CN105810957A - Preparation and application of platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst - Google Patents
Preparation and application of platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst, and application of the platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst in a direct methanol fuel cell. A three-dimensional structured carrier including a multi-stage hole channel is constructed by utilizing the three-dimensional structure of graphene in combination with the net structure of nickel hydroxide-cobalt hydroxide; the aggregation problem of graphene is overcome to a certain degree; simultaneously, the ultra-high specific surface area and the good conductivity of graphene can make up the disadvantage that the conductivity of nickel hydroxide-cobalt hydroxide is poor; therefore, electron transfer and mass transfer in an oxidization-reduction process can be promoted; the dispersibility and the stability of catalyst particles are improved; the catalytic activity of a Pt catalyst to methanol is further increased by utilizing the catalytic performance of nickel hydroxide-cobalt hydroxide to methanol oxidation; and the use amount of the noble metal Pt is reduced. The method disclosed by the invention is simple in step, convenient to operate and high in practicability.
Description
Technical field
The invention belongs to field of nanometer material technology, particularly to a kind of platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite catalyst
Preparation and application.
Background technology
Proton Exchange Membrane Fuel Cells becomes the research weight in current novel energy field due to its economic and environment-friendly and higher generating efficiency
Point.Operate using methanol as the DMFC (DMFC) constructed by the proton energy of Proton Exchange Membrane Fuel Cells
Easy, battery structure simply and can the most quickly start.Noble metal platinum (Pt) is sun the most frequently used for DMFC
Electrode catalyst, is, under acid condition, methanol electro-oxidizing is reacted maximally effective catalyst.But Pt price is high, quality (area)
Specific activity is low and is easily caused poisoning by intermediate products such as the CO in methanol oxidation process, and these shortcomings hinder the business of DMFC
Change process.In order to realize the most considerable catalysis activity, improving the catalytic efficiency of catalyst, substantial amounts of research gets down to Pt base and urges
The macroscopic view composition of agent and the modification to its pattern such that it is able to modulate its micro-scale and level density, fundamentally solve Pt
Defect existing for catalyst.
Graphene is a kind of novel Two-dimensional Carbon nano material, has the advantages such as bigger serface, high conductivity and good stability,
Thus it is often used as the carrier of catalyst, it is possible to increase the dispersibility of Pt catalyst, the size reducing catalyst granules and then raising
The utilization rate of Pt.But Graphene is easily reunited, this reduces its stability as catalyst carrier to a certain extent.Build one
Plant the Graphene of three-dimensional porous structure, the advantage of two-dimensional graphene can be incorporated in three dimensional structure, it is also possible to overcome two dimension stone
The agglomeration traits of ink alkene.But the electrochemically active specific surface area of existing load Pt three-dimensional grapheme and ion diffusion rates are still difficult to be met
The technology requirement of the high-grade, precision and advanced industries such as military, space flight.
Summary of the invention
In order to solve the problems referred to above, the invention provides a kind of platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite catalyst
Preparation method and the application in DMFC thereof.It is intended to utilize the three dimensional structure combining hydrogen oxidation nickel-hydrogen oxygen of Graphene
The network structure changing cobalt builds the three dimensional structure carrier containing multistage pore canal, overcomes the agglomeration traits of Graphene to a certain extent,
The specific surface area of Graphene superelevation and excellent electric conductivity can make up the defect of nickel hydroxide-cobalt hydroxide poorly conductive simultaneously,
Thus promote the electron transmission in oxidation-reduction process and mass transfer, improve dispersibility and the stability of catalyst granules.Utilize hydrogen
The catalytic performance that methanol is aoxidized by nickel oxide-cobalt hydroxide, improves the Pt catalyst catalysis activity to methanol further, reduces your gold
Belong to the consumption of Pt.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of platinum/nickel hydroxide-cobalt hydroxide/Graphene three dimensional composite structure, including:
Three-dimensional graphene framework；
Nickel hydroxide in described three-dimensional graphene framework-cobalt hydroxide network structure；
Platinum metal layer in described nickel hydroxide-cobalt hydroxide network structure；
Wherein, described nickel hydroxide-cobalt hydroxide network structure is made up of nickel hydroxide and cobalt hydroxide nanoscale twins.
