CN106591926A - Method for preparing CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on surface of steel - Google Patents
Method for preparing CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on surface of steel Download PDFInfo
- Publication number
- CN106591926A CN106591926A CN201611128354.XA CN201611128354A CN106591926A CN 106591926 A CN106591926 A CN 106591926A CN 201611128354 A CN201611128354 A CN 201611128354A CN 106591926 A CN106591926 A CN 106591926A
- Authority
- CN
- China
- Prior art keywords
- cnts
- nickel
- steel
- porous
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method for preparing a CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on a surface of steel. The invention aims to solve the problem that the performance of a non-noble metal hydrogen evolution reaction catalyst in an alkaline solution at present is poor. The method for preparing the CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on the surface of steel comprises the following steps: (1) preparing a nickel-copper alloy-CNTs composite electroplating solution; (2) preparing a copper leaching solution; (3) performing pre-treatment on the steel; (4) preparing a CNTs-nickel-copper alloy on the surface of the steel; (5) preparing CNTs-porous nickel on the surface of the steel; (6) preparing CNTs-porous nickel/nickel oxide on the surface of the steel, and preparing a CNTs-porous nickel/nickel oxide composite catalyst layer with good hydrogen evolution reaction catalytic activity on the surface of the steel, wherein the CNTs-porous nickel/nickel oxide composite catalyst layer is beneficial to improving the performance of a non-noble metal catalyst for an electrolysis hydrogen evolution reaction.
Description
Technical field
The invention belongs to the preparation field of evolving hydrogen reaction catalyst, is related to one kind and prepares for alkaline solution in steel surface
The method of the CNTs- porous nickel nickel evolving hydrogen reaction catalyst of electrolysis liberation of hydrogen.
Background technology
Electrolysis water prepares the important means that high-purity hydrogen is industrial hydrogen production, wherein the electrolytic hydrogen production research in alkaline solution
More ripe, application is also more extensive.The principle of electrolytic hydrogen production is exactly using sodium hydroxide as conducting salt, alkali in alkaline solution
Property solution in hydrone generate hydrogen atom and hydroxyl in cathodic reduction, hydroxyl is aoxidized in anode, generation hydrone
And oxygen atom, continue to be combined with each other in the hydrogen atom of cathodic reduction generation, finally discharged in the form of hydrogen.Cause
This, during electrolytic hydrogen production, the selection of cathode hydrogen evolution catalysts is most important, can not only affect hydrone also primary
Into hydrogen atom and reaction activity hydroxy, and may decide that hydrogen atom be combined with each other separate out hydrogen kinetic parameter.
Good cathode hydrogen evolution catalysts can reduce hydrone reduction and generate hydrogen atom and reaction activity hydroxy, also
It is the electrochemical reversibility for improving electric charge transfer step, reduces the activation polarization of liberation of hydrogen process.Just because of this, select suitable
Cathode hydrogen evolution catalysts can improve the efficiency of the conversion of energy in electrolytic hydrogen production process, it is to avoid electric energy is converted to heat energy and releases
Run out, so as to reduce the energy consumption of liberation of hydrogen process.
However, maximally efficient, reliable material is noble metal platinum in current evolving hydrogen reaction catalyst, although it can drop
The activation energy of low electrolysis liberation of hydrogen is so as to save the cost of electric energy, but the price of high enterprise causes the powerless purchase of manufacturing enterprise again.Therefore, select
The liberation of hydrogen catalyst for advantageously reducing liberation of hydrogen process activation polarization is selected so as to reducing energy consumption, with selection liberation of hydrogen process electrochemistry pole
Changing non-precious metal catalyst that is bigger but can reducing catalyst input cost becomes the choice that electrolytic hydrogen production field must face.Cause
This, if preparing, overpotential of hydrogen evolution is low, and the also very low base metal evolving hydrogen reaction catalyst of catalyst input cost, will
The technical barrier that electrolytic hydrogen production can be overcome to avoid.
