CN109065893A - A kind of composite electro catalytic material and its preparation method and application - Google Patents
A kind of composite electro catalytic material and its preparation method and application Download PDFInfo
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- CN109065893A CN109065893A CN201810642233.XA CN201810642233A CN109065893A CN 109065893 A CN109065893 A CN 109065893A CN 201810642233 A CN201810642233 A CN 201810642233A CN 109065893 A CN109065893 A CN 109065893A
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
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Abstract
The invention belongs to field of fuel cell technology, a kind of composite electro catalytic material and its preparation method and application is disclosed.Foam metal is added in glucose solution, 130~180 DEG C of hydro-thermal reactions, product is washed, dry to get being the carrier material of shell by core, carbon material of metal hydroxides；Under room temperature and stirring condition, resulting vehicle material is placed in the plating solution of palladium or platinum or bianry alloy plating solution containing palladium or platinum and is electroplated, washs, dry, obtain composite electro catalytic material.The present invention is using carbon containing hydroxide as carrier-supported precious metal or the composite electro catalytic material of its alloy, glucose hydrothermal carbonization will inhibit the undue growth of hydroxide, control the pattern of hydroxide, improve its electric conductivity, therefore, the performance of composite electro catalytic material is significantly improved, there is high activity and good durability to ethyl alcohol electrocatalytic oxidation.
Description
Technical field
The invention belongs to field of fuel cell technology, and in particular to a kind of composite electro catalytic material and preparation method thereof and answer
With.
Background technique
Fuel cell is a kind of chemical devices for chemical energy possessed by fuel being directly changed into electric energy, researches and develops efficiently peace
Full fuel cell technology realizes that sustainable development is of great significance for solving the global problems such as energy and environment.Phase
Than in conventional hydrogen fuel cell, Direct Ethanol Fuel Cell it is a technical advantage that: alcohol fuel not only theoretical energy density
Height (8.0kWh kg-1), and ethyl alcohol price is low, can be prepared by the fermentation batch of agricultural product.In addition, ethyl alcohol is normal in room temperature
Pressure is liquid, convenient for storing and transporting, and transports/fills in infrastructure in existing liquid fuel (gasoline) and have using simultaneous
Capacitive.Develop high activity, highly selective and good stability anode electrocatalysis material is to develop alcohol fuel cell technology
It is crucial.
Palladium (Pd) or platinum (Pt) have preferable performance to ethyl alcohol electrocatalytic oxidation, but at mild temperature, ethyl alcohol oxygen
Change reaction generate carbon containing intermediate product catalyst surface it is strong adsorb easily cause catalyst poisoning, therefore, monometallic Pd or
Pt is not the anode catalyst of effective electrocatalytic oxidation ethyl alcohol.In response to this problem, catalyst alloy and introducing are generallyd use
Two methods of oxide or hydroxide carrier improve.Introduce noble metal (for example, Au, Ag and Rh etc.) or base metal
(for example, Ni, Co, Cu and Sn etc.) alloying is for the electronic structure of modulation Pd or Pt, to adjust catalyst surface and second
The active force of alcohol or in which product, to improve the latent active and reaction selectivity of catalyst；And introduce oxide or hydrogen-oxygen
Compound is to construct the composite catalyst being made of Pd or Pt noble metal.Noble metal electro-catalysis ethyl alcohol in composite catalyst, and
Oxide or hydroxide carrier not only contribute to the dispersion of metallic catalyst, prevent from reuniting, and hydroxyl (- OH) assistance can also be provided
Further oxidation elimination is adsorbed on precious metal surface and causes the carbon containing intermediate product of catalyst poisoning.Make list using both of these approaches
The performance of metal Pd or Pt electrocatalytic oxidation ethyl alcohol is improved, and is answered especially with prepared by oxide or hydroxide carrier
Catalyst is closed, there is more excellent electrocatalysis characteristic.But usually provide the oxide of hydroxyl or the conduction of hydroxide carrier
Property is poor, limits further increasing for elctro-catalyst efficiency.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of compound
The preparation method of electrocatalysis material.
Another object of the present invention is to provide a kind of composite electro catalytic materials being prepared by the above method.
