CN106702425B - A method of preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface - Google Patents
A method of preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface Download PDFInfo
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Abstract
A method of molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer being prepared in foam iron surface, the present invention relates to a kind of methods preparing flower-shaped molybdenum disulfide Iy self-assembled layer/copper electroplating layer/displacement cobalt coat with good hydrogen evolution activity in foam iron surface.The present invention is to solve the current base metal liberation of hydrogen catalyst relatively low problems of hydrogen evolution activity in an acidic solution.A method of preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface：(1) preparation of flower-shaped molybdenum disulfide colloidal solution；(2) preparation of cationic-type polyacrylamide gel；(3) foamed iron pre-treatment；(4) the flower-shaped molybdenum disulfide of foamed iron surface self-organization；(5) electro-coppering；(6) cobalt plating is replaced, the composite coating of catalytic hydrogen evolution function admirable is obtained in foam iron surface.A kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface is conducive to improve the production capacity of electrolytic hydrogen production and reduces energy consumption.
Description
Technical field
The invention belongs to the preparation field of catalytic hydrogen evolution material, be related to it is a kind of foam iron surface prepare molybdenum disulfide/copper/
The method of cobalt catalytic hydrogen evolution layer.
Background technology
In the today's society of energy increasingly depleted, how to develop and use novel regenerative resource and had become instead of fossil energy
For mostly important one of the topic in the whole world.Under new Energy situation, using renewable energy power generations such as solar energy, wind energies
Be widely studied, however due to the not storability of electric energy, if the energy conversions such as solar energy, wind energy at electric energy be not consumed
Falling can not be stored.If the electric energy that other energy forms generate is converted to clean energy resource --- hydrogen, it can be very
Good solves the problems, such as that energy regeneration and the energy are fixed.So electrolytic catalysis liberation of hydrogen has become solution energy regeneration under the new situation
With fixed important means.
But resistance of all electrolytic catalysis liberation of hydrogen materials when being electrolysed liberation of hydrogen being required for that hydrogen is overcome to be precipitated, i.e.,
Applied voltage when cathode hydrogen evolution needs to overcome additional overpotential of hydrogen evolution, and overpotential of hydrogen evolution is bigger, and hydrogen precipitation is more difficult, disappears
The energy of consumption is also more, and the energy of extra consumption can then be discharged in the form of thermal energy.Therefore, suitable electrolytic catalysis is selected
Liberation of hydrogen material is to reduce overpotential of hydrogen evolution, to reduce energy expenditure when electrolysis liberation of hydrogen, could more efficiently by electric energy
It is converted into the chemical energy that can be stored.
The height of overpotential of hydrogen evolution is related with the attribute of material itself, also related with the catalysis area and electric conductivity of material.
Catalytic hydrogen evolution function admirable is catalyzed the big material of area, and the activation polarization during liberation of hydrogen is small, the material of good conductivity, analysis
Ohmic polarization during hydrogen is small, and the reduction of two kinds of polarization can reduce overpotential of hydrogen evolution, that is, can reduce electricity
Solve energy expenditure when liberation of hydrogen.In all electrolytic catalysis liberation of hydrogen materials, the catalytic hydrogen evolution performance of noble metal platinum is the most excellent,
The minimum energy consumed during liberation of hydrogen.But it is expensive, input-output ratio is very high, is not suitable for industrial life
Production.As the novel electrolytic catalysis liberation of hydrogen material instead of noble metal platinum, molybdenum disulfide is constantly subjected to the concern of scientific circles, especially
Be catalytic activity in acid system it is that other many non-noble metallic materials are incomparable.Currently, preparing high-specific surface area
The method of molybdenum disulfide has very much, and mechanical stripping method, solvent-thermal method and lithium ion graft process etc., the molybdenum disulfide of acquisition has
Two dimension or three-dimensional high catalytic activity surface.But the electric conductivity of molybdenum disulfide itself is poor, can be analysed in this way in electrolytic catalysis
Increase its ohmic polarization when hydrogen, is unfavorable for the reduction of energy consumption.How by the molybdenum disulfide with huge catalytic surface fixed to
The advantage that its catalytic activity is high, catalysis area is big, while the disadvantage for overcoming resistance larger can be preferably played when on electrode, be
Molybdenum disulfide is applied to the problem of engineering field must face at present.Therefore, catalytic surface product big, good conductivity, steady is prepared
Qualitative good molybdenum disulfide composite material is the important channel that acid system electrolytic catalysis liberation of hydrogen realizes that energy consumption reduces, it may have huge
Big potential economic benefit.
