CN107104237A - The preparation method and application of coralliform PdCo bianry alloy catalyst - Google Patents
The preparation method and application of coralliform PdCo bianry alloy catalyst Download PDFInfo
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- CN107104237A CN107104237A CN201710283257.6A CN201710283257A CN107104237A CN 107104237 A CN107104237 A CN 107104237A CN 201710283257 A CN201710283257 A CN 201710283257A CN 107104237 A CN107104237 A CN 107104237A
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- H01M4/00—Electrodes
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Abstract
The invention belongs to catalyst preparation technical field, it is related to Pd base catalyst, and in particular to a kind of preparation method and application of coralliform PdCo bianry alloy catalyst.The present invention use microwave radiation technology one-step synthesis, two kinds of metal precursors of palladium salt and cobalt salt are uniformly mixed with ascorbic acid reducing agent, microwave reaction for a period of time after, taking-up, centrifugal drying, you can acquisition coralliform PdCo bianry alloy catalyst.By controlling the rate of charge of two kinds of metal precursors, the surface chemistry composition of catalyst can effectively be adjusted.Preparation method of the present invention is simple, and step is few, easy to operate, without any dispersing aid.Prepared coralliform PdCo bianry alloys catalyst has excellent activity to the electrocatalytic oxidation of methanol in alkaline environment, is had a good application prospect in low-temp methanol fuel cell field.
Description
Technical field
The invention belongs to catalyst preparation technical field, it is related to Pd base catalyst, and in particular to a kind of coralliform PdCo bis-
The preparation method and application of first alloy catalyst.
Background technology
Pt base catalyst be in fuel cell using at most, the best catalyst of performance, but it is easily poisoned by CO intermediates,
And Pt rare and expensive price hinders its commercial applications, thus in recent years Many researchers to be directed to research and development low
Pt or no-Pt catalyst.In selectable alternative catalysts, Pd bases catalyst effect is best, because Pd and Pt is with main group member
Element, is all face-centered cubic crystal structure with similar atomic radius, performance is similar, but Pd because its price it is relatively low, therefore
It is better than Pt in commercial Application, before having huge application in the low temperature alcohol fuel battery field of exploitation energy conversion efficiency
Scape.
However, single palladium-based catalyst is easily poisoned by oxidized intermediate, and palladium particle pole in preparation process
Easily reunite, its electrocatalysis characteristic is restricted, so as to hinder its large-scale commercial applications.The surface chemistry composition pair of catalyst
Its electrocatalysis characteristic has a great impact, therefore is prepared into multi-component alloy catalytic agent to Pd progress surface dopings or alloying, is
Solve the effective ways of this problem.Compared to the palladium catalyst of one pack system, the electrocatalysis characteristic of Binary Alloy System is obviously improved.
Therefore, binary or polynary palladium-base alloy catalyst are built, is that the small molecule anode of fuel cell for building high-performance and low-cost is used
The conventional process of elctro-catalyst.
Although the palladium-base alloy catalyst type reported at present is various, preparation technology is numerous and diverse, and catalytic performance still needs to be carried
Height, and some environmentally harmful reagents are also used during the course of the reaction.
Chinese patent CN101495232A（The film of elctro-catalyst comprising palladium and ruthenium）, by two kinds of gold of palladium nitrate and ruthenic chloride
Category presoma is calcined using reducing gas by adjusting pH co-precipitation, is prepared for Pd-Ru alloy catalyst.The method uses reduction
Property gas high-temperature calcination.
Chinese patent CN101083325A（A kind of preparation side of fuel cell Technique of Nano Pd or pallas elctro-catalyst
Method）, first the mixed liquor of palladium bichloride and sodium chloroplatinate is dissolved with EDTA, then be co-precipitated with sodium hydroxide, with sodium borohydride also
Original, through 150 DEG C of 2 h of heat treatment in nitrogen after the washing of gained sample is dry.The method be related to heat treatment process and using EDTA,
The reagents such as highly basic.