In numerous base metal evolving hydrogen reaction catalyst, nickel has preferable catalysis activity, at the same it is moderate, therefore
Especially favored by electrolytic hydrogen production field.However, its catalysis activity can not still meet requirement, overpotential of hydrogen evolution and noble metal platinum
Compare and yet suffer from larger gap.Therefore, current many scientific research institutions are all to the nickel catalyst material as electrolytic hydrogen production field
Keen interest is generated, in terms of the preparation of nickel-based metallic material is modified many work have been done.If can from geometrical factor with
And the aspect of capacity factor two is modified to nickel-base catalyst simultaneously if, prepare that catalysis area is big, electrolysis liberation of hydrogen activation energy
Low new nickel-base catalyst, the preparation field and electrolytic hydrogen production field to evolving hydrogen reaction catalyst will all produce far-reaching shadow
Ring.
The content of the invention
The present invention is to solve the base metal evolving hydrogen reaction catalyst liberation of hydrogen for being electrolysed liberation of hydrogen currently used for alkaline solution is lived
Change can the relatively low problem of higher, energy conversion efficiency, and a kind of preparation in steel surface is provided and is electrolysed liberation of hydrogen for alkaline solution
CNTs- porous nickel nickel evolving hydrogen reaction catalyst method.
The present invention's prepares the method for CNTs- porous nickel nickel evolving hydrogen reaction catalyst according to following in steel surface
Step is carried out：
(1) preparation of monel-CNTs composite platings solution：A. the cetyl trimethyl bromination of 0.1 ~ 2.0 g is weighed
Ammonium, in being added to 800 mL deionized waters, after 20 min are stirred at room temperature, adds the CNT of 0.2 ~ 1.0 g；b.
Stir at 25 DEG C and 1.5 h are processed using ultrasonic cell disruptor after 0.5 h；C. repeat step b 1 ~ 5 time；D. press
According to ammonium citrate concentration be 35 ~ 65 g/L, sodium potassium tartrate tetrahydrate concentration be 5 ~ 30 g/L, nickel sulfate concentration be 8 ~ 50 g/
L, the concentration of copper sulfate are the ratio of 2 ~ 25 g/L, and ammonium citrate, sodium potassium tartrate tetrahydrate, nickel sulfate and copper sulfate are sequentially added into step
Solution after rapid c process, adjustment pH is 7.5 ~ 8.5, completes the preparation of monel-CNTs composite plating solution；
(2) preparation of copper leachate：E. by the thiourea of the sulphuric acid of 10 ~ 100 mL and 10 ~ 120 g at a temperature of 40 ~ 70 DEG C
In being dissolved in 700mL deionized waters, 1 L is settled to, completes the preparation of copper leachate；
(3) iron and steel pre-treatment：F. iron and steel is immersed into the min of supersound process 2 ~ 5 in acetone, it is 35 ~ 40 that temperature is immersed after washing
DEG C, concentration expressed in percentage by volume for 5 ~ 8% hydrochloric acid solution in the min of etch 1 ~ 3, iron and steel pre-treatment is completed after washing；
(4) CNTs- monels are prepared in steel surface：G. by iron and steel immersion step (1) after step (3) process
As negative electrode in the monel-CNTs composite plating solution of preparation, graphite cake, as anode, is 0.5 ~ 5.0 in electric current density
A/dm2And apply min ~ 3 h of electro-deposition 10 under conditions of stirring, afterwards through one tap water cleaning, three road deionizations
Complete to prepare CNTs- monels in steel surface after water cleaning；
(5) CNTs- nickel porous are prepared in steel surface：H. iron and steel/CNTs- monel the composite woods for being prepared by step (4)
2 ~ 12 h in the copper leachate that material immersion step (2) is prepared, temperature is 40 ~ 70 DEG C, afterwards through the cleaning of one tap water, three
Complete to prepare CNTs- nickel porous in steel surface after road deionized water cleaning；
(6) CNTs- porous nickel nickels are prepared in steel surface：I. iron and steel/CNTs- the nickel porous for being prepared by step (5) are answered
Condensation material is put into 0.25 ~ 12 h of immersion in 30% hydrogen peroxide, and temperature is 40 ~ 60 DEG C, then through one tap water cleaning, three roads
Cold wind is dried up after deionized water cleaning, and the h of heat treatment 0.5 ~ 3 at 100 DEG C completes steel surface CNTs- porous nickel nickels
The preparation of evolving hydrogen reaction catalyst.