The nickel hydroxide of loose structure has big specific surface area, this electrochemical reaction helping lend some impetus to interface and active material
Effectively utilize.But the electric conductivity of nickel hydroxide is poor, is unfavorable for electron transmission.Electric conductivity is added higher in nickel hydroxide
Cobalt hydroxide, improves its electric conductivity and electro-chemical activity.Meanwhile, nickel hydroxide-cobalt hydroxide complex is anti-for the oxidation of methanol
Should have catalytic action, prepare nickel hydroxide-cobalt hydroxide by co-electrodeposition method on three-dimensional grapheme surface and can obtain by uniformly
The network structure of nanoscale twins composition, this structure makes it have big electrochemically active specific surface area, is more beneficial for charge transfer
Diffusion with ion.Graphene also is able to produce cooperative effect with Pt as the carrier material of DMFC anode catalyst, and raising is urged
The agent catalytic efficiency to methanol, promotes reaction process.
Preferably, in described nickel hydroxide-cobaltous hydroxide layer, the mol ratio of nickel element and cobalt element is 0.0001～1:0.0001～1.
It is furthermore preferred that nickel element is 0.9～1:0.0001～0.1 with the mol ratio of cobalt element in described nickel hydroxide-cobaltous hydroxide layer.
Present invention also offers a kind of platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite material electrode, including:
The three-dimensional graphene framework being deposited on electrode；
Nickel hydroxide in described three-dimensional graphene framework-cobalt hydroxide network structure；
Platinum metal layer in described nickel hydroxide-cobalt hydroxide network structure；
Wherein, described nickel hydroxide-cobalt hydroxide network structure is made up of nickel hydroxide and cobalt hydroxide nanoscale twins.
Preferably, selected electrode material is electro-conductive glass.
Preferably, in described nickel hydroxide-cobaltous hydroxide layer, the mol ratio of nickel element and cobalt element is 0.0001～1:0.0001～1.
It is furthermore preferred that nickel element is 0.9～1:0.0001～0.1 with the mol ratio of cobalt element in described nickel hydroxide-cobaltous hydroxide layer.
Present invention also offers the preparation method of a kind of platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite catalyst, including:
Use electrodeposition process to form network structure in three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet, obtain hydrogen-oxygen
Change nickel-hydrogen cobalt oxide/graphene complex；
Platinum is reverted to nickel hydroxide-cobalt hydroxide/graphene complex surface, obtains platinum/nickel hydroxide-cobalt hydroxide/Graphene three
Dimension composite catalyst.
Preferably, described nickel hydroxide-cobalt hydroxide nanometer sheet is composited by nickel hydroxide and cobalt hydroxide, wherein, and nickel element
It is 0.0001～1:0.0001～1 with the mol ratio of cobalt element.
It is furthermore preferred that nickel element is 0.9～1:0.0001～0.1 with the mol ratio of cobalt element in described nickel hydroxide-cobaltous hydroxide layer.
Preferably, the condition of described electrodeposition process is: cyclic voltammetry scan 10～20 circle in the range of-1.5V～-0.2V, sweeps
Speed is 30-150mV s-1；
It is furthermore preferred that described employing electrodeposition process is in the concrete step of three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet
Suddenly it is: preparation sodium nitrate, cobalt nitrate and the mixed solution of nickel nitrate, the working electrode being loaded with three-dimensional grapheme is immersed in
State in mixed solution, cyclic voltammetry scan in the range of-1.5V～-0.2V, sweep speed for 30-150mV s-1, scan 10～50
Circle, dialysis removes the mixed solution of residual, is dried, obtains nickel hydroxide-cobalt hydroxide/graphene complex.
Preferably, the reducing condition of described platinum is: take nickel hydroxide-cobalt hydroxide/graphene suspension and platinum acid chloride solution, mixing,
Addition sodium hydroxide regulation pH of mixed, to 9～11, adds sodium borohydride, stirs 12～48 hours under room temperature, and washing is dried,
Obtain.
Preferably, described three-dimensional grapheme is adopted and is prepared with the following method: by reference electrode, to electrode and working electrode three electrode body
System is connected on electrochemical workstation, immerses in the mixed solution of graphene oxide and lithium perchlorate, in the scope of-1.5V～0.6V
Inside it is circulated voltammetric scan, sweeps speed for 25mV s-1, scanning 3～10 circle, remove graphene oxide and the lithium perchlorate of residual,
Obtain three-dimensional grapheme.
The method of the graphene oxide and lithium perchlorate of removing residual described in it is furthermore preferred that is: use deionized water rinsing three-dimensional graphite
Alkene, soaks the graphene oxide removing electrode surface absorption the most in deionized water.Then leading of three-dimensional grapheme will be loaded with
Electricity glass is immersed in 1mol L-1Lithium perchlorate solution in, in the range of-1.5V～0.6V, (sweep speed is cyclic voltammetry scan
20-50mV·s-1), scanning 10～20 circle, then electrode is immersed in deionized water dialysis and falls lithium perchlorate.