Chinese patent CN105289588A（High dispersive small-size magnetic load type gold palladium alloy catalysts and its preparation side
Method）, using potassium chloropalladite and gold chloride as metal precursor, using ethylene glycol as reducing agent, PVP as end-capping reagent,
Flow back 1.5-2.5 h at 135-145 DEG C, obtains rhotanium particle.The method needs end-capping reagent and thermal source, and it is time-consuming compared with
It is long.
Chinese patent CN104801316A（A kind of palldium alloy catalytic film material and preparation method thereof）, utilize magnetron sputtering
Method is prepared for PdM in substrate surface cosputteringx（M is Ti or Ni, 0 ＜ x ＜ 0.5）Alloy as catalyst film.The method will to equipment
Ask high, cost of manufacture is higher.
Though palladium-base alloy catalyst can be prepared using the above method, there are some defects.They are needed to ring
The harmful auxiliary agent in border, or external heat source is needed, or expensive equipment is needed, do not meet the requirement for the green syt currently advocated.
Therefore, the catalyst preparation technology that development procedure is simple, easy to operate, with low cost, be adapted to prepare on a large scale undoubtedly has weight
The practical significance wanted.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of system of coralliform PdCo bianry alloy catalyst
Preparation Method.
It is an object of the present invention to using microwave radiation technology one-step synthesis, by palladium salt and two kinds of metal fronts of cobalt salt
Body is uniformly mixed with ascorbic acid reducing agent, and microwave reaction can obtain coralliform PdCo bianry alloy catalyst for a period of time.
By controlling the rate of charge of two kinds of metal precursors, the surface chemistry composition of catalyst can effectively be adjusted.
Technical scheme：
A kind of preparation method of coralliform PdCo bianry alloy catalyst, comprises the following steps：
S1. two kinds of metal precursors of palladium salt and cobalt salt are mixed with ascorbic acid, with deionized water dissolving, are sufficiently mixed uniformly,
Wherein, the palladium salt：The ratio between amount of cobalt salt material is 1：0~4；The ascorbic acid concentrations are 50 mmol/L, with deionized water
Volume ratio is 1:1；
S2. mixed solution is placed in microwave reactor and reacted at a temperature of 20~90 DEG C and reacted at 10~45 min, preferably 60 DEG C
30 min, take out product, and net, centrifugal drying is washed with deionized water, coralliform PdCo bianry alloy catalyst is made, wherein, institute
Microwave reactor power is stated for 400~750 W, preferably 600 W.
Preferably, the palladium salt described in S1：The ratio between amount of material of cobalt salt is 1:1.
In S1, the palladium salt is K2PdCl6、PdCl2Or K2PdCl4, preferably K2PdCl4；The cobalt salt is CoCl2、Co
(NO3)2Or CoSO4, preferably CoSO4。
Reducing agent is made using ascorbic acid in S1, the reducing agent is a kind of nontoxic medium reducing agent, it is to avoid make
With the process of other environmentally harmful reducing agents of possibility, or the dangerous higher reducibility gas high-temperature calcination of use.
Microwave process for synthesizing used in S2 is to pass through energy in situ conversion heating mode accelerationization using microware heating effect
Learn reaction method, with quick, homogeneous with selectivity the characteristics of, have been widely used for the preparation of bimetal nano material.
Another object of the present invention is, prepared coralliform PdCo bianry alloys catalyst is used for into alkaline ring
The electrocatalytic oxidation of methanol in border.
The electrocatalytic oxidation experimental method of methanol in alkaline environment：Weigh catalyst ultrasonic disperse prepared by 5 mg in
In Nafion mixed solutions, then it is added drop-wise on screen printing carbon electrode, electrode is made in drying at room temperature, wherein the Nafion is mixed
Solution is closed to be formulated by 2 mL deionized waters, 2 mL isopropanols and the wt% Nafion solutions of 100 μ L 5.To be added dropwise in silk screen
Coralliform binary metal catalyst on printing carbon electrode is used as working electrode（Its geometry work area is 0.126 cm2）, platinum
Silk electrode builds three-electrode electrochemical test system as the Ag/AgCl electrodes to electrode, saturation as reference electrode；Test
Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions, potential window is -0.8-0.3 V, and sweep speed is 20
mV/s；Test cyclic voltammogram of the catalyst in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol, potential window
For -0.8-0.3 V, sweep speed is 20 mV/s.
