CN106207203B - A kind of nano-sheet Ni (OH)2Catalyst and its preparation method and application - Google Patents
A kind of nano-sheet Ni (OH)2Catalyst and its preparation method and application Download PDFInfo
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- CN106207203B CN106207203B CN201610608945.0A CN201610608945A CN106207203B CN 106207203 B CN106207203 B CN 106207203B CN 201610608945 A CN201610608945 A CN 201610608945A CN 106207203 B CN106207203 B CN 106207203B
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
A kind of nano-sheet Ni (OH)2Catalyst and its preparation method and application.The invention discloses nano-sheet Ni (OH)2The preparation method of catalyst, including：(1) pure nickel matrix is immersed in electrolyte；The electrolyte contains：0.2~3mol L‑1F‑；0.1~1mol L‑1NH4 +；2~7mol L‑1Ethylene glycol；5~10mol L‑1Glycerine；0.1~0.5mol L‑1Na2WO4·2H2O；(2) constant current anodic oxidation preparation is carried out；(3) hydro-thermal process is carried out to step (2) treated sample, cleans drying after hydro-thermal process, obtains nano-sheet Ni (OH)2Catalyst.The invention also discloses the nano-sheet Ni (OH) that above-mentioned preparation method obtains2Catalyst and its application.Prepared by the present invention receives catalyst with higher electro catalytic activity, good cyclical stability and resisting CO poison ability, and preparation process is simple, efficient, at low cost.
Description
Technical field
The present invention relates to electro-catalysis and fuel cell field, more particularly to a kind of nano-sheet Ni (OH)2Catalyst and its
Preparation method and application.
Background technology
In recent years, direct methanol fuel cell (DMFC) is due to lower operating temperature, higher using energy source effect
Rate, fuel store the advantages such as convenient and low stain object discharge, have obtained extensive research and concern.However, with platinum based catalyst
Based on the commercial applications of acid DMFC be faced with some critical problems, such as：Oxidation kinetics is slow, methanol oozes
Thoroughly, catalyst cost is excessively high and to toxicity CO intermediate products excessively sensitivity etc..In contrast, alkaline DMFC is due to its enhancing
Kinetics and less pollutant emission, and have extensive electrode material range of choice, just attract increasingly
More concerns.It can be used base metal and cheap metal as catalyst in alkaline DMFC, wherein nickel-base material (such as metal
The compound etc. of nickel, nickel alloy and nickel) the higher electro catalytic activity of tool, cheap price and good cyclical stability etc. are excellent
Point, it is considered to be very promising non-platinum base alkalinity DMFC catalyst materials.
Anode-catalyzed electrode is the important component of DMFC, and conclusive effect is played to the performance of DMFC.Catalysis is lived
Property is heavily dependent on the surface topography and crystal structure of catalyst.Nanotechnology, which has proved to be, can effectively improve electricity
The method of pole catalytic activity.A large amount of research is devoted to prepare various patterns and the nickel catalyst of structure by different methods
Agent material, such as atomic layer deposition method, sol-gel method, chemical deposition method and electrochemical deposition method.Although above-mentioned preparation method
It makes some progress, but most of technique is still excessively complicated, it is difficult to carry out large-scale industrial production, or make
It needs to use additive and conductive agent during standby, reduces the catalytic activity of catalyst.Meanwhile it is prepared most of Ni-based
The binding force of catalyst and conducting base is weaker, can cause phase transformation during long-term recycling, structure is destroyed or living
The loss of property substance, greatly affected the performance of battery.Therefore, there is a kind of simply and effectively prepare of research high electro-catalysis to live
The method of the nickel catalyst agent material of property and high stability is most important, but is also faced with huge challenge simultaneously.
Anodized is a kind of common electrochemical method preparing nano-alumina film, successfully aluminium, titanium,
Applied on the metal materials such as zirconium, iron and niobium, the structure and pattern of prepared anodic oxidation nanometer film it is easily controllable and
Design, and there is excellent chemical property, it is widely used in ultracapacitor, solar cell, sensor and urges
The fields such as agent.However, due to nickel oxide in common anodic oxidation electrolyte solubility it is very big, be very difficult to control institute
Prepare film layer structure and pattern, can only be observed in the anode oxidation process of nickel under normal conditions serious local dissolution or
Electrobrightening phenomenon.Therefore, up to the present, there are no about the research for preparing Ni-based film catalyst using anodizing
Report.
