CN106702425A - Method for preparing molybdenum disulfide/copper/cobalt catalyzing hydrogen evolution layer on surface of foam iron - Google Patents
Method for preparing molybdenum disulfide/copper/cobalt catalyzing hydrogen evolution layer on surface of foam iron Download PDFInfo
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- CN106702425A CN106702425A CN201611128352.0A CN201611128352A CN106702425A CN 106702425 A CN106702425 A CN 106702425A CN 201611128352 A CN201611128352 A CN 201611128352A CN 106702425 A CN106702425 A CN 106702425A
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Abstract
The invention discloses a method for preparing a molybdenum disulfide/copper/cobalt catalyzing hydrogen evolution layer on the surface of foam iron, and relates to a method for preparing a flower-like molybdenum disulfide self-assembly layer/electrocoppering layer/replacement cobalt plating layer with good hydrogen evolution activity on the surface of the foam iron to solve the problem that the hydrogen evolution activity of an existing base metal hydrogen evolution catalyst is relatively low in an acid solution. The method for preparing the molybdenum disulfide/copper/cobalt catalyzing hydrogen evolution layer on the surface of the foam iron comprises the first step of preparation of flower-like molybdenum disulfide colloidal fluid, the second step of preparation of cationic polyacrylamide gel, the third step of pretreatment of the foam iron, the fourth step of self-assembly of flower-like molybdenum disulfide on the surface of the foam iron, the fifth step of electrocoppering and the sixth step of replacement cobalt plating, and the complex coating with good catalyzing hydrogen evolution performance is obtained on the surface of the foam iron. The method for preparing the molybdenum disulfide/copper/cobalt catalyzing hydrogen evolution layer on the surface of the foam iron can improve the capacity of electrolytic hydrogen production and reduce the energy loss.
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 bisuphide/copper/
The method of cobalt catalytic hydrogen evolution layer.
Background technology
In the today's society of energy increasingly depleted, how to develop new regenerative resource instead of fossil energy into
It is one of mostly important topic in the whole world.Under new Energy situation, using renewable energy power generations such as solar energy, wind energies
It is widely studied, yet with the not storability of electric energy, if the electric energy that solar energy, wind energy equal energy source are changed into is not consumed
Falling to be stored.If the electric energy that other energy forms are generated is changed into clean energy resource --- hydrogen, can be very
Good solves the problems, such as that energy regeneration and the energy are fixed.So, electrolytic catalysis liberation of hydrogen has turned into solution energy regeneration under the new situation
With fixed important means.
But, resistance when all of electrolytic catalysis liberation of hydrogen material is required for overcoming hydrogen to separate out when liberation of hydrogen is electrolysed, i.e.,
Applied voltage during cathode hydrogen evolution needs to overcome extra 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 unnecessary consumption can then be discharged in the form of heat energy.Therefore, suitable electrolytic catalysis are selected
Liberation of hydrogen material is so as to reduce overpotential of hydrogen evolution so that energy ezpenditure when reducing electrolysis liberation of hydrogen, could more efficiently by electric energy
It is converted into the chemical energy that can be stored.
Attribute of the height of overpotential of hydrogen evolution with material in itself is relevant, and also the catalysis area and electric conductivity with material are relevant.
The big material of catalytic hydrogen evolution function admirable, catalysis area, the activation polarization during liberation of hydrogen is small, the material of good conductivity, analysis
Ohmic polarization during hydrogen is small, and two kinds of reductions of polarization can reduce overpotential of hydrogen evolution, that is, can reduce electricity
Energy ezpenditure during solution liberation of hydrogen.In all of electrolytic catalysis liberation of hydrogen material, the catalytic hydrogen evolution performance of noble metal platinum is the most excellent,
The minimum energy consumed during liberation of hydrogen.But its is expensive, input-output ratio is very high, is not suitable for industrial life
Produce.Used as the electrolytic catalysis liberation of hydrogen material of new replacement noble metal platinum, molybdenum bisuphide is constantly subjected to the concern of scientific circles, especially
It is that catalysis activity in acid system is that other many non-noble metallic materials are incomparable.At present, high-specific surface area is prepared
The method of molybdenum bisuphide is a lot, mechanical stripping method, solvent-thermal method and lithium ion graft process etc., and the molybdenum bisuphide of acquisition has
The high catalytic activity surface of two dimension or three-dimensional.But, molybdenum bisuphide electric conductivity in itself is poor, so can be in electrolytic catalysis analysis
Increase its ohmic polarization during hydrogen, be unfavorable for the reduction of energy consumption.How the molybdenum bisuphide with huge catalytic surface to be fixed to
The advantage that its catalysis activity is high, catalysis area is big can be preferably played when on electrode, while overcoming the larger shortcoming of resistance, is
Molybdenum bisuphide is applied to the problem that engineering field must be faced at present.Therefore, catalytic surface product big, good conductivity, steady is prepared
Qualitative good molybdenum bisuphide composite is the important channel that acid system electrolytic catalysis liberation of hydrogen realizes energy consumption reduction, it may have huge
Big potential economic benefit.
