CN108110265A - A kind of Au@Au/Pt nuclear shell structured nano catalyst for alcohol fuel battery - Google Patents
A kind of Au@Au/Pt nuclear shell structured nano catalyst for alcohol fuel battery Download PDFInfo
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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
- H01M4/921—Alloys or mixtures with metallic elements
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- 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
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- 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
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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]
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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]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A kind of Au@Au/Pt nuclear shell structure nano catalyst for alcohol fuel battery, shape are in concave surface cube, and size is 29 ± 4nm；Inside is golden core, and outside is gold/platinum shell；The catalyst is prepared using following methods：Gold nanoparticle is prepared first；Then in the surface deposition of silver of gold nanoparticle, the nanocube of formation Au@Ag nucleocapsids；Then the nanocube of Au@Ag/Au nucleocapsids is prepared using in situ synthesis, chloroplatinic acid is eventually adding and cements out silver, obtain product.Simple platinum shell is changed into the shell collectively constituted by platinum by the catalyst of the present invention, is further reduced the load capacity of platinum, is reduced cost.There is unique nucleocapsid simultaneously, there is more rich Atomic Arrangement and the surface area of bigger, and there is plasmon resonance effect with golden nuclear interaction, can effectively enhance catalytic activity and decrease poisons effect；For the oxidation reaction of ethyl alcohol in alkaline conditions, stability and catalytic activity are more preferable.
Description
Technical field
The invention belongs to fuel-cell catalyst field, it is related to and a kind of is urged for Au/Pt nanometers of the Au@of alcohol fuel battery
Agent and preparation method thereof.
Background technology
Alcohol fuel battery has many advantages, such as that fuel source enriches, is cheap, carrying and storing safe ready, wherein first
Alcohol fuel battery research is more.However, since methanol has certain toxicity, it is removable in mobile phone, notebook, computer etc. to limit it
Application in dynamic field of power supplies.Ethyl alcohol has the following advantages that as simplest organic molecule in chain alcohol compared with methanol：One
It is cheap, safety, it is nontoxic；Second is that easily transport, has smaller volatility；It is third, theoretical higher than energy；Fourth, source
Extensively, it is reproducible green energy resource.Therefore, studying the direct alcohol fuel cell using ethyl alcohol as fuel not only has theoretical meaning
Justice, and application prospect is very wide.The mechanism of alcohol fuel cell anode reaction is：
CH3CH2OH+·OH- →H2O + CO3 2-
Ethyl alcohol has 12 electronics during complete oxidation and generates it can be seen from more than reaction equation, and compare first
For 6 electronics of alcohol, this means that ethyl alcohol has to break C-C during oxidation, so this condition causes second
The complete oxidation of alcohol is extremely difficult.Noble metal catalyst in methanol fuel cell may not be suitable for alcohol fuel cell.
Pt is efficient catalyst of fuel batter with proton exchange film（Nature 2001, 414, 345 –352）, however,
Simple Pt catalyst is easily poisoned be subject to oxidized intermediate product CO, causes catalytic activity reduction, bad stability, power
It learns slowly, and Pt reserves are few, price is high, limits its application.For this purpose, scientific research personnel builds the Pt (J. of unitary nanostructured
Am. Chem. Soc. 2007,129,6974-6975), binary or ternary nano structure Pt (Science 2009,
324,1302-1305), Pt catalyst (the International Journal of Hydorgen of nucleocapsid structure
Energy 2011,6,9151-9154), applied to fuel cell.For example, Zhu H etc.（International Journal
of Hydorgen Energy 2011, 6, 9151-9154）It reports using Vulcan XC-72R as carrier material, using two
Stage reduction method synthesis Cu@Pt/C catalyst with core-casing structure is applied to fuel cell, is shown especially for cathodic oxygen reduction
High activity is directed to and develops the catalyst of low platinum content to improve the utilization rate of noble metal and thus reduce cost.Although such as
This, but the dosage of Pt how is further reduced, enhance precious metals pt base catalyst activity and stability, weaken its catalysis
In the process poison effect, be still one challenge.
