CN106207205B - A kind of fuel cell PtPd elctro-catalysts and preparation method thereof - Google Patents
A kind of fuel cell PtPd elctro-catalysts and preparation method thereof Download PDFInfo
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- CN106207205B CN106207205B CN201610521094.6A CN201610521094A CN106207205B CN 106207205 B CN106207205 B CN 106207205B CN 201610521094 A CN201610521094 A CN 201610521094A CN 106207205 B CN106207205 B CN 106207205B
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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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- 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 present invention relates to a kind of fuel cell PtPd elctro-catalysts and preparation method thereof.This method comprises the following steps：Take triblock copolymer P123 to be dissolved in redistilled water, stir, K is added dropwise into P123 solution at 30 120 DEG C in control temperature2PdCl4Solution, after being added dropwise to complete, is added dropwise K2PtCl6Solution, the h of stirring reaction 26, by reacted black suspension centrifugation, washing three to five times after i.e. obtain fuel cell PtPd elctro-catalysts.Triblock copolymer P123 serves as protective agent, while can effectively reduce K using it2PdCl4But K can not be reduced2PtCl6Reaction selectivity, reduce obtained Pd and K2PtCl6Can occur current potential displacement reaction, resulting PtPd elctro-catalysts possess strange hollow network structure, and possess excellent Electrocatalytic Oxidation of Methanol performance, are a kind of fuel-cell catalysts of great development prospect.
Description
Technical field
The invention belongs to field of fuel cell technology, it is related to the preparation method of catalyst, more particularly, to a kind of fuel
The preparation method of battery PtPd elctro-catalysts.
Background technology
The energy and environment are the focuses of research and development in current world wide.Fuel battery energy is directly by the chemistry of fuel
Electric energy can be converted into, is not limited by Carnot cycle, efficient pollution-free is one of direction that current fungible energy source is given priority to.
Direct alcohol fuel cell possesses (DAFC) low raw-material cost, wide material sources, and it is excellent that cryogenic property is good, energy density is high etc.
Point is most possible at present applied to the power source of electric vehicle, distributed power station and Portable movable power supply.In fuel
During battery research and development, catalyst is one of bottleneck that its most key and wait breaks through, in direct Aalcohols fuel electricity
Chi Zhong, Pt based nano-material are the catalyst that Proton Exchange Membrane Fuel Cells is difficult to substitute, but because Pt belongs to noble metal, reserves
Low, cost is high, seriously constrains the commercialization process of fuel cell.How to be effectively improved while precious metals pt consumption is reduced
The electro catalytic activity of catalyst turns into the focus of current research with its anti-poisoning capability is strengthened.
Due to electronic effect and difunctional mechanism, non-Pt metals and Pt formation intermetallic compounds or alloy energy pole are introduced
The earth promotes catalytic performance.It is also the weight for lifting catalyst efficiency to prepare catalyst that is homogeneous, regular and having special appearance
Want method.Some special structures（Core shell structure, hollow-core construction, reticulated porous structures etc.）The ratio of catalyst can greatly be increased
Surface area, so as to improve catalytic activity.
The content of the invention
It is an object of the invention to reduce while catalyst noble metal consumption, by controlling synthetic mesh hollow-core construction,
A kind of fuel cell for having higher catalytic activity PtPd elctro-catalysts are provided.
The present invention realizes that the technical scheme that above-mentioned purpose is used is as follows：
A kind of fuel cell replaces reactive synthesis technique with the preparation of PtPd elctro-catalysts using current potential, by introducing itself
Catalytic activity is excellent and price be only Pt 1/3rd metal Pd, utilize the protectiveness and preferably of triblock copolymer P123
Reaction selectivity, control synthesis obtains possessing strange hollow network structure and possesses excellent Electrocatalytic Oxidation of Methanol performance
PtPd catalyst.This method comprises the following steps：
(1) take triblock copolymer P123 ultrasonic dissolution in redistilled water, transfer them to three-necked bottle and be placed in band
Have and stirred on the magnetic stirring apparatus of temperature controller, control temperature is at 30 DEG C.
(2) K is slowly added to dropwise into P123 solution2PdCl4Solution, after being added dropwise to complete, immediately continues with dropwise addition K2PtCl6
Solution, magnetic agitation reaction 2h.