The present invention's prepares the method for CNTs- porous nickel nickel evolving hydrogen reaction catalyst by steel in steel surface
Iron surface prepares CNTs- monel composite deposites, and monel can be made to be grown in CNT extension, not only increases multiple
The electric conductivity of condensation material, and increased real table area；And then caused for CNTs- nickel porous by the copper in dissolution alloy
Real table area is further dramatically increased, and the catalysis activity of catalyst is improve in geometrical factor；Finally by nickel surface
Nickel oxide is obtained, the liberation of hydrogen activation energy of material is reduced again, in capacity factor angle the catalytic activity for hydrogen evolution of catalyst is improved.
Therefore, preparing CNTs- porous nickel nickel evolving hydrogen reaction catalyst in steel surface can significantly reduce evolving hydrogen reaction activation
Can, reduce the energy expenditure that liberation of hydrogen is electrolysed in alkaline solution.
Description of the drawings
Fig. 1 is the SEM image for testing a CNTs- nickel porous/nickel oxide composite material prepared in steel surface；
Fig. 2 be test one prepare iron and steel/CNTs- porous nickel nickel evolving hydrogen reaction catalyst in 1.0 M NaOH solutions,
Cathode-current density is 200 mA/cm2Under conditions of time-potential curve for measuring.
Specific embodiment
Specific embodiment one：Present embodiment steel surface prepare CNTs- porous nickel nickel evolving hydrogen reactions urge
The method of agent is carried out according to the following steps：
(1) preparation of monel-CNTs composite platings solution：A. the cetyl trimethyl bromination of 0.1 ~ 2.0 g is weighed
Ammonium, in being added to 800 mL deionized waters, after 20 min are stirred at room temperature, adds the CNT of 0.2 ~ 1.0 g；b.
Stir at 25 DEG C and 1.5 h are processed using ultrasonic cell disruptor after 0.5 h；C. repeat step b 1 ~ 5 time；D. press
According to ammonium citrate concentration be 35 ~ 65 g/L, sodium potassium tartrate tetrahydrate concentration be 5 ~ 30 g/L, nickel sulfate concentration be 8 ~ 50 g/
L, the concentration of copper sulfate are the ratio of 2 ~ 25 g/L, and ammonium citrate, sodium potassium tartrate tetrahydrate, nickel sulfate and copper sulfate are sequentially added into step
Solution after rapid c process, adjustment pH is 7.5 ~ 8.5, completes the preparation of monel-CNTs composite plating solution；
(2) preparation of copper leachate：E. by the thiourea of the sulphuric acid of 10 ~ 100 mL and 10 ~ 120 g at a temperature of 40 ~ 70 DEG C
In being dissolved in 700mL deionized waters, 1 L is settled to, completes the preparation of copper leachate；
(3) iron and steel pre-treatment：F. iron and steel is immersed into the min of supersound process 2 ~ 5 in acetone, it is 35 ~ 40 that temperature is immersed after washing
DEG C, concentration expressed in percentage by volume for 5 ~ 8% hydrochloric acid solution in the min of etch 1 ~ 3, iron and steel pre-treatment is completed after washing；
(4) CNTs- monels are prepared in steel surface：G. by iron and steel immersion step (1) after step (3) process
