CN108832139A - A kind of preparation method and application of fuel cell core-shell structure Cu@Pd nanometer electrical catalyst - Google Patents
A kind of preparation method and application of fuel cell core-shell structure Cu@Pd nanometer electrical catalyst Download PDFInfo
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- CN108832139A CN108832139A CN201810603464.XA CN201810603464A CN108832139A CN 108832139 A CN108832139 A CN 108832139A CN 201810603464 A CN201810603464 A CN 201810603464A CN 108832139 A CN108832139 A CN 108832139A
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- ethylene glycol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000000446 fuel Substances 0.000 title claims abstract description 46
- 239000011258 core-shell material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 93
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 6
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 239000010970 precious metal Substances 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract 3
- 239000011591 potassium Substances 0.000 claims abstract 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract 2
- 235000019441 ethanol Nutrition 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229960004756 ethanol Drugs 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- -1 ultrasonic disperse Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 101100116420 Aedes aegypti DEFC gene Proteins 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The present invention provides a kind of fuel cell core-shell structure Cu@Pd nanometer electrical catalyst, the fuel cell is with Cu@Pd nanometer electrical catalyst using transition metal Cu as nucleus, precious metals pd is shell, the binary core-shell structure Cu@Pd nanometer electrical catalyst with regular tetrakaidecahedron structure.Preparation method is that Cu crystal seed is transferred in cetyl trimethyl sal-ammoniac and the mixed aqueous solution of potassium bromide, and the ethylene glycol solution of potassium chloropalladite is instilled into mixed liquor；The ethylene glycol solution of sodium hydroxide is instilled into mixed liquor, is reacted 8-12 hours at a temperature of 120-200 DEG C and is obtained fuel cell Cu Pd elctro-catalyst.The system uses CTAC & KBr as pattern controlling agent, and the Cu@Pd catalyst size prepared is uniform, and pattern is the regular tetrakaidecahedron.Prepared catalyst has excellent electrocatalytic oxidation alcohol performance, there is biggish application and development prospect in Direct Ethanol Fuel Cell.
Description
Technical field
The invention belongs to field of fuel cell technology, are related to the preparation method of catalyst, more particularly, to a kind of direct ethyl alcohol
The preparation method of fuel cell core-shell structure Cu@Pd elctro-catalyst.
Background technique
Fuel cell (FC) is the forth generation generation technology after thermoelectricity, water power and nuclear power, is a kind of by fuel
In chemical energy be converted directly into the device of electric energy, this energy conversion regime is not limited by Carnot cycle, emission cleaning
It is pollution-free, it is a kind of new energy technology of high-efficiency environment friendly.Direct Ethanol Fuel Cell (DEFCs) belongs to low-temperature fuel cell
One kind will be better than traditional hydrogen-oxygen fuel electricity in storage, transport, safety and cost since fuel is liquid ethanol
Pond.Direct Ethanol Fuel Cell system has the characteristics that structure is simple, starting is rapid, fuel easily supplements and theoretical specific energy is high.
Oxidation of ethanol in alkaline system, Pd based nano-material possess the electrocatalysis characteristic for the Pt sill that matches in excellence or beauty, and are great potentials
Pt substitute.
Summary of the invention
While it is an object of the invention to reduce precious metals pd dosage, pass through structure control and pattern tune appropriate
Control, prepares a kind of with the excellent active fuel cell Cu@Pd elctro-catalyst of alcohol catalysis.
The present invention realizes that technical solution used by above-mentioned purpose is as follows：
(1) it weighs cetyl trimethyl sal-ammoniac (CTAC) and potassium bromide (KBr) is dissolved in secondary distilled water, surpass
Sound dispersion, oil bath pan are heated to 50-70 DEG C, and stirring is passed through N2, anhydrous cupric chloride (CuCl is added dropwise2) ethylene glycol solution (this
Place is passed through N2Inert atmosphere is created, in case Cu is in reduction process by the O in system2Oxidation, generate Cu oxide)；To mixing
The ethylene glycol solution of sodium hydroxide (NaOH), adjustment pH value of solution to 9.5 ~ 10 are instilled in liquid, sealing is heated to 100-120 DEG C,
Remove N2 (N is removed herein2, it is to no longer need to logical N because system has sealed and be in inert atmosphere2), insulation reaction 1 ~ 2 is small
When, cooled to room temperature under 8000 ~ 10000 rrm/min, distinguishes centrifuge washing 2-3 with secondary distilled water and dehydrated alcohol
Secondary, gained Cu crystal seed vacuum drying is sealed.The concentration of CTAC is 10-15mg/ml in mixed liquor, and the concentration of KBr is 3-5
Mg/ml, CuCl2The ethylene glycol solution concentration of ethylene glycol solution concentration is 1.3 ~ 1.5 mg/ml, the ethylene glycol solution concentration of NaOH
For 4 mg/ml.