Screen printing carbon electrode used is commercially produced product, in 1 mol/L H2SO4Used after being activated in solution.
Test result indicates that, compared to pure palladium catalyst, the coralliform PdCo bianry alloys catalyst tool prepared by the present invention
There is more superior electro catalytic activity.
Experiment reagent used of the invention：Tetrachloro-palladium potassium chlorate (K2PdCl4) and ascorbic acid (AA), Aladdin reagent（On
Sea）Co., Ltd；Cobaltous sulfate (CoSO4), methanol (CH3OH) and sodium hydroxide (NaOH), Chinese medicines group chemical reagent is limited
Company, is analysis level.
Beneficial effect
Preparation method of the present invention is simple, and step is few, easy to operate, without any dispersing aid；By controlling two kinds of gold
Belong to presoma（K2PdCl4And CoSO4）Rate of charge, Effective Regulation can be carried out to the surface chemistry of catalyst composition；Invention is made
Standby coralliform PdCo bianry alloys catalyst has excellent activity to the electrocatalytic oxidation of methanol in alkaline environment, in low temperature
Methanol fuel cell field has a good application prospect.
Brief description of the drawings
Fig. 1, coralliform PdCo bianry alloy catalyst preparation flow figure.
Fig. 2, A are the transmission electron microscope picture of coralliform PdCo bianry alloy catalyst described in embodiment 1, and B transmits for high-resolution
Electron microscope.
Circulation volt of the coralliform PdCo bianry alloys catalyst described in Fig. 3, embodiment 1 in 1.0 mol/L NaOH solutions
Antu.
Coralliform PdCo bianry alloys catalyst is in 1.0 mol/L containing 0.1 mol/L methanol described in Fig. 4, embodiment 1
Cyclic voltammogram in NaOH solution.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment the invention will be further described, but protection scope of the present invention is not
It is limited to this.
Embodiment 1
1st, coralliform PdCo bianry alloys catalyst（A）Preparation
By the mmol/L K of 2.3 mL 502PdCl4、7.7 mL 15 mmol/L CoSO4, the mmol/L AA of 10 mL 50 and 10
mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 600 W, 60
DEG C and 30 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions,
The drying on screen printing carbon electrode is added dropwise electrode is made.
Fig. 1 is the preparation flow figure of coralliform PdCo bianry alloy catalyst disclosed by the invention.By microwave radiation technology one
Synthetic method is walked, two kinds of metal precursors of palladium salt and cobalt salt are uniformly mixed with ascorbic acid reducing agent, microwave reaction is for a period of time
Coralliform PdCo bianry alloy catalyst can be obtained.
Fig. 2 (A) is the transmission electron microscope picture of coralliform PdCo bianry alloy catalyst in the embodiment of the present invention 1.As can be seen that
Metallic atom stacks accumulation and shows in coralliform, Fig. 2 (B) that clearly lattice fringe illustrates that Pd and Co are highly alloyed.Through
ICP-OES is determined, and the Pd and Co of catalyst surface atomic ratio are 56:44, it is designated as Pd56Co44。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
So that the coralliform Pd on screen printing carbon electrode is added dropwise56Co44Binary metal catalyst is used as working electrode（Its geometry
Work area is 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation are used as reference electrode, build three
Electrode electro Chemical test system；Test cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions, potential window for-
0.8-0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
In cyclic voltammogram, potential window be -0.8-0.3 V, sweep speed be 20 mV/s.
Fig. 3 is Pd described in the embodiment of the present invention 156Co44Binary metal catalyst following in 1.0 mol/L NaOH solutions
Ring voltammogram.As can be seen that the catalyst prepared shows Pd and Co electrochemical redox characteristic signal, further confirm
Pd56Co44Binary metal catalyst is successfully prepared.
Fig. 4 is Pd described in the embodiment of the present invention 156Co44Binary metal catalyst is in 1.0 containing 0.1 mol/L methanol
Cyclic voltammogram in mol/L NaOH solutions.As can be seen that the catalyst prepared can effectively be catalyzed methanol in alkaline environment
Oxidation, the peak current density provided at -0.185 V vs. Ag/AgCl is 38.477 mA/mgPd。
Embodiment 2
1st, coralliform Pd catalyst（B）Preparation
By the mmol/L K of 10 mL 502PdCl4, the mmol/L AA of 10 mL 50 and 10 mL H2O is uniformly mixed in round-bottomed flask
In；Flask is put into microwave reactor rapidly, setting response parameter is 400 W, 20 DEG C and 10 min；Gained sample is through going
Ion water washing three times, centrifugal drying；After sample is disperseed with Nafion mixed solutions, it is added dropwise and is done on screen printing carbon electrode
It is dry that electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 0, is designated as Pd.
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
Working electrode is used as using the coralliform Pd metallic catalysts that are added dropwise on screen printing carbon electrode（Its geometry work area is
0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation are used as reference electrode, build three-electrode electro Chemical
Test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-0.3 V, is swept
Speed is retouched for 20 mV/s；Test cyclic voltammetric of the catalyst in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Figure, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed first in alkaline environment
The oxidation of alcohol, the peak current density provided at -0.217 V vs. Ag/AgCl is 3.522 mA/mgPd。
Embodiment 3
1st, coralliform PdCo bianry alloys catalyst（C）Preparation
By the mmol/L K of 5.5 mL 502PdCl4、4.5 mL 15 mmol/L CoSO4, the mmol/L AA of 10 mL 50 and 10
mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 450 W, 30
DEG C and 15 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions,
The drying on screen printing carbon electrode is added dropwise electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 1：4, it is designated as
Pd4Co。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
So that the coralliform Pd on screen printing carbon electrode is added dropwise4Co binary metal catalyst is used as working electrode（Its geometry work
Make area for 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electricity as reference electrode
Pole electrochemical test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-
0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Cyclic voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkalescence
The oxidation of methanol in environment, the peak current density provided at -0.182 V vs. Ag/AgCl is 5.645 mA/mgPd。
Embodiment 4
1st, coralliform PdCo bianry alloys catalyst（D）Preparation
By the mmol/L K of 5 mL 502PdCl4、5 mL 15 mmol/L CoSO4, the mmol/L AA of 10 mL 50 and 10 mL
H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 500 W, 40 DEG C
With 20 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions, drop
It is added in drying on screen printing carbon electrode and electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 1：3, it is designated as
Pd3Co。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
So that the coralliform Pd on screen printing carbon electrode is added dropwise3Co binary metal catalyst is used as working electrode（Its geometry work
Make area for 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electricity as reference electrode
Pole electrochemical test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-
0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Cyclic voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkalescence
The oxidation of methanol in environment, the peak current density provided at -0.151 V vs. Ag/AgCl is 34.725 mA/mgPd。
Embodiment 5
1st, coralliform PdCo bianry alloys catalyst（E）Preparation
By the mmol/L K of 3.7 mL 502PdCl4、6.3 mL 15 mmol/L CoSO4, the mmol/L AA of 10 mL 50 and 10
mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 550 W, 50
DEG C and 25 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions,
The drying on screen printing carbon electrode is added dropwise electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 1：2, it is designated as
Pd2Co。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
So that the coralliform Pd on screen printing carbon electrode is added dropwise2Co binary metal catalyst is used as working electrode（Its geometry work
Make area for 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electricity as reference electrode
Pole electrochemical test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-
0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Cyclic voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkalescence
The oxidation of methanol in environment, the peak current density provided at -0.168 V vs. Ag/AgCl is 35.987 mA/mgPd。
Embodiment 6
1st, coralliform PdCo bianry alloys catalyst（F）Preparation
By the mmol/L K of 1.3 mL 502PdCl4、8.7 mL 15 mmol/L CoSO4, the mmol/L AA of 10 mL 50 and 10
mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 650 W, 70
DEG C and 35 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions,
The drying on screen printing carbon electrode is added dropwise electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 2：1, it is designated as
PdCo2。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
So that the coralliform PdCo on screen printing carbon electrode is added dropwise2Binary metal catalyst is used as working electrode（Its geometry work
Make area for 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electricity as reference electrode
Pole electrochemical test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-
0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Cyclic voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkalescence
The oxidation of methanol in environment, the peak current density provided at -0.201 V vs. Ag/AgCl is 6.765 mA/mgPd。
Embodiment 7
1st, coralliform PdCo bianry alloys catalyst（G）Preparation
By the mmol/L K of 0.9 mL 502PdCl4、9.1 mL 15 mmol/L CoSO4, the mmol/L AA of 10 mL 50 and 10
mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 700 W, 80
DEG C and 45 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions,
The drying on screen printing carbon electrode is added dropwise electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 3：1, it is designated as
PdCo3。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
So that the coralliform PdCo on screen printing carbon electrode is added dropwise3Binary metal catalyst is used as working electrode（Its geometry work
Make area for 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electricity as reference electrode
Pole electrochemical test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-
0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Cyclic voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkalescence
The oxidation of methanol in environment, the peak current density provided at -0.211 V vs. Ag/AgCl is 0.286 mA/mgPd。
Embodiment 8
1st, coralliform PdCo bianry alloys catalyst（H）Preparation
By the mmol/L K of 0.7 mL 502PdCl4、9.3 mL 15 mmol/L CoSO4, the mmol/L AA of 10 mL 50 and 10
mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 750 W, 90
DEG C and 45 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions,
The drying on screen printing carbon electrode is added dropwise electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 4：1, it is designated as
PdCo4。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
So that the coralliform PdCo on screen printing carbon electrode is added dropwise4Binary metal catalyst is used as working electrode（Its geometry work
Make area for 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electricity as reference electrode
Pole electrochemical test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-
0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Cyclic voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkalescence
The oxidation of methanol in environment, the peak current density provided at -0.254 V vs. Ag/AgCl is 0.212 mA/mgPd。
Embodiment 9
1st, coralliform PdCo bianry alloys catalyst（I）Preparation
By the mmol/L PdCl of 2.3 mL 502、7.7 mL 15 mmol/L CoSO4, 10 mL 50 mmol/L AA and 10mL
H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 600 W, 60 DEG C
With 30 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions, drop
It is added in drying on screen printing carbon electrode and electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 1：1, it is designated as
PdCo’。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
Working electrode is used as using the coralliform PdCo ' metallic catalysts that are added dropwise on screen printing carbon electrode（Its geometry working face
Product is 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electrodes electricity as reference electrode
Test chemical system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-0.3
V, sweep speed is 20 mV/s；Test circulation of the catalyst in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkaline environment
The oxidation of middle methanol, the peak current density provided at -0.172 V vs. Ag/AgCl is 30.213 mA/mgPd。
Embodiment 10
1st, coralliform PdCo bianry alloys catalyst（J）Preparation
By the mmol/L K of 2.3 mL 502PdCl4、7.7 mL 15 mmol/L Co(NO3)2, the mmol/L AA of 10 mL 50 and
10 mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 600 W,
60 DEG C and 30 min；Gained sample is washed three times through deionized water, centrifugal drying；Sample is disperseed with Nafion mixed solutions
Afterwards, the drying on screen printing carbon electrode is added dropwise electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 1：1, note
For PdCo ' '.