Invention content
In order to overcome the disadvantages mentioned above and deficiency of the prior art, one of the objects of the present invention is to provide a kind of nano-sheets
Ni(OH)2Catalyst, catalytic activity is strong, good cycling stability.
The second object of the present invention is to provide above-mentioned nano-sheet Ni (OH)2The preparation method of catalyst, preparation process
Simply.
The third object of the present invention is to provide above-mentioned nano-sheet Ni (OH)2The application of catalyst.
The purpose of the present invention is achieved through the following technical solutions：
A kind of nano-sheet Ni (OH)2The preparation method of catalyst, includes the following steps：
(1) pure nickel matrix is immersed in electrolyte；
The electrolyte contains：0.2~3mol L-1F-；0.1~1mol L-1NH4 +；2~7mol L-1Second two
Alcohol；5~10mol L-1Glycerine；0.1~0.5mol L-1Na2WO4·2H2O；
(2) constant current anodic oxidation preparation, 30~100mA of current density cm are carried out-2, electrolyte temperature is 10~30 DEG C,
Oxidization time is 5~15min；
(3) hydro-thermal process is carried out to step (2) treated sample, is directly cleaned up with deionized water after hydro-thermal process
After dry up, obtain nano-sheet Ni (OH)2Catalyst.
Step (2) is before carrying out constant current anodic oxidation, first with 5~20mV s-1Rate boost to 3~4.5V, keep 1
After~5min, then carry out constant current anodic oxidation.
Pure nickel matrix described in step (1) is nickel sheet or nickel foam.
Step (3) described hydro-thermal process, actual conditions are：The compactedness of water heating kettle be less than 50%, reason temperature be 100~
200 DEG C, the hydro-thermal time is 2~5h.
Contain in the hydrothermal solution of the hydro-thermal process：1~3mol L-1LiOH；2~5mol L-1Isopropanol；0.5
~2mol L-1Dimethyl phosphate.
Pure nickel matrix described in step (1) is to pass through pretreated Ni substrate, and the pretreatment is：
Ni substrate is cleaned by ultrasonic 10~15min in acetone and alcoholic solution respectively, to remove greasy dirt and the oxidation on surface
Layer finally takes out drying, obtains the pure nickel matrix of clean surface.
Step (2) the constant current anodic oxidation uses three-electrode system, and using pure nickel matrix as working electrode, pure platinized platinum is pair
The calomel electrode of electrode, saturation is reference electrode.
The nano-sheet Ni (OH)2The nano-sheet Ni (OH) that the preparation method of catalyst is prepared2Catalyst.
The nano-sheet Ni (OH)2The application of catalyst, the anode-catalyzed electrode as direct methanol fuel cell.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) nano-sheet Ni (OH) of the invention2The catalytic activity of catalyst is strong.Nano-sheet Ni (OH)2Film is to first
During the electrocatalytic oxidation of alcohol, oxidation voltage is 0.67V vs.Hg/HgO, and oxidate current is up to 72mA cm-2, performance
Go out good electro catalytic activity, while also having the characteristics that resisting CO poison.
(2) nano-sheet Ni (OH) of the invention2The good cycling stability of catalyst.In prolonged loop test process
In, nano-sheet Ni (OH)2Film shows lasting cyclical stability, after 1000 cycle periods, peak point current
Surplus is 84%, while having very strong mechanical stability and electrochemical stability.
(3) nano-sheet Ni (OH) of the invention2The preparation method of catalyst, using specific anodizing technology, directly
It is connected on in-situ preparation nano-sheet nickel based compound film layer on Ni substrate, there is very strong mechanical bonding force between film layer and matrix,
The reunion of nano particle and the loss of active material can be effectively prevented from.
(4) nano-sheet Ni (OH) of the invention2The preparation method of catalyst is advanced optimized by hydro-thermal post-processing
The institutional framework of film layer improves the catalytic performance of film layer.
(5) nano-sheet Ni (OH) of the invention2The preparation method of catalyst, it is simple for process.Anodizing technology has
Processing time is short, operating voltage is low, and treatment process is simple, can be easy to be transplanted and amplify, applied widely, is suitble to big rule
Mould produces.
(6) nano-sheet Ni (OH) of the invention2Catalyst is at low cost.Due to nickel in nature rich reserves, price
Cheaply, it is higher scarce to overcome the noble metals cost such as traditional platiniferous, ruthenium for the catalyst using nickel as direct methanol fuel cell
Point.
Description of the drawings
Fig. 1 is anodic oxidation device schematic diagram used in the embodiment of the present invention.
Fig. 2 is the nano-sheet Ni (OH) prepared in the embodiment of the present invention 12The XRD test results of film layer.
Fig. 3 is the nano-sheet Ni (OH) prepared in the embodiment of the present invention 12The SEM of film layer schemes.
Fig. 4 is the nano-sheet Ni (OH) prepared in the embodiment of the present invention 12It is made in film layer and comparative sample 1~3
CV test chart of the standby film layer to anodic oxidation of methanol.
Fig. 5 is the nano-sheet Ni (OH) prepared in the embodiment of the present invention 12It is made in film layer and comparative sample 1~3
Long term stability tests figure of the standby film layer to anodic oxidation of methanol.
Fig. 6 A are the nano-sheet Ni (OH) prepared in the embodiment of the present invention 12Meter of the film layer to anodic oxidation of methanol
When testing current figure.
Fig. 6 B are the nano-sheet Ni (OH) prepared in the embodiment of the present invention 12Film layer is to the steady of anodic oxidation of methanol
State electric current and methanol concentration relational graph.
Fig. 7 A are the nano-sheet Ni (OH) prepared in the embodiment of the present invention 22The high power SEM figures of film layer.
Fig. 7 B are the nano-sheet Ni (OH) prepared in the embodiment of the present invention 22The low power SEM figures of film layer.
Fig. 8 is the nano-sheet Ni (OH) prepared in the embodiment of the present invention 22Film layer surveys the CV of anodic oxidation of methanol
Attempt.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
The nano-sheet Ni (OH) of this implementation2The preparation method of catalyst, includes the following steps：
(1) it is 0.2mm with thickness, the pure nickel piece that purity is 96.6% is parent metal, is cut into 3.5cm × 0.5cm's
Rectangle, wherein the top half that length is 1.5cm is retained part, is used for connecting with fixture, and length is the lower half portion of 2cm
To actually use part, it is immersed in electrolyte and participates in anodic oxidation reactions.
(2) acetone and alcohol are used and removes the greasy dirt and oxide layer on nickel sheet surface, acetone and wine under ultrasonic environment
The dosage of essence is just to cover nickel sheet sample, is first cleaned by ultrasonic 10 minutes in acetone soln, is placed into ultrasonic in alcoholic solution
Cleaning 10 minutes；After ultrasonic oil removing, then dried up after being cleaned with deionized water.
(3) 1mol L are added in a reservoir-1Ammonium fluoride, 5mol L-1Ethylene glycol, 8mol L-1Glycerine and
0.3mol L-1Na2WO4·2H2O is configured to electrolyte, nickel sheet one end after cleaning is fixed on anode clamp, the other end
It is immersed in electrolyte and carries out anodic oxidation, anodic oxidation device is the CHI 660D electricity of Shanghai Chen Hua Instrument Ltd. production
Chem workstation 1 is working electrode with nickel sheet 2 as shown in Figure 1, using three-electrode system, pure platinized platinum 3 be to electrode, saturation
Calomel electrode 4 (SCE) is reference electrode, first with 10mV s-1The rate of rise boost to 3.5V, under the voltage of 3.5V constant pressure protect
After holding 2min, then using constant current anodic oxidation preparation, oxidation current is 85mA cm-2, oxidization time 10min, electrolyte temperature
It is 25 DEG C.
(4) sample is removed after waiting for oxidization time, is dried up after cleaning up surface with deionized water spare.
(5) hydro-thermal post-processing is carried out to the sample after anodic oxidation, hydrothermal solution uses 1mol L-1LiOH, 3mol
L-1Isopropanol and 1mol L-1Dimethyl phosphate, the solution configured and sample are added to the water heating kettle of 50mL, be added
Liquor capacity is 20mL, and the volume ratio of shared water heating kettle is 40%.
(6) it is put into KMT-F9 type chamber type electric resistance furnaces and heats after closing water heating kettle, hydrothermal temperature is 150 DEG C,
The hydro-thermal time is 3h, directly sample is taken out after hydro-thermal and is dried up to get nano-sheet Ni after cleaning up surface with deionized water
(OH)2Film layer.
For nano-sheet Ni (OH) prepared by the present invention is better described2The performance of catalyst, the present embodiment prepare comparison
Its test result and of the invention are compared by sample 1~3.The preparation process of wherein each comparative sample is as follows：
Comparative sample 1：
(1) it is 0.2mm with thickness, the pure nickel piece that purity is 96.6% is parent metal, is cut into 3.5cm × 0.5cm's
Rectangle, wherein the top half that length is 1.5cm is retained part, is used for connecting with fixture, and length is the lower half portion of 2cm
To actually use part, it is immersed in electrolyte and participates in anodic oxidation reactions.
(2) acetone and alcohol are used and removes the greasy dirt and oxide layer on nickel sheet surface, acetone and wine under ultrasonic environment
The dosage of essence is just to cover nickel sheet sample, is first cleaned by ultrasonic 10 minutes in acetone soln, is placed into ultrasonic in alcoholic solution
Cleaning 10 minutes；After ultrasonic oil removing, then dried up after being cleaned with deionized water.
(3) 1mol L are added in a reservoir-1Ammonium fluoride, 5mol L-1Ethylene glycol, 8mol L-1Glycerine and
0.3mol L-1Na2WO4·2H2O is configured to electrolyte, nickel sheet one end after cleaning is fixed on anode clamp, the other end
It is immersed in electrolyte and carries out anodic oxidation, anodic oxidation device is the CHI 660D electricity of Shanghai Chen Hua Instrument Ltd. production
Chem workstation, using three-electrode system, using nickel sheet as working electrode, pure platinized platinum is to electrode, the calomel electrode (SCE) of saturation
It is first with 10mV s for reference electrode-1The rate of rise boost to 3.5V, after constant pressure keeps 2min under the voltage of 3.5V, then adopt
It is prepared with constant current anodic oxidation, oxidation current is 85mA cm-2, oxidization time 10min, electrolyte temperature is 25 DEG C.
(4) sample is removed after waiting for oxidization time, is dried up after cleaning up surface with deionized water spare.
(5) hydro-thermal post-processing is carried out to the sample after anodic oxidation, hydrothermal solution uses 1mol L-1NaOH, 3mol
L-1Isopropanol and 1mol L-1Dimethyl phosphate, the solution configured and sample are added to the water heating kettle of 50mL, be added
Liquor capacity is 20mL, and the volume ratio of shared water heating kettle is 40%.
(6) it is put into KMT-F9 type chamber type electric resistance furnaces and heats after closing water heating kettle, hydrothermal temperature is 150 DEG C,
The hydro-thermal time is 3h, directly sample is taken out after hydro-thermal and is dried up after cleaning up surface with deionized water.
Comparative sample 2：
(1) it is 0.2mm with thickness, the pure nickel piece that purity is 96.6% is parent metal, is cut into 3.5cm × 0.5cm's
Rectangle, wherein the top half that length is 1.5cm is retained part, is used for connecting with fixture, and length is the lower half portion of 2cm
To actually use part, it is immersed in electrolyte and participates in anodic oxidation reactions.
(2) acetone and alcohol are used and removes the greasy dirt and oxide layer on nickel sheet surface, acetone and wine under ultrasonic environment
The dosage of essence is just to cover nickel sheet sample, is first cleaned by ultrasonic 10 minutes in acetone soln, is placed into ultrasonic in alcoholic solution
Cleaning 10 minutes；After ultrasonic oil removing, then dried up after being cleaned with deionized water.
(3) 1mol L are added in a reservoir-1Ammonium fluoride, 5mol L-1Ethylene glycol, 8mol L-1Glycerine and
0.3mol L-1Na2WO4·2H2O is configured to electrolyte, nickel sheet one end after cleaning is fixed on anode clamp, the other end
It is immersed in electrolyte and carries out anodic oxidation, anodic oxidation device is the CHI 660D electricity of Shanghai Chen Hua Instrument Ltd. production
Chem workstation, using three-electrode system, using nickel sheet as working electrode, pure platinized platinum is to electrode, the calomel electrode (SCE) of saturation
It is first with 10mV s for reference electrode-1The rate of rise boost to 3.5V, after constant pressure keeps 2min under the voltage of 3.5V, then adopt
It is prepared with constant current anodic oxidation, oxidation current is 85mA cm-2, oxidization time 10min, electrolyte temperature is 25 DEG C.
(4) sample is removed after waiting for oxidization time, is dried up after cleaning up surface with deionized water spare.
(5) hydro-thermal post-processing is carried out to the sample after anodic oxidation, hydrothermal solution uses 1mol L-1KOH, 3mol L-1Isopropanol and 1mol L-1Dimethyl phosphate, the solution configured and sample are added to the water heating kettle of 50mL, be added
Liquor capacity is 20mL, and the volume ratio of shared water heating kettle is 40%.
(6) it is put into KMT-F9 type chamber type electric resistance furnaces and heats after closing water heating kettle, hydrothermal temperature is 150 DEG C,
The hydro-thermal time is 3h, directly sample is taken out after hydro-thermal and is dried up after cleaning up surface with deionized water.
Comparative sample 3
(1) it is 0.2mm with thickness, the pure nickel piece that purity is 96.6% is parent metal, is cut into 3.5cm × 0.5cm's
Rectangle, wherein the top half that length is 1.5cm is retained part, is used for connecting with fixture, and length is the lower half portion of 2cm
To actually use part, it is immersed in electrolyte and participates in anodic oxidation reactions.
(2) acetone and alcohol are used and removes the greasy dirt and oxide layer on nickel sheet surface, acetone and wine under ultrasonic environment
The dosage of essence is just to cover nickel sheet sample, is first cleaned by ultrasonic 10 minutes in acetone soln, is placed into ultrasonic in alcoholic solution
Cleaning 10 minutes；After ultrasonic oil removing, then dried up after being cleaned with deionized water.
(3) 1mol L are added in a reservoir-1Ammonium fluoride, 5mol L-1Ethylene glycol, 8mol L-1Glycerine and
0.3mol L-1Na2WO4·2H2O is configured to electrolyte, nickel sheet one end after cleaning is fixed on anode clamp, the other end
It is immersed in electrolyte and carries out anodic oxidation, anodic oxidation device is the CHI 660D electricity of Shanghai Chen Hua Instrument Ltd. production
Chem workstation, using three-electrode system, using nickel sheet as working electrode, pure platinized platinum is to electrode, the calomel electrode (SCE) of saturation
It is first with 10mV s for reference electrode-1The rate of rise boost to 3.5V, after constant pressure keeps 2min under the voltage of 3.5V, then adopt
It is prepared with constant current anodic oxidation, oxidation current is 85mA cm-2, oxidization time 10min, electrolyte temperature is 25 DEG C.
(4) sample is removed after waiting for oxidization time, is dried up after being cleaned up with deionized water.
To nano-sheet Ni (OH) manufactured in the present embodiment2The institutional framework of film layer is characterized, and XRD test results are such as
(Xing of wherein nickel penetrates peak and comes from matrix) shown in Fig. 2, it can be seen from the figure that after hydro-thermal process, the ingredient of film layer is all
β-Ni(OH)2(JCPDS card No.14-117)。
To nano-sheet Ni (OH) manufactured in the present embodiment2The surface topography of film layer is characterized, SEM test knots
Fruit is as shown in figure 3, as can be observed from Figure, after anodic oxidation and hydro-thermal process, the film surface finally prepared generates
A large amount of 3D flaky nanometer structures.
By nano-sheet Ni (OH) manufactured in the present embodiment2Institute in film layer and comparative sample 1, comparative sample 2 and comparative sample 3
The film layer of preparation is used for DMFC anode catalysts, and electro catalytic activity to the electrode catalyst of gained and electrochemical stability into
Row measures.
Fig. 4 indicates nano-sheet Ni (OH) made from the present embodiment2Film and comparative sample 1, comparative sample 2 and comparative sample 3
In prepared film layer in 0.1mol L-1NaOH and 1mol L-1Cyclic voltammetry curve (CV) in methanol solution.From figure
In as can be seen that non-hydro-thermal sample and the sample after LiOH, NaOH, KOH solution hydro-thermal one is shown to methanol
Fixed catalytic capability, but the catalytic performance of the sample after LiOH solution hydro-thermals is obviously better than other samples, oxidation electricity
Pressure is 0.67V vs.Hg/HgO, is minimum in four, oxidate current is 72mA cm-2, it is highest in four, shows
Nano-sheet Ni (OH) after LiOH solution hydro-thermals2Film has highest catalytic activity to the oxidation of methanol.Anti-
Occurs a new oxidation peak into figure when scanning, this oxidation peak is formed by production among residual carbon when representing forward scan
The elimination reaction of object, and flyback curve does not form with forward scan curve and intersects, and reflects nano-sheet Ni (OH)2Film
Poison performance with good anti-intermediate product.
Fig. 5 indicates nano-sheet Ni (OH) made from the present embodiment2Film and comparative sample 1, comparative sample 2 and comparative sample 3
In prepared film layer in 0.1mol L-1NaOH+1mol L-1CH3Prolonged CV loop tests result is carried out in OH solution.From
It can be seen from the figure that, compared with before test, sample after LiOH solution hydro-thermals experienced 1000 cycle periods with
Afterwards, the surplus of peak current density has reached 84%, and the sample of non-hydro-thermal process and after NaOH, KOH solution hydro-thermal
The surplus of peak current density of sample be respectively 45%, 65% and 55%, thus demonstrate by LiOH solution hydro-thermals
Nano-sheet Ni (OH) afterwards2Film has best electro-catalysis cyclical stability.
Fig. 6 A are nano-sheet Ni (OH) made from the present embodiment20.1mol L of the film before and after adding methanol-1NaOH
Chrono-amperometric in solution tests (CA) figure, and the step potential of selection is 0.67V (i.e. the current potential of methanol oxidation peak), and the time is more than
1h.For each chronoa mperometric plot, oxidation current all declines rapidly in preceding 20s, and will gradually tend towards stability shape later
State.After methanol is added into solution, the measured value when measured value of steady-state current is significantly larger than without addition methanol, this is therewith
Preceding CV test results are consistent, further illustrate nano-sheet Ni (OH)2Film there is very high catalysis to live the oxidation of methanol
Property.Also, the CA test current values for continuing one hour or more are highly stable, show nano-sheet Ni (OH)2Film is to methanol
The intermediate product of oxidation reaction has good tolerance and resists poisoning.
Fig. 6 B illustrate nano-sheet Ni (OH) made from the present embodiment2Between the CA steady-state currents and methanol concentration of film
Relation curve.From curve as can be seen that after potential step to stable state, with the increase that methanol concentration is added, oxidation electricity
Stream gradually increases, until methanol concentration increases to 3mol L-1Later, steady-state current increase at this time is no longer apparent, reaches one
Platform.Nano-sheet Ni (OH)2Methanol saturated concentration (the 3mol L of film-1) it is significantly larger than the nickel-base catalyst in other reports
(<1mol L-1), show stronger catalytic kinetics.
Embodiment 2
The nano-sheet Ni (OH) of this implementation2The preparation method of catalyst, includes the following steps：
(1) it is 0.5mm with thickness, the nickel foam that purity is 96.6% is parent metal, is cut into 3.5cm × 0.5cm's
Rectangle, wherein the top half that length is 1.5cm is retained part, is used for connecting with fixture, and length is the lower half portion of 2cm
To actually use part, it is immersed in electrolyte and participates in anodic oxidation reactions.
(2) use acetone and alcohol and the nickel surface that defoams under ultrasonic environment greasy dirt and oxide layer, acetone and
The dosage of alcohol is just to cover nickel sheet sample, is first cleaned by ultrasonic 10 minutes in acetone soln, places into alcoholic solution and surpass
Sound cleans 10 minutes；After ultrasonic oil removing, then dried up after being cleaned with deionized water.
(3) 0.5mol L are added in a reservoir-1Ammonium fluoride, 5mol L-1Ethylene glycol, 8mol L-1Glycerine and
0.4mol L-1Na2WO4·2H2O is configured to electrolyte, nickel sheet one end after cleaning is fixed on anode clamp, the other end
It is immersed in electrolyte and carries out anodic oxidation, anodic oxidation device is the CHI 660D electricity of Shanghai Chen Hua Instrument Ltd. production
Chem workstation, using three-electrode system, using nickel sheet as working electrode, pure platinized platinum is to electrode, the calomel electrode (SCE) of saturation
It is first with 10mV s for reference electrode-1The rate of rise boost to 3V, under the voltage of 3V constant pressure keep 2min after, then using perseverance
It flows anodic oxidation to prepare, oxidation current is 100mA cm-2, oxidization time 10min, electrolyte temperature is 25 DEG C.
(4) sample is removed after waiting for oxidization time, is dried up after cleaning up surface with deionized water spare.
(5) hydro-thermal post-processing is carried out to the sample after anodic oxidation, hydrothermal solution uses 1mol L-1LiOH, 3mol
L-1Isopropanol and 1mol L-1Dimethyl phosphate, the solution configured and sample are added to the water heating kettle of 50mL, be added
Liquor capacity is 20mL, and the volume ratio of shared water heating kettle is 40%.