Platinum base nanocatalyst is had been a great concern due to its unique catalytic performance.Yet with platinum resource
The deficient business demand powerful with it so that platinum based catalyst cost is very expensive.For reduce platinum and dosage, nucleocapsid structure
Au@Au/Pt nano-particles be a kind of novel nano-material with wide application prospect, but due to the consolute temperature of Au and Pt
Height, therefore prepare AuPt alloy nano particles and generally require higher temperature, such as Xu (J. Phys. Chem. Lett.,
2010,1:2514-2518) report and use metal inorganic salt as presoma, oleyl amine be solvent, stabilizer and reducing agent,
Under 160 DEG C of hot conditions, when reaction 2 is small, AuPt Nanoalloys are made.The Chinese patent of Application No. 201310667345.8
Application " preparation method of Au@AuPt alloy nano particles and colloidal dispersion system " is reduced using part Au ions by ascorbic acid
For gold nanoparticle, the hydrazine hydrate aqueous solution that Pt ions and remaining Au ions are subsequently added in system is reduced to AuPt simultaneously
Alloy is simultaneously deposited on the Au@Au/Pt alloy nano particles that nucleocapsid is formed as the gold nanoparticle surface of cenotype seed, from
And realize the lower two step reduction synthesis Au Au/Pt alloy nano particles of a pot of room temperature condition.But make in the preparation method of the invention
With virose hydrazine hydrate, although more quick, toxicity is inevitable, and its material for preparing in structure not
Suitable for the effect of plasmonic enhancing active sites.
The content of the invention
It is easily poisoned for current noble metal nano catalyst alcohol fuel cell and the problem of catalytic efficiency is low, this
Invention provides a kind of Au@Au/Pt nuclear shell structured nano catalyst for alcohol fuel battery, catalytic efficiency higher, without catalysis
Agent intoxicating phenomenon, noble metal service efficiency are high.
The present invention also provides a kind of preparation methods of above-mentioned catalyst.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of Au@Au/Pt nuclear shell structured nano catalyst for alcohol fuel battery, shape are in concave surface cube, greatly
Small is 29 ± 4 nm；Inside is golden core（Au cores）, outside is gold/platinum shell（Au/Pt shells）.
The Au@Au/Pt nuclear shell structured nano catalyst, is prepared using following methods：Jenner's grain of rice is prepared first
Son；Then in the surface deposition of silver of gold nanoparticle, the nanocube of formation Au@Ag nucleocapsid structures；Then using in situ raw
Regular way prepares the nanocube of Au@Ag/Au nucleocapsid structures, is eventually adding chloroplatinic acid and cements out silver, obtains Au@Au/Pt
Core-shell structure copolymer concave surface nanocube.
A kind of preparation method of above-mentioned Au@Au/Pt nuclear shell structured nano catalyst, comprises the following steps：
（1）By gold chloride, CTAB（Cetyl trimethylammonium bromide）It is added to the mixed solution of sodium borohydride containing CTAC（Ten
Six alkyl trimethyl ammonium chlorides）、AA（Ascorbic acid）In the mixed solution of gold chloride, red, transparent solution is stirred to get；
（2）By step（1）Solution centrifugation after precipitation 60 DEG C of stirring in water bath are mixed with CTAC, while add in silver nitrate, AA and
CTAC, solution become brown color；
（3）By step（2）Solution centrifugation after precipitation be added with stirring hydroxylamine hydrochloride and gold chloride after boil, solution becomes red
Color；
（4）By step（3）Solution be dispersed in CTAB and PVP（Polyvinylpyrrolidone）Mixed solution in, 100 DEG C heating,
Chloroplatinic acid is slowly added to, solution centrifuges after becoming purple, obtains Au Au/Pt nuclear shell structured nano catalyst.
Step（1）In, gold chloride, CTAB and the preferred molar ratio of sodium borohydride are 37:50000:5000.
Step（1）In, gold chloride, CTAC and the preferred molar ratios of AA are 1:400:200.