(3) reacted black suspension is centrifuged under the r/min of 5000 r/min ~ 11000, with water and anhydrous
Ethanol is washed three to five times, you can obtain fuel cell PtPd elctro-catalysts.
In step (1), triblock copolymer P123 is simultaneously as protective agent and reducing agent, present invention discover that similar three block
Copolymer F127, P103 and F108 are likewise supplied with above-mentioned effect.
In step (2), metal front liquid solution is slowly added to dropwise with constant pressure funnel, and drop speed control is in 5-10 s/ drops.
In step (3), in centrifugal separation processes, first with second distillation water washing 1-2 times, then 3- is washed with absolute ethyl alcohol
4 times, it is ensured that the complete triblock copolymer P123 of unreacted is removed from catalyst surface.
With PtPd elctro-catalysts dispersiveness preferably, average grain diameter is in 2 nm-10 nm for the fuel cell.
The fuel cell is 2-30 cm with PtPd elctro-catalyst electrochemical surface areas2。
The fuel cell is 1 with the atomic ratio of Pt, Pd in PtPd elctro-catalysts：1.
The fuel cell with PtPd elctro-catalysts triblock copolymer P123 protectiveness and preferable reaction selectivity
In the presence of, replaced and reacted by current potential, can the webbed hollow-core construction of shape.
A kind of fuel cell involved in the present invention has following outstanding feature with PtPd elctro-catalysts and preparation method thereof：
(1) preparation method is common aqueous phase reactions, and generated time is short, easy, efficient, quick.
(2) triblock copolymer P123 is green non-poisonous simultaneously as protective agent and the reducing agent for possessing high reaction selectivity
It is pollution-free.
(3) the characteristics of current potential displacement reaction is in metal nano material preparation and advantage, the PtPd prepared are made full use of
Catalyst is netted hollow-core construction intermetallic compound.
(4) catalyst prepared by possesses excellent Electrocatalytic Oxidation of Methanol performance, has in direct alcohol fuel cell
Larger application and development prospect.
Brief description of the drawings
Fig. 1：For transmission electron microscope picture of the fuel cell prepared by embodiment 1 with PtPd-1 elctro-catalysts.
Fig. 2：For transmission electron microscope picture of the fuel cell prepared by embodiment 2 with PtPd-2 elctro-catalysts.
Fig. 3：For transmission electron microscope picture of the fuel cell prepared by embodiment 3 with PtPd-100 elctro-catalysts.
Fig. 4：Fuel cell PtPd elctro-catalysts and commercialization Pt/C (JM) catalyst prepared for embodiment 1,2,3
The cyclic voltammetric comparison diagram of catalysis oxidation methanol.
Fig. 5：Fuel cell PtPd elctro-catalysts and Pt, Pd standard card (JCPDS) prepared for embodiment 1,2,3
X-ray diffraction (XRD) figure.
Embodiment
Below in conjunction with the accompanying drawings with specific implementation case, the present invention is expanded on further, it should be understood that these embodiments are only used for
The bright present invention rather than limitation the scope of the present invention, after the present invention has been read, those skilled in the art are to the present invention's
The modification of the various equivalent form of values falls within the application appended claims limited range.
Embodiment 1
(1) take 1.0 g triblock copolymer P123s to stir ultrasonic dissolution in 30 mL redistilled waters, transfer them to
It is placed in stirring on the magnetic stirring apparatus with temperature controller in three-necked bottle, control temperature is at 30 DEG C.
(2) 10 mL K are slowly added to dropwise into P123 solution2PdCl4Solution (0.02mmol/ L), is added dropwise to complete
Afterwards, 10 mL K of dropwise addition are immediately continued with2PtCl6Solution (0.02mmol/ L), magnetic agitation reaction 2h.
(3) room temperature is naturally cooled to, the black suspension obtained after reaction is centrifuged under 10000 r/min, first
Washed 3 times with second distillation water washing 2 times, then with absolute ethyl alcohol, the product after washes clean is finally added into absolute ethyl alcohol point
Dissipate protection and obtain fuel cell PtPd-1 elctro-catalysts.
Fig. 1 show transmission electron microscope (TEM) figure that the present embodiment prepares gained fuel cell PtPd-1 elctro-catalysts,
By Fig. 1 a, it is well dispersed that b can be seen that the elctro-catalyst obtained by preparing, and is that network structure its average grain diameter is 4.8 nm, by
Square constituency enlarged drawing understands that gained PtPd-1 elctro-catalysts are hollow-core construction in Fig. 1 c, and Fig. 1 d are high resolution electron microscopy figure, measurement
Its spacing of lattice obtains the nm of d=0.23, correspondence PtPd-1 (111) crystal face.