Invention content
The present invention is to solve the current base metal liberation of hydrogen catalyst relatively low problem of hydrogen evolution activity in an acidic solution,
And provide a kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface.
The a kind of of the present invention prepares the method for molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer according to following step in foam iron surface
It is rapid to carry out：
(1) preparation of flower-shaped molybdenum disulfide colloidal solution：A. the anionic surfactant for weighing 0.5 ~ 5.0 g, adds
Enter into 1000 mL deionized waters, be stirred at room temperature after 5 ~ 15 min, the flower-shaped molybdenum disulfide of 0.2 ~ 1.2 g is added；b.
It is stirred at 60 DEG C and 2 h is handled using ultrasonic cell disruptor after 2 h；C. it repeats step b 1 ~ 6 time, completes flower-shaped two
The preparation of molybdenum sulfide colloidal liquid；
(2) preparation of cationic-type polyacrylamide gel：D. by the cationic poly third of a concentration of 3.0 ~ 6.0 g/L
Acrylamide is dissolved in deionized water, matches to obtain cationic-type polyacrylamide solution after 3 ~ 5 h are stirred at 40 ~ 60 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed in acetone and is ultrasonically treated 1 ~ 5 min removing surface and oil contaminants；f.
It will be cleaned by one of tap water by the foamed iron of oil removing, after the cleaning of three deionized waters, immerse volume basis at room temperature
10 ~ 30 s of etch in a concentration of 0.1 ~ 0.5% hydrochloric acid solution is cleaned using one of tap water, three deionized waters are cleaned
Afterwards, the pre-treatment of foamed iron is completed；
(4) the flower-shaped molybdenum disulfide of foamed iron surface self-organization：G. the cationic polyacrylamide for using step (2) to prepare
Amine gel to by step (3) handle after foamed iron carry out 0.5 ~ 5 min of shower, be then immersed in slight oscillatory 2 in acetone ~
10 s, naturally dry after taking-up immerse 6 ~ 12 min in the flower-shaped molybdenum disulfide colloidal solution that step (1) is prepared, are then immersed in third
30 ~ 90 s of slight oscillatory in ketone, naturally dry after taking-up complete the flower-shaped molybdenum disulfide of foamed iron surface self-organization；
(5) electro-coppering：H. foamed iron/molybdenum disulfide composite material is prepared as cathode, phosphor-copper using prepared by step (4)
Plate immerses in acid copper plating bath at room temperature as anode, is 1.0 ~ 3.0 A/dm in current density2Under conditions of electro-deposition 10
~ 30 s immerse 1 ~ 5 s in etching solution, then wash again after washing；I. step h is repeated 5 ~ 30 times, completion foamed iron/
The preparation of molybdenum disulfide/carbon/carbon-copper composite material；
(6) cobalt plating is replaced：J. it is 30 that the foamed iron/molybdenum disulfide prepared by step (5)/carbon/carbon-copper composite material, which immerses temperature,
1 ~ 5 min in ~ 45 DEG C of displacement plating cobalt liquor, is completed after one of tap water cleaning, the cleaning of three deionized waters later
Foam iron surface prepares the preparation of molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer.
Anionic surfactant described in a of step (1) be lauryl sodium sulfate, dodecyl sodium sulfate or
One kind in dodecyl alcohol polyoxyethylene ether sodium sulfate；The molecule of cationic-type polyacrylamide described in the d of step (2)
Amount is 18,000,000 ~ 25,000,000；The acid copper plating bath used in the h of step (5) by sulfuric acid a concentration of 50 ~ 150 mL/L, five water
The ratio of a concentration of 120 ~ 150g/L of copper sulphate, by sulfuric acid and cupric sulfate pentahydrate sequentially add in water be uniformly mixed preparation and
At；Etching solution described in the h of step (5) is by a concentration of 20 ~ 50 mL/L of sulfuric acid, a concentration of 0.5 ~ 5 g/ of copper sulphate
Sulfuric acid, copper sulphate and potassium peroxydisulfate are sequentially added in water and are uniformly mixed by the L, ratio of a concentration of 35 ~ 60 g/L of potassium peroxydisulfate
It is formulated；Displacement plating cobalt liquor described in step (6) by a concentration of 5 ~ 35 g/L of ammonium citrate, cobaltous sulfate it is a concentration of
8 ~ 60 g/L, a concentration of 2 ~ 10 g/L of hydroquinone, thiocarbamide a concentration of 20 ~ 80 g/L ratio, by ammonium citrate, sulfuric acid
Cobalt, hydroquinone and thiocarbamide are sequentially added in water and are uniformly mixed, and adjustment pH is formulated for 4.0 ~ 6.5.
A kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface of the present invention passes through in foam
Iron surface self assembly prepares flower-shaped layer of molybdenum-disulfide, by flower-shaped two sulphur in an acidic solution with good electrocatalytic hydrogen evolution performance
Change molybdenum and is securely adsorbed in foam iron surface；Subsequent electro-coppering step not only further increases leading for composite catalyzing material entirety
Electrically, and for subsequent displacement cobalt plating the surface area of bigger is provided；After copper surface replacement cobalt plating, displacement cobalt coat is not
Protection can only be played the role of to copper, and its excellent catalytic performance can further increase compound liberation of hydrogen material entirety
Catalytic effect.After foam iron surface prepares the flower-shaped layer of molybdenum-disulfide/copper electroplating layer/displacement cobalt coat of self assembly, preparation
Composite material in an acidic solution large-current electric solution liberation of hydrogen when with excellent catalytic activity, be conducive to the production for improving electrolytic hydrogen production
Can and it reduce energy consumption.
Description of the drawings
Fig. 1 is to test a SEM image after the flower-shaped molybdenum disulfide of foamed iron surface self-organization；
Fig. 2 is to test one before and after foam iron surface prepares molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in 0.5 M H2SO4It is molten
In liquid, cathode-current density be 250 mA/cm2Under conditions of the time-potential curve that measures.
Specific implementation mode
Specific implementation mode one：One kind of present embodiment prepares molybdenum disulfide/copper/cobalt catalytic hydrogen evolution in foam iron surface
The method of layer carries out according to the following steps：
(1) preparation of flower-shaped molybdenum disulfide colloidal solution：A. the anionic surfactant for weighing 0.5 ~ 5.0 g, adds
Enter into 1000 mL deionized waters, be stirred at room temperature after 5 ~ 15 min, the flower-shaped molybdenum disulfide of 0.2 ~ 1.2 g is added；b.
It is stirred at 60 DEG C and 2 h is handled using ultrasonic cell disruptor after 2 h；C. it repeats step b 1 ~ 6 time, completes flower-shaped two
The preparation of molybdenum sulfide colloidal liquid；
(2) preparation of cationic-type polyacrylamide gel：D. by the cationic poly third of a concentration of 3.0 ~ 6.0 g/L
Acrylamide is dissolved in deionized water, matches to obtain cationic-type polyacrylamide solution after 3 ~ 5 h are stirred at 40 ~ 60 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed in acetone and is ultrasonically treated 1 ~ 5 min removing surface and oil contaminants；f.
It will be cleaned by one of tap water by the foamed iron of oil removing, after the cleaning of three deionized waters, immerse volume basis at room temperature
10 ~ 30 s of etch in a concentration of 0.1 ~ 0.5% hydrochloric acid solution is cleaned using one of tap water, three deionized waters are cleaned
Afterwards, the pre-treatment of foamed iron is completed；
(4) the flower-shaped molybdenum disulfide of foamed iron surface self-organization：G. the cationic polyacrylamide for using step (2) to prepare
Amine gel to by step (3) handle after foamed iron carry out 0.5 ~ 5 min of shower, be then immersed in slight oscillatory 2 in acetone ~
10 s, naturally dry after taking-up immerse 6 ~ 12 min in the flower-shaped molybdenum disulfide colloidal solution that step (1) is prepared, are then immersed in third
30 ~ 90 s of slight oscillatory in ketone, naturally dry after taking-up complete the flower-shaped molybdenum disulfide of foamed iron surface self-organization；
(5) electro-coppering：H. foamed iron/molybdenum disulfide composite material is prepared as cathode, phosphor-copper using prepared by step (4)
Plate immerses in acid copper plating bath at room temperature as anode, is 1.0 ~ 3.0 A/dm in current density2Under conditions of electro-deposition 10
~ 30 s immerse 1 ~ 5 s in etching solution, then wash again after washing；I. step h is repeated 5 ~ 30 times, completion foamed iron/
The preparation of molybdenum disulfide/carbon/carbon-copper composite material；
(6) cobalt plating is replaced：J. it is 30 that the foamed iron/molybdenum disulfide prepared by step (5)/carbon/carbon-copper composite material, which immerses temperature,
1 ~ 5 min in ~ 45 DEG C of displacement plating cobalt liquor, is completed after one of tap water cleaning, the cleaning of three deionized waters later
Foam iron surface prepares the preparation of molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer.