The content of the invention
The present invention is to solve current base metal liberation of hydrogen catalyst in an acidic solution hydrogen evolution activity than relatively low problem,
And a kind of method for preparing molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface is provided.
It is of the invention a kind of to prepare the method for molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer according to following step in foam iron surface
Suddenly carry out：
(1) preparation of flower-shaped molybdenum bisuphide colloidal solution：A. the anionic surfactant of 0.5 ~ 5.0 g is weighed, is added to
In 1000 mL deionized waters, it is stirred at room temperature after 5 ~ 15 min, adds the flower-shaped molybdenum bisuphide of 0.2 ~ 1.2 g；B. exist
Stirred at 60 DEG C and 2 h are processed using ultrasonic cell disruptor after 2 h；C. repeat 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. it is the cationic polyacrylamide of 3.0 ~ 6.0 g/L by concentration
Amine is dissolved in deionized water, and cationic-type polyacrylamide solution is matched somebody with somebody to obtain after stirring 3 ~ 5 h at 40 ~ 60 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed into ultrasonically treated 1 ~ 5 min in acetone and removes surface and oil contaminant；F. will be through
The foamed iron of oil removing is crossed to clean by one running water, after three road deionized waters cleanings, concentration expressed in percentage by volume is immersed at room temperature
It is the s of etch 10 ~ 30 in 0.1 ~ 0.5% hydrochloric acid solution, then by after one running water cleaning, three road deionized water cleanings, it is complete
Into the pre-treatment of foamed iron；
(4) the flower-shaped molybdenum bisuphide of foamed iron surface self-organization：G. the cationic-type polyacrylamide prepared using step (2) is coagulated
Glue carries out the min of shower 0.5 ~ 5 to the foamed iron after being processed by step (3), is then immersed in slight oscillatory 2 ~ 10 in acetone
S, dries naturally after taking-up, 6 ~ 12 min in the flower-shaped molybdenum bisuphide colloidal solution that immersion step (1) is prepared, and is then immersed in acetone
The s of slight oscillatory 30 ~ 90, dries naturally after taking-up, completes the flower-shaped molybdenum bisuphide of foamed iron surface self-organization；
(5) electro-coppering：H. what be prepared by step (4) prepares foamed iron/molybdenum bisuphide composite as negative electrode, and phosphorus copper plate is made
It is 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 after washing, then wash again；I. repeat step h 5 ~ 30 times, complete foamed iron/bis- sulphur
Change the preparation of molybdenum/carbon/carbon-copper composite material；
(6) cobalt plating is replaced：J. foamed iron/the molybdenum bisuphide for being prepared by step (5)/carbon/carbon-copper composite material immersion temperature is 30 ~ 45
DEG C displacement plating cobalt liquor in 1 ~ 5 min, completed in foam by after the cleaning of one running water, three road deionized waters cleanings afterwards
Iron surface prepares the preparation of molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer.