Idiographic flow is as follows: first on electro-conductive glass, electrochemical deposition prepares three-dimensional grapheme, then at three-dimensional grapheme
On prepare nickel hydroxide-cobalt hydroxide by electrodeposition process and obtain nickel hydroxide-cobalt hydroxide/graphene complex, then by hydroxide
Nickel-hydrogen cobalt oxide/graphene complex is scattered in the mixed solution of water and methanol, adds platinum acid chloride solution, drip under conditions of stirring
Hydro-oxidation sodium regulation pH, the most ultrasonic mix homogeneously, add sodium borohydride, stirring reaction certain time under room temperature, by platinum
It is three-dimensional that nano-particle reverts to obtain platinum/nickel hydroxide-cobalt hydroxide/Graphene on nickel hydroxide-cobalt hydroxide/graphene complex
Composite catalyst.Electrochemical deposition method is simple to operate, low cost, by electrochemical deposition method prepare nickel hydroxide-cobalt hydroxide/
Graphene three dimensional composite structure, requires low to experimental implementation, simultaneously it can be avoided that poisonous reducing agent or the use of dispersant, is one
The method planting environmental protection and economy.
Present invention also offers the preparation method of a kind of preferably platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite catalyst,
Including:
The preparation of composite catalyst
It is graphite oxide according to Hummers method by the graphite oxidation of 325 mesh, takes a certain amount of graphite oxide and add deionized water,
In ultrasonic washing unit, supersound process is uniformly dispersed to graphite oxide, and obtaining concentration is 2mg mL-1～4.5mg mL-1Oxidation
Graphene solution, adds a certain amount of lithium perchlorate, obtains variable concentrations graphene oxide and concentration is 0.1mol L-1Height
The mixed solution of lithium chlorate.
By reference electrode (calomel electrode), electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system are connected
On electrochemical workstation, immerse in the mixed solution of graphene oxide and lithium perchlorate, carry out in the range of-1.5V～0.6V
Cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 3～10 circle, thus on electro-conductive glass, prepare three-dimensional grapheme, circulation
After voltammetric scan terminates, rinse three-dimensional grapheme with deionized water gently, soak the most in deionized water and remove electrode surface suction
Attached graphene oxide.Then the electro-conductive glass being loaded with three-dimensional grapheme is immersed in 1mol L-1Lithium perchlorate solution in,
In the range of-1.5V～0.6V, cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 10～20 circle, then immerses electrode
In deionized water, lithium perchlorate is fallen in dialysis.
Preparation sodium nitrate, cobalt nitrate and the mixed solution of nickel nitrate, wherein the concentration of sodium nitrate is 0.1mol L-1, cobalt nitrate is dense
Degree is xmol L-1, the concentration of nickel nitrate is (0.1-x) mol L-1(x=0,0.02,0.04,0.05,0.06,0.08,0.1).By naked
Electro-conductive glass and the electro-conductive glass being loaded with three-dimensional grapheme are immersed in above-mentioned mixed solution, respectively at the model of-1.5V～-0.2V
Enclose interior cyclic voltammetry scan and (sweep speed for 50mV s-1), scanning 10～20 circle, then immerses in deionized water by electrode, dialysis
Remove the mixed solution of residual, be dried under the conditions of 40～50 DEG C, obtain nickel hydroxide-cobalt hydroxide complex and nickel hydroxide-hydrogen-oxygen
Change cobalt/graphene complex.
2mg mL is prepared with deionized water-30% methanol mixed solution (volume ratio 1:1)-1Nickel hydroxide-cobalt hydroxide/graphite
Alkene suspension, ultrasonic washing unit is ultrasonic to being uniformly dispersed.Take 30mL nickel hydroxide-cobalt hydroxide/graphene suspension, stirring
(concentration is respectively 3mg mL to add 5mL platinum acid chloride solution under the conditions of mixing-1, 5mg mL-1, 7mg mL-1, 9mg mL-1,
11mg·mL-1), add sodium hydroxide regulation pH of mixed to 9～11.It is then slowly added into 200～300mg sodium borohydrides,
Stir 12～48 hours under room temperature.Be centrifuged repeatedly washing products therefrom with deionized water, under the conditions of 40～50 DEG C be dried, obtain platinum/
Nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Replace nickel hydroxide-cobalt hydroxide/graphene complex with Graphene, nickel hydroxide-cobalt hydroxide complex respectively, repeat
Above-mentioned steps, prepares platinum/graphen composite catalyst and platinum/nickel hydroxide-cobalt hydroxide composite catalyst respectively.
Catalyst prepared by any of the above-described method.Described catalyst can be used for catalysis methanol oxidation, prepares pem fuel
Battery or methanol fuel cell.