A further object of the present invention is to provide application of the above-mentioned composite electro catalytic material in alcohol fuel cell.
A kind of preparation method of composite electro catalytic material, including following preparation step:
(1) foam metal being added in glucose solution, 130~180 DEG C of hydro-thermal reactions, product is washed, dry,
It is able to the carrier material that metal hydroxides is core, carbon material is shell；
(2) under room temperature and stirring condition, step (1) resulting vehicle material is placed in the plating solution of palladium or platinum or containing palladium or platinum
Bianry alloy plating solution in be electroplated, wash, dry, obtain composite electro catalytic material.
Preferably, foam metal described in step (1) is handled before first washing through pickling and alcohol before.
Preferably, foam metal described in step (1) refers to nickel foam, foam copper or foam dilval.
Preferably, the concentration of glucose solution described in step (1) is 0.02~0.08M.
Preferably, the time of hydro-thermal reaction described in step (1) be 12~for 24 hours.
Preferably, washing described in step (1) refers to washes through washing and alcohol, and the drying refers at 40~80 DEG C dry 4
~8h.
Preferably, the plating solution of palladium described in step (2) or platinum refers to containing palladium chloride (PdCl2) or chloroplatinic acid (H2PtCl6)
Aqueous solution；The bianry alloy plating solution containing palladium or platinum refers to containing PdCl2Or H2PtCl6Appoint with gold, silver, copper, nickel, cobalt
It anticipates the aqueous solution of element compound a kind of.
Preferably, the condition of plating described in step (2) are as follows: current density is 0.20~30mA/cm2, electroplating time is
60~300s.
A kind of composite electro catalytic material, is prepared by the above method.
The composite electro catalytic material is made of noble metal or its alloy and carbon containing hydroxide carrier.
Hydroxide is lamella pattern in the carbon containing hydroxide carrier, and with a thickness of 1~5nm, carbon has amorphous knot
Structure or graphited carbon.
Application of the above-mentioned composite electro catalytic material in alcohol fuel cell, the application is the following steps are included: with compound
Electrocatalysis material is used as anode, under the catalytic action of composite electro catalytic material, ethyl alcohol electrocatalytic oxidation in alcohol fuel cell
Change obtains acetic acid, releases four electronics, is supplied to cathode, and the oxygen reduction for being adsorbed in cathode generates water, to realize chemistry
Electric energy can be converted into.
The preparation principle of composite electro catalytic material of the present invention are as follows:
Foam metal (for example, nickel foam) is placed in the water heating kettle containing glucose solution, electrification occurs for foam metal
It learns corrosion and generates metal hydroxides [Ni (OH) in its surface in situ2], reaction is as shown in (1)-(3).It is 130 in reaction temperature
Under the conditions of~180 DEG C, gluconate dehydratase is carbonized to form carbon material, and reacting available (4) indicates, and the carbon material formed will be deposited on
The Ni (OH) of growth2On, the carbon material of generation can inhibit Ni (OH)2Undue growth, carbon containing metal hydroxides have core-shell structure copolymer
Structure, core are hydroxide, and shell is carbon material.In addition, in-between product is organic acid in gluconate dehydratase carbonisation,
Organic acid can inhibit the progress of reaction (3), prevent foam metal surface in situ from generating Ni (OH)2Undue growth.Then, to system
Standby carrier material carries out electroplate precious metal or alloy, so that the support type composite electro catalytic material be made.
By taking nickel foam as an example, the chemical reaction that above-mentioned preparation process is occurred is as follows:
Ni→Ni2++2e– (1)
1/2O2+H2O+2e–→2OH– (2)
Ni2++2OH–→Ni(OH)2 (3)
C6H12O6→H2O+C (4)
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) present invention is by preparation using carbon containing hydroxide as carrier-supported precious metal or the composite electro catalytic material of its alloy
Material, hydroxide can assist Precious metal oxidation elimination to be adsorbed on the carbon containing intermediate product that catalyst poisoning is caused on its surface, grape
Sugared hydrothermal carbonization will inhibit the undue growth of hydroxide, control the pattern of hydroxide, improve its electric conductivity, because
This, significantly improves the performance of composite electro catalytic material.