As negative electrode in the monel-CNTs composite plating solution of preparation, graphite cake, as anode, is 0.5 ~ 5.0 in electric current density
A/dm2And apply min ~ 3 h of electro-deposition 10 under conditions of stirring, afterwards through one tap water cleaning, three road deionizations
Complete to prepare CNTs- monels in steel surface after water cleaning；
(5) CNTs- nickel porous are prepared in steel surface：H. iron and steel/CNTs- monel the composite woods for being prepared by step (4)
2 ~ 12 h in the copper leachate that material immersion step (2) is prepared, temperature is 40 ~ 70 DEG C, afterwards through the cleaning of one tap water, three
Complete to prepare CNTs- nickel porous in steel surface after road deionized water cleaning；
(6) CNTs- porous nickel nickels are prepared in steel surface：I. iron and steel/CNTs- the nickel porous for being prepared by step (5) are answered
Condensation material is put into 0.25 ~ 12 h of immersion in 30% hydrogen peroxide, and temperature is 40 ~ 60 DEG C, then through one tap water cleaning, three roads
Cold wind is dried up after deionized water cleaning, and the h of heat treatment 0.5 ~ 3 at 100 DEG C completes steel surface CNTs- porous nickel nickels
The preparation of evolving hydrogen reaction catalyst.
The method for preparing CNTs- porous nickel nickel evolving hydrogen reaction catalyst in steel surface of present embodiment passes through
CNTs- monel composite deposites are prepared in steel surface, monel can be made to be grown in CNT extension, not only increased
The electric conductivity of composite, and increased real table area；And then by the copper in dissolution alloy for CNTs- nickel porous
So that real table area is further dramatically increased, the catalysis activity of catalyst is improve in geometrical factor；Finally by nickel
Surface obtains nickel oxide, and the liberation of hydrogen activation energy of material is reduced again, and in capacity factor angle the liberation of hydrogen catalysis of catalyst is improved
Activity.Therefore, present embodiment can be shown by preparing CNTs- porous nickel nickel evolving hydrogen reaction catalyst in steel surface
Writing reduces evolving hydrogen reaction activation energy, reduces the energy expenditure that liberation of hydrogen is electrolysed in alkaline solution.
Specific embodiment two：Present embodiment and the sulfur unlike specific embodiment one described in the d of step (1)
The concentration of sour nickel is 12 ~ 40 g/L, and the concentration of described copper sulfate is 3 ~ 20 g/L.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment is sunk from the electricity in step unlike specific embodiment one or two (4)
The product time is 20 min ~ 2 h.Other are identical with specific embodiment one or two.
Specific embodiment four：Will in step (6) unlike one of present embodiment and specific embodiment one to three
The time that iron and steel/CNTs- porous nickel composite material soaks in 30% hydrogen peroxide is 0.5 ~ 10 h.Other and specific embodiment
One of one to three is identical.
