueous solutions (1wt%), 0.25mL silver nitrate aqueous solutions (1wt%), 50 μ L aqueous sodium bromides
(20mmol·L-1) and 87.5 μ L copper nitrate aqueous solutions (10mmolL-1) mix at room temperature, aging at room temperature
After 5min, mixed liquor is expelled to aqueous ascorbic acid (AA, the 0.1mmolL of 47.5mL boilings-1), under stirring
Seethe with excitement 1h, obtains silver nanoparticle crystalline substance solution, its TEM and uv-vis spectra measurement result are shown in Fig. 2.
Embodiment 4. is with the preparation of the self-supporting palladium monofilm of the homogeneous nanocrystalline hollow-core constructions for template of spherical Ag
Under magnetic stirring, with syringe pump with 100 μ Lmin-1Speed is by 5mL tetrachloro-palladium acids sodium water solution (125 μm of ol
L-1) be expelled in 50mL silver nanoparticle crystalline substance solution.In measuring cup, the 5mL mixed liquors, 15mL water and the mixing of 5mL enanthol are taken, dropwise
Ethanol is added dropwise, after removing enanthol, by measuring cup in 48 DEG C of water-bath 3h, finally formed on air-water interface hollow-core construction from
Palladium monofilm is supported, its optical photograph and TEM results are shown in Fig. 3.
The ethanol electrocatalytic oxidation property test of the self-supporting palladium monofilm of the hollow-core construction of the present invention of embodiment 5.
Electrochemical properties test is carried out in CHI 660d types electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), is repaiied
The glass-carbon electrode of the self-supporting palladium monofilm of 3mm hollow-core constructions is adornd as working electrode, Ag/AgCl electrodes are as reference electricity
Pole, platinum electrode is as auxiliary electrode.Ethanol electrocatalytic oxidation cyclic voltammetry condition is：In 0.3molL-1Potassium hydroxide water
Solution and 0.5molL-1Carried out in alcohol mixed solution, sweep speed 20mVs-1.The scanning speed of potential cycle stability
Rate is 100mVs-1.As a comparison, in this test condition, the ethanol electrocatalytic oxidation of commercial palladium carbon (Pd/C) catalyst is tested
Change performance.Test obtains cyclic voltammetry curve figure and current potential cyclical stability curve map, its result are shown in Fig. 4.
Claims (3)
1. a kind of self-supporting palladium monofilm of hollow-core construction, it is characterized in that：The palladium monofilm size is 2-5cm2, palladium monofilm by
Pd nano-hollow ball self assemblies form, and palladium hollow ball size is 18-25nm；
The preparation method of the self-supporting palladium monofilm of the hollow-core construction is：By 1wt% sodium citrate aqueous solutions, 1wt% nitric acid
The silver-colored aqueous solution, 20mmolL-1Aqueous sodium bromide and 10mmolL-1Copper nitrate aqueous solution mixes at room temperature, each thing
The amount ratio of matter is：1wt% sodium citrate aqueous solutions：1wt% silver nitrate aqueous solutions：20mmol·L-1Aqueous sodium bromide：
10mmol·L-1Copper nitrate aqueous solution=1mL：0.25mL：50μL：0-100μL；At room temperature after aging 5min, mixed liquor is noted
It is mapped to the 0.1mmolL of 47.5mL boilings-1Aqueous ascorbic acid, seethe with excitement 1h under stirring, and it is molten to obtain silver nanoparticle crystalline substance
Liquid；Under magnetic stirring, with syringe pump with 100 μ Lmin-1Speed is by 125 μm of olL of 5mL-1Tetrachloro-palladium acid sodium water solution
It is expelled in 50mL silver nanoparticle crystalline substance solution；In measuring cup, take 5mL add tetrachloro-palladium acid sodium water solution silver nanoparticle crystalline substance solution,
15mL water and the mixing of 5mL enanthol, are added dropwise ethanol dropwise, after removing enanthol, by measuring cup in 48 DEG C of water-bath 3h, finally air-
The self-supporting palladium monofilm of hollow-core construction is formed in water termination.
2. a kind of method for the self-supporting palladium monofilm for preparing the hollow-core construction described in claim 1, it is characterized in that：By 1wt%
Sodium citrate aqueous solution, 1wt% silver nitrate aqueous solutions, 20mmolL-1Aqueous sodium bromide and 10mmolL-1Nitric acid copper water
Solution mixes at room temperature, and the amount ratio of each material is：1wt% sodium citrate aqueous solutions：1wt% silver nitrate aqueous solutions：
20mmol·L-1Aqueous sodium bromide：10mmol·L-1Copper nitrate aqueous solution=1mL：0.25mL：50μL：0-100μL；In room
After the lower aging 5min of temperature, mixed liquor is expelled to the 0.1mmolL of 47.5mL boilings-1Aqueous ascorbic acid, in stirring
Lower boiling 1h, obtain silver nanoparticle crystalline substance solution；Under magnetic stirring, with syringe pump with 100 μ Lmin-1Speed is by the μ of 5mL 125
mol·L-1Tetrachloro-palladium acid sodium water solution be expelled in 50mL silver nanoparticle crystalline substance solution；In measuring cup, 5mL is taken to add tetrachloro palladium
Silver nanoparticle crystalline substance solution, 15mL water and the mixing of 5mL enanthol of acid sodium aqueous solution, are added dropwise ethanol, after removing enanthol, by measuring cup dropwise
In 48 DEG C of water-bath 3h, the self-supporting palladium monofilm of hollow-core construction is finally formed on air-water interface.
3. the self-supporting palladium monofilm of the hollow-core construction described in claim 1 is in Direct Ethanol Fuel Cell and ethanol electrocatalytic oxidation
Application in change.
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| CN103184441A (en) * | 2011-12-30 | 2013-07-03 | 中国科学院长春应用化学研究所 | Palladium nano film preparation method and palladium/platinum nano film preparation method |
| CN104259476A (en) * | 2014-09-26 | 2015-01-07 | 中国科学院深圳先进技术研究院 | Palladium nano-particle and preparation method thereof |
| CN104907557A (en) * | 2015-05-12 | 2015-09-16 | 济南大学 | Flower-like gold palladium heterogeneous nano particle with good electro-catalytic property and preparing method thereof |
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| US20130177838A1 (en) * | 2010-07-14 | 2013-07-11 | Brookhaven Science Associates, Llc | Hollow nanoparticles as active and durable catalysts and methods for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103184441A (en) * | 2011-12-30 | 2013-07-03 | 中国科学院长春应用化学研究所 | Palladium nano film preparation method and palladium/platinum nano film preparation method |
| CN104259476A (en) * | 2014-09-26 | 2015-01-07 | 中国科学院深圳先进技术研究院 | Palladium nano-particle and preparation method thereof |
| CN104907557A (en) * | 2015-05-12 | 2015-09-16 | 济南大学 | Flower-like gold palladium heterogeneous nano particle with good electro-catalytic property and preparing method thereof |
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