Step（2）In, silver nitrate, AA and the preferred molar ratios of CTAC are 1:25:20.
Step（4）In, PVP and the preferred molar ratios of CTAB are 9:3125, wherein the mole of PVP is by its polymerized monomer
Molar amount.
Preferably, step（1）When preservation 3 is small at 27 DEG C after gold chloride, CTAB and sodium borohydride mixing.
Preferably, step（1）Gained red, transparent solution with 15000rpm centrifuge 20min, washing of precipitate once, after dissolving
For the next step.
Preferably, step（2）When solution becomes brown color after 60 DEG C of stirring in water bath 3h, 15000rpm centrifugation 15min sink
Shallow lake washed once, and the next step is used for after dissolving.
Preferably, step（4）Gained purple solution 10000rmp centrifuges 10min, and washing of precipitate twice, obtains Au@Au/Pt
Nuclear shell structured nano catalyst.
A kind of application of above-mentioned Au@Au/Pt nuclear shell structured nanos catalyst in methanol or alcohol fuel cell.
The present invention has the following advantages：
The present invention provides a kind of Au@Au/Pt nuclear shell structured nano catalyst for alcohol fuel battery, by simple platinum
Shell changes the shell collectively constituted by platinum into, further reduces the load capacity of platinum, reduces cost.There is uniqueness simultaneously
Nucleocapsid structure has more rich Atomic Arrangement and the surface area of bigger, and swashs with golden nuclear interaction with plasma
First resonance effects can effectively enhance catalytic activity and decrease poisons effect；For the oxidation reaction of ethyl alcohol in alkaline conditions,
Stability and catalytic activity are more preferable.Gold/golden platinum core-shell structure copolymer plasma nano cube, the party have been synthesized using displacement reaction
Method is feasible effectively, and the simple raw material of preparation method are easy to get, and are a kind of sun of Proton Exchange Membrane Fuel Cells of good performance
Electrode catalyst.
The method of present invention synthesis Au@Au/Pt core-shell structure copolymers concave surface nano-particle is simple and effective, synthesizes gold nanoparticle first,
Deposition of silver on the surface of gold nanoparticle afterwards forms Au@Ag core-shell structure copolymer nanocubes, adds in gold chloride and is synthesized with hydroxylamine hydrochloride
Au@Ag/Au core-shell structure copolymer nanocubes, then add in chloroplatinic acid and Au@Ag/Au core-shell structure copolymers nanocubes using displacement react into
Row reaction, adding in excessive chloroplatinic acid, all displacement is complete by silver, forms the alternate Au Ag/Pt core-shell structure copolymers concave surface of gold core, golden platinum
Nanocube.
Description of the drawings
Fig. 1 is the transmission electron micrograph of each nano-particle of synthesis, wherein（a）Gold/silver-colored core-shell structure copolymer nano cubic
Body, (b) gold/platinum core-shell structure copolymer nano-particle；（c）Gold/golden platinum core-shell structure copolymer nano-particle；
Fig. 2 is gold nanoparticle, gold/silver core-shell structure copolymer nanocube particle, gold/platinum core-shell structure copolymer nano-particle, gold/gold platinum core-shell structure copolymer
The UV-visible spectrum of nano-particle；
Fig. 3 is gold nanoparticle, and gold/silver-colored core-shell structure copolymer nanocube, gold/golden platinum core-shell structure copolymer nanocube is in 1.0M sodium hydroxides
With the chronoa mperometric plot in 1.0M alcohol mixed solutions, speed is swept as 50mV/s；
Fig. 4 is gold nanoparticle, gold/silver-colored core-shell structure copolymer nanocube, gold/platinum core-shell structure copolymer nano-particle, gold/golden platinum core-shell structure copolymer nanometer
Cyclic voltamogram curve of the cube in 1M sodium hydroxides and 1M alcohol mixed solutions sweeps speed as 50mV/s；
Fig. 5 be the electrode of gold/platinum core-shell structure copolymer nano-particle and gold/golden platinum core-shell structure copolymer nanocube modification in 1.0M sodium hydroxides and
Cyclic voltamogram curve and electrochemical surface in 1.0M alcohol mixed solutions after the normalization of electrochemical surface active area are lived
Time current curve after property area normalization.