Anionic surfactant described in a of step (1) is lauryl sodium sulfate, dodecyl sodium sulfate or
One kind in Brij 35 sodium sulphate；The molecule of the cationic-type polyacrylamide described in the d of step (2)
Measure is 18,000,000 ~ 25,000,000；The acid copper plating bath used in the h of step (5) is 50 ~ 150 mL/L, five water by the concentration of sulfuric acid
The concentration of copper sulphate is the ratio of 120 ~ 150g/L, sulfuric acid and cupric sulfate pentahydrate are sequentially added be well mixed in water prepare and
Into；The concentration that etching solution described in the h of step (5) presses sulfuric acid is 20 ~ 50 mL/L, the concentration of copper sulphate is 0.5 ~ 5 g/
L, the concentration of potassium peroxydisulfate are the ratio of 35 ~ 60 g/L, are well mixed during sulfuric acid, copper sulphate and potassium peroxydisulfate are sequentially added into water
It is formulated；Displacement plating cobalt liquor described in step (6) is 5 ~ 35 g/L by the concentration of ammonium citrate, the concentration of cobaltous sulfate is
8 ~ 60 g/L, the concentration of hydroquinones are 2 ~ 10 g/L, the concentration of thiocarbamide is the ratio of 20 ~ 80 g/L, by ammonium citrate, sulfuric acid
Cobalt, hydroquinones and thiocarbamide are well mixed in sequentially adding water, and adjustment pH is formulated for 4.0 ~ 6.5.
It is of the invention a kind of to prepare the method for molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer by foam in foam iron surface
Iron surface self assembly prepares flower-shaped layer of molybdenum-disulfide, will in an acidic solution have flower-shaped two sulphur of good electrocatalytic hydrogen evolution performance
Change molybdenum and be firmly adsorbed in foam iron surface；Follow-up electro-coppering step not only further increases leading for composite catalyzing material entirety
Electrically, and for follow-up displacement cobalt plating provides bigger surface area；After copper surface replacement cobalt plating, displacement cobalt coat is not
Protection can only be played a part of to copper, and its excellent catalytic performance can further improve 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 in an acidic solution large-current electric solution liberation of hydrogen when there is excellent catalysis activity, be conducive to improve electrolytic hydrogen production product
Energy and reducing energy consumption.
Brief description of the drawings
Fig. 1 is one SEM image after the flower-shaped molybdenum bisuphide of foamed iron surface self-organization of experiment；
It is front and rear in 0.5 M H that Fig. 2 prepares molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer for experiment one in foam iron surface2SO4Solution
In, cathode-current density be 250 mA/cm2Under conditions of time-potential curve for measuring.
Specific embodiment
Specific embodiment one：One kind of present embodiment prepares molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution in foam iron surface
The method of layer is carried out according to the following steps：
(1) preparation of flower-shaped molybdenum bisuphide colloidal solution：A. the anionic surfactant of 0.5 ~ 5.0 g is weighed, is added to
In 1000 mL deionized waters, it is stirred at room temperature after 5 ~ 15 min, adds the flower-shaped molybdenum bisuphide of 0.2 ~ 1.2 g；B. exist
Stirred at 60 DEG C and 2 h are processed using ultrasonic cell disruptor after 2 h；C. repeat 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. it is the cationic polyacrylamide of 3.0 ~ 6.0 g/L by concentration
Amine is dissolved in deionized water, and cationic-type polyacrylamide solution is matched somebody with somebody to obtain after stirring 3 ~ 5 h at 40 ~ 60 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed into ultrasonically treated 1 ~ 5 min in acetone and removes surface and oil contaminant；F. will be through
The foamed iron of oil removing is crossed to clean by one running water, after three road deionized waters cleanings, concentration expressed in percentage by volume is immersed at room temperature
It is the s of etch 10 ~ 30 in 0.1 ~ 0.5% hydrochloric acid solution, then by after one running water cleaning, three road deionized water cleanings, it is complete
Into the pre-treatment of foamed iron；
(4) the flower-shaped molybdenum bisuphide of foamed iron surface self-organization：G. the cationic-type polyacrylamide prepared using step (2) is coagulated
Glue carries out the min of shower 0.5 ~ 5 to the foamed iron after being processed by step (3), is then immersed in slight oscillatory 2 ~ 10 in acetone
S, dries naturally after taking-up, 6 ~ 12 min in the flower-shaped molybdenum bisuphide colloidal solution that immersion step (1) is prepared, and is then immersed in acetone
The s of slight oscillatory 30 ~ 90, dries naturally after taking-up, completes the flower-shaped molybdenum bisuphide of foamed iron surface self-organization；
(5) electro-coppering：H. what be prepared by step (4) prepares foamed iron/molybdenum bisuphide composite as negative electrode, and phosphorus copper plate is made
It is 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 after washing, then wash again；I. repeat step h 5 ~ 30 times, complete foamed iron/bis- sulphur
Change the preparation of molybdenum/carbon/carbon-copper composite material；
(6) cobalt plating is replaced：J. foamed iron/the molybdenum bisuphide for being prepared by step (5)/carbon/carbon-copper composite material immersion temperature is 30 ~ 45
DEG C displacement plating cobalt liquor in 1 ~ 5 min, completed in foam by after the cleaning of one running water, three road deionized waters cleanings afterwards
Iron surface prepares the preparation of molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer.