Beneficial effects of the present invention:
(1) the invention provides a kind of platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite catalyst preparation method and
Application in DMFC.Making programme is as follows: first on electro-conductive glass, electrochemical deposition prepares three-dimensional stone
Ink alkene, then prepares nickel hydroxide-cobalt hydroxide by electrodeposition process on three-dimensional grapheme and obtains nickel hydroxide-cobalt hydroxide/stone
Ink alkene complex, then nickel hydroxide-cobalt hydroxide/graphene complex is scattered in the mixed solution of water and methanol, the bar of stirring
Add platinum acid chloride solution, hydro-oxidation sodium regulation pH, the most ultrasonic mix homogeneously under part, add and stir under sodium borohydride, room temperature
Mix certain time, Pt nanoparticle reverts to obtain on nickel hydroxide-cobalt hydroxide/graphene complex platinum/nickel hydroxide-hydrogen-oxygen
Change cobalt/Graphene three-dimensional composite catalyst.
(2) electrochemical deposition method is simple to operate, low cost, prepares nickel hydroxide-cobalt hydroxide/graphite by electrochemical deposition method
Alkene three dimensional composite structure, requires low to experimental implementation, simultaneously it can be avoided that poisonous reducing agent or the use of dispersant, is a kind of ring
Protect economic method.
(3) it is contemplated that utilize the network structure of the three dimensional structure combining hydrogen oxidation nickel-hydrogen cobalt oxide of Graphene to build containing many
The three dimensional structure carrier in level duct, overcomes the agglomeration traits of Graphene, the simultaneously specific surface area of Graphene superelevation to a certain extent
With the defect that excellent electric conductivity can make up nickel hydroxide-cobalt hydroxide poorly conductive, thus promote in oxidation-reduction process
Electron transmission and mass transfer, improve the dispersibility of catalyst granules and stability.Utilize nickel hydroxide-cobalt hydroxide that methanol is aoxidized
Catalytic performance, improve further the Pt catalyst catalysis activity to methanol, reduce the consumption of precious metals pt.
(4) manufacturing process of the present invention is simple, practical, be prone to industrialization promotion.
Accompanying drawing explanation
Fig. 1 is the synthesis schematic diagram of platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Fig. 2 is (a) platinum/graphen, and (b) platinum/nickel hydroxide-cobalt hydroxide and (c) platinum/nickel hydroxide-cobalt hydroxide/Graphene are 1
mol·L-1Methanol and 1mol L-1Cyclic voltammetry curve in potassium hydroxide mixed solution.
Fig. 3 is (a) platinum/graphen, and (b) platinum/nickel hydroxide-cobalt hydroxide and (c) platinum/nickel hydroxide-cobalt hydroxide/Graphene three kinds are urged
Agent is at 1mol L-1Methanol and 1mol L-1Current-time curvel in potassium hydroxide mixed solution.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Embodiment 1
1. the preparation of composite catalyst
It is graphite oxide according to Hummers method by the graphite oxidation of 325 mesh, takes a certain amount of graphite oxide and add deionized water,
In ultrasonic washing unit, supersound process is uniformly dispersed to graphite oxide, and obtaining concentration is 2mg mL-1～4.5mg mL-1Oxidation
Graphene solution, adds a certain amount of lithium perchlorate, obtains variable concentrations graphene oxide and concentration is 0.1mol L-1Height
The mixed solution of lithium chlorate.
By reference electrode (calomel electrode), electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system are connected
On electrochemical workstation, immerse in the mixed solution of graphene oxide and lithium perchlorate, carry out in the range of-1.5V～0.6V
Cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 3～10 circle, thus on electro-conductive glass, prepare three-dimensional grapheme, circulation
After voltammetric scan terminates, rinse three-dimensional grapheme with deionized water gently, soak the most in deionized water and remove electrode surface suction
Attached graphene oxide.Then the electro-conductive glass being loaded with three-dimensional grapheme is immersed in 1mol L-1Lithium perchlorate solution in,
In the range of-1.5V～0.6V, cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 10～20 circle, then immerses electrode
In deionized water, lithium perchlorate is fallen in dialysis.
Preparation sodium nitrate, cobalt nitrate and the mixed solution of nickel nitrate, wherein the concentration of sodium nitrate is 0.1mol L-1, cobalt nitrate is dense
Degree is x mol L-1, the concentration of nickel nitrate is (0.1-x) mol L-1(x=0,0.02,0.04,0.05,0.06,0.08,0.1).By naked
Electro-conductive glass and the electro-conductive glass being loaded with three-dimensional grapheme are immersed in above-mentioned mixed solution, respectively at the model of-1.5V～-0.2V
Enclose interior cyclic voltammetry scan and (sweep speed for 50mV s-1), scanning 10～20 circle, then immerses in deionized water by electrode, dialysis
Remove the mixed solution of residual, be dried under the conditions of 40～50 DEG C, obtain nickel hydroxide-cobalt hydroxide complex and nickel hydroxide-hydrogen-oxygen
Change cobalt/graphene complex.