(2) a certain amount of Cu crystal seed, CTAC & KBr are weighed, distilled water ultrasonic dissolution is added；To mixed after 60 DEG C of stirring 30min
It closes in liquid and K is added dropwise2PdCl4Ethylene glycol solution, the final ethylene glycol solution for instilling NaOH.The concentration of CTAC is in mixed liquor
1 mg/ml of concentration of 2.67 mg/ml, KBr, Cu seed concentration are 0.01 ~ 0.03 mg/ml, K2PdCl4Concentration is 0.3 ~ 0.4
Mg/ml, NaOH concentration are 4 mg/ml.
(3) uniformly mixed reaction solution is transferred in ptfe autoclave liner, screws, is placed on after sealing
In air dry oven, reacted 8-14 hours at 120-200 DEG C.
(4) cooled to room temperature is centrifugated under the rpm/min of 5000 rpm/min ~ 12000, secondary distilled water and
Dehydrated alcohol is distinguished centrifuge washing three to five times, and final products therefrom is redissolved in dehydrated alcohol distributed and saved and obtains fuel
Battery Cu@Pd elctro-catalyst.
In step (1), secondary distilled water and ethylene glycol function simultaneously as solvent, and wherein ethylene glycol serves as reducing agent, CTAC &
KBr serves as pattern controlling agent, and KBr can be replaced with KI in the present invention, and CTAC & KBr can use cetyl trimethylammonium bromide
(CTAB) it replaces,.
In step (2), the mixeding liquid volume in ptfe autoclave liner is 10-30 ml.
In step (3), during centrifuge washing, first uses second distillation water washing 2-3 times, then wash 3- with dehydrated alcohol
4 times, it is ensured that the complete reactant of unreacted is removed from catalyst surface.
Fuel cell Cu@Pd elctro-catalyst regular appearance is the typical tetrakaidecahedron, size uniformity, average grain
Diameter is in 10-30 nm.
Fuel cell Cu@Pd elctro-catalyst electrochemical surface area (ECSA) is 25-60 m2/gPd。
The fuel cell is 15%-65% with hundred content of quality of Pd in Cu@Pd elctro-catalyst.
The fuel cell has core-shell structure feature with Cu@Pd elctro-catalyst, and the rich surface Pd greatly reduces in body phase
The dosage of noble metal.
A kind of fuel cell according to the present invention has following distinguishing feature with Cu@Pd elctro-catalyst and preparation method thereof：
(1) preparation method is divided into two steps, and the first step synthesizes transition metal Cu core, and second step synthesizes precious metals pd shell.
(2) ethylene glycol functions simultaneously as solvent and reducing agent, low in cost, green non-pollution.
(3) system uses CTAC & KBr as pattern controlling agent, and the Cu@Pd catalyst size prepared is uniform, pattern
For the regular tetrakaidecahedron.
(4) catalyst prepared by has excellent electrocatalytic oxidation alcohol performance, has in Direct Ethanol Fuel Cell
Biggish application and development prospect.
It, can be while not losing electrocatalysis characteristic into one by preparing core-shell structure Cu@Pd elctro-catalyst in the present invention
Step reduces the dosage of precious metals pd, effectively improves the utilization rate of Pd atom.Precious metals pd is to reduce to urge with non-noble metal combine
A kind of effective means of Pd dosage in agent, and the particularity of core-shell structure is that the ess-strain between xenogenesis element is imitated
It answers, and this effect can be by changing the regulation of predecessor ratio.Since catalysis reaction mainly carries out on surface, preparation tool
There is the catalyst energy significant increase of core-shell structure and special shape to be catalyzed reaction efficiency.It is with transition metal Cu in the present invention
Core, with hydrothermal synthesis technology, ethylene glycol and secondary distilled water serve as solvent, and wherein ethylene glycol serves as reducing agent, CTAC & KBr
Pattern controlling agent is served as, prepares that particle size is uniform, with tetrakaidecahedron feature and Cu@Pd that oxidation of ethanol is had excellent performance is urged
Agent.