Present embodiment it is a kind of foam iron surface prepare the method for molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer by
Foamed iron surface self-organization prepares flower-shaped layer of molybdenum-disulfide, will be flower-shaped with good electrocatalytic hydrogen evolution performance in an acidic solution
Molybdenum disulfide is securely adsorbed in foam iron surface；It is whole that subsequent electro-coppering step not only further increases composite catalyzing material
Electric conductivity, and be that subsequent displacement cobalt plating provides the surface area of bigger；After copper surface replacement cobalt plating, cobalt plating is replaced
Layer can not only play the role of copper protection, but also can to further increase compound liberation of hydrogen material whole for its excellent catalytic performance
The catalytic effect of body.After foam iron surface prepares the flower-shaped layer of molybdenum-disulfide/copper electroplating layer/displacement cobalt coat of self assembly, system
Standby composite material in an acidic solution large-current electric solution liberation of hydrogen when with excellent catalytic activity.
Specific implementation mode two：The present embodiment is different from the first embodiment in that the moon described in a of step (1)
Ionic surfactant is in lauryl sodium sulfate, dodecyl sodium sulfate or dodecyl alcohol polyoxyethylene ether sodium sulfate
One kind.It is other same as the specific embodiment one.
Specific implementation mode three：The present embodiment is different from the first and the second embodiment in that described in the d of step (2)
Cationic-type polyacrylamide molecular weight be 18,000,000 ~ 25,000,000.It is other the same as one or two specific embodiments.
Specific implementation mode four：In the h of step (5) unlike one of present embodiment and specific implementation mode one to three
The acid copper plating bath of use in a concentration of 50 ~ 150 mL/L of sulfuric acid, a concentration of 120 ~ 150g/L of cupric sulfate pentahydrate ratio,
Sulfuric acid and cupric sulfate pentahydrate are sequentially added to be uniformly mixed in water and are formulated.Other phases one of with specific implementation mode one to three
Together.
Specific implementation mode five：In the h of step (5) unlike one of present embodiment and specific implementation mode one to four
The etching solution presses the concentration of a concentration of 20 ~ 50 mL/L of sulfuric acid, a concentration of 0.5 ~ 5 g/L of copper sulphate, potassium peroxydisulfate
For the ratio of 35 ~ 60 g/L, sulfuric acid, copper sulphate and potassium peroxydisulfate are sequentially added into uniformly mixed in water be formulated.It is other with
One of specific implementation mode one to four is identical.
Specific implementation mode six：Institute in step (6) unlike one of present embodiment and specific implementation mode one to five
The displacement plating cobalt liquor stated is by a concentration of 5 ~ 35 g/L of ammonium citrate, a concentration of 8 ~ 60 g/L of cobaltous sulfate, hydroquinone
A concentration of 2 ~ 10 g/L, thiocarbamide a concentration of 20 ~ 80 g/L ratio, by ammonium citrate, cobaltous sulfate, hydroquinone and thiocarbamide according to
Secondary to be added to the water uniformly mixed, adjustment pH is 4.0 ~ 6.5 to be formulated.It is other identical as one of specific implementation mode one to five.
