A kind of Pt-Pd alloy catalysts of morphology controllable and preparation method and application
Technical field
The invention belongs to catalyst field, particular use is related to the Pt-Pd alloy catalysts and its system of a kind of morphology controllable
Preparation Method and application.
Background technology
Proton Exchange Membrane Fuel Cells is the TRT that the chemical energy that fuel has directly is changed into electric energy, because of its energy
High conversion efficiency, it is low in the pollution of the environment, reliability is high and noiseless the advantages that, be listed in 21 century important fungible energy source.So
And so far, the cost of fuel cell and life-span limit its extensive use especially in the application of civil area.Film electricity
Pole is the core component of Proton Exchange Membrane Fuel Cells, decides performance, life-span and the cost of Proton Exchange Membrane Fuel Cells.
Membrane electrode is mainly made up of Catalytic Layer, gas diffusion layers and PEM, and wherein Catalytic Layer is that the field of electrochemical reaction occurs
Institute, decide performance and the life-span of membrane electrode.The catalyst of Catalytic Layer uses precious metals pt catalyst mostly at present, its whole world storage
Standby amount is limited, with high costs, seriously hinders the process of commercializing fuel cells development.
Therefore, reduce the Pt contents of catalyst, improve its catalytic activity and durability for reduce fuel cell cost and
It is significant to improve fuel battery service life.In recent years, Pt based alloy catalysts are improving Pt utilization rates and are improving catalyst
Durability in terms of cause the concern of each researcher.Further study show that the pattern of Pt based alloys has to its catalytic activity
There is the influence of highly significant.Wherein, the Pt-Ni alloys of pattern control turn into the heat of research because showing outstanding catalytic activity
Point, the cube Pt-Ni alloys with (100) advantage crystal face are up to the present successfully synthesized, with (111) advantage crystalline substance
The octahedron in face and the Pt-Ni alloys of the various different-shapes such as icosahedron, and these alloy catalysts show it is outstanding
Catalytic activity, but Pt-Ni alloy catalysts (such as highly acid, high potential) under fuel cell operating conditions are easy to occur
The dissolving failure of non-noble metal Ni, it is difficult to meet the stability requirement of fuel-cell catalyst.Research is found, in octahedron
Pt3One layer of Pt of Ni Surface coatings3After Pd shells, on the premise of high catalytic activity is ensured, than single octahedra Pt3Ni alloys are urged
Agent shows higher electrochemical stability, and therefore, compared with Pt-Ni alloys, the Pt-Pd alloys of pattern control are that development is high
Preferably one of the selection of active high stability Pt based alloy catalysts.
But up to the present, most of surface for controlling the process of Pt based alloy patterns to be directed to use different Long carbon chains
Activating agent, and surfactant is very strong in the suction-operated of alloy surface, synthetic reaction terminate after be difficult from metallic particles by it
Surface removes completely, is unfavorable for the raising of Pt based alloy catalyst electro catalytic activities.
The content of the invention
The technology of the present invention will solve the problems, such as:Overcome prior art insufficient, there is provided a kind of Pt-Pd alloys of morphology controllable
Catalyst and preparation method and application is to improve catalyst activity.
For achieving the above object, the present invention adopts the following technical scheme that:
A kind of preparation method of the Pt-Pd alloy catalysts of morphology controllable, comprises the following steps:
Step 1, platinum salt and palladium salt are dissolved in the first solvent and reacted, obtain Pt-Pd alloy nanometer crystals solution, its
Described in the first solvent be made up of dimethylformamide and carboxylic acid, carbon carrier is dispersed in the second solvent, obtain carbon carrier suspension
Liquid;
Step 2, the Pt-Pd alloy nanometer crystals solution is dispersed in the carbon carrier suspension, stirring is at least
4h, then filtration washing, drying, obtain the Pt-Pd alloy catalysts of morphology controllable.
In an alternative embodiment, in the first solvent described in step 1 volume ratio of dimethylformamide and carboxylic acid be 5~
23:1.
In an alternative embodiment, the carboxylic acid described in step 1 is the one or more in formic acid, acetic acid or propionic acid
Combination.
In an alternative embodiment, the mol ratio of platinum salt and palladium salt described in step 1 is 1:(0.3~3).