By the present embodiment prepare obtained by PtPd-1 elctro-catalysts modified on glass-carbon electrode be made working electrode, its electrification
Learn active area and be measured as 19.7cm-2, to its nitrogen saturation 0.1 mol/L H2SO4+0.1 mol/LCH3OH solution is carried out
Cyclic voltammetry, test condition：Scanning range is -0.2-1.0 V (vs SCE), and sweep speed is 50 mV/s, test knot
Fruit is as shown in Fig. 4.
As seen from Figure 4, there is maximum methanol under 0.58 V current potential in preparation-obtained PtPd-1 elctro-catalysts
Oxidation peak current density, about 347 mA/mgPt, show higher Electrocatalytic Oxidation of Methanol activity.
Embodiment 2
(1) take 1.0 g triblock copolymer P123s to stir ultrasonic dissolution in 30 mL redistilled waters, transfer them to
It is placed in stirring on the magnetic stirring apparatus with temperature controller in three-necked bottle, control temperature is at 30 DEG C.
(2) 10 mL K are slowly added to dropwise into P123 solution2PdCl4(0.02mmol/ L) and 10 mL K2PtCl6
The mixed solution of solution (0.02mmol/ L), magnetic agitation reaction 2h.
(3) room temperature is naturally cooled to, the black suspension obtained after reaction is centrifuged under 10000 r/min, first
Washed 3 times with second distillation water washing 2 times, then with absolute ethyl alcohol, the product after washes clean is finally added into absolute ethyl alcohol point
Dissipate protection and obtain fuel cell PtPd-2 elctro-catalysts.
Fig. 2 show transmission electron microscope (TEM) figure that the present embodiment prepares gained fuel cell PtPd-2 elctro-catalysts,
Elctro-catalyst obtained by being prepared it can be seen from Fig. 2 a has slight reunion, and its average grain diameter is 7.8 nm, by particle enlarged drawing
It is hollow-core construction to understand gained PtPd elctro-catalysts, and Fig. 2 b are high resolution electron microscopy figure, measures its spacing of lattice and obtains the nm of d=0.23,
Correspondence PtPd-2 (111) crystal face.
By the present embodiment prepare obtained by PtPd-2 elctro-catalysts modified on glass-carbon electrode be made working electrode, its electrification
Learn active area and be measured as 21.1 cm-2, to its nitrogen saturation 0.1 mol/L H2SO4+0.1 mol/LCH3OH solution enters
Row cyclic voltammetry, test condition：Scanning range is -0.2-1.0 V (vs SCE), and sweep speed is 50 mV/s, test
As a result as shown in Fig. 4.
As seen from Figure 4, there is maximum methanol under 0.57 V current potential in preparation-obtained PtPd-2 elctro-catalysts
Oxidation peak current density, about 217 mA/mgPt。
Embodiment 3
(1) take 1.0 g triblock copolymer P123s to stir ultrasonic dissolution in 30 mL redistilled waters, transfer them to
It is placed in stirring on the magnetic stirring apparatus with temperature controller in three-necked bottle, control temperature is at 100 DEG C.
(2) 10 mL K are slowly added to dropwise into P123 solution2PdCl4(0.02mmol/ L) and 10 mL K2PtCl6
The mixed solution of solution (0.02mmol/ L), magnetic agitation reaction 2h.
(3) room temperature is naturally cooled to, the black suspension obtained after reaction is centrifuged under 10000 r/min, first
Washed 3 times with second distillation water washing 2 times, then with absolute ethyl alcohol, the product after washes clean is finally added into absolute ethyl alcohol point
Dissipate protection and obtain fuel cell PtPd-100 elctro-catalysts.
Fig. 3 show the transmission electron microscope (TEM) that the present embodiment prepares gained fuel cell PtPd-100 elctro-catalysts
Figure, the elctro-catalyst favorable dispersibility it can be seen from Fig. 3 a obtained by preparation, size is homogeneous, and its average grain diameter is 3.4 nm,
Fig. 3 b are high resolution electron microscopy figure, measure its spacing of lattice and obtain the nm of d=0.23, correspondence PtPd-100 (111) crystal face.