Specific embodiment
With reference to embodiment and attached drawing, the present invention will be further described, but the present invention is from the limit of following embodiments
System.
The preparation of 1 Au@AuPt nanometer nuclear shell nano-structures of embodiment
The preparation of 1.1 Au nano-particles
（1）Before experiment, prepare several 25 mL beakers, spoon, a 50 mL beakers, magnetic stir bar 2,50 mL graduated cylinders
It one, is impregnated with chloroazotic acid for use after clean dry.And 5-50 μ L liquid-transfering guns, 100-1000 μ L liquid-transfering guns.
（2）A clean beaker is taken, pours into a small amount of deionized water, is put into freezer compartment of refrigerator freezing, for use.Spoon spend from
Sub- water after ethyl alcohol is cleaned and dried, takes 0.364 g cetyl trimethylammonium bromides with electronic balance scale, 10 is pipetted with liquid-transfering gun
ML deionized waters, which are added in beaker, to be dissolved.With 0.033 g sodium borohydrides of electronic balance weighing, 10 mL ice water are measured, pour into 25
ML beakers dissolve.Under the conditions of 27 DEG C, 42.5 μ L gold chlorides are pipetted with 5-50 μ L liquid-transfering guns（1%）It is slowly added into 5 configured
The cetyl trimethylammonium bromide CTAB of mL（100 mM）In, it is ice-cold rapidly to add in 0.3 mL thereto after mixing
The sodium borohydride of Fresh（100 mM）Solution, quickly reversion vibration preserves 3 hours after 2 minutes at 27 DEG C, with true
Unreacted sodium borohydride is protected completely to decompose.
（3）290 μ L gold chlorides are pipetted with 100-1000 μ L liquid-transfering guns（1%）Prepare 12 mL gold chlorides（0.5 mM）Solution,
Electronic balance weighs 0.768 g hexadecyltrimethylammonium chloride CTAC, and graduated cylinder measures 12 mL deionized waters and is configured to 12 mL
Hexadecyltrimethylammonium chloride CTAC（200 mM）Solution, with 0.288 g ascorbic acid of electronic balance weighing, graduated cylinder measures 10
ML deionized waters pour into the dissolving of 25 mL beakers.By the chlorauric acid solution of 12mL（0.5 mM）, the CTAC solution of 12 mL（200
mM）9 mL ascorbic acid（100 mM）It is uniformly mixed in 50 mL beakers, the gold kind of 0.6 mL is added to above-mentioned mix under stirring
It closes in solution, about 1 minute solution becomes red from colourless, this shows that the gold nanoparticle of bulky grain has been formed.1 it is small when
Afterwards, centrifugal purification product for several times, is finally distributed in the water of 2 mL.
The 1.2 cubical preparations of Au@Ag nucleocapsids
CTAC solution with 20 mM with 0.640 g hexadecyltrimethylammonium chloride CTAC of electronic balance weighing, is claimed with graduated cylinder
10 mL deionized waters are measured, pours into 25 mL beakers and mixes.The ascorbic acid of 0.144 g of electronic balance weighing, graduated cylinder measure 10
ML deionized waters, pour into beaker and mix.Golden nanometer particle dispersion liquid is added in 9 mL CTAC aqueous solutions, is added in magnetic force and is stirred
It mixes son to be vigorously stirred down, 60 DEG C of constant temperature were after 20 minutes in a water bath in constant temperature blender with magnetic force, with the speed of 0.2 mL/ minutes
1 mL silver nitrates are added in simultaneously（2 mM）Solution and 1 mL ascorbic acid（50 mM）With CTAC（40 mM）Mixed solution.It adds in
Silver concentration is 0.17 mM in solution after silver nitrate.During two kinds of solution are added in, reaction solution becomes brown color from red.Reaction 4
After hour, it is placed in ice-water bath and cools down, centrifugal purification product is distributed in the water of 2 mL afterwards for several times.