In an alternative embodiment, being dissolved in platinum salt and palladium salt in the first solvent described in step 1 or 4 carries out anti-
Should, including:10.5~21h is reacted at 120~180 DEG C.
In an alternative embodiment, being dispersed in the Pt-Pd alloy nanometer crystals solution described in step 2 is described
In carbon carrier suspension, including:
While stirring the carbon carrier suspension, the Pt-Pd alloys are added into the carbon carrier suspension dropwise
Nanocrystal solution, at least 0.5h is ultrasonically treated after adding, the Pt-Pd alloy nanometer crystals solution is dispersed in the carbon and carry
In liquid suspension.
In an alternative embodiment, the drying described in step 2, it is included at 60~80 DEG C and is dried in vacuo.
The Pt-Pd alloy catalysts of morphology controllable prepared by above-mentioned preparation method.
The Pt-Pd alloy catalysts of described morphology controllable, pattern are that cube, icosahedron or rescinded angle are octahedra
The application of the Pt-Pd alloy catalysts of described morphology controllable in a fuel cell.
The present invention has the beneficial effect that compared with prior art:
(1) preparation method of the Pt-Pd alloy catalysts of morphology controllable provided in an embodiment of the present invention, by platinum salt and palladium salt
Reacted in the solvent that dimethylformamide (DMF) and carboxylic acid form, because the aldehyde that DMF and carboxylic acid reaction generate plays covering
Effect, so as to realize the Pt-Pd alloy as catalyst that morphology controllable is prepared under conditions of the surfactant without using Long carbon chain
Agent, this method is simple to operate, and yield is higher, reduces Catalyst Production cost, and the Pt-Pd alloy catalyst tables being prepared
Face is very clean, and avtive spot will not be occupied by SURFACTANT ADSORPTION, effectively increases the catalytic activity of catalyst;
(2) when the Pt-Pd alloy catalysts of morphology controllable provided in an embodiment of the present invention are applied in a fuel cell, have
Higher catalytic activity and resisting CO poison ability;When the catalyst pattern is icosahedron, have in step or defective locations
Just like high energy crystal faces such as (533), (553) and (554), methanol oxidation catalytic activity, electrochemical stability and anti-CO poison are improved
Change ability.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo and high magnification transmission electron microscope for the Pt-Pd alloy catalysts that the embodiment of the present invention 1 provides
Photo;
Fig. 2 is the transmission electron microscope photo and high magnification transmission electron microscope for the Pt-Pd alloy catalysts that the embodiment of the present invention 2 provides
Photo;
Fig. 3 is the transmission electron microscope photo and high magnification transmission electron microscope for the Pt-Pd alloy catalysts that the embodiment of the present invention 3 provides
Photo;
Fig. 4 is the transmission electron microscope photo and high magnification transmission electron microscope for the Pt-Pd alloy catalysts that the embodiment of the present invention 4 provides
Photo;
Fig. 5 is the transmission electron microscope photo and high magnification transmission electron microscope for the Pt-Pd alloy catalysts that the embodiment of the present invention 5 provides
Photo;
Fig. 6 is the methanol oxidation cycle volt-ampere curve that 1-5 of the embodiment of the present invention is provided.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The embodiments of the invention provide a kind of preparation method of the Pt-Pd alloy catalysts of morphology controllable, including following step
Suddenly:
Step 1, platinum salt and palladium salt are dissolved in the first solvent and reacted, obtain Pt-Pd alloy nanometer crystals solution, its
Described in the first solvent be made up of dimethylformamide (DMF) and carboxylic acid, carbon carrier is dispersed in the second solvent, obtains carbon carrier
Suspension;
Specifically, the preferred Pt of platinum salt (acac) in the embodiment of the present invention2、K2PtCl6、H2PtCl6In one kind or it is a kind of with
Upper combination, the preferred Pd of palladium salt (acac)2、PdCl2、NaPdCl4In one or more kinds of combinations;