Detailed description of the invention
Fig. 1：For the transmission electron microscope picture of Cu@Pd elctro-catalyst of fuel cell prepared by embodiment 1.
Fig. 2：For the cyclic voltammetric of Cu@Pd elctro-catalyst electrocatalytic oxidation ethyl alcohol of fuel cell prepared by embodiment 1
Curve graph.
Fig. 3：For the transmission electron microscope picture of Cu@Pd elctro-catalyst of fuel cell prepared by embodiment 2.
Fig. 4：For the cyclic voltammetric of Cu@Pd elctro-catalyst electrocatalytic oxidation ethyl alcohol of fuel cell prepared by embodiment 2
Curve graph.
Fig. 5：For the Cu@Pd elctro-catalyst of fuel cell prepared by embodiment 1,2 and business Pd black appliances catalysis oxidation second
The cyclic voltammetry curve figure of alcohol.
Fig. 6：For the Cu@Pd elctro-catalyst of fuel cell prepared by embodiment 1,2 and business Pd black appliances catalysis oxidation second
The activity comparison column diagram of alcohol.
Specific embodiment
Below with reference to attached drawing and specific implementation case, the present invention is further explained, herein it is to be understood that, these realities
Case is applied to be merely to illustrate the present invention rather than be used to limit the scope of the invention, after the present invention has been read, this field skill
Art personnel fall within the application range as defined in the appended claims to the modification of various equivalent forms.
Embodiment 1
(1) 384mg CTAC is weighed in 50ml round bottom aryballos, and 15ml secondary distilled water ultrasonic dissolution is added；To mixed liquor
Middle addition CuCl2Ethylene glycol solution (40.335mg CuCl2It is dissolved in 5ml ethylene glycol), oil bath pan is transferred to after ultrasound is molten
In, it is passed through N2, constant temperature stirs 30min at 60 DEG C；(96mg NaOH is dissolved in 10ml second two to the ethylene glycol solution of instillation NaOH
In alcohol) after, 110 DEG C are heated to, N is removed2, insulation reaction 1 ~ 2 hour, cooled to room temperature, with secondary distilled water and anhydrous
Ethyl alcohol is under the revolving speed of 10000 rpm/min, and centrifuge washing 2-3 times respectively, gained Cu crystal seed vacuum drying is sealed.
(2) 0.4mg Cu crystal seed is weighed, 12ml bis- times steamings are added in 50ml aryballos in 96mg CTAC and 24mg KBr
Distilled water ultrasonic dissolution；Ethylene glycol solution (the 96mg of NaOH is successively added dropwise into mixed liquor after 60 DEG C of constant temperature stir 30min
NaOH is dissolved in 10ml ethylene glycol) and K2PdCl4Ethylene glycol solution (8.16mg K2PdCl4It is dissolved in 2ml ethylene glycol
In), it stirs evenly completely.
(3) mixed solution is transferred in 30mL ptfe autoclave liner, screwing hermetic reaction kettle is placed in drum
In wind drying box, reacted 10 hours at 180 DEG C.
(4) cooled to room temperature keeps standing, the black precipitate obtained after reaction is carried out at 10000 r/min
Centrifuge separation is first used second distillation water washing 3 times, then with dehydrated alcohol 3 times, and last products therefrom is added dehydrated alcohol dispersion and protects
Shield obtains fuel cell Cu Pd elctro-catalyst.
Fig. 1 is the transmitted electron figure of the present embodiment preparation-obtained fuel cell Cu@Pd elctro-catalyst（TEM）, by
1a can be seen that prepared nanoparticle and possess plane hexagonal structure in figure, while have partial phantom in Fig. 1 a, this is not
Isolated nanoparticle accumulates the blocked up difficulty that penetrates for causing electronics, forms blackspot.Fig. 1 b is single hexagon nano particle
Amplify figure, surface there are apparent 4 ribs, 2 trigonums and 2 rhomboids are divided into surface, is the apparent tetrakaidecahedron
Structure.
