CN105810957B - The preparation and application of a kind of platinum/nickel hydroxide cobalt hydroxide/graphene three-dimensional composite catalyst - Google Patents
The preparation and application of a kind of platinum/nickel hydroxide cobalt hydroxide/graphene three-dimensional composite catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of platinum/nickel hydroxide cobalt hydroxide/graphene three-dimensional composite catalyst and its application in DMFC.The three-dimensional structure carrier containing multistage pore canal is built using the network structure of the three-dimensional structure combining hydrogen oxidation ni-mh cobalt oxide of graphene, the agglomeration traits of graphene are overcome to a certain extent, the defects of specific surface area of graphene superelevation and excellent electric conductivity can make up nickel hydroxide cobalt hydroxide poorly conductive simultaneously, so as to promote the electron transmission and mass transfer in oxidation-reduction process, the dispersiveness and stability of catalyst granules are improved.The catalytic performance aoxidized using nickel hydroxide cobalt hydroxide to methanol, catalytic activity of the Pt catalyst to methanol is further improved, reduce the dosage of precious metals pt.Method and step is simple and convenient to operate, is practical.
Description
Technical field
The invention belongs to field of nanometer material technology, more particularly to a kind of platinum/nickel hydroxide-cobalt hydroxide/graphene is three-dimensional multiple
Close the preparation and application of catalyst.
Background technology
Proton Exchange Membrane Fuel Cells turns into current novel energy field due to its economic and environment-friendly and higher generating efficiency
Research emphasis.The DMFC constructed by the proton energy using methanol as Proton Exchange Membrane Fuel Cells
(DMFC) easy to operate, battery structure is simple and can quickly start under cryogenic.Noble metal platinum (Pt) be DMFC most
Conventional anode catalyst, it is that maximally effective catalyst is reacted to methanol electro-oxidizing under acid condition.But Pt prices are high, matter
Amount (area) specific activity is low and easily causes poisoning by intermediate products such as the CO in methanol oxidation process, and these shortcomings hinder DMFC
Commercialization process.In order to realize more considerable catalytic activity, the catalytic efficiency of catalyst is improved, substantial amounts of research is got down to
The macroscopic view composition of Pt base catalyst and the modification to its pattern, so as to modulate its micro-scale and level density, from basic
The defects of present in upper solution Pt catalyst.
Graphene is a kind of new two-dimentional carbon nanomaterial, has bigger serface, high conductivity and good stability
The advantages that, thus it is often used as the carrier of catalyst, it is possible to increase the dispersiveness of Pt catalyst, the size for reducing catalyst granules
And then improve Pt utilization rate.But graphene is easily reunited, this reduces its stabilization as catalyst carrier to a certain extent
Property.A kind of graphene of three-dimensional porous structure is built, the advantages of two-dimensional graphene can be incorporated into three-dimensional structure, also can
Overcome the agglomeration traits of two-dimensional graphene.But electrochemically active specific surface area and the ion diffusion of existing load Pt three-dimensional graphemes
The still difficult technical requirements for meeting the high-grade, precision and advanced industry such as military, space flight of speed.
The content of the invention
In order to solve the above problems, the invention provides a kind of platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional is compound
The preparation method of catalyst and its application in DMFC.It is intended to the three-dimensional structure combination hydrogen using graphene
Three-dimensional structure carrier of the network structure structure containing multistage pore canal of nickel oxide-cobalt hydroxide, overcomes graphite to a certain extent
The agglomeration traits of alkene, while the specific surface area of graphene superelevation and excellent electric conductivity can make up nickel hydroxide-hydroxide
The defects of cobalt poorly conductive, so as to promote the electron transmission and mass transfer in oxidation-reduction process, improve point of catalyst granules
Dissipate property and stability.The catalytic performance aoxidized using nickel hydroxide-cobalt hydroxide to methanol, Pt catalyst is further improved to first
The catalytic activity of alcohol, reduce the dosage of precious metals pt.
To achieve 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-cobalt hydroxide network structure in the three-dimensional graphene framework；
Platinum metal layer on the nickel hydroxide-cobalt hydroxide network structure；
Wherein, described nickel hydroxide-cobalt hydroxide network structure is by nickel hydroxide and cobalt hydroxide nanoscale twins group
Into.