(2) composite electro catalytic material preparation process of the invention is simple, is easy to large-scale production, the composite electro catalytic of preparation
Agent has high activity and good durability to ethyl alcohol electrocatalytic oxidation.
Detailed description of the invention
Fig. 1 is Pd/Ni (OH) prepared by embodiment 12/ nickel foam and Pd/Ni (OH)2@C/ nickel foam composite electro catalytic material
Pattern compares and Pd/Ni (OH)2The distribution map of@C/ nickel foam composite electro catalytic material component.(a, b) is Pd/Ni (OH)2/
Nickel foam scanning nuclear microprobe figure；(c, d) is Pd/Ni (OH)2@C/ nickel foam scanning nuclear microprobe figure；It (e-i) is Pd/
Ni(OH)2The distribution of@C/ nickel foam composite electro catalytic material angle of elevation annular dark field-scanning transmission electron microscope figure and Pd, Ni and C element
Figure.
Fig. 2 is the Pd/Ni (OH) that embodiment 1 obtains2/ nickel foam and Pd/Ni (OH)2@C/ nickel foam elctro-catalyst Raman light
Spectrum analysis figure.
Fig. 3 be embodiment 1 obtain Pd/ nickel foam, Pd/Ni (OH)2/ nickel foam and Pd/Ni (OH)2@C/ nickel foam electricity is urged
The performance for changing material oxidation ethyl alcohol compares.(a) three kinds of elctro-catalyst cyclic voltammetry active testing figures, scanning range be 0.12~
1.16V, sweep speed are 50mV s-1；(b) activity of three kinds of elctro-catalysts is tested using cyclic voltammetry, scanning range is
0.12~1.16V, sweep speed are 50mV s-1, recycle 2000 times, extract positive mass peak current density pair from each circulation
Cycle-index mapping；(c) the durability figure of three kinds of elctro-catalysts, initial potential 0.70V are tested using chrono-amperometric Amperometric
Vs.RHE (reversible hydrogen electrode), sweep time 5000s, sweep speed are 50mV s-1；All tests are carried out in room temperature, institute
It is 1.0M C with fuel fluid2H5OH+1.0M NaOH。
Fig. 4 is Pt/ foam copper, the Pt/Cu (OH) that embodiment 2 obtains2/ foam copper and Pt/Cu (OH)2@C/ foam copper electricity is urged
The performance for changing material oxidation ethyl alcohol compares.(a) activity of three kinds of elctro-catalysts is tested using cyclic voltammetry, scanning range is
0.12~1.16V, sweep speed are 50mV s-1, recycle 2000 times, extract positive mass peak current density pair from each circulation
Cycle-index mapping；(b) the durability figure of three kinds of elctro-catalysts, initial potential 0.70V are tested using chrono-amperometric Amperometric
Vs.RHE (reversible hydrogen electrode), sweep time 5000s, sweep speed are 50mV s-1；All tests are carried out in room temperature, institute
It is 1.0M C with fuel fluid2H5OH+1.0M NaOH。
Fig. 5 is Pd-Ni/ foam ferronickel, the Pd-Ni/Ni (OH) that embodiment 3 obtains2-Fe(OH)3/ foam ferronickel and Pd-
Ni/Ni(OH)2-Fe(OH)3The performance of@C/ nickel foam ferroelectricity catalysis material Oxidation of Alcohol compares.Using cyclic voltammetry test three
The activity of kind elctro-catalyst, scanning range are 0.12~1.16V, and sweep speed is 50mV s-1, recycle 2000 times, from following every time
Ring extracts positive mass peak current density and maps to cycle-index.All tests are carried out in room temperature, and fuel used liquid is
1.0M C2H5OH+1.0M NaOH。
Fig. 6 be embodiment 4 obtain Pd-Ag/ nickel foam, Pd-Ag/Ni (OH)2/ nickel foam and Pd-Ag/Ni (OH)2@C/
The performance of nickel foam electrocatalysis material Oxidation of Alcohol compares.The activity of three kinds of elctro-catalysts, scanning are tested using cyclic voltammetry
Range is 0.12~1.16V, and sweep speed is 50mV s-1, recycle 2000 times, extract positive mass peak electric current from each circulation
Density maps to cycle-index.All tests are carried out in room temperature, and fuel used liquid is 1.0M C2H5OH+1.0M NaOH。
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of composite electro catalytic material Pd/Ni (OH) of the present embodiment2@C/ nickel foam, preparation method are as follows:
(1) hydro-thermal method preparation Ni (OH)2@C/ foam nickel carrier
By nickel foam (1 × 1.45cm after pre-treatment is washed in pickling and alcohol2) it is placed in the water of the glucose solution containing 0.06M
It in hot kettle, is reacted for 24 hours at 140 DEG C of reaction temperature, naturally cools to room temperature, the nickel foam of collection is washed dry in 50 DEG C through washing and alcohol
For dry 6h to get using nickel hydroxide as core, carbon material is the carrier material of shell.