With following verification experimental verification beneficial effects of the present invention：
Experiment one：This experiment it is a kind of foam iron surface prepare the method for molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer by with
Lower step carries out：
(1) preparation of flower-shaped molybdenum disulfide colloidal solution：A. the lauryl sodium sulfate for weighing 1.5 g, is added to 1000
It in mL deionized waters, is stirred at room temperature after 10 min, the flower-shaped molybdenum disulfide of 0.6 g is added；B. 2 are stirred at 60 DEG C
2 h are handled using ultrasonic cell disruptor after h；C. it repeats step b 6 times, completes matching for flower-shaped molybdenum disulfide colloidal solution
System；
(2) preparation of cationic-type polyacrylamide gel：D. the sun for being 22,000,000 by a concentration of 3.0 g/L molecular weight
Polyacrylamide is dissolved in deionized water, matches to obtain cationic-type polyacrylamide solution after 3 h are stirred at 40 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed in acetone and is ultrasonically treated 2 min removing surface and oil contaminants；F. will
It is cleaned by one of tap water by the foamed iron of oil removing, after the cleaning of three deionized waters, it is dense to immerse volume basis at room temperature
Degree is 10 s of etch in 0.2% hydrochloric acid solution, is cleaned using one of tap water, after the cleaning of three deionized waters, completes foam
The pre-treatment of iron；
(4) the flower-shaped molybdenum disulfide of foamed iron surface self-organization：G. the cationic polyacrylamide for using step (2) to prepare
Amine gel carries out 2 min of shower to the foamed iron after being handled by step (3), is then immersed in 10 s of slight oscillatory in acetone,
Naturally dry after taking-up immerses 6 min in the flower-shaped molybdenum disulfide colloidal solution that step (1) is prepared, and is then immersed in acetone slight
60 s are vibrated, naturally dry after taking-up completes the flower-shaped molybdenum disulfide of foamed iron surface self-organization；
(5) electro-coppering：H. foamed iron/molybdenum disulfide composite material is prepared as cathode, phosphor-copper using prepared by step (4)
Plate immerses in acid copper plating bath at room temperature as anode, is 3.0 A/dm in current density2Under conditions of 20 s of electro-deposition,
3 s in etching solution are immersed after washing, are then washed again；I. it repeats step h 8 times, completes foamed iron/molybdenum disulfide/copper
The preparation of composite material；
(6) cobalt plating is replaced：J. it is 40 that the foamed iron/molybdenum disulfide prepared by step (5)/carbon/carbon-copper composite material, which immerses temperature,
DEG C displacement plating cobalt liquor in 2 min, completed later in foamed iron after the cleaning of one tap water, the cleaning of three deionized waters
Surface prepares the preparation of molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer.
The acid copper plating bath used in the h of step (5) by a concentration of 80 mL/L of sulfuric acid, cupric sulfate pentahydrate it is a concentration of
Sulfuric acid and cupric sulfate pentahydrate are sequentially added uniformly mixed in water be formulated by the ratio of 120 g/L；Described in the h of step (5)
Etching solution by a concentration of 30 mL/L of sulfuric acid, a concentration of 1 g/L of copper sulphate, potassium peroxydisulfate a concentration of 40 g/L
Sulfuric acid, copper sulphate and potassium peroxydisulfate are sequentially added uniformly mixed in water be formulated by ratio；Displacement described in step (6)
Plate cobalt liquor by a concentration of 25 g/L of ammonium citrate, a concentration of 18 g/L of cobaltous sulfate, hydroquinone a concentration of 4 g/L,
Ammonium citrate, cobaltous sulfate, hydroquinone and thiocarbamide are sequentially added in water and are mixed by the ratio of a concentration of 60 g/L of thiocarbamide
Even, adjustment pH is formulated for 5.6.
SEM image of this experiment after the flower-shaped molybdenum disulfide of foamed iron surface self-organization is as shown in Figure 1.It spends as can be seen from Figure 1
Shape molybdenum disulfide can equably self assembly in foam iron surface.
This experiment is before and after foam iron surface prepares molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in 0.5 M H2SO4In solution,
Cathode-current density is 250 mA/cm2Under conditions of the time-potential curve that measures it is as shown in Figure 2.As can be seen from Figure 2, it is steeping
Foam iron surface is prepared after molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in 0.5 M H2SO4Overpotential of hydrogen evolution in solution is only 150
MV or so（Foamed iron is in 0.5 M H2SO4In solution, cathode-current density be 250 mA/cm2Under conditions of overpotential of hydrogen evolution>
560 mV）, illustrate that the compound liberation of hydrogen material prepared hydrogen evolution activity in acid medium is very good.