With following verification experimental verification beneficial effects of the present invention：
Test one：This test in steel surface prepares the method for CNTs- porous nickel nickel evolving hydrogen reaction catalyst by following
Step is carried out：
(1) preparation of monel-CNTs composite platings solution：A. the cetyl trimethylammonium bromide of 0.8 g is weighed, plus
Enter in 800 mL deionized waters, after 20 min are stirred at room temperature, add the CNT of 0.6 g；B. at 25 DEG C
Stir and 1.5 h are processed using ultrasonic cell disruptor after 0.5 h；C. repeat step b 5 times；D. according to ammonium citrate
Concentration be 45 g/L, the concentration of sodium potassium tartrate tetrahydrate be 25 g/L, the concentration of nickel sulfate be 12 g/L, the concentration of copper sulfate be 17
The ratio of g/L, by ammonium citrate, sodium potassium tartrate tetrahydrate, nickel sulfate and copper sulfate the solution after step c is processed is sequentially added, and is adjusted
Whole pH is 7.5, completes the preparation of monel-CNTs composite plating solution；
(2) preparation of copper leachate：E. the thiourea of the sulphuric acid of 80 mL and 100 g is dissolved in into 700mL at a temperature of 60 DEG C
In deionized water, 1 L is settled to, completes the preparation of copper leachate；
(3) iron and steel pre-treatment：F. iron and steel is immersed into the min of supersound process 4 in acetone, it is 35 DEG C, body that temperature is immersed after washing
The min of etch 3 in the hydrochloric acid solution that percentage concentration is 5% is accumulated, iron and steel pre-treatment is completed after washing；
(4) CNTs- monels are prepared in steel surface：G. by iron and steel immersion step (1) after step (3) process
As negative electrode in the monel-CNTs composite plating solution of preparation, graphite cake, as anode, is 2.0 A/ in electric current density
dm2And apply the min of electro-deposition 30 under conditions of stirring, afterwards after one tap water cleaning, three road deionized water cleanings
Complete to prepare CNTs- monels in steel surface；
(5) CNTs- nickel porous are prepared in steel surface：H. iron and steel/CNTs- monel the composite woods for being prepared by step (4)
6 h in the copper leachate that material immersion step (2) is prepared, temperature is 50 DEG C, afterwards through the cleaning of one tap water, three roads go from
Complete to prepare CNTs- nickel porous in steel surface after sub- water cleaning；
(6) CNTs- porous nickel nickels are prepared in steel surface：I. iron and steel/CNTs- the nickel porous for being prepared by step (5) are answered
Condensation material is put in 30% hydrogen peroxide and soaks 1 h, and temperature is 50 DEG C, then through one tap water cleaning, three road deionized waters
Cold wind is dried up after cleaning, the h of heat treatment 1 at 100 DEG C, completes the catalysis of steel surface CNTs- porous nickel nickels evolving hydrogen reaction
The preparation of agent.
The SEM image of CNTs- nickel porous/nickel oxide composite material that this test is prepared in steel surface is as shown in Figure 1.From
Fig. 1 understands that monel is co-deposited with CNTs in steel surface, and the growth pattern for obtaining composite deposite is metal in the outer of CNTs
Epitaxial growth, porous nickel skeleton is attached to CNTs extensions after copper is leached, and generates after subsequent heat treatment oxidation and has very high ratio
CNTs- nickel porous/the nickel oxide composite material of surface area.
This test prepare iron and steel/CNTs- porous nickel nickel evolving hydrogen reaction catalyst in 1.0 M NaOH solutions,
Cathode-current density is 200 mA/cm2Under conditions of time-potential curve for measuring it is as shown in Figure 2.As can be seen from Figure 2, this examination
Iron and steel/overpotential of hydrogen evolution of the CNTs- porous nickel nickel evolving hydrogen reaction catalyst in 1.0 M NaOH solutions for testing preparation is steady
It is scheduled on 180 mV or so（Iron and steel is in 200 mA/cm2Overpotential of hydrogen evolution under electric current density>570 mV）, with good catalysis
Activity.
Iron and steel/CNTs- porous nickel nickel evolving hydrogen reaction catalyst prepared by this test is little in continuous electrolysis hydrogen manufacturing 960
When after, catalyst structure is well not corrupted, and overpotential of hydrogen evolution illustrates to be prepared using the method still within 190 mV
Evolving hydrogen reaction catalyst performance stabilised.
Claims (4)
1. the method for preparing CNTs- porous nickel nickel evolving hydrogen reaction catalyst in steel surface, it is characterised in that in iron and steel table
Face prepares the method for CNTs- porous nickel nickel evolving hydrogen reaction catalyst and carries out according to the following steps：
(1) preparation of monel-CNTs composite platings solution：A. the cetyl trimethyl bromination of 0.1 ~ 2.0 g is weighed
Ammonium, in being added to 800 mL deionized waters, after 20 min are stirred at room temperature, adds the CNT of 0.2 ~ 1.0 g；b.