The nickel hydroxide of loose structure has big specific surface area, and this helps lend some impetus to the electrochemical reaction and activity at interface
Effective utilization of material.But the electric conductivity of nickel hydroxide is poor, is unfavorable for electron transmission.Electric conductivity is added in nickel hydroxide
Higher cobalt hydroxide, improve its electric conductivity and electro-chemical activity.Meanwhile nickel hydroxide-cobalt hydroxide compound is for methanol
Oxidation reaction there is catalytic action, nickel hydroxide-cobalt hydroxide is prepared on three-dimensional grapheme surface by co-electrodeposition method can be with
The network structure being made up of uniform nanoscale twins is obtained, this structure makes it have big electrochemically active specific surface area, more
Be advantageous to the diffusion of charge transfer and ion.Graphene also can produce association as the carrier material of DMFC anode catalysts with Pt
Same effect, catalytic efficiency of the catalyst to methanol is improved, promote reaction process.
Preferably, the mol ratio of nickel element and cobalt element is 0.0001~1 in the nickel hydroxide-cobaltous hydroxide layer：
0.0001~1.
It is furthermore preferred that the mol ratio of nickel element and cobalt element is 0.9~1 in the nickel hydroxide-cobaltous hydroxide layer：
0.0001~0.1.
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-cobalt hydroxide network structure in the three-dimensional graphene framework；
Platinum metal layer on the nickel hydroxide-cobalt hydroxide network structure；
Wherein, described nickel hydroxide-cobalt hydroxide network structure is by nickel hydroxide and cobalt hydroxide nanoscale twins group
Into.
Preferably, selected electrode material is electro-conductive glass.
Preferably, the mol ratio of nickel element and cobalt element is 0.0001~1 in the nickel hydroxide-cobaltous hydroxide layer：
0.0001~1.
It is furthermore preferred that the mol ratio of nickel element and cobalt element is 0.9~1 in the nickel hydroxide-cobaltous hydroxide layer：
0.0001~0.1.
Present invention also offers a kind of preparation side of platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst
Method, including：
Network structure is formed in three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet using electrodeposition process,
Obtain nickel hydroxide-cobalt hydroxide/graphene complex；
Platinum is reverted into nickel hydroxide-cobalt hydroxide/graphene complex surface, obtains platinum/nickel hydroxide-hydroxide
Cobalt/graphene three-dimensional composite catalyst.
Preferably, the nickel hydroxide-cobalt hydroxide nanometer sheet is combined by nickel hydroxide and cobalt hydroxide, wherein,
The mol ratio of nickel element and cobalt element is 0.0001~1：0.0001~1.
It is furthermore preferred that the mol ratio of nickel element and cobalt element is 0.9~1 in the nickel hydroxide-cobaltous hydroxide layer：
0.0001~0.1.
Preferably, the condition of the electrodeposition process is：Cyclic voltammetry scan 10~20 in the range of -1.5V~-0.2V
Circle, it is 30-150mVs to sweep speed-1；
It is furthermore preferred that described use electrodeposition process in three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet
Concretely comprise the following steps：The mixed solution of sodium nitrate, cobalt nitrate and nickel nitrate is prepared, the working electrode of three-dimensional grapheme will be loaded with
It is immersed in above-mentioned mixed solution, the cyclic voltammetry scan in the range of -1.5V~-0.2V, it is 30-150mVs to sweep speed-1, sweep
10~50 circles are retouched, dialysis removes the mixed solution of residual, dries, obtains nickel hydroxide-cobalt hydroxide/graphene complex.
Preferably, the reducing condition of the platinum is：Take nickel hydroxide-cobalt hydroxide/graphene suspension and chloroplatinic acid molten
Liquid, mixing, addition sodium hydroxide regulation pH of mixed to 9~11, add sodium borohydride, stir 12~48 hours at room temperature, washing,
Dry, produce.
Preferably, the three-dimensional grapheme is prepared with the following method：By reference electrode, to electrode and the electricity of working electrode three
Polar body system is connected on electrochemical workstation, is immersed in the mixed solution of graphene oxide and lithium perchlorate, in -1.5V~0.6V
In the range of carry out cyclic voltammetry scan, it is 25mVs to sweep speed-1, 3~10 circles are scanned, remove the graphene oxide and height of residual
Lithium chlorate, produce three-dimensional grapheme.