2mg mL is prepared with deionized water-30% methanol mixed solution (volume ratio 1:1)-1Nickel hydroxide-cobalt hydroxide/graphite
Alkene suspension, ultrasonic washing unit is ultrasonic to being uniformly dispersed.Take 30mL nickel hydroxide-cobalt hydroxide/graphene suspension, stirring
(concentration is respectively 3mg mL to add 5mL platinum acid chloride solution under the conditions of mixing-1, 5mg mL-1, 7mg mL-1, 9mg mL-1,
11mg·mL-1), pH value of solution is regulated to 9～11 by dropping sodium hydroxide.It is then slowly added into 200～300mg sodium borohydrides,
Stir 12～48 hours under room temperature.Be centrifuged repeatedly washing products therefrom with deionized water, under the conditions of 40～50 DEG C be dried, obtain platinum/
Nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Replace nickel hydroxide-cobalt hydroxide/graphene complex with Graphene, nickel hydroxide-cobalt hydroxide complex respectively, repeat
Above-mentioned steps, prepares platinum/graphen composite catalyst and platinum/nickel hydroxide-cobalt hydroxide composite catalyst respectively.
1. the sign of composite catalytic performance
1mg mL is prepared respectively with dehydrated alcohol-1Above-mentioned three kinds of composite catalyst suspensions, ultrasonic washing unit ultrasonic to catalysis
Agent is uniformly dispersed.Use the Al of 0.3,0.05 μm respectively2O3Glass-carbon electrode (diameter 3mm) is polished by powder, uses the most successively
Acetone, dehydrated alcohol, redistilled water supersound washing 5min, dry naturally.
Pipette 10 μ L above-mentioned composite catalyst hanging drop respectively to be coated onto on glass-carbon electrode, naturally dry.Utilize above-mentioned three kinds of electricity
Pole, in the potential range of-1.0V～0V, is 1mol L to concentration-1Potassium hydroxide solution be circulated voltammetric scan and (sweep speed
For 50mV s-1).Observe the adsorption desorption peak of hydrogen according to gained cyclic voltammogram and calculate peak area, thus obtaining three kinds of electrodes and urge
The electrochemical active surface of agent.
Utilize above-mentioned three kinds of electrodes, in the potential range of-0.8V～0.2V, methanol and concentration of potassium hydroxide are 1mol L-1's
Mixed solution is circulated voltammetric scan and (sweeps speed for 50mV s-1).The initial of methanol oxidation is obtained according to gained cyclic voltammogram
Current potential and peak current, can try to achieve the catalytic current density that methanol is aoxidized by three kinds of catalyst after calculating.
Setting current potential is-0.25V, utilizes above-mentioned three kinds of electrodes that methanol and concentration of potassium hydroxide are 1mol L-1Mixed solution
Sweep current time graph, the time is 3600s.Com-parison and analysis initial current and attenuation trend, it is judged that the stability of three kinds of catalyst.
From figure 2 it can be seen that compared with platinum/graphen (a) and platinum/nickel hydroxide-cobalt hydroxide (b), platinum/nickel hydroxide
-cobalt hydroxide/Graphene (c) catalyst shows higher catalysis activity.During just sweeping, platinum/nickel hydroxide-cobalt hydroxide/
The produced electric current density of graphen catalyst catalysis methanol oxidation is more than platinum/graphen (a) and platinum/nickel hydroxide-cobalt hydroxide (b)
Both composite catalysts.Meanwhile, the initial electricity of platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst catalysis methanol oxidation
Position will be low than other two kinds of catalyst.This owing to: on the one hand, with the three dimensional structure of Graphene as framework, combining hydrogen oxidation
The network structure of nickel-hydrogen cobalt oxide, has constructed the three dimensional structure carrier containing multistage pore canal, it is possible to increase dividing of catalyst granules
Dissipate property, thus increase its active surface area.On the other hand, nickel hydroxide-cobalt hydroxide composite can produce collaborative effect with Pt
Should, promote the process of methanol oxidation reaction, so that the more avtive spot of catalyst comes out, contact with methanol molecules,
It is catalyzed the carrying out of next step reaction.
From figure 3, it can be seen that compared with platinum/graphen (a) and platinum/nickel hydroxide-cobalt hydroxide (b), platinum/nickel hydroxide
The electric current density attenuation trend of-cobalt hydroxide/Graphene (c) catalyst is minimum, and the current density value after tending towards stability is maximum.