(2) carrier plating Pd preparation Pd/Ni (OH)2@C/ nickel foam composite electro catalytic material
Under room temperature and stirring condition, carrier prepared by step (1) is placed in 8mM PdCl2,0.5M H3BO3,1.0M
NaCl plating solution is 0.25mA cm in current density-2Under the conditions of, 100s is electroplated in constant current, to get support type after washed drying
Composite electro catalytic material.The load capacity of Pd is determined using inductively coupled plasma atomic emission spectrometry (ICP-AES).
In order to carry out performance comparison, under similar conditions, it is prepared for Pd/ nickel foam and Pd/Ni (OH)2/ nickel foam electricity is urged
Agent.Pd/ nickel foam elctro-catalyst, which refers to, is directly electroplated Pd in nickel foam；Pd/Ni(OH)2/ nickel foam elctro-catalyst refers to
Hydro-thermal reaction is carried out in no glucose dress water reaction kettle, first prepares Ni (OH)2/ foam nickel carrier, then re-plating Pd.
The support type composite electro catalytic material of the present embodiment is in ethyl alcohol (C2H5OH) the application in fuel cell, concrete application
Process is as follows:
The composite electro catalytic material oxidation alcohol performance test of preparation is carried out in three-electrode electro Chemical device, the electrode of preparation
Material is working electrode (1 × 1cm2), a piece of Pt (1.5 × 1.5cm2) it is to electrode, HgO/Hg electrode is reference electrode, is used
Current potential refer to compared to reversible hydrogen electrode (RHE).The activity of elctro-catalyst is tested using cyclic voltammetry, and scanning range is
0.12~1.16V, sweep speed are 50mV s-1.The durability of elctro-catalyst uses cyclic voltammetry and chrono-amperometric Amperometric
Test.The performance test of elctro-catalyst is carried out in room temperature, and fuel used liquid is 1.0M C2H5OH+1.0M NaOH。
The Pd/Ni (OH) that the present embodiment obtains2/ nickel foam and Pd/Ni (OH)2@C/ nickel foam composite electro catalytic material morphology
It is studied with Elemental redistribution using scanning electron microscope and transmission electron microscope, as shown in Figure 1.It can be seen that from Fig. 1 (a, b) in no grape
When sugared, through hydro-thermal reaction, grown one layer in nickel foam surface in situ has hexagonal nanosheet layer Ni (OH)2, thickness is about
For 50nm；When there is glucose, the Ni (OH) that is grown through hydro-thermal reaction in foam nickel surface2It is thick for the nanoscale twins of hair wrinkle
Degree is about 3nm.The reason of pattern generation significant change, may have occurred under hydrothermal conditions what dehydration carbonization was formed with glucose
Carbon material is related, and the carbon material deposition of formation is in Ni (OH)2On, it can inhibit the undue growth of hydroxide.In addition, glucose is de-
In water carbonisation, in-between product is organic acid, and organic acid can inhibit the progress of reaction (3), causes foam nickel electro-chemistry rotten
Lose the Ni (OH) generated2Growth is suppressed.From Pd/Ni (OH)2@C/ nickel foam composite electro catalytic material angle of elevation annular dark field-sweep
Retouching transmission electron microscope picture [Fig. 1 (e-i)] can be seen that Pd nanometers of a small bundle of straw, etc. for silkworms to spin cocoons ons are uniformly distributed in Ni (OH)2On, glucose also can be observed and exist
Carbon (C) element that dehydration carbonization is formed under hydrothermal condition.When carrying out hydro-thermal reaction there are glucose, gluconate dehydratase carbonization shape
It is further proved by Raman spectrum analysis at carbon material.As shown in Fig. 2, compared in hydro-thermal reaction without sample prepared by glucose
The Raman spectrogram of product, there are samples prepared by glucose, in about 1360cm-1And 1587cm-1When there are two peaks, this
Two peaks can identify as the D band and G of amorphous carbon or graphitized carbon band characteristic peak.