Stir at 25 DEG C and 1.5 h are processed using ultrasonic cell disruptor after 0.5 h；C. repeat step b 1 ~ 5 time；D. press
According to ammonium citrate concentration be 35 ~ 65 g/L, sodium potassium tartrate tetrahydrate concentration be 5 ~ 30 g/L, nickel sulfate concentration be 8 ~ 50 g/
L, the concentration of copper sulfate are the ratio of 2 ~ 25 g/L, and ammonium citrate, sodium potassium tartrate tetrahydrate, nickel sulfate and copper sulfate are sequentially added into step
Solution after rapid c process, adjustment pH is 7.5 ~ 8.5, completes the preparation of monel-CNTs composite plating solution；
(2) preparation of copper leachate：E. by the thiourea of the sulphuric acid of 10 ~ 100 mL and 10 ~ 120 g at a temperature of 40 ~ 70 DEG C
In being dissolved in 700mL deionized waters, 1 L is settled to, completes the preparation of copper leachate；
(3) iron and steel pre-treatment：F. iron and steel is immersed into the min of supersound process 2 ~ 5 in acetone, it is 35 ~ 40 that temperature is immersed after washing
DEG C, concentration expressed in percentage by volume for 5 ~ 8% hydrochloric acid solution in the min of etch 1 ~ 3, iron and steel pre-treatment is completed after washing；
(4) CNTs- monels are prepared in steel surface：G. by iron and steel immersion step (1) after step (3) process
As negative electrode in the monel-CNTs composite plating solution of preparation, graphite cake, as anode, is 0.5 ~ 5.0 in electric current density
A/dm2And apply min ~ 3 h of electro-deposition 10 under conditions of stirring, afterwards through one tap water cleaning, three road deionizations
Complete to prepare CNTs- monels in steel surface after water cleaning；
(5) CNTs- nickel porous are prepared in steel surface：H. iron and steel/CNTs- monel the composite woods for being prepared by step (4)
2 ~ 12 h in the copper leachate that material immersion step (2) is prepared, temperature is 40 ~ 70 DEG C, afterwards through the cleaning of one tap water, three
Complete to prepare CNTs- nickel porous in steel surface after road deionized water cleaning；
(6) CNTs- porous nickel nickels are prepared in steel surface：I. iron and steel/CNTs- the nickel porous for being prepared by step (5) are answered
Condensation material is put into 0.25 ~ 12 h of immersion in 30% hydrogen peroxide, and temperature is 40 ~ 60 DEG C, then through one tap water cleaning, three roads
Cold wind is dried up after deionized water cleaning, and the h of heat treatment 0.5 ~ 3 at 100 DEG C completes steel surface CNTs- porous nickel nickels
The preparation of evolving hydrogen reaction catalyst.
2. the side that CNTs- porous nickel nickel evolving hydrogen reaction catalyst is prepared in steel surface according to claim 1
Method, it is characterised in that the concentration of the nickel sulfate described in the d of step (1) is 12 ~ 40 g/L, the concentration of described copper sulfate is 3 ~
20 g/L。
3. the side that CNTs- porous nickel nickel evolving hydrogen reaction catalyst is prepared in steel surface according to claim 1
Method, it is characterised in that the electrodeposition time in step (4) is 20 min ~ 2 h.