This is owing to nickel hydroxide-cobalt hydroxide/Graphene is the three dimensional structure carrier with multistage pore canal, it is possible to make catalyst granules more preferable
Ground attachment, prevents catalyst granules from reuniting, improves active surface area and the stability of catalyst.
Embodiment 2
1. the preparation of composite catalyst
It is graphite oxide according to Hummers method by the graphite oxidation of 325 mesh, takes a certain amount of graphite oxide and add deionized water,
In ultrasonic washing unit, supersound process is uniformly dispersed to graphite oxide, and obtaining concentration is 2mg mL-1～4.5mg mL-1Oxidation
Graphene solution, adds a certain amount of lithium perchlorate, obtains variable concentrations graphene oxide and concentration is 0.1mol L-1Height
The mixed solution of lithium chlorate.
By reference electrode (calomel electrode), electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system are connected
On electrochemical workstation, immerse in the mixed solution of graphene oxide and lithium perchlorate, carry out in the range of-1.5V～0.6V
Cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 3～10 circle, thus on electro-conductive glass, prepare three-dimensional grapheme, circulation
After voltammetric scan terminates, rinse three-dimensional grapheme with deionized water gently, soak the most in deionized water and remove electrode surface suction
Attached graphene oxide.Then the electro-conductive glass being loaded with three-dimensional grapheme is immersed in 1mol L-1Lithium perchlorate solution in,
In the range of-1.5V～0.6V, cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 10～20 circle, then immerses electrode
In deionized water, lithium perchlorate is fallen in dialysis.
Preparation sodium nitrate, cobalt nitrate and the mixed solution of nickel nitrate, wherein the concentration of sodium nitrate is 0.1mol L-1, cobalt nitrate is dense
Degree is x mol L-1, the concentration of nickel nitrate is (0.1-x) mol L-1(x=0.0001).The conduction glass of three-dimensional grapheme will be loaded with
Glass is immersed in above-mentioned mixed solution respectively, and in the range of-1.5V～-0.2V, cyclic voltammetry scan (sweeps speed for 50mV s-1),
Scanning 10～20 circle, then immerses in deionized water by electrode, and dialysis removes the mixed solution of residual, dry under the conditions of 40～50 DEG C
Dry, obtain nickel hydroxide-cobalt hydroxide/graphene complex.
2mg mL is prepared with deionized water-30% methanol mixed solution (volume ratio 1:1)-1Nickel hydroxide-cobalt hydroxide/graphite
Alkene suspension, ultrasonic washing unit is ultrasonic to being uniformly dispersed.Take 30mL nickel hydroxide-cobalt hydroxide/graphene suspension, stirring
(concentration is respectively 3mg mL to add 5mL platinum acid chloride solution under the conditions of mixing-1, 5mg mL-1, 7mg mL-1, 9mg mL-1,
11mg·mL-1), pH value of solution is regulated to 9～11 by dropping sodium hydroxide.It is then slowly added into 200～300mg sodium borohydrides,
Stir 12～48 hours under room temperature.Be centrifuged repeatedly washing products therefrom with deionized water, under the conditions of 40～50 DEG C be dried, obtain platinum/
Nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Embodiment 3
1. the preparation of composite catalyst
It is graphite oxide according to Hummers method by the graphite oxidation of 325 mesh, takes a certain amount of graphite oxide and add deionized water,
In ultrasonic washing unit, supersound process is uniformly dispersed to graphite oxide, and obtaining concentration is 2mg mL-1～4.5mg mL-1Oxidation
Graphene solution, adds a certain amount of lithium perchlorate, obtains variable concentrations graphene oxide and concentration is 0.1mol L-1Height
The mixed solution of lithium chlorate.
By reference electrode (calomel electrode), electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system are connected
On electrochemical workstation, immerse in the mixed solution of graphene oxide and lithium perchlorate, carry out in the range of-1.5V～0.6V
Cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 3～10 circle, thus on electro-conductive glass, prepare three-dimensional grapheme, circulation
After voltammetric scan terminates, rinse three-dimensional grapheme with deionized water gently, soak the most in deionized water and remove electrode surface suction
Attached graphene oxide.Then the electro-conductive glass being loaded with three-dimensional grapheme is immersed in 1mol L-1Lithium perchlorate solution in,
In the range of-1.5V～0.6V, cyclic voltammetry scan (sweeps speed for 25mV s-1), scanning 10～20 circle, then immerses electrode
In deionized water, lithium perchlorate is fallen in dialysis.
