CN106784881B - A kind of noble metal/vertical growth hydrotalcite nano piece methanol fuel cell catalyst and preparation method thereof - Google Patents
A kind of noble metal/vertical growth hydrotalcite nano piece methanol fuel cell catalyst and preparation method thereof Download PDFInfo
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- CN106784881B CN106784881B CN201710099791.1A CN201710099791A CN106784881B CN 106784881 B CN106784881 B CN 106784881B CN 201710099791 A CN201710099791 A CN 201710099791A CN 106784881 B CN106784881 B CN 106784881B
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/9075—Catalytic material 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]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of noble metal/vertical growth hydrotalcite nano piece methanol fuel cell catalyst and preparation method thereof, this method includes：First by LDH grow needed for template cleaning after perform etching；Then hydro-thermal reaction is utilized, in the mixed solution for two or three of presoma metal salt that mould material is put into required for LDH growths, adds the cetyl trimethylammonium bromide of certain mass（CTAB）After being reacted with certain temperature, cooling, that is, the LDH nanometer sheets grown vertically on mould material surface are obtained；Finally the LDH nanometer sheets of obtained vertical growth are positioned in the one or more precious metal salt solutions of pH adjustment within the specific limits, noble metal/vertical growth LDH nanometer sheets are obtained using redox reaction.The precious metal support LDH nanometer sheets formed using heretofore described method, are grown, provide bigger specific surface area for the load of noble metal catalyst, and the LDH grown on mould material has more preferable rigid structure vertically on mould material surface.
Description
Technical field
The invention belongs to composite catalyst preparation field, more particularly to a kind of noble metal/grow hydrotalcite nano piece vertically
The preparation method of methanol fuel cell catalyst.
Background technology
In today that productivity and human living standard are showing improvement or progress day by day, demand and dependence sharp increase to the energy so that
The consumption of conventional fossil fuel is growing day by day, and the thing followed is the destruction to living environment.Therefore, being badly in need of searching one kind can be again
Raw alternative energy source, the burning of fossil fuel is reduced, alleviate the pressure of environment.Methanol fuel cell is as a kind of Portable novel
The energy, because chemical energy can be converted into electric energy by it, therefore do not limited by Carnot cycle, energy transformation ratio can reach
More than 80%, there is the advantages of energy density is high, while do not need the cumbersome charge and discharge process of tradition, simple to operate, user
Just, attracted wide attention in recent years.But use for methanol fuel cells is in the noble metal catalyst of catalyticing anode oxidation reaction,
Intermediate product CO is easy to be adsorbed in precious metal surface in catalytic process, occupies the avtive spot of methanol catalytic oxidation, so as to
Greatly reduce precious metal catalyst activity.Simultaneously with the continuous progress of reaction in catalytic process, noble metal catalyst can be with
That reaction carries out generation aggregation, reduce further the catalytic activity of noble metal.
Hydrotalcite is also known as layered double hydroxide, is a kind of typical anionic intercalation material, and its chemistry is tied
Structure formula can be expressed as [M2+ 1-x M3+ x(OH)2](An-)x/n﹒ mH2O, wherein M2+And M3+The metal of divalence and trivalent is represented respectively
Cation, An-For interlayer anion.Hydrotalcite is as a kind of supermolecule composite, because it has special topological structure,
Larger specific surface area, and excellent electrochemical properties, have been caused extensively in fields such as ultracapacitor, electro-catalysis in recent years
Concern.
On being prepared in the prior art by the use of hydrotalcite as precursor in methanol fuel cell catalyst, Li Feng, Zhang Chunfang
Et al. have studied a kind of electrocatalyst for fuel cell, be used as precursor, one-step synthesis method metal simple-substance/more walls carbon by the use of hydrotalcite
Nano-tube shaped composite；Then the composite and graphite, polytetrafluoroethylene (PTFE) are mixed into paste, uniform apply is born in carbon paper
Surface, the area for making coating is 0.5~1.0cm2；Recycle electrochemical deposition method, the precious metals pt grain on its area load
Son, making fuel cell elctro-catalyst.Wherein, the effect of precursor hydrotalcite is to form CNT, and the catalyst
Preparation method is relative complex, and preparation temperature is high, it is necessary to the process conditions accurately controlled are more, is not suitable for large-scale production, simultaneously
The precious metals pt particle size loaded using electro-deposition is larger, skewness.With the progress of methanol oxidation, noble metal
Surface easily occupies avtive spot by intermediate products such as CO, and stability is poor.