The preparation of growth in situ Au on 1.3 Ag shells
By freshly prepd 5 mL Au/Ag nano-solutions（Nano-particle or nanocube）It is diluted in the water of 5 mL, uses
0.126 g hydroxylamine hydrochlorides of electronic balance weighing measure 10 mL deionized waters with graduated cylinder, are mixed in 25 mL beakers.Afterwards in play
It is added with stirring the hydroxylamine hydrochloride of 0.1 mL（0.02 M）With 100 μ L gold chlorides（0.1%）, solution becomes red, then boils
Several minutes of postcoolings are to room temperature.
The preparation of 1.4 Au@AuPt nanometer nuclear shell nano-structures
The step is carried out by replacing reaction.With 0.040 g PVP of electronic balance weighing, with 0.364 g CTAB, graduated cylinder measures
10 mL deionized waters, mix in beaker.0.8 mL Au/Ag-Au core-shell structure copolymer nanocubes are distributed to 8 mL polyethylene pyrroles
Pyrrolidone（0.5%）And CTAB（0.1 M）Mixed solution in, solution is heated to 100 DEG C, added in after 2 minutes 140 μ L dilution
To the chloroplatinic acid of 10 mL（0.01%）, it is ensured that silver is replaced completely.Solution colour becomes purple.After being cooled to room temperature, centrifugation is pure
Change product to be distributed in water for several times.
The preparation of 1 Au@Pt nano-particles of comparative example
1.1 the same as implementation 1.1
1.2 the same as implementation 1.2
The preparation of 1.3 concave surface Au@Pt nanotubes
Pass through Au@Ag nucleocapsids cubes and K2PtCl6Electricity between aqueous solution replaces reaction to prepare Au@Pt nano-particles.
In typical method, 0.8 mL Au@Ag are dispersed in 8 mL PVP again（0.5wt%）And CTAB（0.1M）In solution.
Then, Au@Ag nucleocapsids cubes at 100 DEG C are heated 2 minutes, then adds in the 0.1%K of 20 μ L2PtCl6Solution.Mixing
The color of object becomes navy blue.By final product and 6 M HNO of same volume3It mixes to remove AgCl sediments and unreacted
Silver.Afterwards, centrifugation is passed through（10000 rpm, 10 minutes）Product is collected, is then washed twice with water.
Embodiment 2 prepares nucleocapsid physicochemical property characterization
2.1 form
In embodiment 1 in gold nanoparticle, Au@Ag core-shell structure copolymers nanocube, Au@AuPt core-shell structure copolymers nanostructureds and comparative example 1
In the transmission electron microscope picture such as Fig. 1 of Au Pt core-shell structure copolymer nano-particles（a）-（c）It is shown.As seen from the figure, gained Au@AuPt nucleocapsids are received
Rice structure is concave surface cube, and average grain diameter is 29 ± 4 nm.And gold nanoparticle, Au@Ag core-shell structure copolymers nanocube are in single point
Property is dissipated, average grain diameter is 10 ± 2 nm, the average grain diameter of Au@Pt core-shell structure copolymer nano-particles is 33 ± 3 nm.
2.2 UV-Vis spectra
By gold nanoparticle, Au@Ag core-shell structure copolymers nanocube, Au@AuPt core-shell structure copolymers nanostructureds and comparative example 1 in embodiment 1
Middle Au@Pt core-shell structure copolymers nano-particle carries out UV-Vis spectra scanning, and collection of illustrative plates is as shown in Figure 2.As shown in Figure 2, Jenner's grain of rice
The ultraviolet-ray visible absorbing peak of son exists respectively in 520 nm or so, Au@Ag core-shell structure copolymers nanocube there are two characteristic absorption peak
410 nm and 490 nm, Au@Au/Pt core-shell structure copolymer nanocubes it is ultraviolet-absworption peak can be added near 530 nm, gold/platinum
Nucleocapsid structure does not have ultraviolet-ray visible absorbing peak in 520 nm, is because gold nanoparticle is wrapped up completely by platinum, so as to gold nano
The ultraviolet-ray visible absorbing peak of particle disappears.