4. the side that CNTs- porous nickel nickel evolving hydrogen reaction catalyst is prepared in steel surface according to claim 1
Method, it is characterised in that the time for soaking iron and steel/CNTs- porous nickel composite material in 30% hydrogen peroxide in step (6) be 0.5 ~
10 h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128354.XA CN106591926B (en) | 2016-12-09 | 2016-12-09 | In the method that steel surface prepares the porous nickel nickel evolving hydrogen reaction catalyst of CNTs- |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611128354.XA CN106591926B (en) | 2016-12-09 | 2016-12-09 | In the method that steel surface prepares the porous nickel nickel evolving hydrogen reaction catalyst of CNTs- |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106591926A true CN106591926A (en) | 2017-04-26 |
| CN106591926B CN106591926B (en) | 2018-10-02 |
Family
ID=58598214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611128354.XA Expired - Fee Related CN106591926B (en) | 2016-12-09 | 2016-12-09 | In the method that steel surface prepares the porous nickel nickel evolving hydrogen reaction catalyst of CNTs- |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106591926B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107723735A (en) * | 2017-09-27 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of nano metal simple substance and its modified oxide transient metal sulfide array catalyst and its preparation method and application |
| CN111108233A (en) * | 2017-09-21 | 2020-05-05 | 海默斯有限公司 | Method for producing electrocatalyst |
| CN111135873A (en) * | 2019-12-24 | 2020-05-12 | 郑州大学 | Device and method for continuously preparing carbon nanotube fiber composite electrolysis water hydrogen evolution catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005085716A (en) * | 2003-09-11 | 2005-03-31 | Nobuyuki Koura | Manufacturing method of composite electrode of oxide and carbon material, and lithium secondary battery |
| CN101003909A (en) * | 2006-12-21 | 2007-07-25 | 上海交通大学 | Electrochemical combined deposition method for preparing structure of composite membrane of Nano carbon tube - metal |
| US20100304182A1 (en) * | 2009-06-02 | 2010-12-02 | Integran Technologies, Inc. | Electrodeposited metallic-materials comprising cobalt |
| CN103022450A (en) * | 2012-12-21 | 2013-04-03 | 湘潭大学 | Three-dimensional netted tin-copper-nickel-carbon nanotube alloy negative electrode and preparation method thereof |
| CN105220205A (en) * | 2015-11-03 | 2016-01-06 | 哈尔滨工业大学 | A kind of composite electrodeposition prepares the method for CNTs/Ni matrix material |
-
2016
- 2016-12-09 CN CN201611128354.XA patent/CN106591926B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005085716A (en) * | 2003-09-11 | 2005-03-31 | Nobuyuki Koura | Manufacturing method of composite electrode of oxide and carbon material, and lithium secondary battery |
| CN101003909A (en) * | 2006-12-21 | 2007-07-25 | 上海交通大学 | Electrochemical combined deposition method for preparing structure of composite membrane of Nano carbon tube - metal |
| US20100304182A1 (en) * | 2009-06-02 | 2010-12-02 | Integran Technologies, Inc. | Electrodeposited metallic-materials comprising cobalt |
| CN103022450A (en) * | 2012-12-21 | 2013-04-03 | 湘潭大学 | Three-dimensional netted tin-copper-nickel-carbon nanotube alloy negative electrode and preparation method thereof |
| CN105220205A (en) * | 2015-11-03 | 2016-01-06 | 哈尔滨工业大学 | A kind of composite electrodeposition prepares the method for CNTs/Ni matrix material |
Non-Patent Citations (5)
| Title |
|---|
| KEJU JI 等: "Fabrication and electromagnetic interference shielding performance of open-cell foam of a Cu–Ni alloy integrated with CNTs", 《APPLIED SURFACE SCIENCE》 * |
| 山东工学院化学教研室: "《无机化学基础知识》", 31 October 1978, 山东人民出版社 * |
| 李永涛 等: "铜基电镀镍的浸出", 《上海市化学化工学会2007年学术年会论文摘要集》 * |
| 杨宏孝 主编: "《无机化学简明教程》", 31 December 2010, 高等教育出版社 * |
| 贾巍 等: "NiO/CNTs 的制备及其电化学电容行为研究", 《化学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111108233A (en) * | 2017-09-21 | 2020-05-05 | 海默斯有限公司 | Method for producing electrocatalyst |