Pd/Ni (OH) manufactured in the present embodiment2The performance of@C/ nickel foam composite electro catalytic material oxidation ethyl alcohol is surveyed
Examination, and with Pd/ nickel foam and Pd/Ni (OH)2/ nickel foam electrocatalysis material compares.As shown in Fig. 3 (a), three kinds of catalysis
Agent is active to ethyl alcohol electrocatalytic oxidation, it was found from positive mass peak current density: Pd/Ni (OH)2@C/ nickel foam is multiple
Closing elctro-catalyst has optimal electrocatalysis characteristic, positive mass peak current density (1295mA mg-1) it is Pd/ bubble respectively
Foam nickel (187mA mg-1) and Pd/Ni (OH)2/ nickel foam (457mA mg-1) 7 times and 3 times of elctro-catalyst.In addition, using this hair
The Pd/Ni (OH) of bright preparation2@C/ nickel foam composite electrocatalyst also has preferable durability.As shown in Fig. 3 (b), through 2000
Secondary circulation, Pd/ nickel foam and Pd/Ni (OH)2/ nickel foam elctro-catalyst activity loses the 2/3 and 1/2 of its initial activity；And
Pd/Ni(OH)2@C/ nickel foam composite electrocatalyst is still able to maintain the 89.6% of its initial activity.The survey of chrono-amperometric Amperometric
Examination further demonstrates that Pd/Ni (OH)2@C/ nickel foam composite electrocatalyst has preferable durability.As shown in Fig. 3 (c), warp
After 5000s, the activity of three kinds of catalyst is reduced, but Pd/Ni (OH)2The amplitude that@C/ nickel foam composite electro catalytic material reduces
Minimum shows that the catalyst has preferable anti-poisoning capability.The performance of electrocatalysis material is mainly by its latent active, active sites
Quantity and conductive capability determine, using composite electro catalytic material prepared by the present invention, can control the excessive of metal hydroxides
Growth, therefore, is conducive to improve its electrocatalysis characteristic.
Embodiment 2
A kind of composite electro catalytic material Pt/Cu (OH) of the present embodiment2@C/ foam copper, preparation method are as follows:
(1) hydro-thermal method preparation Cu (OH)2@C/ foam copper carrier
By foam copper (1 × 1.45cm after pre-treatment is washed in pickling and alcohol2) it is placed in the water of the glucose solution containing 0.08M
In hot kettle, in 160 DEG C of reaction 18h of reaction temperature, room temperature is naturally cooled to, the foam copper of collection is washed dry in 80 DEG C through washing and alcohol
For dry 4h to get using Kocide SD as core, carbon material is the carrier material of shell；
(2) carrier plating Pt preparation Pt/Cu (OH)2@C/ foam copper composite electro catalytic material
Under room temperature and stirring condition, carrier prepared by step (1) is placed in 6mM H2PtCl6Plating solution is in current density
15mA cm-2Under the conditions of, 180s is electroplated in constant current, to get support type composite electro catalytic material after washed drying.The load of Pt
Amount is determined using ICP-AES.
In order to carry out performance comparison, under similar conditions, it is prepared for Pt/ foam copper and Pt/Cu (OH)2/ foam copper electricity is urged
Agent.Pt/ foam copper elctro-catalyst, which refers to, is directly electroplated Pt in foam copper；Pt/Cu(OH)2/ foam copper elctro-catalyst refers to
Hydro-thermal reaction is carried out in no glucose dress water reaction kettle, first prepares Cu (OH)2/ foam copper carrier, then re-plating Pt.