By the present embodiment prepare obtained by PtPd-100 elctro-catalysts modified on glass-carbon electrode be made working electrode, its electricity
Chemism area is measured as 5.3 cm-2, to its nitrogen saturation 0.1 mol/L H2SO4+0.1 mol/LCH3OH solution enters
Row cyclic voltammetry, test condition：Scanning range is -0.2-1.0 V (vs SCE), and sweep speed is 50 mV/s, test
As a result as shown in Fig. 4.
As seen from Figure 4, there is maximum first under 0.69 V current potential in preparation-obtained PtPd-100 elctro-catalysts
Alcohol oxidation peak current density, about 139 mA/mgPt。
Fig. 4 show three kinds of fuel cell PtPd elctro-catalysts and business obtained by the catalyst preparation of embodiment 1,2,3
The cyclic voltammetric comparison diagram of industry Pt/C (JM) catalyst Oxidation of Methanol.From Fig. 4, the fuel of the gained of embodiment 1
Battery with PtPd Electrocatalytic Oxidation of Methanol spike potentials are smaller and peak current density peak performance preferably, be higher by than commercialization Pt/C
2.7 times, possess optimal catalysis oxidation methanol ability, the morphology analysis of gained PtPd elctro-catalysts is prepared with reference to three embodiments
Understand, the performance of the netted hollow-core construction catalyst of PtPd prepared using 30 DEG C of methods of fractional steps is optimal.
Fig. 5 show three kinds of fuel cell PtPd elctro-catalysts and Pt, Pd mark obtained by the preparation of embodiment 1,2,3
X-ray powder diffraction (XRD) figure of quasi- card (JCPDS), as seen from the figure, contrast Pt, Pd standard card, PtPt-1,
PtPt-2 diffraction maximum has negative shifting, and PtPd-100 diffraction maximum is then between Pt, Pd standard card, it was demonstrated that PtPt-
1, PtPt-2 is intermetallic compound, and PtPd-100 is then alloy structure.
Claims (3)
1. a kind of fuel cell PtPd elctro-catalysts, it is characterised in that the fuel cell belongs to net with PtPd elctro-catalysts
Shape hollow-core construction, average grain diameter is 2-30cm in 2 nm-10 nm, electrochemical surface area2, Pt, Pd atomic ratio are 1：3-3：
1, its preparation method is that current potential replaces reaction synthesis process, and specific method step is as follows：
(1) triblock copolymer P123 ultrasonic dissolution is taken in redistilled water, is transferred them in container and is placed in temperature
Spend on the agitator of controller and stir, control temperature obtains the P123 solution that concentration is 33 mg/mL at 30 DEG C；
(2) K is added dropwise into P123 solution2PdCl4Solution, after being added dropwise to complete, immediately continues with dropwise addition K2PtCl6Solution, magnetic force
Stirring reaction 2-4 h, obtain black suspension, wherein K used is added dropwise2PdCl4Concentration is 0.02 mmol/L, K2PtCl6It is dense
Spend for 0.02 mmol/L, the drop speed control of metal front liquid solution is in 5-10 s/ drops；
(3) reacted black suspension is centrifuged under the r/min of 5000 r/min ~ 11000, with water and absolute ethyl alcohol
Washing three to five times, you can obtain fuel cell PtPd elctro-catalysts.
2. fuel cell PtPd elctro-catalysts according to claim 1, it is characterised in that in step (3), centrifuged
Cheng Zhong, first with second distillation water washing 1-2 times, is then washed 3-4 times, it is ensured that the complete triblock copolymer of unreacted with absolute ethyl alcohol
Thing P123 is removed from catalyst surface.
3. application of the fuel cell with PtPd elctro-catalysts on electrocatalytic oxidation alcohol type organic described in claim 1 or 2,
Described alcohol type organic includes methanol, ethanol, ethylene glycol.
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| CN109638297A (en) * | 2018-11-27 | 2019-04-16 | 浙江工业大学 | A kind of mesoporous platinum nickel phosphorus nanocages elctro-catalyst and preparation method thereof |
| CN109659573A (en) * | 2018-11-27 | 2019-04-19 | 浙江工业大学 | A kind of mesoporous platinum porpezite elctro-catalyst and preparation method thereof |
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