The mol ratio of platinum salt and palladium salt preferably 1:(0.3~3), the proportioning not only improve control crystal morphology, and and can is enough protected
Catalyst activity is demonstrate,proved, is advantageous to improve the catalytic effect of catalyst, when the mol ratio of platinum salt and palladium salt preferably 1:Obtained when 0.3
Catalyst best results;
One or more kinds of combinations in the preferred formic acid of described carboxylic acid, acetic acid or propionic acid, preferably propionic acid;First solvent
Middle DMF and carboxylic acid volume ratio are preferably (5~23):1, when carboxylic acid content is less in the first solvent, reaction solution acidity is extremely weak,
Which limits the formation for the aldehyde for playing covering, so the nanoparticle size of synthesis is very big and pattern is almost irregular;
When carboxylic acid content is more in the first solvent, reaction solution acidity can be caused too strong, the pH value of solution is reduced, it is suppressed that OH is adsorbed
The formation of functional group, so that the cladding agent content in solution is very low, equally make the nanoparticle size of synthesis very big and pattern
It is almost irregular;When the volume ratio of DMF and carboxylic acid is (5~23):When 1, it can ensure that granule-morphology is controllable;
In the embodiment of the present invention, platinum salt and palladium salt react 10.5~21h at 120~180 DEG C;When reaction temperature is too high or
When too low, sedimentation rate difference very little of the metallic atom on each crystal face of Pt-Pd alloys, easily cause the nanometer finally synthesized
Granule-morphology is irregular, when reaction temperature is 120~180 DEG C, it can be ensured that the nano particle pattern rule finally synthesized can
Control;
In the embodiment of the present invention, the second solvent is small molecule solvent, such as ethanol, acetone, water, is carried for dispersed carbon
Body;
Step 2, the Pt-Pd alloy nanometer crystals solution is dispersed in the carbon carrier suspension, stirring is at least
4h, then filtration washing, drying, obtain the Pt-Pd alloy catalysts of morphology controllable.
Specifically, in the embodiment of the present invention preferably while carbon carrier suspension described in high-speed stirred, dropwise to described
The Pt-Pd alloy nanometer crystals solution is slowly added in carbon carrier suspension, at least 0.5h is ultrasonically treated after adding, is made described
Pt-Pd alloy nanometer crystals solution is dispersed in the carbon carrier suspension;Stirring reaction at least 4h after being uniformly dispersed, preferably
6-12h after reaction completely, passes through small molecule solvent such as methanol, ethanol, water etc. to ensure crystal uniform load in carbon support
Filtration washing is carried out, is dried in vacuo after washing at 60~80 DEG C, drying time preferred 5-8h.
The preparation method of the Pt-Pd alloy catalysts of morphology controllable provided in an embodiment of the present invention, platinum salt and palladium salt are existed
Reacted in the solvent of DMF and carboxylic acid composition, because the aldehyde that DMF and carboxylic acid reaction generate plays covering, so as to realize
The Pt-Pd alloy catalysts of morphology controllable, this method operation are prepared under conditions of the surfactant without using Long carbon chain
Simply, yield is higher, reduces Catalyst Production cost, and the Pt-Pd alloy catalysts surface being prepared is very clean, living
Property site will not be occupied by SURFACTANT ADSORPTION, effectively increase the catalytic activity of catalyst.
The embodiment of the present invention additionally provides a kind of Pt-Pd alloy catalysts of morphology controllable, and the catalyst is by the above method
Embodiment is prepared.The Pt-Pd alloy catalysts of described morphology controllable, the preferred cube of pattern, icosahedron or rescinded angle
It is octahedra.
Morphology controllable provided in an embodiment of the present invention Pt-Pd alloy catalysts application in a fuel cell when, have compared with
High catalytic activity and resisting CO poison ability;When the catalyst pattern is icosahedron, have in step or defective locations
Such as (533), (553) and (554) high energy crystal face, improve methanol oxidation catalytic activity, electrochemical stability and resisting CO poison
Ability.