Take the Pt/Cu (OH) of the present embodiment2@C/ foam copper composite electro catalytic material carries out the performance test experiment of catalyst
(by embodiment 1 performance test methods and condition carry out), as a result as shown in Figure 4.As seen from Figure 4: preparation Pt/Cu
(OH)2@C/ foam copper composite electro catalytic material activity and durability are better than the Pt/ foam copper and Pt/Cu prepared under conditions of similarity
(OH)2/ foam copper elctro-catalyst.In room temperature, Pt/Cu (OH)2@C/ foam copper composite electro catalytic material initial peak currents are close
Degree is 982mA mg-1, the catalyst 2000 times recyclings and 5000s use, catalyst are still able to maintain its initial activity
82% and 35%.
Embodiment 3
A kind of composite electro catalytic material Pd-Ni/Ni (OH) of the present embodiment2-Fe(OH)3@C/ foam ferronickel, preparation side
Method is as follows:
(1) hydro-thermal method preparation Ni (OH)2-Fe(OH)3@C/ foam ferronickel
By foam ferronickel (1 × 1.45cm after pre-treatment is washed in pickling and alcohol2) it is placed in the glucose solution containing 0.05M
In water heating kettle, in 150 DEG C of reaction 15h of reaction temperature, room temperature is naturally cooled to, the foam ferronickel of collection is washed through washing and alcohol in 60
To get using nickel hydroxide-iron hydroxide as core, carbon material is the carrier material of shell by DEG C dry 5h；
(2) carrier plating Pd-Ni preparation Pd-Ni/Ni (OH)2-Fe(OH)3@C/ foam ferronickel composite electro catalytic material
Under room temperature and stirring condition, carrier prepared by step (1) is placed in 6mM PdCl2With 6mM NiCl2Plating solution,
Current density is 10mA cm-2Under the conditions of, 120s is electroplated in constant current, to get support type composite electro catalytic material after washed drying
Material.The load capacity and Pd-Ni component (Pd content is about 55atm%) of Pd is determined using ICP-AES.
In order to carry out performance comparison, under similar conditions, it is prepared for Pd-Ni/ foam ferronickel and Pd-Ni/Ni (OH)2-Fe
(OH)3/ nickel foam ferroelectricity catalyst.Pd-Ni/ nickel foam ferroelectricity catalyst, which refers to, directly plates Pd-Ni in nickel foam ferroelectricity；Pd-
Ni/Ni(OH)2-Fe(OH)3/ nickel foam ferroelectricity catalyst, which refers to, carries out hydro-thermal reaction in no glucose dress water reaction kettle, first makes
Standby/Ni (OH)2-Fe(OH)3/ nickel foam siderophore, then re-plating Pd-Ni.
Take the Pd-Ni/Ni (OH) of the present embodiment2-Fe(OH)3@C/ foam ferronickel composite electro catalytic material carries out catalyst
Performance test experiment (by embodiment 1 performance test methods and condition carry out), as a result as shown in Figure 5.It can be seen by Fig. 5
Out: preparation Pd-Ni/Ni (OH)2-Fe(OH)3@C/ foam ferronickel composite electro catalytic material activity and durability are better than conditions of similarity
The Pd-Ni/ foam ferronickel and Pd-Ni/Ni (OH) of lower preparation2-Fe(OH)3/ nickel foam iron catalyst.In room temperature, Pd-Ni/Ni
(OH)2-Fe(OH)3@C/ foam ferronickel composite electro catalytic material initial peak currents density is 3450mA mg-1, the catalyst
2000 recyclings, catalyst are still able to maintain the 92% of its initial activity.
Embodiment 4
A kind of support type composite electro catalytic material Pd-Ag/Ni (OH) of the present embodiment2@C/ nickel foam, preparation method is such as
Under:
(1) hydro-thermal method preparation Ni (OH)2@C/ nickel foam
By nickel foam (1 × 1.45cm after pre-treatment is washed in pickling and alcohol2) it is placed in the water of the glucose solution containing 0.06M
In hot kettle, in 140 DEG C of reaction 12h of reaction temperature, room temperature is naturally cooled to, the nickel foam of collection is washed dry in 50 DEG C through washing and alcohol
For dry 6h to get using nickel hydroxide as core, carbon material is the carrier material of shell.