It is furthermore preferred that the method for the graphene oxide for removing residual and lithium perchlorate is：With deionized water rinsing three
Graphene is tieed up, then the graphene oxide of electrode surface absorption is removed in immersion in deionized water.Then three-dimensional stone will be loaded with
The electro-conductive glass of black alkene is immersed in 1molL-1Lithium perchlorate solution in, cyclic voltammetric is swept in the range of -1.5V~0.6V
Retouch that (it is 20-50mVs to sweep speed-1), the circle of scanning 10~20, electrode is then immersed in dialysis in deionized water and falls lithium perchlorate.
Idiographic flow is as follows：Three-dimensional grapheme is prepared in electrochemical deposition first on electro-conductive glass, then in three-dimensional
Nickel hydroxide-cobalt hydroxide is prepared by electrodeposition process on graphene and obtains nickel hydroxide-cobalt hydroxide/graphene complex,
Nickel hydroxide-cobalt hydroxide/graphene complex is scattered in the mixed solution of water and methanol again, added under conditions of stirring
Platinum acid chloride solution, sodium hydroxide regulation pH is added dropwise, then ultrasonic mixing is uniform, adds sodium borohydride, at room temperature stirring reaction
Certain time, Pt nanoparticle is reverted on nickel hydroxide-cobalt hydroxide/graphene complex and obtains platinum/hydroxide nickel-hydrogen
Cobalt oxide/graphene three-dimensional composite catalyst.Electrochemical deposition method is simple to operate, cost is low, is prepared by electrochemical deposition method
Nickel hydroxide-cobalt hydroxide/graphene three dimensional composite structure, low is required to experimental implementation, while poisonous reducing agent can be avoided
Or the use of dispersant, it is a kind of method of environmental protection and economy.
Present invention also offers a kind of system of preferably platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst
Preparation Method, including：
The preparation of composite catalyst
By the graphite oxidation of 325 mesh it is graphite oxide according to Hummers methods, takes a certain amount of graphite oxide to add deionization
Water, it is ultrasonically treated in supersonic wave cleaning machine and is uniformly dispersed to graphite oxide, it is 2mgmL to obtain concentration-1~4.5mgmL-1
Graphene oxide solution, add a certain amount of lithium perchlorate, obtain various concentrations graphene oxide and concentration is
0.1mol·L-1Lithium perchlorate mixed solution.
Connect by reference electrode (calomel electrode), to electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system
It is connected on electrochemical workstation, immerses in the mixed solution of graphene oxide and lithium perchlorate, in the range of -1.5V~0.6V
Carrying out cyclic voltammetry scan, (it is 25mVs to sweep speed-1), the circle of scanning 3~10, so as to which three-dimensional grapheme be made on electro-conductive glass,
After cyclic voltammetry scan terminates, three-dimensional grapheme is gently rinsed with deionized water, then electrode is removed in immersion in deionized water
The graphene oxide of adsorption.Then the electro-conductive glass for being loaded with three-dimensional grapheme is immersed in 1molL-1Lithium perchlorate
In solution, (it is 25mVs to sweep speed to cyclic voltammetry scan in the range of -1.5V~0.6V-1), the circle of scanning 10~20, then will
Electrode is immersed in dialysis in deionized water and falls lithium perchlorate.
The mixed solution of sodium nitrate, cobalt nitrate and nickel nitrate is prepared, the wherein concentration of sodium nitrate is 0.1molL-1, nitric acid
Cobalt concentration is xmolL-1, the concentration of nickel nitrate is (0.1-x) molL-1(x=0,0.02,0.04,0.05,0.06,0.08,
0.1).Naked electro-conductive glass and the electro-conductive glass for being loaded with three-dimensional grapheme are immersed in above-mentioned mixed solution respectively, in -1.5V
(it is 50mVs to sweep speed to cyclic voltammetry scan in the range of~-0.2V-1), the circle of scanning 10~20, electrode is then immersed into deionization
In water, dialysis removes the mixed solution of residual, dries under the conditions of 40~50 DEG C, obtain nickel hydroxide-cobalt hydroxide compound and
Nickel hydroxide-cobalt hydroxide/graphene complex.