| US11542615B2 (en) | 2017-09-21 | 2023-01-03 | Hymeth Aps | Method of producing an electrocatalyst |
| CN107723735A (en) * | 2017-09-27 | 2018-02-23 | 中国科学院长春应用化学研究所 | A kind of nano metal simple substance and its modified oxide transient metal sulfide array catalyst and its preparation method and application |
| CN107723735B (en) * | 2017-09-27 | 2019-05-07 | 中国科学院长春应用化学研究所 | A kind of nano metal nickel and nickel oxide modification tungsten disulfide array catalyst and its preparation method and application |
| CN111135873A (en) * | 2019-12-24 | 2020-05-12 | 郑州大学 | Device and method for continuously preparing carbon nanotube fiber composite electrolysis water hydrogen evolution catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106591926B (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107081163B (en) | Preparation and application of NiWP electrocatalyst material with three-dimensional structure | |
| CN105734606B (en) | A kind of SPE water electrolysis structure of ultra-thin membrane electrode and its preparation and application | |
| CN101717951B (en) | Cathode-catalyzed electrode producing method in coal electrolyzing, hydrogenizing and liquefying process | |
| CN105107535A (en) | Self-supporting transition metal-phosphorus alloy catalyst, and preparation method and application thereof | |
| CN102127776A (en) | Amorphous plating layer with high hydrogen evolution catalytic activity and preparation method thereof | |
| CN110205636A (en) | A kind of preparation method of self-cradling type three-dimensional porous structure double-function catalyzing electrode | |
| CN108607586B (en) | Nickel phosphide, preparation method thereof and method for producing hydrogen by electrolyzing water | |
| CN106702425B (en) | A method of preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface | |
| WO2020252820A1 (en) | Ferronickel catalytic material, preparation method therefor, and application thereof in preparing hydrogen from electrolyzed water and preparing liquid solar fuel | |
| CN105148920A (en) | Self-supporting transition metal-metal alloy catalyst as well as preparation method and application of self-supporting transition metal-metal alloy catalyst | |
| CN106591926B (en) | In the method that steel surface prepares the porous nickel nickel evolving hydrogen reaction catalyst of CNTs- | |
| CN114293201A (en) | Preparation method of nickel-iron catalyst for hydrogen production by water electrolysis | |
| Solmaz et al. | Fabrication, characterization and application of three-dimensional copper nanodomes as efficient cathodes for hydrogen production | |
| CN113529120B (en) | Transition metal sulfide composite electrode, preparation method and application thereof | |
| CN106319558B (en) | A kind of MoS of high-efficiency multiple2- Zn hydrogen-precipitating electrodes and preparation method thereof | |
| Zhang et al. | Hydrogen production by traditional and novel alkaline water electrolysis on nickel or iron based electrocatalysts | |
| CN110195234B (en) | Electrooxidation preparation method of copper-cuprous oxide-copper oxide core-shell structure oxygen evolution electrode | |
| CN106521496A (en) | Method for conducting chemical nickel plating to prepare high-hydrogen-evolution-activity electrode after electrophoresis of carbon nano tube on surface of carbon steel | |
| CN114045509B (en) | Seawater electrolysis device with sodium ion conduction and application thereof | |
| CN111250102A (en) | TiO22Preparation method of NiMo alloy catalyst supported by nanotube array | |
| CN106498436B (en) | The preparation method of foam copper as electrolysis water cathode/reduced graphene cluster/Ni/Cr | |
| CN113174607B (en) | Electrochemical preparation method of porous Ni-Co/graphene electrode | |
| JP2008138282A (en) | Anode for alkaline electrolysis | |
| CN102899684A (en) | Preparation method for cathodic porous supported catalytic electrode used in electrolysis and hydro-liquefaction of coal | |
| CN110227467B (en) | Three-layer coaxial oxygen production electrocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181002 Termination date: 20201209 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |