CN103103562A - Ni-Co-W-Cu-B multicomponent cathode material, and preparation method and application thereof - Google Patents
Ni-Co-W-Cu-B multicomponent cathode material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN103103562A CN103103562A CN2011103589635A CN201110358963A CN103103562A CN 103103562 A CN103103562 A CN 103103562A CN 2011103589635 A CN2011103589635 A CN 2011103589635A CN 201110358963 A CN201110358963 A CN 201110358963A CN 103103562 A CN103103562 A CN 103103562A
- Authority
- CN
- China
- Prior art keywords
- quality
- preparation
- cathode material
- hydrogen
- deionized water
- 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
Images
Classifications
-
- 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 provides an Ni-Co-W-Cu-B multicomponent cathode material, and a preparation method and application thereof. The Ni-Co-W-Cu-B multicomponent cathode material comprises a substrate and an Ni-Co-W-Cu-B alloy plating layer formed on the substrate by electrodeposition, wherein the alloy plating layer comprises the following components in percentage by mass: 26.5-36.6%of Ni, 6.6-9.2% of Co, 50.8-60.7% of W, 2.3-4.6% of Cu and 0.8-2.4% of B. The Ni-Co-W-Cu-B multicomponent cathode material has the advantages of high hydrogen production rate and high stability, and is especially suitable for a hydrogen production system by photoelectric catalytic decomposition of water.
Description
Technical field
The present invention relates to a kind of cathode material and its production and use, particularly, relate to a kind of Ni-Co-W-Cu-B polycomponent cathode material that uses in photoelectrocatalysis hydrogen production by water decomposition system, and preparation method thereof.
Background technology
The energy has been subject to the great attention of various countries as the lifeblood of world economy and the power of social development.Yet, account for world energy sources and supply with the reserves of 90% fossil oil day by day exhausted.Simultaneously, along with expanding economy, the production of the energy, conversion and use have brought serious environmental pollution, the ecosystem to destroy and the problem such as climatic shift, and mankind itself's the survival and development have been consisted of serious threat.Scientist thinks, Hydrogen Energy will become a kind of very important energy on 21 century energy stage.Utilizing Hydrogen Energy is the effective way that solves China energy problem and challenge, is also the important guarantee of realizing China's Sustainable development simultaneously, in China, bright prospect is arranged.
The method for preparing at present hydrogen is very many, and is both economic effective ways of environmental protection by solar photolysis water hydrogen.The photoelectrocatalysis hydrogen production by water decomposition has reduced the compound of electron-hole pair, makes the separation efficiency of electron-hole pair improve, and can obtain respectively hydrogen and oxygen on the two poles of the earth, and can effectively collect hydrogen.The photoelectrocatalysis hydrogen production by water decomposition utilizes sun power and water to make hydrogen, there is no byproduct, and is pollution-free, shown powerful advantage and development potentiality.
Anode material commonly used is WO in photoelectrocatalysis hydrogen production by water decomposition system
3, Fe
2O
3, TiO
2, (Ga
1-xZn
x) (N
1-xO
x), Co-SrTiO
3Deng, cathode material commonly used is that platinized platinum, carbon carry the precious metals such as platinum, palladium, ruthenium, but commonly uses the expensive of precious metal cathode material, and the material producing hydrogen effects such as graphite carbon are relatively poor, affected applying of photoelectrocatalysis hydrogen production by water decomposition technology.
Alloy material can reduce overpotential of hydrogen evolution, especially transition metal alloy to a great extent, and very superior Hydrogen Evolution Performance is arranged.According to the Brewer-Engel valence bond theory, electrode surface will have paired d electronics and d track in midair simultaneously in the liberation of hydrogen process, so just is conducive to the transmission of electronics in the liberation of hydrogen process, and the adsorption and desorption of H, form so-called synergistic effect, obtain the higher coating of catalytic activity.Can find out from " volcano effect curve " figure, be in the metal of the ascent stage of curve, a little less than absorption relatively to H, and the absorption of metal pair H that is in downcomer is stronger, studies show that, the alloy that the metal at curve two ends, office forms can demonstrate good synergistic effect, can obtain the good alloy electrode of Hydrogen Evolution Performance, as the Ni-Mo alloy.
In the preparation for the alloy material that is used for photoelectrocatalysis hydrogen production by water decomposition technology, at present existing material has following classification: binary alloy (Ni-Mo, Ni-V, Ni-W, Ni-Mo, Fe-Mo, several alloys of Co-Mo, wherein the Ni-Mo alloy to do the overpotential of hydrogen evolution of negative electrode minimum), ternary alloy (Ni-Mo-Fe, Ni-Mo-Cu, Ni-Mo-Zn, Ni-Mo-W, Ni-Mo-Co, Ni-Mo-Cr, Ni-Zn-P, Ni-Co-W, Ni-W-B etc.), multicomponent alloy (Co-W-B-P, W-Ni-Fe-Co etc.).
For example, these two pieces of patents of CN200410061157 and CN200510018226 relate to take Ti-Ni alloy as substrate Electroless Plating Ni-Co-W alloy, but its purposes is the medical carrier, the not purposes of relative photo electrocatalysis hydrogen production by water decomposition statement.Document Journal of Alloys and Compounds489 (2010) 488-492, reported the related process of the synthetic Ni-Co-W alloy take Cu as the substrate electro-deposition method, and tested correlated performance, but there is no the related application report on photoelectrocatalysis hydrogen production by water decomposition system yet.
Summary of the invention
In order to promote the development of photoelectrocatalysis hydrogen production by water decomposition technology, the contriver is considering in Hydrogen Evolution Performance, acid corrosion-resistant performance, the isoparametric situation of liberation of hydrogen stability, utilize alloy material, especially transition metal alloy, can reduce to a great extent the characteristic of overpotential of hydrogen evolution, a kind of Ni-Co-W-Cu-B polycomponent cathode material has been synthesized in design.
For this reason, the invention provides following several aspect:
＜1 〉. a kind of Ni-Co-W-Cu-B polycomponent cathode material, wherein said Ni-Co-W-Cu-B polycomponent cathode material comprises substrate and is formed on suprabasil Ni-Co-W-Cu-B alloy layer, wherein based on the total mass meter of described alloy layer, Ni is that 26.5 quality %～36.6 quality %, Co is that 6.6 quality %～9.2 quality %, W is that 50.8 quality %～60.7 quality %, Cu is 2.3～4.6 quality %, and B is 0.8～2.4 quality %.
＜2 〉. according to＜1〉described Ni-Co-W-Cu-B polycomponent cathode material, wherein said substrate is copper sheet or copper mesh.
＜3 〉. a kind of for the preparation of＜1 the method for described Ni-Co-W-Cu-B polycomponent cathode material, described method comprises the steps:
Provide the metal that is adapted at using in the photoelectrocatalysis hydrogen production by water decomposition as substrate;
The plating solution that is suitable in the enterprising electroplating deposition of described substrate is provided, described plating solution contains Ni, Co, W, Cu and B, and the total mass based on the Ni in plating solution, Co, W, Cu and B, Ni is that 26.5 quality %～36.6 quality %, Co is that 6.6 quality %～9.2 quality %, W is that 50.8 quality %～60.7 quality %, Cu is 2.3～4.6 quality %, and B is 0.8～2.4 quality %;
Described substrate is placed in resulting electroplate liquid electroplates, can obtain Ni-Co-W-Cu-B polycomponent cathode material.
＜4 〉. according to＜3〉described preparation method, wherein said substrate is copper mesh or copper sheet.
＜5 〉. according to＜3〉described preparation method, wherein said plating is to carry out at least twice plating under the different voltages of at least two groups.
＜6 〉. according to＜5 described preparation method, wherein said plating comprises: successively at 1.4-1.8V galvanic deposit 30-60min, at 1.8-2.2V galvanic deposit 60-90min, at 2.2-2.6V galvanic deposit 90-120min and at 2.6-3.0V galvanic deposit 4-8h.
＜7 〉. according to＜ask 3〉described preparation method, the preparation process of wherein said plating solution is as follows:
Nickel salt in deionized water for stirring, is added cobalt salt after dissolving, stir, then add mantoquita, after dissolve complete, add successively the first sodium salt, then ammonium salt, the second sodium salt, ammoniacal liquor and boron-containing compound and make their dissolvings slowly add Tungstenic compound, then stirring and dissolving.
＜8 〉. according to＜7〉described preparation method, wherein said the second sodium salt is Trisodium Citrate.
＜9 〉. according to＜7〉described preparation method, wherein said the first sodium salt, nickel salt, cobalt salt and mantoquita are the salt that can be dissolved in the correspondence in deionized water.
10. basis＜1〉or＜2〉described Ni-Co-W-Cu-B polycomponent cathode material or by＜3-＜8 in the purposes of Ni-Co-W-Cu-B polycomponent cathode material aspect the photoelectrocatalysis hydrogen production by water decomposition of the described methods preparation of any one.
The present invention has prepared a kind of Ni-Co-W-Cu-B multi-component material with the technique of galvanic deposit first, and has tested its performance performance in photoelectrocatalysis hydrogen production by water decomposition system, and result shows that it has high hydrogen-producing speed and stability, has actual application value.
Description of drawings
Fig. 1 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 1.
Fig. 2 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 2.
Fig. 3 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 3.
Fig. 4 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 4.
Fig. 5 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 5.
Fig. 6 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 6.
Fig. 7 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 7.
Fig. 8 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 8.
Fig. 9 is obtained the product hydrogen graphic representation of Ni-Co-W-Cu-B polycomponent cathode material by embodiment 9.
Embodiment
The invention provides a kind of Ni-Co-W-Cu-B polycomponent cathode material and preparation method thereof and the purposes in photoelectrocatalysis hydrogen production by water decomposition system.
Ni-Co-W-Cu-B polycomponent cathode material of the present invention comprises substrate and the Ni-Co-W-Cu-B alloy layer that forms by galvanic deposit in substrate.Described substrate is adopted and is adapted at the metal that uses as substrate in photoelectrocatalysis hydrogen production by water decomposition system, for example copper sheet and copper mesh.Copper mesh is compared with copper sheet, and copper mesh can increase the surface-area of material, and therefore under equal conditions resulting Ni-Co-W-Cu-B polycomponent cathode material can produce better product hydrogen performance usually.
In Ni-Co-W-Cu-B polycomponent cathode material of the present invention, the Ni-Co-W-Cu-B alloy layer has metalluster, and based on the total mass meter of galvanic deposit at suprabasil alloy layer, Ni is that 26.5 quality %～36.6 quality %, Co is that 6.6 quality %～9.2 quality %, W is that 50.8 quality %～60.7 quality %, Cu is 2.3～4.6 quality %, and B is 0.8～2.4 quality %.The composition of alloy layer of the present invention can adopt inductively coupled plasma atomic emission spectrometry to measure.For example, scrape gently the 0.1g alloy layer at alloy surface, then clear up with the 10mL chloroazotic acid, after sample dissolves fully, test its component content.
Comprise the steps: to provide the metal that uses in being adapted at the photoelectrocatalysis hydrogen production by water decomposition as substrate in the method for the Ni-Co-W-Cu-B of preparation polycomponent cathode material of the present invention; The plating solution that is suitable in the enterprising electroplating deposition of described substrate is provided, described plating solution contains Ni, Co, W, Cu and B, and the total mass based on the Ni in plating solution, Co, W, Cu and B, Ni is that 26.5 quality %～36.6 quality %, Co is that 6.6 quality %～9.2 quality %, W is that 50.8 quality %～60.7 quality %, Cu is 2.3～4.6 quality %, and B is 0.8～2.4 quality %; Described substrate is placed in resulting electroplate liquid electroplates, can obtain Ni-Co-W-Cu-B polycomponent cathode material.
At this, described substrate is preferably copper sheet and copper mesh.
The described step of substrate that provides comprises the step of cleaning substrate.For example, be 0.25mm with thickness, long is 8cm, and wide (or thickness is 1.0mm for the copper sheet of 2cm, long is 8cm, wide is the copper mesh of 2cm) with the sand papering surface, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, use a large amount of washed with de-ionized water after removing, then standby.
The described step that is suitable at the plating solution of the enterprising electroplating of described substrate deposition that provides comprises: with the nickel salt of calculated amount in deionized water for stirring, the cobalt salt that adds calculated amount after dissolving, stir, then the mantoquita that adds calculated amount, after dissolve complete, add successively the first sodium salt of calculated amount, ammonium salt, the second sodium salt, ammoniacal liquor and boron-containing compound and make their the dissolving, then slowly add the Tungstenic compound of calculated amount, then stirring and dissolving.
At this, wording " calculated amount " refers to calculate according to the composition of Ni-Co-W-Cu-B alloy layer in the needed Ni-Co-W-Cu-B polycomponent cathode material that finally obtains, for example, the amount of nickel salt, or consider and the amount that calculates the amount of the first sodium salt, ammonium salt and the second sodium salt for example from the electric conductivity that improves plating solution or the shock absorption plating solution.At this, the first sodium salt can be sodium sulfate or sodium-chlor, and the second sodium salt is Trisodium Citrate preferably.
Nickel salt, cobalt salt and mantoquita should be all the salt that can be dissolved in deionized water, can be for example nitrate, vitriol etc.For example, nickel salt can be single nickel salt, nickelous nitrate, nickelous chloride, nickel acetate, nickelous carbonate etc., and cobalt salt can be rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride etc., and mantoquita can be Salzburg vitriol, cupric chloride, venus crystals etc.Ammonium salt can be ammonium chloride, ammonium sulfate, ammonium nitrate etc.Described boron-containing compound can be boric acid, and Tungstenic compound can be sodium wolframate and ammonium tungstate etc.