With the methanol of deionized water -30% mixed solution (volume ratio 1:1) 2mgmL is prepared-1Nickel hydroxide-hydroxide
Cobalt/graphene suspension, supersonic wave cleaning machine ultrasound is to being uniformly dispersed.30mL nickel hydroxides-cobalt hydroxide/graphene is taken to suspend
Liquid, adding 5mL platinum acid chloride solutions under agitation, (concentration is respectively 3mgmL-1, 5mgmL-1, 7mgmL-1, 9mg
mL-1, 11mgmL-1), add sodium hydroxide and adjust pH of mixed to 9~11.It is then slowly added into 200~300mg hydroborations
Sodium, stir 12~48 hours at room temperature.Washing products therefrom is centrifuged repeatedly with deionized water, dries, obtains under the conditions of 40~50 DEG C
To platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Replace nickel hydroxide-cobalt hydroxide/graphene compound with graphene, nickel hydroxide-cobalt hydroxide compound respectively
Thing, repeat the above steps, platinum/graphen composite catalyst and platinum/nickel hydroxide-cobalt hydroxide composite catalyst are made respectively.
Catalyst prepared by any of the above-described method.Described catalyst can be used for catalysis methanol oxidation, prepare proton exchange
Membrane cell or methanol fuel cell.
Beneficial effects of the present invention：
(1) the invention provides a kind of preparation side of platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst
Method and its application in DMFC.Making programme is as follows：First on electro-conductive glass prepared by electrochemical deposition
Three-dimensional grapheme is obtained, then preparing nickel hydroxide-cobalt hydroxide by electrodeposition process on three-dimensional grapheme obtains hydroxide
Nickel-hydrogen cobalt oxide/graphene complex, then nickel hydroxide-cobalt hydroxide/graphene complex is scattered in the mixed of water and methanol
Close in solution, platinum acid chloride solution is added under conditions of stirring, hydrogenation sodium oxide molybdena regulation pH, then ultrasonic mixing is uniform, adds
Sodium borohydride, certain time is stirred at room temperature, Pt nanoparticle is reverted into nickel hydroxide-cobalt hydroxide/graphene complex
On obtain platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst.
(2) electrochemical deposition method is simple to operate, cost is low, by electrochemical deposition method prepare nickel hydroxide-cobalt hydroxide/
Graphene three dimensional composite structure, low is required to experimental implementation, while the use of poisonous reducing agent or dispersant can be avoided, be one
The method of kind environmental protection and economy.
(3) it is contemplated that being built using the network structure of the three-dimensional structure combining hydrogen oxidation nickel-hydrogen cobalt oxide of graphene
Three-dimensional structure carrier containing multistage pore canal, overcomes the agglomeration traits of graphene to a certain extent, while graphene superelevation
Specific surface area and excellent electric conductivity can make up the defects of nickel hydroxide-cobalt hydroxide poorly conductive, so as to promote oxygen
Change the electron transmission and mass transfer in reduction process, improve the dispersiveness and stability of catalyst granules.Utilize nickel hydroxide-hydrogen-oxygen
Change the catalytic performance that cobalt aoxidizes to methanol, further improve catalytic activity of the Pt catalyst to methanol, reduce the use of precious metals pt
Amount.
(4) manufacturing process of the present invention it is simple, it is practical, be easy to industrialization promotion.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Fig. 2 is (a) platinum/graphen, (b) platinum/nickel hydroxide-cobalt hydroxide and (c) platinum/nickel hydroxide-cobalt hydroxide/stone
Black alkene is in 1molL-1Methanol and 1molL-1Cyclic voltammetry curve in potassium hydroxide mixed solution.
Fig. 3 is (a) platinum/graphen, (b) platinum/nickel hydroxide-cobalt hydroxide and (c) platinum/nickel hydroxide-cobalt hydroxide/stone
Black three kinds of catalyst of alkene are in 1molL-1Methanol and 1molL-1Current-time curvel in potassium hydroxide mixed solution.
Embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
1. the preparation of composite catalyst
By the graphite oxidation of 325 mesh it is graphite oxide according to Hummers methods, takes a certain amount of graphite oxide to add deionization
Water, it is ultrasonically treated in supersonic wave cleaning machine and is uniformly dispersed to graphite oxide, it is 2mgmL to obtain concentration-1~4.5mgmL-1
Graphene oxide solution, add a certain amount of lithium perchlorate, obtain various concentrations graphene oxide and concentration is
0.1mol·L-1Lithium perchlorate mixed solution.
Connect by reference electrode (calomel electrode), to electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system
It is connected on electrochemical workstation, immerses in the mixed solution of graphene oxide and lithium perchlorate, in the range of -1.5V~0.6V
Carrying out cyclic voltammetry scan, (it is 25mVs to sweep speed-1), the circle of scanning 3~10, so as to which three-dimensional grapheme be made on electro-conductive glass,
After cyclic voltammetry scan terminates, three-dimensional grapheme is gently rinsed with deionized water, then electrode is removed in immersion in deionized water
The graphene oxide of adsorption.Then the electro-conductive glass for being loaded with three-dimensional grapheme is immersed in 1molL-1Lithium perchlorate
In solution, (it is 25mVs to sweep speed to cyclic voltammetry scan in the range of -1.5V~0.6V-1), the circle of scanning 10~20, then will
Electrode is immersed in dialysis in deionized water and falls lithium perchlorate.
The mixed solution of sodium nitrate, cobalt nitrate and nickel nitrate is prepared, the wherein concentration of sodium nitrate is 0.1molL-1, nitric acid
Cobalt concentration is x molL-1, the concentration of nickel nitrate is (0.1-x) molL-1(x=0,0.02,0.04,0.05,0.06,
0.08,0.1).Naked electro-conductive glass and the electro-conductive glass for being loaded with three-dimensional grapheme are immersed in above-mentioned mixed solution respectively,
(it is 50mVs to sweep speed to cyclic voltammetry scan in the range of -1.5V~-0.2V-1), the circle of scanning 10~20, then electrode is soaked
Enter in deionized water, dialysis removes the mixed solution of residual, is dried under the conditions of 40~50 DEG C, obtains nickel hydroxide-cobalt hydroxide
Compound and nickel hydroxide-cobalt hydroxide/graphene complex.
With the methanol of deionized water -30% mixed solution (volume ratio 1:1) 2mgmL is prepared-1Nickel hydroxide-hydroxide
Cobalt/graphene suspension, supersonic wave cleaning machine ultrasound is to being uniformly dispersed.30mL nickel hydroxides-cobalt hydroxide/graphene is taken to suspend
Liquid, adding 5mL platinum acid chloride solutions under agitation, (concentration is respectively 3mgmL-1, 5mgmL-1, 7mgmL-1, 9mg
mL-1, 11mgmL-1), sodium hydroxide is added dropwise and adjusts pH value of solution to 9~11.It is then slowly added into 200~300mg hydroborations
Sodium, stir 12~48 hours at room temperature.Washing products therefrom is centrifuged repeatedly with deionized water, dries, obtains under the conditions of 40~50 DEG C
To platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Replace nickel hydroxide-cobalt hydroxide/graphene compound with graphene, nickel hydroxide-cobalt hydroxide compound respectively
Thing, repeat the above steps, platinum/graphen composite catalyst and platinum/nickel hydroxide-cobalt hydroxide composite catalyst are made respectively.
1. the sign of composite catalytic performance
1mgmL is prepared respectively with absolute ethyl alcohol-1Above-mentioned three kinds of composite catalyst suspension, supersonic wave cleaning machine ultrasound
It is uniformly dispersed to catalyst.0.3,0.05 μm of Al is used respectively2O3Powder polishes to glass-carbon electrode (diameter 3mm), then uses successively
Acetone, absolute ethyl alcohol, redistilled water supersound washing 5min, naturally dry.
Pipette the above-mentioned composite catalyst hanging drops of 10 μ L respectively to be coated onto on glass-carbon electrode, naturally dry.Utilize above-mentioned three
Kind electrode is 1molL to concentration in -1.0V~0V potential range-1Potassium hydroxide solution carry out cyclic voltammetry scan
(it is 50mVs to sweep speed-1).The adsorption desorption peak of hydrogen is observed according to gained cyclic voltammogram and calculates peak area, so as to obtain three kinds
The electrochemical active surface of electrode catalyst.