Present embodiment it is a kind of foam iron surface prepare the method for molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer by
Foamed iron surface self-organization prepares flower-shaped layer of molybdenum-disulfide, will in an acidic solution have the flower-shaped of good electrocatalytic hydrogen evolution performance
Molybdenum bisuphide is firmly adsorbed in foam iron surface；Follow-up electro-coppering step not only further increases composite catalyzing material entirety
Electric conductivity, and for follow-up displacement cobalt plating provides bigger surface area；After copper surface replacement cobalt plating, cobalt plating is replaced
Layer can not only play a part of protection to copper, and its excellent catalytic performance can further to improve compound liberation of hydrogen material whole
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 in an acidic solution large-current electric solution liberation of hydrogen when there is excellent catalysis activity.
Specific embodiment two：Present embodiment and the moon unlike specific embodiment one described in a of step (1)
Ionic surfactant is in lauryl sodium sulfate, dodecyl sodium sulfate or Brij 35 sodium sulphate
One kind.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment from described in the d of step unlike specific embodiment one or two (2)
Cationic-type polyacrylamide molecular weight be 18,000,000 ~ 25,000,000.Other are identical with specific embodiment one or two.
Specific embodiment four：In the h of step (5) unlike one of present embodiment and specific embodiment one to three
The acid copper plating bath for using is the ratio that the concentration of 50 ~ 150 mL/L, cupric sulfate pentahydrate is 120 ~ 150g/L in the concentration of sulfuric acid,
Sulfuric acid and cupric sulfate pentahydrate are sequentially added to be well mixed in water and is formulated.Other phases one of with specific embodiment one to three
Together.
Specific embodiment five：In the h of step (5) unlike one of present embodiment and specific embodiment one to four
The concentration that described etching solution presses sulfuric acid is 20 ~ 50 mL/L, the concentration of copper sulphate is 0.5 ~ 5 g/L, the concentration of potassium peroxydisulfate
It is the ratio of 35 ~ 60 g/L, sulfuric acid, copper sulphate and potassium peroxydisulfate are sequentially added to be well mixed in water is formulated.Other with
One of specific embodiment one to four is identical.
Specific embodiment six：Institute in step (6) unlike one of present embodiment and specific embodiment one to five
The displacement plating cobalt liquor stated is 5 ~ 35 g/L by the concentration of ammonium citrate, the concentration of cobaltous sulfate is 8 ~ 60 g/L, hydroquinones
Concentration be 2 ~ 10 g/L, thiocarbamide concentration for 20 ~ 80 g/L ratio, by ammonium citrate, cobaltous sulfate, hydroquinones and thiocarbamide according to
Secondary to be added to the water well mixed, adjustment pH is formulated for 4.0 ~ 6.5.Other are identical with one of specific embodiment one to five.