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
Working electrode is used as using coralliform the PdCo ' ' metallic catalysts that are added dropwise on screen printing carbon electrode（Its geometry working face
Product is 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation build three electrodes electricity as reference electrode
Test chemical system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-0.3
V, sweep speed is 20 mV/s；Test circulation of the catalyst in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkaline environment
The oxidation of middle methanol, the peak current density provided at -0.201 V vs. Ag/AgCl is 30.128 mA/mgPd。
Embodiment 11
1st, coralliform PdCo bianry alloys catalyst（K）Preparation
By the mmol/L PdCl of 2.3 mL 502、7.7 mL 15 mmol/L Co(NO3)2, the mmol/L AA of 10 mL 50 and 10
mL H2O is uniformly mixed in round-bottomed flask；Flask is put into microwave reactor rapidly, setting response parameter is 600 W, 60
DEG C and 30 min；Gained sample is washed three times through deionized water, centrifugal drying；After sample is disperseed with Nafion mixed solutions,
The drying on screen printing carbon electrode is added dropwise electrode is made.The ratio between amount of the catalyst cobalt salt and palladium salt material is 1：1, it is designated as
PdCo’’’。
2nd, the electrocatalytic oxidation of methanol is studied in alkaline environment
Working electrode is used as using the coralliform PdCo ' ' ' metallic catalysts that are added dropwise on screen printing carbon electrode（Its geometry works
Area is 0.126 cm2）, platinum electrode is as to electrode, and the Ag/AgCl electrodes of saturation are used as reference electrode, build three electrodes
Electrochemical test system；Cyclic voltammogram of the catalyst in 1.0 mol/L NaOH solutions is tested, potential window is -0.8-
0.3 V, sweep speed is 20 mV/s；Catalyst is tested in the 1.0 mol/L NaOH solutions containing 0.1 mol/L methanol
Cyclic voltammogram, potential window is -0.8-0.3 V, and sweep speed is 20 mV/s.The catalyst of preparation can effectively be catalyzed alkalescence
The oxidation of methanol in environment, the peak current density provided at -0.223 V vs. Ag/AgCl is 24.532 mA/mgPd。
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification is made, or other related technical fields are directly or indirectly used in,
Similarly it is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of coralliform PdCo bianry alloy catalyst, it is characterised in that comprise the following steps：
S1. two kinds of metal precursors of palladium salt and cobalt salt are mixed with ascorbic acid, with deionized water dissolving, are sufficiently mixed uniformly,
Wherein, the palladium salt：The ratio between amount of cobalt salt material is 1：0~4；
S2. mixed solution is placed in microwave reactor and 10~45 min is reacted at a temperature of 20~90 DEG C, taken out product, spend
Ionized water is cleaned, centrifugal drying, and coralliform PdCo bianry alloy catalyst is made, wherein, the microwave reactor power is 400
~750 W.
2. the preparation method of coralliform PdCo bianry alloy catalyst according to claim 1, it is characterised in that：Step S1
Described in ascorbic acid concentrations be 50 mmol/L, with deionized water volume ratio be 1:1.
3. the preparation method of coralliform PdCo bianry alloy catalyst according to claim 1, it is characterised in that：Step S1
Described in palladium salt：The ratio between amount of material of cobalt salt is 1:1.
4. the preparation method of coralliform PdCo bianry alloy catalyst according to claim 1, it is characterised in that：Step S1
Described in palladium salt be K2PdCl6,、PdCl2Or K2PdCl4；The cobalt salt is CoCl2、Co(NO3)2Or CoSO4。
5. the preparation method of coralliform PdCo bianry alloy catalyst according to claim 1, it is characterised in that：Step S1
Described in palladium salt be K2PdCl4, the cobalt salt is CoSO4。
6. the preparation method of coralliform PdCo bianry alloy catalyst according to claim 1, it is characterised in that：Step S2
Described in microwave reaction temperature 60 C.
7. the preparation method of coralliform PdCo bianry alloy catalyst according to claim 1, it is characterised in that：Step S2
Described in the min of microwave reaction time 30.
8. the preparation method of coralliform PdCo bianry alloy catalyst according to claim 1, it is characterised in that：Step S2
Described in microwave reactor power be 600 W.
9. the coralliform PdCo bianry alloy catalyst prepared according to any methods describeds of claim 1-8.
10. the application of coralliform PdCo bianry alloy catalyst described in a kind of claim 9, it is characterised in that：It is applied to
The electrocatalytic oxidation of methanol in alkaline environment.
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