Claims (5)
1. a kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface, it is characterised in that one kind is in foam
The method that iron surface prepares molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer carries out according to the following steps：
(1) preparation of flower-shaped molybdenum disulfide colloidal solution：A. the anionic surfactant for weighing 0.5 ~ 5.0 g, is added to
It in 1000 mL deionized waters, is stirred at room temperature after 5 ~ 15 min, the flower-shaped molybdenum disulfide of 0.2 ~ 1.2 g is added；B. exist
2 h are stirred at 60 DEG C, and 2 h are handled using ultrasonic cell disruptor later；C. it repeats step b 1 ~ 6 time, completes flower-shaped two sulphur
Change the preparation of molybdenum colloidal solution；
(2) preparation of cationic-type polyacrylamide gel：D. by the cationic polyacrylamide of a concentration of 3.0 ~ 6.0 g/L
Amine is dissolved in deionized water, matches to obtain cationic-type polyacrylamide solution after 3 ~ 5 h are stirred at 40 ~ 60 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed in acetone and is ultrasonically treated 1 ~ 5 min removing surface and oil contaminants；It f. will be through
The foamed iron for crossing oil removing is cleaned by one of tap water, after the cleaning of three deionized waters, immerses concentration expressed in percentage by volume at room temperature
For 10 ~ 30 s of etch in 0.1 ~ 0.5% hydrochloric acid solution, cleaned using one of tap water, after the cleaning of three deionized waters, it is complete
At the pre-treatment of foamed iron；
(4) the flower-shaped molybdenum disulfide of foamed iron surface self-organization：G. use the cationic-type polyacrylamide that step (2) is prepared solidifying
Glue carries out 0.5 ~ 5 min of shower to the foamed iron after being handled by step (3), is then immersed in slight oscillatory 2 ~ 10 in acetone
S, naturally dry after taking-up immerse 6 ~ 12 min in the flower-shaped molybdenum disulfide colloidal solution that step (1) is prepared, are then immersed in acetone
30 ~ 90 s of slight oscillatory, naturally dry after taking-up complete the flower-shaped molybdenum disulfide of foamed iron surface self-organization；
(5) electro-coppering：H. foamed iron/molybdenum disulfide composite material is prepared as cathode using prepared by step (4), phosphorus copper plate is made
It for anode, immerses in acid copper plating bath at room temperature, is 1.0 ~ 3.0 A/dm in current density2Under conditions of electro-deposition 10 ~ 30
S immerses 1 ~ 5 s in etching solution, then washes again after washing；I. step h 5 ~ 30 times is repeated, the sulphur of foamed iron/bis- is completed
Change the preparation of molybdenum/carbon/carbon-copper composite material；
(6) cobalt plating is replaced：J. it is 30 ~ 45 that the foamed iron/molybdenum disulfide prepared by step (5)/carbon/carbon-copper composite material, which immerses temperature,
DEG C displacement plating cobalt liquor in 1 ~ 5 min, completed later in foam after the cleaning of one tap water, the cleaning of three deionized waters
Iron surface prepares the preparation of molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer, wherein displacement plating cobalt liquor by ammonium citrate a concentration of 5 ~
A concentration of 20 ~ 80 g/L of 35 g/L, a concentration of 8 ~ 60 g/L of cobaltous sulfate, a concentration of 2 ~ 10 g/L of hydroquinone, thiocarbamide
Ratio, ammonium citrate, cobaltous sulfate, hydroquinone and thiocarbamide are sequentially added in water and are uniformly mixed, adjustment pH is 4.0 ~ 6.5 to match
It makes.
2. a kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface according to claim 1,
It is characterized in that the anionic surfactant described in a of step (1) is lauryl sodium sulfate, dodecyl sodium sulfate
Or one kind in dodecyl alcohol polyoxyethylene ether sodium sulfate.
3. a kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface according to claim 1,
It is characterized in that the molecular weight of the cationic-type polyacrylamide described in the d of step (2) is 18,000,000 ~ 25,000,000.
4. a kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface according to claim 1,
It is characterized in that the acid copper plating bath used in the h of step (5) is by a concentration of 50 ~ 150 mL/L of sulfuric acid, cupric sulfate pentahydrate
Sulfuric acid and cupric sulfate pentahydrate are sequentially added uniformly mixed in water be formulated by the ratio of a concentration of 120 ~ 150g/L.