Preparation sodium nitrate, cobalt nitrate and the mixed solution of nickel nitrate, wherein the concentration of sodium nitrate is 0.1mol L-1, cobalt nitrate is dense
Degree is x mol L-1, the concentration of nickel nitrate is (0.1-x) mol L-1(x=0.01).The electro-conductive glass of three-dimensional grapheme will be loaded with
Being immersed in respectively in above-mentioned mixed solution, in the range of-1.5V～-0.2V, cyclic voltammetry scan (sweeps speed for 50mV s-1), sweep
Retouching 10～20 circles, then immerse in deionized water by electrode, dialysis removes the mixed solution of residual, is dried under the conditions of 40～50 DEG C,
Obtain nickel hydroxide-cobalt hydroxide/graphene complex.
2mg mL is prepared with deionized water-30% methanol mixed solution (volume ratio 1:1)-1Nickel hydroxide-cobalt hydroxide/graphite
Alkene suspension, ultrasonic washing unit is ultrasonic to being uniformly dispersed.Take 30mL nickel hydroxide-cobalt hydroxide/graphene suspension, stirring
(concentration is respectively 3mg mL to add 5mL platinum acid chloride solution under the conditions of mixing-1, 5mg mL-1, 7mg mL-1, 9mg mL-1,
11mg·mL-1), pH value of solution is regulated to 9～11 by dropping sodium hydroxide.It is then slowly added into 200～300mg sodium borohydrides,
Stir 12～48 hours under room temperature.Be centrifuged repeatedly washing products therefrom with deionized water, under the conditions of 40～50 DEG C be dried, obtain platinum/
Nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Finally should be noted that and the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to the greatest extent
The present invention has been described in detail by pipe with reference to previous embodiment, and for a person skilled in the art, it still can be right
Technical scheme described in previous embodiment is modified, or wherein part is carried out equivalent.All spirit in the present invention
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.On
Although state and combine accompanying drawing the detailed description of the invention of the present invention is described, but not limiting the scope of the invention, institute
Belonging to skilled person and should be understood that on the basis of technical scheme, those skilled in the art need not pay creation
Property the various amendments that can make of work or deformation still within protection scope of the present invention.
Claims (10)
1. platinum/nickel hydroxide-cobalt hydroxide/Graphene three dimensional composite structure, it is characterised in that including:
Three-dimensional graphene framework；
Nickel hydroxide in described three-dimensional graphene framework-cobalt hydroxide network structure；
Platinum metal layer in described nickel hydroxide-cobalt hydroxide network structure；
Wherein, described nickel hydroxide-cobalt hydroxide network structure is made up of nickel hydroxide and cobalt hydroxide nanoscale twins.
2. composite construction as claimed in claim 1, it is characterised in that nickel element and cobalt in described nickel hydroxide-cobaltous hydroxide layer
The mol ratio of element is 0.0001～1:0.0001～1；
Preferably, in described nickel hydroxide-cobaltous hydroxide layer, the mol ratio of nickel element and cobalt element is 0.9～1:0.0001～0.1.
3. platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite material electrode, it is characterised in that including:
Three-dimensional graphene framework；
Nickel hydroxide in described three-dimensional graphene framework-cobalt hydroxide network structure；
Platinum metal layer in described nickel hydroxide-cobalt hydroxide network structure；
Wherein, described nickel hydroxide-cobalt hydroxide network structure is made up of nickel hydroxide and cobalt hydroxide nanoscale twins.
4. electrode as claimed in claim 3, it is characterised in that described nickel hydroxide-cobaltous hydroxide layer is network structure.
5. electrode as claimed in claim 3, it is characterised in that nickel element and cobalt element in described nickel hydroxide-cobaltous hydroxide layer
Mol ratio be 0.0001～1:0.0001～1；
Preferably, in described nickel hydroxide-cobaltous hydroxide layer, the mol ratio of nickel element and cobalt element is 0.9～1:0.0001～0.1.
6. the preparation method of platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional composite catalyst, it is characterised in that including:
Use electrodeposition process in three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet, obtain nickel hydroxide-cobalt hydroxide
/ graphene complex；
Platinum is reverted to nickel hydroxide-cobalt hydroxide/graphene complex surface, obtains platinum/nickel hydroxide-cobalt hydroxide/Graphene three-dimensional
Composite catalyst.
7. the method described in claim 1, it is characterised in that described nickel hydroxide-cobalt hydroxide nanometer sheet is by nickel hydroxide and hydrogen
Cobalt oxide is composited, and wherein, nickel element is 0.0001～1:0.0001～1 with the mol ratio of cobalt element；
Preferably, in described nickel hydroxide-cobaltous hydroxide layer, the mol ratio of nickel element and cobalt element is 0.9～1:0.0001～0.1.