Embodiment 3 prepares catalytic effect of the nucleocapsid to alcohol fuel cell
3.1 chrono-amperometrics and Cyclic voltamogram
By Au@Pt core-shell structure copolymers in Au@Ag core-shell structure copolymers nanocube, Au@AuPt core-shell structure copolymers nanostructureds and comparative example 1 in embodiment 1
Nano-particle is detected chrono-amperometric and C-V characteristic.Testing conditions are：1.0 M sodium hydroxides and the mixing of 1.0 M ethyl alcohol are molten
Liquid mixes, scanning voltage -1V ~ 0.6V, sweeps speed as 50 mV/s.
The results are shown in Figure 3 for chrono-amperometric, illustrates that Au@AuPt core-shell structure copolymers nanocube has preferable catalytic performance,
There is higher stability.
The results are shown in Figure 4 for volt-ampere cyclic curve：The spike potential of Au@Pt core-shell structure copolymer nano-particles（About -0.3 V）Than gold
The spike potential of nano-particle（About 0.2 V）It is low, illustrate catalytic effect of the platinum shell enhancing to ethyl alcohol；Au@Au/Pt core-shell structure copolymer nanometers
Cubical oxidation peak illustrates it with better electrocatalysis characteristic than the oxidation peak higher of Au@Pt core-shell structure copolymer nanocubes.
Compared to other catalyst, Au@Au/Pt have lower spike potential and higher oxidation peak, and in flyback process, oxidation peak is bright
It is aobvious weaker, it is weak to illustrate that it poisons effect, better than other catalyst.Because silver-colored, Au@Ag oxygen bad to the catalytic effect of ethyl alcohol
Change peak reduction peak unobvious.
In order to more accurately react electrocatalysis characteristic, electro catalytic activity curve is normalized to electro-chemical activity face by us
Product, as a result as in Fig. 5（a）With（b）It is shown.During catalysis ethanol, Au@Au/Pt core-shell structure copolymer nanocubes are in electrochemistry
In the Cyclic voltamogram curve of surface-active area normalization（Fig. 5（a））, there is lower spike potential, illustrate it to ethyl alcohol
Catalysis there is better effect, and in flyback process, oxidation peak is substantially weaker, and it is weak to illustrate that it poisons effect.In electrochemistry table
In the normalized time current curve of face active area（Fig. 5（b））, Au@Au/Pt core-shell structure copolymer plasma nano cubes have
Higher electric current.This illustrate the cubical stability of Au@Au/Pt core-shell structure copolymer plasma nanos and activity all than Au@Pt cores-
The height of core/shell nanoparticles.
Claims (10)
1. a kind of Au@Au/Pt nuclear shell structured nano catalyst for alcohol fuel battery, which is characterized in that shape is in concave surface
Cube, size are 29 ± 4 nm；Inside is golden core, and outside is gold/platinum shell.
2. a kind of preparation method of Au@Au/Pt nuclear shell structured nano catalyst as described in claim 1, which is characterized in that
Comprise the following steps：
（1）The mixed solution of gold chloride, CTAB and sodium borohydride is added in the mixed solution containing CTAC, AA and gold chloride,
Stir to get red, transparent solution；
（2）By step（1）Solution centrifugation after precipitation 60 DEG C of stirring in water bath are mixed with CTAC, while add in silver nitrate, AA and
CTAC, solution become brown color；
（3）By step（2）Solution centrifugation after precipitation be added with stirring hydroxylamine hydrochloride and gold chloride after boil, solution becomes red
Color；
（4）By step（3）Solution be dispersed in CTAB and PVP（Polyvinylpyrrolidone）Mixed solution in, 100 DEG C heating,
Chloroplatinic acid is slowly added to, solution centrifuges after becoming purple, obtains Au Au/Pt nuclear shell structured nano catalyst.
3. preparation method according to claim 2, which is characterized in that step（1）In, gold chloride, CTAB and sodium borohydride
Molar ratio be 37:50000:5000；The molar ratio of gold chloride, CTAC and AA is 1:400:200.