It is to methanol and concentration of potassium hydroxide in -0.8V~0.2V potential range using above-mentioned three kinds of electrodes
1mol·L-1Mixed solution carry out cyclic voltammetry scan (it is 50mVs to sweep speed-1).First is obtained according to gained cyclic voltammogram
The take-off potential and peak current of alcohol oxidation, can try to achieve the catalytic current density that three kinds of catalyst aoxidize to methanol after calculating.
Current potential is set as -0.25V, is 1molL using above-mentioned three kinds of electrode pair methanol and concentration of potassium hydroxide-1It is mixed
Close solution sweep current time graph, time 3600s.Com-parison and analysis initial current and attenuation trend, judge three kinds of catalyst
Stability.
From figure 2 it can be seen that compared with platinum/graphen (a) and platinum/nickel hydroxide-cobalt hydroxide (b), platinum/hydroxide
Nickel-hydrogen cobalt oxide/graphene (c) catalyst shows higher catalytic activity.During just sweeping, platinum/nickel hydroxide-hydroxide
Cobalt/current density caused by the oxidation of graphen catalyst catalysis methanol is more than platinum/graphen (a) and platinum/nickel hydroxide-hydrogen-oxygen
Change cobalt (b) both composite catalysts.Meanwhile platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst catalysis methanol oxygen
The take-off potential of change will be low than other two kinds of catalyst.This is attributed to：On the one hand, using the three-dimensional structure of graphene as framework,
The network structure of combining hydrogen oxidation nickel-hydrogen cobalt oxide, the three-dimensional structure carrier containing multistage pore canal is constructed, it is possible to increase urge
The dispersiveness of catalyst particles, so as to increase its active surface area.On the other hand, nickel hydroxide-cobalt hydroxide composite can
Cooperative effect is produced with Pt, promotes the process of methanol oxidation reaction, so that the more avtive spots of catalyst are exposed, with
Methanol molecules contact, the progress that catalysis is reacted in next step.
From figure 3, it can be seen that compared with platinum/graphen (a) and platinum/nickel hydroxide-cobalt hydroxide (b), platinum/hydroxide
The current density attenuation trend of nickel-hydrogen cobalt oxide/graphene (c) catalyst is minimum, and the current density value after tending towards stability is most
Greatly.This is due to that nickel hydroxide-cobalt hydroxide/graphene is the three-dimensional structure carrier for having multistage pore canal, can make catalyst
Particle preferably adheres to, and prevents catalyst granules from reuniting, and improves the active surface area and stability of catalyst.
Embodiment 2
1. the preparation of composite catalyst
By the graphite oxidation of 325 mesh it is graphite oxide according to Hummers methods, takes a certain amount of graphite oxide to add deionization
Water, it is ultrasonically treated in supersonic wave cleaning machine and is uniformly dispersed to graphite oxide, it is 2mgmL to obtain concentration-1~4.5mgmL-1
Graphene oxide solution, add a certain amount of lithium perchlorate, obtain various concentrations graphene oxide and concentration is
0.1mol·L-1Lithium perchlorate mixed solution.
Connect by reference electrode (calomel electrode), to electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system
It is connected on electrochemical workstation, immerses in the mixed solution of graphene oxide and lithium perchlorate, in the range of -1.5V~0.6V
Carrying out cyclic voltammetry scan, (it is 25mVs to sweep speed-1), the circle of scanning 3~10, so as to which three-dimensional grapheme be made on electro-conductive glass,
After cyclic voltammetry scan terminates, three-dimensional grapheme is gently rinsed with deionized water, then electrode is removed in immersion in deionized water
The graphene oxide of adsorption.Then the electro-conductive glass for being loaded with three-dimensional grapheme is immersed in 1molL-1Lithium perchlorate
In solution, (it is 25mVs to sweep speed to cyclic voltammetry scan in the range of -1.5V~0.6V-1), the circle of scanning 10~20, then will
Electrode is immersed in dialysis in deionized water and falls lithium perchlorate.