The present embodiment is prepared resulting Cu Pd elctro-catalyst to carry out modifying obtained working electrode on glass-carbon electrode, is repaired
The content of electrode surface Pd is about 0.05mg after decorations, and (ECSA is 52 m to electrochemical surface area2/gPd), it is recycled
Volt-ampere test, test condition：Scanning range is -0.8-0.2 V (vs. SCE), and scanning speed is 50 mV/s, and solution is nitrogen
1 mol/L KOH+1 mol/LC of saturation2H5OH solution, test result is as shown in Fig. 2.
As seen from Figure 2, there is maximum ethyl alcohol oxygen under the current potential of -0.1 V in preparation-obtained Cu@Pd elctro-catalyst
Change peak current density, about 529.66 mA/mgPd -1, show optimal electrocatalytic oxidation ethyl alcohol activity.
Embodiment 2
(1) 384mg CTAC is weighed in 50ml round bottom aryballos, and 15ml secondary distilled water ultrasonic dissolution is added；To mixed liquor
Middle addition CuCl2Ethylene glycol solution (40.335mg CuCl2It is dissolved in 5ml ethylene glycol), oil bath pan is transferred to after ultrasound is molten
In, it is passed through N2, constant temperature stirs 30min at 60 DEG C；(96mg NaOH is dissolved in 10ml second two to the ethylene glycol solution of instillation NaOH
In alcohol) after, 110 DEG C are heated to, N is removed2, insulation reaction 1 ~ 2 hour, cooled to room temperature, with secondary distilled water and anhydrous
Ethyl alcohol is under the revolving speed of 10000 rpm/min, and centrifuge washing 2-3 times respectively, gained Cu crystal seed vacuum drying is sealed.
(2) 0.4mg Cu crystal seed is weighed, it is molten that 12ml secondary distilled water ultrasound is added in 50ml aryballos in 96mg CTAC
Solution；The ethylene glycol solution of NaOH is successively added dropwise into mixed liquor after 60 DEG C of constant temperature stir 30min, and (96mg NaOH is dissolved in
In 10ml ethylene glycol) and K2PdCl4Ethylene glycol solution (8.16mg K2PdCl4It is dissolved in 2ml ethylene glycol), it stirs completely
Uniformly.
(3) cooled to room temperature, keep stand, by the black precipitate obtained after reaction at 10000 r/min into
Row centrifuge separation, is first used second distillation water washing 3 times, then with dehydrated alcohol 3 times, and dehydrated alcohol dispersion is added in last products therefrom
Protection obtains fuel cell Cu Pd elctro-catalyst.
Fig. 2 is the transmitted electron figure of the present embodiment preparation-obtained fuel cell Cu@Pd elctro-catalyst（TEM）, by
For figure as can be seen that under the conditions of prepared nanoparticle is existing for no KBr, crystal boundary profile is obvious, it is basic present it is random
It is spherical.
The present embodiment is prepared resulting Cu Pd elctro-catalyst to carry out modifying obtained working electrode on glass-carbon electrode, is repaired
The content of electrode surface Pd is about 0.05mg after decorations, and (ECSA is 52 m to electrochemical surface area2/gPd), it is recycled
Volt-ampere test, test condition：Scanning range is -0.8-0.2 V (vs. SCE), and scanning speed is 50 mV/s, and solution is nitrogen
1 mol/L KOH+1 mol/LC of saturation2H5OH solution, test result is as shown in Fig. 2.
As seen from Figure 2, there is maximum ethyl alcohol under the current potential of -0.13 V in preparation-obtained Cu@Pd elctro-catalyst
Oxidation peak current density, about 393.44 mA/mgPd -1, show preferable electrocatalytic oxidation ethyl alcohol activity.
Fig. 5 is fuel cell Cu@Pd elctro-catalyst and the black catalyst electrocatalytic oxidation of business Pd prepared by embodiment 1,2
Change the cyclic voltammetry curve figure of ethyl alcohol,
Fig. 6 is fuel cell Cu@Pd elctro-catalyst and the black Catalysts for Electrocatalytic Oxidation second of business Pd prepared by embodiment 1,2
The activity comparison column diagram of alcohol, listed is respectively the current density value under respective spike potential, can be more intuitive from figure
The electrocatalytic oxidation ethyl alcohol activity of embodiment 1,2 is better than that business Pd is black out, and wherein the alcohol catalysis mass activity of embodiment 1 is most
Height, about the 1.34 of embodiment 2 times are black 1.67 times of business Pd；The alcohol catalysis specific activity highest of embodiment 2, about in fact
1.37 times for applying example 1 are black 1.84 times of business Pd.
Claims (8)
1. a kind of fuel cell core-shell structure Cu@Pd nanometer electrical catalyst, which is characterized in that the fuel electricity
With Cu@Pd nanometer electrical catalyst using transition metal Cu as nucleus, precious metals pd is shell in pond, has regular tetrakaidecahedron knot
The binary core-shell structure Cu@Pd nanometer electrical catalyst of structure.
2. fuel cell described in claim 1 core-shell structure Cu@Pd nanometer electrical catalyst, which is characterized in that
The core-shell structure Cu@Pd nanometer electrical catalyst average grain diameter is 10 ~ 50nm, and electrochemical surface area is 25 ~ 60m2/gPd, the mass percentage that the mass percentage of Pd is 15% ~ 65%, Cu is 85% ~ 35%.
3. the fuel cell described in claim 1 preparation method of Cu@Pd elctro-catalyst, which is characterized in that specific steps are such as
Under：
（1）It weighs cetyl trimethyl sal-ammoniac and potassium bromide is dissolved in secondary distilled water, ultrasonic disperse, oil bath pan heating
To 50-70 DEG C, stirring is passed through N2, the ethylene glycol solution of anhydrous cupric chloride is added dropwise；The second two of sodium hydroxide is instilled into mixed liquor
Alcoholic solution, adjustment pH value of solution to 9.5 ~ 10, sealing are heated to 100-120 DEG C, remove N2, insulation reaction 1 ~ 2 hour, naturally cold
But to room temperature, under 8000 ~ 10000 rrm/min, distinguished centrifuge washing 2-3 times with secondary distilled water and dehydrated alcohol, gained Cu
Crystal seed vacuum drying is sealed；
（2）Cu crystal seed is taken, is transferred in cetyl trimethyl sal-ammoniac and the mixed aqueous solution of potassium bromide, is dripped into mixed liquor
Enter the ethylene glycol solution of potassium chloropalladite；The ethylene glycol solution of instillation sodium hydroxide into mixed liquor, adjustment pH value of solution to 9.5 ~
10, by mixed solution fast transfer into ptfe autoclave liner, after sealing, it is placed in air dry oven, 120-200
It is reacted 8-12 hours at a temperature of DEG C；
（3）Cooled to room temperature under 8000 ~ 10000 rpm/min, distinguishes centrifuge washing with secondary distilled water and dehydrated alcohol
2-3 times to get arrive fuel cell Cu@Pd elctro-catalyst.
4. the preparation method of fuel cell Cu@Pd elctro-catalyst according to claim 3, which is characterized in that step（1）
In, the concentration of cetyl trimethyl sal-ammoniac is 10-15mg/ml, and the concentration of potassium bromide is 3-5 mg/ml, CuCl2Second two
Alcoholic solution concentration is 1.3 ~ 1.5 mg/ml, and the ethylene glycol solution concentration of NaOH is 3-5 mg/ml.
5. the preparation method of fuel cell Cu@Pd elctro-catalyst according to claim 3, which is characterized in that step（2）
In, the concentration of cetyl trimethyl sal-ammoniac is 2.67 mg/ml, 1 mg/ml of concentration of KBr, Cu seed concentration is 0.01 ~
0.03 mg/ml, the ethylene glycol solution concentration of potassium chloropalladite are 0.3 ~ 0.4 mg/ml, and NaOH ethylene glycol solution concentration is 3-5
mg/ml。
6. the preparation method of fuel cell Cu@Pd elctro-catalyst according to claim 4, which is characterized in that step（1）With
（2）Middle KBr replaces with KI；Hexadecyltrimethylammonium chloride and potassium bromide replace with cetyl trimethylammonium bromide.
7. the preparation method of fuel cell Cu@Pd elctro-catalyst according to claim 4, which is characterized in that step (2)
In, mixed liquor volume accounts for ptfe autoclave liner 3/5-4/5.
8. application of the described in any item fuel cells of claim 1-7 with Cu@Pd elctro-catalyst on electrocatalytic oxidation ethyl alcohol.
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