4. preparation method according to claim 2, which is characterized in that step（2）In, mole of silver nitrate, AA and CTAC
Than for 1:25:20.
5. preparation method according to claim 2, which is characterized in that step（4）In, the molar ratio of PVP and CTAB are 9:
3125, the wherein mole of PVP presses the molar amount of its polymerized monomer.
6. preparation method according to claim 2, which is characterized in that step（1）Gold chloride, CTAB and sodium borohydride mixing
When preservation 3 is small at 27 DEG C afterwards.
7. preparation method according to claim 2, which is characterized in that step（1）Gained red, transparent solution with
15000rpm centrifuges 20min, and washing of precipitate once, is used for the next step after dissolving.
8. preparation method according to claim 2, which is characterized in that step（2）In 60 DEG C of water when solution becomes brown color
After bath stirring 3h, 15000rpm centrifugation 15min, washing of precipitate once, is used for the next step after dissolving.
9. preparation method according to claim 2, which is characterized in that step（4）Gained purple solution 10000rmp is centrifuged
10min, washing of precipitate twice, obtain Au@Au/Pt nuclear shell structured nano catalyst.
10. a kind of Au@Au/Pt nuclear shell structured nanos catalyst as described in claim 1 is in methanol or alcohol fuel cell
Application.
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| CN111347059A (en) * | 2020-03-30 | 2020-06-30 | 江南大学 | Synthesis method of porous gold @ silver @ gold nanocubes |
| CN111889696A (en) * | 2020-07-28 | 2020-11-06 | 无锡英特派金属制品有限公司 | Method for producing noble metal powder |
| CN113231643A (en) * | 2021-05-06 | 2021-08-10 | 中南大学 | Biomedical noble metal frame material and preparation method and application thereof |
| CN114361477A (en) * | 2021-12-17 | 2022-04-15 | 上海电力大学 | PdPb @ Pt cubic electrocatalyst and preparation method and application thereof |
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| CN103055895A (en) * | 2013-01-15 | 2013-04-24 | 山东大学 | Method for preparing core-shell type nano-porous platinum alloy catalyst |
| CN103600090A (en) * | 2013-12-10 | 2014-02-26 | 天津商业大学 | Au@AuPt alloy nanoparticles and preparation method of colloidal dispersion system |
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| CN103055895A (en) * | 2013-01-15 | 2013-04-24 | 山东大学 | Method for preparing core-shell type nano-porous platinum alloy catalyst |
| CN103600090A (en) * | 2013-12-10 | 2014-02-26 | 天津商业大学 | Au@AuPt alloy nanoparticles and preparation method of colloidal dispersion system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110202163A (en) * | 2019-05-21 | 2019-09-06 | 山东理工大学 | A kind of preparation method of Ag@Au@Pd nano cubic hollow shell structure |
| CN110202163B (en) * | 2019-05-21 | 2023-03-21 | 山东理工大学 | Preparation method of Ag @ Au @ Pd nano cubic hollow shell structure |
| CN111347059A (en) * | 2020-03-30 | 2020-06-30 | 江南大学 | Synthesis method of porous gold @ silver @ gold nanocubes |
| CN111347059B (en) * | 2020-03-30 | 2023-03-17 | 江南大学 | Synthetic method of porous gold @ silver @ gold nanocubes |
| CN111889696A (en) * | 2020-07-28 | 2020-11-06 | 无锡英特派金属制品有限公司 | Method for producing noble metal powder |
| CN113231643A (en) * | 2021-05-06 | 2021-08-10 | 中南大学 | Biomedical noble metal frame material and preparation method and application thereof |
| CN113231643B (en) * | 2021-05-06 | 2022-09-13 | 中南大学 | Biomedical precious metal frame material and preparation method and application thereof |
| CN114361477A (en) * | 2021-12-17 | 2022-04-15 | 上海电力大学 | PdPb @ Pt cubic electrocatalyst and preparation method and application thereof |
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