The mixed solution of sodium nitrate, cobalt nitrate and nickel nitrate is prepared, the wherein concentration of sodium nitrate is 0.1molL-1, nitric acid
Cobalt concentration is x molL-1, the concentration of nickel nitrate is (0.1-x) molL-1(x=0.0001).Three-dimensional grapheme will be loaded with
Electro-conductive glass be immersed in respectively in above-mentioned mixed solution, (sweep speed is cyclic voltammetry scan in the range of -1.5V~-0.2V
50mV·s-1), the circle of scanning 10~20, then electrode is immersed in deionized water, the mixed solution of dialysis removing residual, 40~50
Dried under the conditions of DEG C, obtain nickel hydroxide-cobalt hydroxide/graphene complex.
With the methanol of deionized water -30% mixed solution (volume ratio 1:1) 2mgmL is prepared-1Nickel hydroxide-hydroxide
Cobalt/graphene suspension, supersonic wave cleaning machine ultrasound is to being uniformly dispersed.30mL nickel hydroxides-cobalt hydroxide/graphene is taken to suspend
Liquid, adding 5mL platinum acid chloride solutions under agitation, (concentration is respectively 3mgmL-1, 5mgmL-1, 7mgmL-1, 9mg
mL-1, 11mgmL-1), sodium hydroxide is added dropwise and adjusts pH value of solution to 9~11.It is then slowly added into 200~300mg hydroborations
Sodium, stir 12~48 hours at room temperature.Washing products therefrom is centrifuged repeatedly with deionized water, dries, obtains under the conditions of 40~50 DEG C
To platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Embodiment 3
1. the preparation of composite catalyst
By the graphite oxidation of 325 mesh it is graphite oxide according to Hummers methods, takes a certain amount of graphite oxide to add deionization
Water, it is ultrasonically treated in supersonic wave cleaning machine and is uniformly dispersed to graphite oxide, it is 2mgmL to obtain concentration-1~4.5mgmL-1
Graphene oxide solution, add a certain amount of lithium perchlorate, obtain various concentrations graphene oxide and concentration is
0.1mol·L-1Lithium perchlorate mixed solution.
Connect by reference electrode (calomel electrode), to electrode (platinum electrode) and working electrode (electro-conductive glass) three-electrode system
It is connected on electrochemical workstation, immerses in the mixed solution of graphene oxide and lithium perchlorate, in the range of -1.5V~0.6V
Carrying out cyclic voltammetry scan, (it is 25mVs to sweep speed-1), the circle of scanning 3~10, so as to which three-dimensional grapheme be made on electro-conductive glass,
After cyclic voltammetry scan terminates, three-dimensional grapheme is gently rinsed with deionized water, then electrode is removed in immersion in deionized water
The graphene oxide of adsorption.Then the electro-conductive glass for being loaded with three-dimensional grapheme is immersed in 1molL-1Lithium perchlorate
In solution, (it is 25mVs to sweep speed to cyclic voltammetry scan in the range of -1.5V~0.6V-1), the circle of scanning 10~20, then will
Electrode is immersed in dialysis in deionized water and falls lithium perchlorate.
The mixed solution of sodium nitrate, cobalt nitrate and nickel nitrate is prepared, the wherein concentration of sodium nitrate is 0.1molL-1, nitric acid
Cobalt concentration is x molL-1, the concentration of nickel nitrate is (0.1-x) molL-1(x=0.01).Three-dimensional grapheme will be loaded with
Electro-conductive glass is immersed in above-mentioned mixed solution respectively, and (sweep speed is cyclic voltammetry scan in the range of -1.5V~-0.2V
50mV·s-1), the circle of scanning 10~20, then electrode is immersed in deionized water, the mixed solution of dialysis removing residual, 40~50
Dried under the conditions of DEG C, obtain nickel hydroxide-cobalt hydroxide/graphene complex.