With following verification experimental verification beneficial effects of the present invention：
Experiment one：The a kind of of this experiment prepares the method for molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer by following step in foam iron surface
Suddenly carry out：
(1) preparation of flower-shaped molybdenum bisuphide colloidal solution：A. the lauryl sodium sulfate of 1.5 g is weighed, 1000 mL is added to and is gone
In ionized water, it is stirred at room temperature after 10 min, adds the flower-shaped molybdenum bisuphide of 0.6 g；B. stirred at 60 DEG C 2 h it
2 h are processed using ultrasonic cell disruptor afterwards；C. repeat step b 6 times, complete the preparation of flower-shaped molybdenum bisuphide colloidal solution；
(2) preparation of cationic-type polyacrylamide gel：D. it is the cation that 3.0 g/L molecular weight are 22,000,000 by concentration
Type polyacrylamide is dissolved in deionized water, and cationic-type polyacrylamide solution is matched somebody with somebody to obtain after 3 h are stirred at 40 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed into ultrasonically treated 2 min in acetone and removes surface and oil contaminant；F. will pass through
The foamed iron of oil removing is cleaned by one running water, after three road deionized waters cleanings, concentration expressed in percentage by volume is immersed at room temperature is
The s of etch 10 in 0.2% hydrochloric acid solution, then by after one running water cleaning, three road deionized water cleanings, completing foamed iron
Pre-treatment；
(4) the flower-shaped molybdenum bisuphide of foamed iron surface self-organization：G. the cationic-type polyacrylamide prepared using step (2) is coagulated
Glue carries out the min of shower 2 to the foamed iron after being processed by step (3), is then immersed in the s of slight oscillatory 10 in acetone, takes out
Dry naturally afterwards, 6 min in the flower-shaped molybdenum bisuphide colloidal solution that immersion step (1) is prepared are then immersed in slight oscillatory in acetone
60 s, dry naturally after taking-up, complete the flower-shaped molybdenum bisuphide of foamed iron surface self-organization；
(5) electro-coppering：H. what be prepared by step (4) prepares foamed iron/molybdenum bisuphide composite as negative electrode, and phosphorus copper plate is made
It is anode, immerses in acid copper plating bath at room temperature, is 3.0 A/dm in current density2Under conditions of the s of electro-deposition 20, washing
3 s in immersion etching solution, then wash again afterwards；I. repeat step h 8 times, complete foamed iron/molybdenum bisuphide/copper and are combined
The preparation of material；
(6) cobalt plating is replaced：J. foamed iron/the molybdenum bisuphide for being prepared by step (5)/carbon/carbon-copper composite material immersion temperature is 40 DEG C
Displacement plating cobalt liquor in 2 min, completed in foamed iron table by after the cleaning of one running water, three road deionized waters cleanings afterwards
Face prepares the preparation of molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer.
The acid copper plating bath used in the h of step (5) is by the concentration of sulfuric acid for the concentration of 80 mL/L, cupric sulfate pentahydrate is
The ratio of 120 g/L, sulfuric acid and cupric sulfate pentahydrate is sequentially added to be well mixed in water is formulated；Described in the h of step (5)
Etching solution by the concentration of sulfuric acid be 30 mL/L, copper sulphate concentration be 1 g/L, potassium peroxydisulfate concentration be 40 g/L
Ratio, sulfuric acid, copper sulphate and potassium peroxydisulfate is sequentially added to be well mixed in water is formulated；Displacement described in step (6)
Plating cobalt liquor by the concentration of ammonium citrate be 25 g/L, cobaltous sulfate concentration be 18 g/L, hydroquinones concentration for 4 g/L,
The concentration of thiocarbamide is the ratio of 60 g/L, and mixing is equal during ammonium citrate, cobaltous sulfate, hydroquinones and thiocarbamide are sequentially added into water
Even, adjustment pH is formulated for 5.6.
SEM image of this experiment after the flower-shaped molybdenum bisuphide of foamed iron surface self-organization is as shown in Figure 1.Spend as can be seen from Figure 1
Shape molybdenum bisuphide can equably self assembly in foam iron surface.
This experiment is before and after foam iron surface prepares molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer in 0.5 M H2SO4In solution,
Cathode-current density is 250 mA/cm2Under conditions of time-potential curve for measuring it is as shown in Figure 2.As can be seen from Figure 2, in bubble
Foam iron surface is prepared after molybdenum bisuphide/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 for preparing hydrogen evolution activity in acid medium is very good.