It is below several specific embodiments of the present invention:
Embodiment 1
By 23.4mg Pt (acac)2With 6.1mg Pd (acac)2The mixing for being dissolved in 12mL dimethylformamides and propionic acid is molten
In agent, and magnetic agitation 30min is well mixed, wherein the volume ratio of the in the mixed solvent dimethylformamide and propionic acid is 5:1;
Then obtained well mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate and incited somebody to action
It is sealed, and reactor then is heated into 160 DEG C from room temperature in 1h, and dropped naturally after keeping 21h, reaction to terminate in 160 DEG C
Warm to room temperature, obtain Pt-Pd alloy nanometer crystals solution;
25mg activated carbon is added in 10mL ethanol solutions, and ultrasonic 1h, 1h is stirred for, obtains carbon carrier suspension;
Obtained Pt-Pd alloy nanometer crystals solution ultrasound 30min will be synthesized, it is uniformly dispersed, under 700rpm rotating speeds
While stirring the carbon carrier suspension, the finely dispersed Pt-Pd alloy nanometer crystals solution is slowly added into dropwise
In carbon carrier suspension, continue to stir 12h at room temperature, filter, wash, dry, that is, obtain morphology controllable Pt-Pd alloy as catalyst
Agent.
As shown in figures i a andb, Pt-Pd alloys pattern made from the present embodiment is that rescinded angle is octahedra.
Embodiment 2
By 23.4mg Pt (acac)2With 6.1mg Pd (acac)2The mixing for being dissolved in 12mL dimethylformamides and propionic acid is molten
In agent, and magnetic agitation 30min is well mixed, wherein the volume ratio of the in the mixed solvent dimethylformamide and propionic acid is 11:
1;
Then obtained well mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate and incited somebody to action
It is sealed, and reactor then is heated into 160 DEG C from room temperature in 1h, and dropped naturally after keeping 21h, reaction to terminate in 160 DEG C
Warm to room temperature, obtain Pt-Pd alloy nanometer crystals solution;
25mg activated carbon is added in 10mL ethanol solutions, and ultrasonic 1h, 1h is stirred for, obtains carbon carrier suspension;
Obtained Pt-Pd alloy nanometer crystals solution ultrasound 30min will be synthesized, it is uniformly dispersed, under 700rpm rotating speeds
While stirring the carbon carrier suspension, the finely dispersed Pt-Pd alloy nanometer crystals solution is slowly added into dropwise
In carbon carrier suspension, continue to stir 12h at room temperature, filter, wash, dry, that is, obtain morphology controllable Pt-Pd alloy as catalyst
Agent.
As shown in Fig. 2 a and b, Pt-Pd alloys pattern made from the present embodiment is icosahedron.
Embodiment 3
By 23.4mg Pt (acac)2With 6.1mg Pd (acac)2The mixing for being dissolved in 12mL dimethylformamides and propionic acid is molten
In agent, and magnetic agitation 30min is well mixed, wherein the volume ratio of the in the mixed solvent dimethylformamide and propionic acid is 23:
1;
Then obtained well mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate and incited somebody to action
It is sealed, and reactor then is heated into 160 DEG C from room temperature in 1h, and dropped naturally after keeping 21h, reaction to terminate in 160 DEG C
Warm to room temperature, obtain Pt-Pd alloy nanometer crystals solution;
25mg activated carbon is added in 10mL ethanol solutions, and ultrasonic 1h, 1h is stirred for, obtains carbon carrier suspension;
Obtained Pt-Pd alloy nanometer crystals solution ultrasound 30min will be synthesized, it is uniformly dispersed, under 700rpm rotating speeds
While stirring the carbon carrier suspension, the finely dispersed Pt-Pd alloy nanometer crystals solution is slowly added into dropwise
In carbon carrier suspension, continue to stir 12h at room temperature, filter, wash, dry, that is, obtain morphology controllable Pt-Pd alloy as catalyst
Agent.
As shown in Fig. 3 a and b, Pt-Pd alloys pattern made from the present embodiment is cube.
Embodiment 4
By 20.0mg Pt (acac)2With 8.1mg Pd (acac)2The mixing for being dissolved in 12mL dimethylformamides and propionic acid is molten
In agent, and magnetic agitation 30min is well mixed, wherein the volume ratio of the in the mixed solvent dimethylformamide and propionic acid is 11:
1;
Then obtained well mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate and incited somebody to action
It is sealed, and reactor then is heated into 160 DEG C from room temperature in 1h, and dropped naturally after keeping 21h, reaction to terminate in 160 DEG C
Warm to room temperature, obtain Pt-Pd alloy nanometer crystals solution;
25mg activated carbon is added in 10mL ethanol solutions, and ultrasonic 1h, 1h is stirred for, obtains carbon carrier suspension;
Obtained Pt-Pd alloy nanometer crystals solution ultrasound 30min will be synthesized, it is uniformly dispersed, under 700rpm rotating speeds
While stirring the carbon carrier suspension, the finely dispersed Pt-Pd alloy nanometer crystals solution is slowly added into dropwise
In carbon carrier suspension, continue to stir 12h at room temperature, filter, wash, dry, that is, obtain morphology controllable Pt-Pd alloy as catalyst
Agent.
As shown in Fig. 4 a and b, Pt-Pd alloys pattern made from the present embodiment is cube.
Embodiment 5
By 7.9mg Pt (acac)2With 18.3mg Pd (acac)2The mixing for being dissolved in 12mL dimethylformamides and propionic acid is molten
In agent, and magnetic agitation 30min is well mixed, wherein the volume ratio of the in the mixed solvent dimethylformamide and propionic acid is 11:
1;
Then obtained well mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate and incited somebody to action
It is sealed, and reactor then is heated into 160 DEG C from room temperature in 1h, and dropped naturally after keeping 21h, reaction to terminate in 160 DEG C
Warm to room temperature, obtain Pt-Pd alloy nanometer crystals solution;
25mg activated carbon is added in 10mL ethanol solutions, and ultrasonic 1h, 1h is stirred for, obtains carbon carrier suspension;
Obtained Pt-Pd alloy nanometer crystals solution ultrasound 30min will be synthesized, it is uniformly dispersed, under 700rpm rotating speeds
While stirring the carbon carrier suspension, the finely dispersed Pt-Pd alloy nanometer crystals solution is slowly added into dropwise
In carbon carrier suspension, continue to stir 12h at room temperature, filter, wash, dry, that is, obtain morphology controllable Pt-Pd alloy as catalyst
Agent.
As shown in Fig. 5 a and b, Pt-Pd alloys pattern made from the present embodiment is cube.
Working electrode is made in the Pt-Pd alloy catalysts that embodiment 1-5 is provided, preparation method is as follows:
3.0mgPt-Pd alloy catalysts are taken, add 1.0mL isopropanols, ultrasonic wave disperses 1min, then adds 4.0mL and surpasses
Pure water and the pure 117-Nafion solution of 25.0 μ L, ultrasonic disperse 15min are configured to the catalyst pulp that concentration is 0.6mg/mL,
10.0 μ L catalyst pulps are drawn with micropipettor, are coated in a diameter of 5mm rotating disk electrode (r.d.e) surface, after natural drying,
Repeat above procedure 3 times, eventually form homogeneous Catalytic Layer, obtain working electrode;
Methanol oxidation catalytic activity test is carried out to the working electrode, method of testing is:
Working electrode is inserted in electrolyte, using RHE electrodes as reference electrode, using 1.0cm × 1.0cm Pt pieces
As to electrode, electrochemical property test is carried out, wherein electrolyte is HClO4And CH3The OH aqueous solution, wherein HClO4Concentration
For 0.1mol.L-1, CH3OH concentration is 0.5mol.L-1, nitrogen 30min is led in the forward direction electrolyte of test.Test potential range
For 0.05~1.2V, sweep speed 50mVs-1.Test result is as shown in fig. 6, the Pt-Pd catalyst that embodiment 1-5 is provided
Electro catalytic activity is shown, the electro catalytic activity of each catalyst is as shown in table 1.
Embodiment |
Methanol oxidation peak current potential/V |
Methanol oxidative peak current density/mA.cm-2 |
1 |
0.884 |
1.40 |
2 |
0.888 |
1.98 |
3 |
0.895 |
1.57 |
4 |
0.889 |
1.28 |
5 |
0.894 |
1.14 |
Unspecified part of the present invention belongs to general knowledge as well known to those skilled in the art.Described specific embodiment is only pair
Spirit explanation for example of the invention.The personnel of the technical field of the invention can do different repair to described specific embodiment
Change or supplement or replaced using similar mode, but spirit without departing from the present invention or surmount appended claims and defined
Scope.