With the methanol of deionized water -30% mixed solution (volume ratio 1:1) 2mgmL is prepared-1Nickel hydroxide-hydroxide
Cobalt/graphene suspension, supersonic wave cleaning machine ultrasound is to being uniformly dispersed.30mL nickel hydroxides-cobalt hydroxide/graphene is taken to suspend
Liquid, adding 5mL platinum acid chloride solutions under agitation, (concentration is respectively 3mgmL-1, 5mgmL-1, 7mgmL-1, 9mg
mL-1, 11mgmL-1), sodium hydroxide is added dropwise and adjusts pH value of solution to 9~11.It is then slowly added into 200~300mg hydroborations
Sodium, stir 12~48 hours at room temperature.Washing products therefrom is centrifuged repeatedly with deionized water, dries, obtains under the conditions of 40~50 DEG C
To platinum/nickel hydroxide-cobalt hydroxide/graphene composite catalyst.
Finally it should be noted that the foregoing is only the preferred embodiments of the present invention, this hair is not limited to
Bright, although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it is still
Technical scheme described in previous embodiment can be modified, or equivalent substitution is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc., protection scope of the present invention should be included in
Within.Above-mentioned although the embodiment of the present invention is described with reference to accompanying drawing, not to the scope of the present invention
Limitation, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
Various modifications or deformation that creative work can make are paid still within protection scope of the present invention.
Claims (6)
- A kind of 1. preparation method of platinum/nickel hydroxide-cobalt hydroxide/graphene three-dimensional composite catalyst, it is characterised in that bag Include：Using electrodeposition process in three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet, nickel hydroxide-hydrogen-oxygen is obtained Change cobalt/graphene complex；Platinum is reverted into nickel hydroxide-cobalt hydroxide/graphene complex surface, obtains platinum/nickel hydroxide-cobalt hydroxide/graphite Alkene three-dimensional composite catalyst；The three-dimensional grapheme is prepared with the following method：Connected by reference electrode, to electrode with working electrode three-electrode system On electrochemical workstation, immerse in the mixed solution of graphene oxide and lithium perchlorate, in the range of the V of -1.5 V ~ 0.6 Cyclic voltammetry scan is carried out, it is 25 mVs to sweep speed-1, 3 ~ 10 circles are scanned, remove the graphene oxide and lithium perchlorate of residual, i.e., Obtain three-dimensional grapheme.
- 2. the method described in claim 1, it is characterised in that the nickel hydroxide-cobalt hydroxide nanometer sheet by nickel hydroxide and Cobalt hydroxide is combined, wherein, the mol ratio of nickel element and cobalt element is 0.0001 ~ 1：0.0001~1.
- 3. the method described in claim 2, it is characterised in that the mol ratio of nickel element and cobalt element is 0.9 ~ 1：0.0001~ 0.1。
- 4. the method as described in claim 1, it is characterised in that the condition of the electrodeposition process is：The V's of -1.5 V ~ -0.2 In the range of cyclic voltammetry scan 10 ~ 20 enclose, it is 50 mVs to sweep speed-1；Or it is described using electrodeposition process three-dimensional grapheme surface depositing nickel hydroxide-cobalt hydroxide nanometer sheet specific steps For：The mixed solution of sodium nitrate, cobalt nitrate and nickel nitrate is prepared, the working electrode for being loaded with three-dimensional grapheme is immersed in above-mentioned In mixed solution, the cyclic voltammetry scan in the range of the V of -1.5 V ~ -0.2, it is 50 mVs to sweep speed-1, the circle of scanning 10 ~ 20, thoroughly Analysis removes the mixed solution of residual, dries, obtains nickel hydroxide-cobalt hydroxide/graphene complex.
- 5. catalyst prepared by any described methods of claim 1-4.
- 6. catalyst described in claim 5 in catalysis methanol oxidation, prepare Proton Exchange Membrane Fuel Cells or methanol fuel electricity Application in pond.
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| 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 |
| 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 |
| 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 |
| 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 |
| CN108539208B (en) * | 2018-04-12 | 2020-11-17 | 辽宁大学 | NiS/Ni(OH)2@ PPy/GO nanosheet and methanol electrocatalytic modification electrode |
| CN109686581B (en) * | 2019-01-11 | 2020-07-24 | 南昌航空大学 | Cobalt hydroxide/rGO/nickel hydroxide sandwich-shaped flexible electrode material and preparation method thereof |
| CN112362713B (en) * | 2020-11-24 | 2021-12-07 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
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