Claims (6)
1. a kind of method for preparing molybdenum bisuphide/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 bisuphide/copper/cobalt catalytic hydrogen evolution layer is carried out according to the following steps：
(1) preparation of flower-shaped molybdenum bisuphide colloidal solution：A. the anionic surfactant of 0.5 ~ 5.0 g is weighed, is added to
In 1000 mL deionized waters, it is stirred at room temperature after 5 ~ 15 min, adds the flower-shaped molybdenum bisuphide of 0.2 ~ 1.2 g；B. exist
Stirred at 60 DEG C and 2 h are processed using ultrasonic cell disruptor after 2 h；C. repeat 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. it is the cationic polyacrylamide of 3.0 ~ 6.0 g/L by concentration
Amine is dissolved in deionized water, and cationic-type polyacrylamide solution is matched somebody with somebody to obtain after stirring 3 ~ 5 h at 40 ~ 60 DEG C；
(3) foamed iron pre-treatment：E. foamed iron is immersed into ultrasonically treated 1 ~ 5 min in acetone and removes surface and oil contaminant；F. will be through
The foamed iron of oil removing is crossed to clean by one running water, after three road deionized waters cleanings, concentration expressed in percentage by volume is immersed at room temperature
It is the s of etch 10 ~ 30 in 0.1 ~ 0.5% hydrochloric acid solution, then by after one running water cleaning, three road deionized water cleanings, it is complete
Into the pre-treatment of foamed iron；
(4) the flower-shaped molybdenum bisuphide of foamed iron surface self-organization：G. the cationic-type polyacrylamide prepared using step (2) is coagulated
Glue carries out the min of shower 0.5 ~ 5 to the foamed iron after being processed by step (3), is then immersed in slight oscillatory 2 ~ 10 in acetone
S, dries naturally after taking-up, 6 ~ 12 min in the flower-shaped molybdenum bisuphide colloidal solution that immersion step (1) is prepared, and is then immersed in acetone
The s of slight oscillatory 30 ~ 90, dries naturally after taking-up, completes the flower-shaped molybdenum bisuphide of foamed iron surface self-organization；
(5) electro-coppering：H. what be prepared by step (4) prepares foamed iron/molybdenum bisuphide composite as negative electrode, and phosphorus copper plate is made
It is 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 after washing, then wash again；I. repeat step h 5 ~ 30 times, complete foamed iron/bis- sulphur
Change the preparation of molybdenum/carbon/carbon-copper composite material；
(6) cobalt plating is replaced：J. foamed iron/the molybdenum bisuphide for being prepared by step (5)/carbon/carbon-copper composite material immersion temperature is 30 ~ 45
DEG C displacement plating cobalt liquor in 1 ~ 5 min, completed in foam by after the cleaning of one running water, three road deionized waters cleanings afterwards
Iron surface prepares the preparation of molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer.
2. a kind of method for preparing molybdenum bisuphide/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 the one kind in Brij 35 sodium sulphate.
3. a kind of method for preparing molybdenum bisuphide/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 for preparing molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface according to claim 1,
It is characterized in that the acid copper plating bath that is used in the h of step (5) is 50 ~ 150 mL/L, cupric sulfate pentahydrate by the concentration of sulfuric acid
Concentration is the ratio of 120 ~ 150g/L, sulfuric acid and cupric sulfate pentahydrate are sequentially added to be well mixed in water is formulated.
5. a kind of method for preparing molybdenum bisuphide/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) be 20 ~ 50 mL/L by the concentration of sulfuric acid, the concentration of copper sulphate be
0.5 ~ 5 g/L, the concentration of potassium peroxydisulfate are the ratio of 35 ~ 60 g/L, during sulfuric acid, copper sulphate and potassium peroxydisulfate sequentially added into water
It is well mixed to be formulated.
6. a kind of method for preparing molybdenum bisuphide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface according to claim 1,
It is characterized in that the concentration that the displacement plating cobalt liquor described in step (6) presses ammonium citrate is 5 ~ 35 g/L, the concentration of cobaltous sulfate
It is the ratio that the concentration of 8 ~ 60 g/L, hydroquinones is 2 ~ 10 g/L, the concentration of thiocarbamide is 20 ~ 80 g/L, by ammonium citrate, sulphur
Sour cobalt, hydroquinones and thiocarbamide are well mixed in sequentially adding water, and adjustment pH is formulated for 4.0 ~ 6.5.
Priority Applications (1)
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| 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 |
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