In summary, intermediate product CO be present for methanol fuel cell catalyst in the prior art and easily adsorb noble metal
The problems such as aggregation and method for preparing catalyst complexity, easily occurs for surface, noble metal catalyst, still lacks effective solution party
Case.
The content of the invention
The shortcomings that in order to overcome the preparation method of methanol fuel cell catalyst in the prior art, of the invention first mesh
The preparation method that there is provided a kind of noble metal/vertical growth hydrotalcite nano piece, the preparation method simply easily operates, excellent
In the operating procedure of methanol fuel cell catalyst in the prior art, while very big reduction may be reused in precious metal salt solution
Use cost.
To achieve the above object, the present invention specifically uses following technical scheme：
A kind of preparation method of noble metal/vertical growth hydrotalcite nano piece, comprises the following steps：
(1) it will perform etching after template cleaning needed for hydrotalcite (LDH) growth, cleaned up after etching；
(2) using the mixed solution of first alcohol and water as solvent, two or three of forerunner required for dissolving hydrotalcite growth
Body metal salt and cetyl trimethylammonium bromide (CTAB), form uniform solution；
(3) template after being cleaned up in step (1) is put into the uniform solution in step (2), carries out hydro-thermal reaction；
Reaction finishes, and cleans template surface and drying, that is, obtains the hydrotalcite nano piece grown vertically on template surface；
(4) hydrotalcite nano piece grown vertically on template surface in step (3) is placed on precious metal salt solution
In, redox reaction is carried out, after completion of the reaction cleaning, drying to obtain noble metal/grow hydrotalcite nano piece vertically.
Step (1) and the order of (2) can intermodulation.
In step (1), template needed for hydrotalcite (LDH) growth is conductive substrates, such as：Nickel foam, carbon cloth, carbon paper
Deng.
It is using the effect of this growth templates：Attaching substratum is provided for the growth of hydrotalcite, hydrotalcite is given birth to vertically
It is long.
The present invention is performed etching using hydrochloric acid solution to template, and effect is caused by etching：Conductive substrates surface produces
Defect, beneficial to the attachment of subsequent hydrotalcite nano piece, and the formation of vertical pattern.
The specific method of step (1), including：By hydrotalcite grow needed for template thoroughly cleaned with acetone, it is and molten with hydrochloric acid
Liquid performs etching, and is cleaned after etching with absolute ethyl alcohol and secondary water, to thoroughly cleaning up.
Preferably, during first time cleaning treatment, the usage amount of acetone is 200~500mL, is cleaned several times, for template
Size is (0.4~1) cm × (2~4) cm.
To reach more preferable etching effect, the concentration of the hydrochloric acid solution is 0.5~5molL-1, usage amount is can be complete
Portion's covering template is advisable；Etch period is 10~20min.
During second of cleaning treatment, absolute ethyl alcohol and secondary water should replace cleaning 6~8 times, just can be thorough by template
Clean up.
In step (2), those skilled in the art know the species of the presoma metal salt of synthetic hydrotalcite, to this and are not required to
It is particularly limited to.
Preferably, for the catalytic effect of the noble metal/vertical growth hydrotalcite nano piece ultimately formed, the forerunner
Body metal salt is nickel salt, cobalt salt, molysite, aluminium salt, mantoquita, magnesium salts, zinc salt or other metal salts.
Preferably, for the catalytic effect of the noble metal/vertical growth hydrotalcite nano piece ultimately formed, two kinds of LDH
Or three kinds of presoma metal salt molar ratios, two kinds are 1:3~1:8, three kinds are 1:3:5~1:8:10, found by research, this
The hydrotalcite nano piece that ratio is formed is uniformly dispersed, and size is more uniform, effectively increases its surface area, is advantageous to noble metal nano
The load of particle.
The present invention is using cetyl trimethylammonium bromide as directed agents.Cetyl trimethylammonium bromide as a kind of sun from
Sub- surfactant, during hydrotalcite is formed, using first alcohol and water as solvent, hydrotalcite pattern can be controlled, it is easy to obtain
To the hydrotalcite nano piece more uniform with size that be evenly distributed.Preferably, the mol ratio of total metal ion and CTAB for (5~
100)：1.
The hydrotalcite material of different-shape can be synthesized using different solvents, the mixing of present invention selection first alcohol and water is molten
Liquid is solvent, can obtain the stable hydrotalcite nano piece of property.Preferably, the volume ratio of the first alcohol and water is：5:1~
3:1。
In step (3), the temperature and time of hydro-thermal reaction have on the pattern of hydrotalcite product it is certain influence, from obtaining water
For the good lamellar morphology of talcum product, it is preferred that the temperature of the hydro-thermal reaction is 120~200 DEG C, the reaction time 12
~24h.
The special appearance grown vertically possessed by the LDH obtained in the step, it is significantly increased as carrier
Specific surface area, it is more beneficial for supported precious metal catalyst material.
In step (4), in order to be more beneficial for the redox reaction of noble metal, it is preferred that the pH of precious metal salt solution is 7
~11.
Preferably, the precious metal salt is the one or more in Pt salt, Ru salt, Au salt or other precious metal salts, specifically
Can be Na2PtCl6, RuCl3·3H2O, HAuCl4·4H2O etc..From the catalysis for improving noble metal/vertical growth hydrotalcite nano piece
For effect, it is preferred that the concentration of the precious metal salt solution is 0.01~0.1mol ﹒ L-1。
The noble metal size uniformity obtained compared to electrochemical deposition method, the present invention using natural redox reaction,
It is evenly distributed, the temperature of the redox reaction is room temperature (15~37 DEG C), and the reaction time is 1~24h.
To keep the good physico-chemical property of the hydrotalcite nano piece for noble metal/grow vertically, it is preferred that the drying is true
Sky is dried, and temperature is 40~65 DEG C, and drying time is 4~6h.
Obtained LDH materials are placed in precious metal salt solution by the step, by between noble metal and LDH active metals
Redox reaction, can make noble metal granule LDH surfaces occur reduction reaction, the noble metal granule after reduction is in LDH
Surface distributed is uniform, and diameter significantly increases the electrochemical active surface of noble metal between 2.2~2.8nm.Lead to simultaneously
Oxidization-reduction reacts the noble metal granule for being fixed on LDH surfaces, has very strong interaction between LDH, reduces and urging
Change the generation of the agglomeration in methanol oxidation process, the persistence and stability for making precious metal catalyst are greatly improved.
To overcome the shortcomings of methanol fuel cell catalyst in the prior art, second object of the present invention is to provide one kind
The noble metal being prepared using the above method/grow hydrotalcite nano piece vertically.The nanometer sheet presents perpendicular on template surface
The state of growing straight lengthy motion picture, nanoscale twins are evenly distributed, and thickness is homogeneous, are 45~55nm (preferably 50nm)；In nanometer sheet uniformly
Fixed noble metal granule, the noble metal granule is evenly distributed, size uniformity, and particle diameter is 2.2~2.8nm.
Specific surface area of catalyst is controlled by catalyst grain size (noble metal granule), is obtained by the oxide-reduction method of the present invention
2.2~2.8nm noble metal granules of the size uniformity arrived act synergistically with laminate metal material, can significantly improve to methanol oxygen
The catalytic capability of change.
To overcome the shortcomings of carbinol dye cell catalyst in the prior art, third object of the present invention is to provide above-mentioned
Noble metal/application of the vertical growth hydrotalcite nano piece in methanol fuel cell catalyst is prepared.In use, will entirely have
The template for having nanometer sheet is used in methanol fuel cell.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the precious metal support LDH nanometer sheets formed using the method in the present invention, are given birth to vertically on mould material surface
It is long, bigger specific surface area is provided for the load of noble metal catalyst, and the LDH grown on mould material has more preferably
Rigid structure.
Meanwhile LDH prepared by the present invention enhances as the synergy between a kind of laminate metal material and noble metal
The anti-CO toxicity of noble metal, the stability of noble metal catalyst is improved, so as to add the service life of composite catalyst.
(2) the noble metal granule size uniformity (2.2~2.8nm) that is obtained using redox reaction, it is evenly distributed, sudden and violent leakage
Go out bigger electrochemical active surface, hence it is evident that improve the catalytic capability that noble metal catalyst aoxidizes to methanol.
(3) synthetic method of the present invention is simple to operation, and temperature is gentle needed for preparation, is urged better than traditional methanol fuel cell
Agent operating procedure, while precious metal salt solution may be reused and greatly reduce use cost.
Catalyst performance can be greatly improved in the nano lamellar material that method involved in the present invention is prepared, to solve
Methanol fuel cell, which is commercially produced, provides new thinking.
Brief description of the drawings
Fig. 1 is the preparation flow schematic diagram of noble metal/vertical growth LDH nanometer sheets；
Fig. 2 is the SEM phenograms of noble metal/vertical growth LDH nanometer sheets；
Fig. 3 is noble metal/vertical growth LDH nanometer sheets in 0.5mol ﹒ L-1Methanol and 1.0mol ﹒ L-1Sodium hydroxide mixes
Cyclic voltammetry curve in solution.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the present invention.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step and/or combinations thereof.
Term is explained：
Vertically：When an object is only in " previous-next " direction alinement, it is vertical to be referred to as.It is vertical in the present invention
Growth refers to：On template surface, the nanometer sheet state grown vertically is presented in hydrotalcite.
Room temperature：It refers to indoor temperature, and room temperature scope of the invention is 15~37 DEG C.
As background technology is introduced, it is easy intermediate product CO to be present in methanol fuel cell catalyst of the prior art
The problems such as aggregation and method for preparing catalyst complexity easily occur for absorption precious metal surface, noble metal catalyst, in order to solve
As above technical problem, the present invention propose a kind of preparation method of noble metal/vertical growth hydrotalcite nano piece, including following
Step：
(1) it will perform etching after template cleaning needed for hydrotalcite (LDH) growth, cleaned up after etching；
(2) using the mixed solution of first alcohol and water as solvent, two or three of forerunner required for dissolving hydrotalcite growth
Body metal salt and cetyl trimethylammonium bromide (CTAB), form uniform solution；
(3) template after being cleaned up in step (1) is put into the uniform solution in step (2), carries out hydro-thermal reaction；
Reaction finishes, and cleans template surface and drying, that is, obtains the hydrotalcite nano piece grown vertically on template surface；
(4) hydrotalcite nano piece grown vertically on template surface in step (3) is placed on precious metal salt solution
In, redox reaction is carried out, after completion of the reaction cleaning, drying to obtain noble metal/grow hydrotalcite nano piece vertically.
Step (1) and the order of (2) can intermodulation.
In certain specific embodiments of the invention, the specific method of step (1), including：Needed for hydrotalcite is grown
Template is thoroughly cleaned with acetone, and is performed etching with hydrochloric acid solution, is cleaned after etching with absolute ethyl alcohol and secondary water, to thorough
Clean up.
The present invention other embodiments in, in step (2), the presoma metal salt be nickel salt, cobalt salt,
Molysite, aluminium salt, magnesium salts, two or three of zinc salt.Two kinds of molar ratios are 1:3~1:8, three kinds of molar ratios are 1:3:5~
1:8:10.The volume ratio of the first alcohol and water is 5:1~3:1, the species and ratio of mixed solvent are to product of the present invention
Formation has important influence, using this volume ratio first alcohol and water mixed solvent can forming properties it is stable and it is scattered
Even hydrotalcite nano piece.
In still other embodiment of the present invention, in step (3), the temperature of the hydro-thermal reaction is 120~200
DEG C, the reaction time is 12~24h.Formation of the hydrothermal temperature to product of the present invention has important influence, hydro-thermal reaction temperature
Spend low, nanometer sheet pattern can not be formed.Hydrothermal temperature is too high, not only wastes the energy, while the size of nanometer sheet is also
Decrease, be unfavorable for being formed the hydrotalcite nano piece of rationality pattern.
In the other embodiment of the present invention, in step (4), the precious metal salt is Pt salt, Ru salt, Au salt
Or the one or more in other precious metal salts, concretely Na2PtCl6, RuCl3·3H2O, HAuCl4·4H2O etc..In alkalescence
Redox reaction is carried out in environment, its pH is 7~11, and concentration is 0.01~0.1mol ﹒ L-1。
The noble metal being prepared by above method/vertical growth hydrotalcite nano piece is presented vertically on template surface
The state of piece is grown, nanoscale twins are evenly distributed, and thickness is homogeneous, is 45~55nm (preferably 50nm)；Uniformly divide in nanometer sheet
Noble metal granule is dissipated, due to being to reduce to obtain by precious metal salt solution using natural redox reaction, so, noble metal
It is stronger in the adhesive force of nanometer sheet, it is not easy to be scattered, the noble metal granule is evenly distributed, size uniformity, and particle diameter is 2.2~2.8nm.
In order that technical scheme can clearly be understood by obtaining those skilled in the art, below with reference to tool
The embodiment of body describes technical scheme in detail with comparative example.
Embodiment 1
A kind of preparation method of noble metal/vertical growth hydrotalcite nano piece methanol fuel cell catalyst is intended to referring to figure
1, detailed preparation process is as follows：Carbon cloth (CFP) is cut into 0.5 × 3cm first, with 250mL acetone solns in five times
Cleaning, removes surface attachment greasy dirt, with 0.5mol ﹒ L-1Salt acid etch 15min after, clean 6 with absolute ethyl alcohol and secondary water
It is secondary.Then with 5:1 mol ratio weighs Ni (NO3)2﹒ 6H2O (0.2mL 0.2M) and Co (NO3)2﹒ 6H2O (0.04mL0.2M), adds
Enter 1.5g CTAB, with 60mL methanol and the mixed solution (volume ratio of 12mL deionized waters：5:1) dissolved simultaneously as solvent
Form uniform solution.Above-mentioned solution and LDH templates are transferred to 100mL reactors, after 200 DEG C of reaction 24h, dropped naturally
Temperature, surface is cleaned with ethanol and secondary water.It is transferred in vacuum drying chamber, 55 DEG C of dry 4h, is grown vertically after drying
NiCo LDH nanometer sheets.
Using SEM as shown in Fig. 2 it is observed that using obtained by preparation method involved in the present invention
The LDH nanometer sheets arrived, the special appearance of vertical growth piece is presented in template surface, and nanoscale twins are evenly distributed, and thickness is equal
One, it is 50nm.Obtained LDH is then placed on 0.05mol ﹒ L-1Na2PtCl612h is stored at room temperature in (pH=10) in solution,
Transfer to 0.05mol ﹒ L-1RuCl3·3H212h is stood in O (pH=11), template is taken out, is then dried in vacuo, temperature
For 45 DEG C, drying time 6h, that is, obtain PtRu/NiCo LDH-CFP composite catalysts.PtRu/NiCo LDH-CFP are compound to be urged
Noble metal granule is uniformly fixed wtih in LDH nanometer sheets in agent, the noble metal granule is evenly distributed, size uniformity, and particle diameter is
2.2~2.8nm.
As shown in figure 3, by the PtRu/LDH-CFP composite catalysts of preparation, in 1.0M CH3In OH+0.5M NaOH, profit
Scanned, be computed it can be seen that the PtRu/LDH-CFP obtained using method involved in the present invention is compound urges with cyclic voltammetry
Agent has good catalytic performance to methanol, and repeatedly, measuring its oxidation peak current density to methanol oxidation is for experiment
32mA·cm-2, 1.2~2 times are improved compared to conventional method of the prior art.
Embodiment 2
The preparation method of a kind of noble metal/vertical growth hydrotalcite nano piece methanol fuel cell catalyst, first by carbon
Fiber cloth nickel foam (NF) is cut into 0.5 × 3cm, is cleaned in four times with 200mL acetone solns, removes surface attachment greasy dirt, uses
2.0mol·L-1Salt acid etch 20min after, cleaned 6 times with absolute ethyl alcohol and secondary water.Then with 1:3 mol ratio weighs
(CH3COO)2Ni ﹒ 4H2O (0.2mL, 0.2M) and Fe (NO3)3﹒ 9H2O (0.6mL, 0.2M), add 3g cetyl trimethyl
Ammonium bromide (CTAB), with 48mL methanol and the mixed solution (volume ratio of 12mL deionized waters：4:1) dissolved simultaneously as solvent
Form uniform solution.Above-mentioned solution and LDH templates are transferred to 100mL reactors, after 180 DEG C of reaction 12h, dropped naturally
Temperature, surface is cleaned with ethanol and secondary water.It is transferred in vacuum drying chamber, 40 DEG C of dry 6h, is grown vertically after drying
NiFe LDH nanometer sheets.Obtained LDH is placed on 0.01mol ﹒ L-1RuCl3·3H218h is stored at room temperature in O (pH=11), is taken
Go out template, be then dried in vacuo, temperature is 50 DEG C, drying time 5h, that is, obtains Ru/NiFe LDH-NF composite catalyzings
Agent.The state of vertical growth piece, nanometer is presented in LDH nanometer sheets in Ru/NiFe LDH-NF composite catalysts on template surface
Lamella is evenly distributed, and thickness is homogeneous, is 50nm；Noble metal granule is uniformly fixed wtih in nanometer sheet, noble metal granule distribution
Uniformly, size uniformity, particle diameter are 2.2~2.8nm.
The Ru/NiFe LDH-NF composite catalysts that the present embodiment obtains have good catalytic performance to methanol, and it is right to measure its
The oxidation peak current density of methanol oxidation is higher, and 1.2~2 times are improved compared to conventional method of the prior art.
Embodiment 3
The preparation method of a kind of noble metal/vertical growth hydrotalcite nano piece methanol fuel cell catalyst, first by carbon
Paper (CP) is cut into 0.5 × 3cm, is cleaned in four times with 200mL acetone solns, removes surface attachment greasy dirt, uses 2.5molL-1
Salt acid etch 10min after, cleaned 6 times with absolute ethyl alcohol and secondary water.Then with 1:3:8 mol ratio weighs Al (NO3)3﹒
9H2O(0.2mL,0.2M)、Mg(NO3)2﹒ 6H2O (0.6mL, 0.2M) and Zn (NO3)2﹒ 6H2O (1.6mL, 0.2M), add 4.5g
Cetyl trimethylammonium bromide (CTAB), with 54mL methanol and the mixed solution (volume ratio of 12mL deionized waters：4.5:1)
Dissolved as solvent and form uniform solution.Above-mentioned solution and LDH templates are transferred to 100mL reactors, with 200 DEG C
After reacting 20h, Temperature fall, surface is cleaned with ethanol and secondary water.It is transferred in vacuum drying chamber, after 45 DEG C of dry 5h are dried
The LDH nanometer sheets grown vertically.Obtained LDH is placed on 0.1mol ﹒ L-1Na2PtCl6Room temperature (pH=10) in solution
Middle standing 12h, template is taken out, is then dried in vacuo, temperature is 65 DEG C, drying time 4h, that is, obtains Pt/NiFe
LDH-CP composite catalysts.LDH nanometer sheets in Pt/NiFe LDH-CP composite catalysts present vertical raw on template surface
The state of lengthy motion picture, nanoscale twins are evenly distributed, and thickness is homogeneous, are 50nm；Noble metal granule is uniformly fixed wtih in nanometer sheet, should
Noble metal granule is evenly distributed, size uniformity, and particle diameter is 2.2~2.8nm.
The Pt/NiFe LDH-CP composite catalysts that the present embodiment obtains have good catalytic performance to methanol, and it is right to measure its
The oxidation peak current density of methanol oxidation is higher, and 1.2~2 times are improved compared to conventional method of the prior art.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (13)
1. a kind of preparation method of noble metal/vertical growth hydrotalcite nano piece, it is characterized in that, comprise the following steps：
（1）By hydrotalcite grow needed for template cleaning after perform etching, specific method includes：By hydrotalcite grow needed for template use
Acetone thoroughly cleans, and is performed etching with hydrochloric acid solution, is cleaned after etching with absolute ethyl alcohol and secondary water, dry to thorough cleaning
Only；The concentration of the hydrochloric acid solution is 0.5 ~ 5molL-1；Etch period is 10 ~ 20min；
（2）Using the mixed solution of first alcohol and water as solvent, two or three of presoma gold required for dissolving hydrotalcite growth
Belong to salt and cetyl trimethylammonium bromide, form uniform solution；Always metal ion and CTAB mol ratio are（5~100）：1；
（3）By step（1）In clean up after template be put into step（2）In uniform solution in, carry out hydro-thermal reaction；Reaction
Finish, clean template surface and drying, that is, obtain the hydrotalcite nano piece grown vertically on template surface；
（4）By step（3）In the hydrotalcite nano piece grown vertically on template surface be placed in precious metal salt solution, institute
The concentration for stating precious metal salt solution is 0.01 ~ 0.1 mol ﹒ L-1, redox reaction is carried out, cleans, dry after completion of the reaction
Noble metal/grow vertically hydrotalcite nano piece is obtained, the state of vertical growth piece is presented in the nanometer sheet on template surface,
Nanoscale twins are evenly distributed, and thickness is homogeneous, are 45 ~ 55nm；Noble metal granule is uniformly fixed wtih in nanometer sheet, the noble metal
Grain is evenly distributed, size uniformity, and particle diameter is 2.2 ~ 2.8nm；
Step（1）With（2）Order being capable of intermodulation.
2. preparation method as claimed in claim 1, it is characterized in that：Step（1）In, template needed for the hydrotalcite growth is bubble
Foam nickel, carbon cloth or carbon paper.
3. preparation method as claimed in claim 1, it is characterized in that：Step（1）In, during first time cleaning treatment, acetone makes
Dosage is 200 ~ 500mL, and what it is for template size is（0.4~1）cm×（2~4）cm；
During second of cleaning treatment, absolute ethyl alcohol and secondary water should replace cleaning 6 ~ 8 times, and template is thoroughly cleaned up.
4. preparation method as claimed in claim 1, it is characterized in that：Step（2）In, the presoma metal salt is nickel salt, cobalt
Salt, molysite, aluminium salt, magnesium salts, two or three of zinc salt.
5. preparation method as claimed in claim 4, it is characterized in that：Two or three of presoma metal salt molar ratio of LDH, two
Kind is 1:3 ~ 1:8, three kinds are 1:3:5 ~ 1:8:10.
6. preparation method as claimed in claim 1, it is characterized in that：Step（3）In, the temperature of the hydro-thermal reaction for 120 ~
200 DEG C, the reaction time is 12 ~ 24h.
7. preparation method as claimed in claim 1, it is characterized in that：Step（4）In, the pH of precious metal salt solution is 7 ~ 11.
8. preparation method as claimed in claim 1, it is characterized in that：Step（4）In, the precious metal salt is Pt salt, Ru salt, Au
Salt or other precious metal salts.
9. preparation method as claimed in claim 1, it is characterized in that：Step（4）In, the temperature of the redox reaction is room
Temperature, reaction time are 1 ~ 24 h.
10. preparation method as claimed in claim 1, it is characterized in that：Step（4）In, the drying is vacuum drying, and temperature is
40 ~ 65 DEG C, drying time is 4 ~ 6 h.
11. the noble metal being prepared using the method any one of claim 1 ~ 10/grow hydrotalcite nano vertically
Piece.
12. noble metal as claimed in claim 11/grow hydrotalcite nano piece vertically, it is characterized in that：Nanometer sheet is in template table
The state of vertical growth piece is presented on face, nanoscale twins are evenly distributed, and thickness is homogeneous, is 45 ~ 55nm；It is uniformly solid in nanometer sheet
Determine noble metal granule, the noble metal granule is evenly distributed, size uniformity, and particle diameter is 2.2 ~ 2.8nm.
13. noble metal/vertical growth hydrotalcite nano piece described in claim 11 or 12 is preparing methanol fuel cell catalysis
Application in agent.
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