5. a kind of method preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface according to claim 1,
It is characterized in that etching solution described in the h of step (5) by a concentration of 20 ~ 50 mL/L of sulfuric acid, copper sulphate it is a concentration of
0.5 ~ 5 g/L, potassium peroxydisulfate a concentration of 35 ~ 60 g/L ratio, sulfuric acid, copper sulphate and potassium peroxydisulfate are sequentially added in water
It is uniformly mixed and is formulated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128352.0A CN106702425B (en) | 2016-12-09 | 2016-12-09 | A method of preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128352.0A CN106702425B (en) | 2016-12-09 | 2016-12-09 | A method of preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106702425A CN106702425A (en) | 2017-05-24 |
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| CN108118362B (en) * | 2018-01-09 | 2020-03-10 | 国家纳米科学中心 | Molybdenum disulfide electrocatalytic hydrogen production electrode and preparation method and application thereof |
| CN111822024B (en) * | 2019-04-18 | 2023-04-18 | 湖北大学 | Environment-friendly copper-iron MOF material with two-dimensional nano wall array structure and controllable iron content and preparation method thereof |
| CN111118537B (en) * | 2019-07-24 | 2022-01-11 | 天津大学 | Molybdenum disulfide modified carbon layer coated cuprous oxide nanowire material growing on surface of foam copper and preparation method and application thereof |
| CN114540869A (en) * | 2022-02-15 | 2022-05-27 | 武汉工程大学 | Molybdenum disulfide/cobalt composite catalyst and preparation method and application thereof |
| CN115233253A (en) * | 2022-06-16 | 2022-10-25 | 厦门大学 | Electro-catalytic nitrate radical reduction ammonia production catalyst, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113021A (en) * | 2007-07-03 | 2008-01-30 | 浙江大学 | Method for preparing flower-shaped molybdenum disulfide micro-balloon |
| CN103924260A (en) * | 2014-04-14 | 2014-07-16 | 太原理工大学 | Composite hydrogen evolution electrode with copper and cobalt loaded on three-dimensional foamed nickel and preparation method thereof |
| JP2015086420A (en) * | 2013-10-29 | 2015-05-07 | 国立大学法人横浜国立大学 | Anode for alkali water electrolysis |
| CN105200450A (en) * | 2015-09-10 | 2015-12-30 | 北京航空航天大学 | Molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material and preparation method therefor |
| CN105797756A (en) * | 2016-04-20 | 2016-07-27 | 燕山大学 | Preparation method of molybdenum disulfide-graphite-nickel phosphorus hydrogen evolution composite |
| CN105879891A (en) * | 2016-04-20 | 2016-08-24 | 燕山大学 | Preparation method of nickel phosphorus and molybdenum disulfide hydrogen-evolution composite |
-
2016
- 2016-12-09 CN CN201611128352.0A patent/CN106702425B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113021A (en) * | 2007-07-03 | 2008-01-30 | 浙江大学 | Method for preparing flower-shaped molybdenum disulfide micro-balloon |
| JP2015086420A (en) * | 2013-10-29 | 2015-05-07 | 国立大学法人横浜国立大学 | Anode for alkali water electrolysis |
| CN103924260A (en) * | 2014-04-14 | 2014-07-16 | 太原理工大学 | Composite hydrogen evolution electrode with copper and cobalt loaded on three-dimensional foamed nickel and preparation method thereof |
| CN105200450A (en) * | 2015-09-10 | 2015-12-30 | 北京航空航天大学 | Molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material and preparation method therefor |
| CN105797756A (en) * | 2016-04-20 | 2016-07-27 | 燕山大学 | Preparation method of molybdenum disulfide-graphite-nickel phosphorus hydrogen evolution composite |
| CN105879891A (en) * | 2016-04-20 | 2016-08-24 | 燕山大学 | Preparation method of nickel phosphorus and molybdenum disulfide hydrogen-evolution composite |
Non-Patent Citations (1)
| Title |
|---|
| 二硫化钼纳米材料在光催化应用中的研究进展;黄飞 等;《材料导报》;20160831;第30卷(第8期);第12-17页 * |
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