8. method as claimed in claim 6, it is characterised in that the condition of described electrodeposition process is: at the model of-1.5V～-0.2V
Enclose interior cyclic voltammetry scan 10～20 circle, sweep speed for 50mV s-1；
Or described employing electrodeposition process concretely comprising the following steps in three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet: join
The mixed solution of sodium nitrate processed, cobalt nitrate and nickel nitrate, is immersed in above-mentioned mixing by the working electrode being loaded with three-dimensional grapheme molten
In liquid, cyclic voltammetry scan in the range of-1.5V～-0.2V, sweep speed for 50mV s-1, scanning 10～20 circle, dialysis removes
The mixed solution of residual, is dried, obtains nickel hydroxide-cobalt hydroxide/graphene complex.
9. the catalyst that prepared by the arbitrary described method of claim 6-8.
10. the catalyst described in claim 9 aoxidizes at catalysis methanol, prepares Proton Exchange Membrane Fuel Cells or methanol fuel cell
In application.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252094A (en) * | 2016-08-20 | 2016-12-21 | 海南师范大学 | The preparation of a kind of three-dimensional grapheme/cobalt hydroxide combination electrode and the research of capacitive property thereof |
| CN106531993A (en) * | 2016-11-10 | 2017-03-22 | 无锡市明盛强力风机有限公司 | Preparation method of Co-containing graphene negative electrode material |
| CN106807349A (en) * | 2017-01-24 | 2017-06-09 | 中国科学院长春应用化学研究所 | A kind of nano metal simple substance modification transition metal hydroxide array catalyst and its preparation method and application |
| CN106841337A (en) * | 2016-12-01 | 2017-06-13 | 西北大学 | Platinum Nanoparticles/nickel hydroxide/multi-walled carbon nano-tubes nano composite material and its application |
| CN107579240A (en) * | 2017-09-20 | 2018-01-12 | 吉林省凯禹电化学储能技术发展有限公司 | A kind of preparation method of C-base composte material for lead carbon battery negative pole |
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| CN108539208A (en) * | 2018-04-12 | 2018-09-14 | 辽宁大学 | NiS/Ni(OH)2@PPy/GO nanometer sheets and methanol electro-catalysis modified electrode |
| CN109686581A (en) * | 2019-01-11 | 2019-04-26 | 南昌航空大学 | A kind of cobalt hydroxide/rGO/ nickel hydroxide sandwich-like flexible electrode material and preparation method thereof |
| CN112362713A (en) * | 2020-11-24 | 2021-02-12 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN104525218A (en) * | 2014-12-12 | 2015-04-22 | 江苏大学 | Preparation method of efficient Pt-CoSi2/graphene composite electric catalyst |
| CN104646026A (en) * | 2015-02-11 | 2015-05-27 | 青岛大学 | Hollow core-shell Pt@Ni/graphene three-dimensional composite catalyst and preparation method |
| CN105406088A (en) * | 2015-10-30 | 2016-03-16 | 苏州大学 | Small-molecular alcohol oxidation electro-catalysis material and preparation method and application therefor |
-
2016
- 2016-03-25 CN CN201610181590.1A patent/CN105810957B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354609A (en) * | 2011-08-23 | 2012-02-15 | 吉林大学 | Method for preparing graphene-nickel hydroxide composite electrode material for super capacitor |
| CN104525218A (en) * | 2014-12-12 | 2015-04-22 | 江苏大学 | Preparation method of efficient Pt-CoSi2/graphene composite electric catalyst |
| CN104646026A (en) * | 2015-02-11 | 2015-05-27 | 青岛大学 | Hollow core-shell Pt@Ni/graphene three-dimensional composite catalyst and preparation method |
| CN105406088A (en) * | 2015-10-30 | 2016-03-16 | 苏州大学 | Small-molecular alcohol oxidation electro-catalysis material and preparation method and application therefor |
Non-Patent Citations (1)
| Title |
|---|
| JING JIANG ET AL.: "Nickel-cobalt layered double hydroxide nanosheets as high-performance electrocatalyst for oxygen evolution reaction", 《JOURNAL OF POWER SOURCES》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252094A (en) * | 2016-08-20 | 2016-12-21 | 海南师范大学 | The preparation of a kind of three-dimensional grapheme/cobalt hydroxide combination electrode and the research of capacitive property thereof |
| CN106531993A (en) * | 2016-11-10 | 2017-03-22 | 无锡市明盛强力风机有限公司 | Preparation method of Co-containing graphene negative electrode material |
| CN106841337A (en) * | 2016-12-01 | 2017-06-13 | 西北大学 | Platinum Nanoparticles/nickel hydroxide/multi-walled carbon nano-tubes nano composite material and its application |
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| CN108281294A (en) * | 2017-12-24 | 2018-07-13 | 桂林理工大学 | The preparation method of polyaniline/nickel hydroxide composite electrode material for super capacitor |
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