(6) it is put into KMT-F9 type chamber type electric resistance furnaces and heats after closing water heating kettle, hydrothermal temperature is 150 DEG C,
The hydro-thermal time is 3h, is directly taken out sample after hydro-thermal, dried up after cleaning up surface with deionized water to get.
To the nano-sheet Ni (OH) prepared by the present embodiment2The institutional framework of film layer, surface topography are characterized, and
Its catalytic performance is detected：
Fig. 7 A, Fig. 7 B are the nano-sheet Ni (OH) prepared on nickel foam substrate2The SEM of film schemes, can from figure
To find out, the nano-sheet Ni (OH) that is prepared on nickel foam substrate2Film has with the film layer being grown on nickel sheet matrix
Similar structure；Can be that methanol aoxidizes also, since the 3D structures of foam nickel material inherently have very high specific surface area
More active sites are provided, its catalytic activity is made to be further enhanced.
Fig. 8 is the nano-sheet Ni (OH) prepared on nickel foam substrate2Film is in 0.1mol L-1NaOH +1mol
L-1CH3CV test results in OH solution, from CV it can be seen from the figure thats, methanol is in electrocatalytic oxidation on nickel foam base membrane layer
Peak current density is very big, has reached 170mA cm-2, oxidation peak voltage is 0.72V, is shown than using nickel sheet matrix
The taller catalytic activity of the film layer prepared.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (8)
1. a kind of nano-sheet Ni (OH)2The preparation method of catalyst, which is characterized in that include the following steps：
(1) pure nickel matrix is immersed in electrolyte；
The electrolyte contains：0.2~3mol L-1F-；0.1~1mol L-1NH4 +；2~7mol L-1Ethylene glycol；5~
10mol L-1Glycerine；0.1~0.5mol L-1Na2WO4·2H2O；
(2) constant current anodic oxidation preparation, 30~100mA of current density cm are carried out-2, electrolyte temperature is 10~30 DEG C, when oxidation
Between be 5~15min；
(3) hydro-thermal process is carried out to step (2) treated sample, directly after-blow is cleaned up with deionized water after hydro-thermal process
It is dry, obtain nano-sheet Ni (OH)2Catalyst；
Contain in the hydrothermal solution of the hydro-thermal process：1~3mol L-1LiOH；2~5mol L-1Isopropanol；0.5~
2mol L-1Dimethyl phosphate.
2. nano-sheet Ni (OH) according to claim 12The preparation method of catalyst, which is characterized in that step (2) exists
Before carrying out constant current anodic oxidation, first with 5~20mV s-1Rate boost to 3~4.5V, after keeping 1~5min, then carry out perseverance
Flow anodic oxidation.
3. nano-sheet Ni (OH) according to claim 12The preparation method of catalyst, which is characterized in that step (1) institute
The pure nickel matrix stated is nickel sheet or nickel foam.
4. nano-sheet Ni (OH) according to claim 12The preparation method of catalyst, which is characterized in that step (3) institute
Hydro-thermal process is stated, actual conditions are：The compactedness of water heating kettle be less than 50%, temperature be 100~200 DEG C, the hydro-thermal time be 2~
5h。
5. nano-sheet Ni (OH) according to claim 12The preparation method of catalyst, which is characterized in that step (1) institute
The pure nickel matrix stated is to pass through pretreated Ni substrate, and the pretreatment is：
Ni substrate is cleaned by ultrasonic 10~15min in acetone and alcoholic solution respectively, to remove the greasy dirt and oxide layer on surface, most
Drying is taken out afterwards, obtains the pure nickel matrix of clean surface.
6. nano-sheet Ni (OH) according to claim 12The preparation method of catalyst, which is characterized in that step (2) institute
It states constant current anodic oxidation and uses three-electrode system, using pure nickel matrix as working electrode, pure platinized platinum is to electrode, the calomel electricity of saturation
Extremely reference electrode.
7. claim 1~6 any one of them nano-sheet Ni (OH)2The nanometer sheet that the preparation method of catalyst is prepared
Shape Ni (OH)2Catalyst.
8. the nano-sheet Ni (OH) described in claim 72The application of catalyst, which is characterized in that as direct methanol fuel electricity
The anode-catalyzed electrode in pond.
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| CN101275266A (en) * | 2007-12-20 | 2008-10-01 | 江苏大学 | High electric insulation sealing method for anodized aluminum film |
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