(2) carrier plating Pd-Ag preparation Pd-Ag/Ni (OH)2@C/ nickel foam composite electro catalytic material
Under room temperature and stirring condition, carrier prepared by step (1) is placed in 10mM PdCl2With 10mM AgNO3Plating solution,
It is 1.50mA cm in current density-2Under the conditions of, 180s is electroplated in constant current, to get support type composite electro catalytic after washed drying
Material.The load capacity and Pd-Ag component (Pd content is about 48atm%) of Pd is determined using ICP-AES.
In order to carry out performance comparison, under similar conditions, it is prepared for Pd-Ag/ nickel foam and Pd-Ag/Ni (OH)2/ foam
Nickel elctro-catalyst.Pd-Ag/ nickel foam ferroelectricity catalyst, which refers to, is directly electroplated Pd-Ag in nickel foam；Pd-Ag/Ni(OH)2/ foam
Nickel elctro-catalyst, which refers to, carries out hydro-thermal reaction in no glucose dress water reaction kettle, first prepares Ni (OH)2/ foam nickel carrier, so
Re-plating Pd-Ag afterwards.
Take the Pd-Ag/Ni (OH) of the present embodiment2The performance test of@C/ nickel foam composite electro catalytic material progress catalyst
Experiment (by embodiment 1 performance test methods and condition carry out), as a result as Fig. 6 shows.As seen from Figure 6: preparation Pd-
Ag/Ni(OH)2@C/ nickel foam composite electro catalytic material activity and durability are better than the Pd-Ag/ nickel foam prepared under conditions of similarity
With Pd-Ag/Ni (OH)2The agent of/foamed nickel catalyst.In room temperature, Pd-Ag/Ni (OH)2@C/ nickel foam composite electro catalytic material is initial
Peak current density is 4580mA mg-1, the catalyst 2000 times recyclings, catalyst is still able to maintain its initial activity
95%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of composite electro catalytic material, it is characterised in that including following preparation step:
(1) foam metal is added in glucose solution, 130~180 DEG C of hydro-thermal reactions, product is washed, it is dry to get
It is the carrier material of shell by core, carbon material of metal hydroxides；
(2) under room temperature and stirring condition, by step (1) resulting vehicle material be placed in the plating solution of palladium or platinum or containing palladium or platinum two
It is electroplated in first alloy electroplating bath, washs, dries, obtain composite electro catalytic material.
2. a kind of preparation method of composite electro catalytic material according to claim 1, it is characterised in that: institute in step (1)
The foam metal stated is handled before first washing through pickling and alcohol before.
3. a kind of preparation method of composite electro catalytic material according to claim 1, it is characterised in that: institute in step (1)
The foam metal stated refers to nickel foam, foam copper or foam dilval.
4. a kind of preparation method of composite electro catalytic material according to claim 1, it is characterised in that: institute in step (1)
The concentration for stating glucose solution is 0.02~0.08M.
5. a kind of preparation method of composite electro catalytic material according to claim 1, it is characterised in that: institute in step (1)
State hydro-thermal reaction time be 12~for 24 hours.
6. a kind of preparation method of composite electro catalytic material according to claim 1, it is characterised in that: institute in step (1)
State washing refer to through washing and alcohol wash, the drying refers in 40~80 DEG C of dry 4~8h.
7. a kind of preparation method of composite electro catalytic material according to claim 1, it is characterised in that: institute in step (2)
The plating solution for stating palladium or platinum refers to containing PdCl2Or H2PtCl6Aqueous solution；The bianry alloy plating solution containing palladium or platinum, which refers to, to be contained
There is PdCl2Or H2PtCl6With the aqueous solution of any one element compound in gold, silver, copper, nickel, cobalt.
8. a kind of preparation method of composite electro catalytic material according to claim 1, it is characterised in that described in step (2)
The condition of plating are as follows: current density is 0.20~30mA/cm2, electroplating time is 60~300s.
9. a kind of composite electro catalytic material, it is characterised in that: be prepared by method according to any one of claims 1 to 8.
10. application of the composite electro catalytic material as claimed in claim 9 in alcohol fuel cell.
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