It is worthy of note, in plating solution of the present invention, metal ion and citric acid have certain complexing action, the effect of complexing agent is the cationic deposition potential that furthered, make metal ion can realize codeposition, strengthened bath stability, ammoniacal liquor and ammonium salt for example ammonium chloride have certain shock absorption, keep the plating solution pH value stable.
In order to understand better the preparation of the plating solution in the present invention, the below has enumerated the concrete preparation process of plating solution 1-8, but these are not restrictive for example.
Plating solution 1: take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g, after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Plating solution 2: take nickelous nitrate 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 40mL, boric acid 2g, after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Plating solution 3: take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 40mL, boric acid 2g, after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Plating solution 4: take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g, after the solution dissolve complete, slowly add the 30g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Plating solution 5: take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g, after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Plating solution 6: take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 20mL, boric acid 2g, after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Plating solution 7: take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g, after the solution dissolve complete, slowly add the 20g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Plating solution 8: take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium sulfate 14.2g, ammonium sulfate 26.4g, Trisodium Citrate 89.3g, ammoniacal liquor 20mL, boric acid 2g, after the solution dissolve complete, slowly add the 20g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be 1000mL, places stand-by.
Need to use electrochemical workstation described substrate being placed in the step that resulting electroplate liquid electroplates, for example the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan.described electroplating process comprises: get the plating solution for preparing and pour in beaker, with the Ag/AgCl electrode, copper sheet substrate (or copper mesh substrate), platinized platinum respectively with the reference electrode of electrochemical workstation, supporting electrode, working electrode is connected, and insert in plating solution, then adopt the different voltages of at least two groups to carry out at least twice galvanic deposit, for example, be followed successively by at 1.4-1.8V galvanic deposit 30-60min, at 1.8-2.2V galvanic deposit 60-90min, at 2.2-2.6V galvanic deposit 90-120min and at 2.6-3.0V galvanic deposit 4-8h, can obtain galvanic deposit of the present invention at described suprabasil Ni-Co-W-Cu-B alloy layer.
It is worthy of note, the advantage that the different voltages of described employing at least two groups carry out at least twice galvanic deposit is: the purpose of selecting low voltage when electroplating reaction begins is to reduce speed of reaction, make coating and substrate contact tight, later stage increases voltage gradually, sedimentation rate is improved, serving has certain sedimentation, has increased specific surface area, thereby can increase the activity of electrode.
The inventor has tested the hydrogen-producing speed of the prepared Ni-Co-W-Cu-B of the present invention, and test process is as follows: with WO
3Be light anode material (its preparation is carried out with reference to the people's such as fourth sky friend patent application 201010269960.x), take Ni-Co-W-Cu-B of the present invention as cathode material, ionogen uses the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is its Hydrogen Evolution Performance of test under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.
In addition, the present invention has investigated the impact of the kinds of processes parameters such as base type, ammonia volume, sodium wolframate consumption on material property, draw to draw a conclusion: the impact of the amount of different ammoniacal liquor, embodiment 3, embodiment 5, embodiment 6 contrasts illustrate that 80mL ammoniacal liquor content is better; Different sodium wolframate content embodiment 4, embodiment 5, embodiment 7 comparative illustration 30g sodium wolframate content are better; Embodiment 2 and embodiment 9 comparative illustration add boron, improved material property; Embodiment 1 and embodiment 5 ratios illustrate that the copper mesh substrate is better than the copper sheet substrate., and optimized preparation technology, thereby finally obtained the Ni-Co-W-Cu-B polycomponent cathode material of the high and stable performance of hydrogen-producing speed.
The below will be described in more detail the present invention by embodiment, but these embodiment are not limitation of the scope of the invention, and scope of the present invention should be defined by the claims.
Embodiment
1, the cleaning of copper mesh substrate: be 1.0mm with thickness, long is 8cm, wide is the copper mesh deionized water rinsing of 2cm, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g is after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper mesh substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, then adopt the different voltages of many groups to carry out galvanic deposit, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 29.8%, Co is 6.9%, W is 58.8%, Cu is 3.1%, B is 1.4%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO
3Be the light anode material, its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x, and the anode illuminating area is 9cm
2, Ni-Co-W-Cu-B is cathode material, ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.Produce the hydrogen curve as shown in Figure 1, wherein the x in Fig. 1 and y represent respectively corresponding X-coordinate and ordinate zou, and R
2(these explain and to be suitable for equally following Fig. 2-Fig. 9) the expression degree of fitting.As can be seen from Figure 1, the hydrogen-producing speed of the cathode material of the Ni-Co-W-Cu-B of gained is 0.4846mmol/h, and under equal conditions, the hydrogen-producing speed of compacting carbon plate is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
1, the cleaning of copper sheet substrate: be 0.25mm with thickness, long is 8cm, wide is the copper sheet use sand papering surface of 2cm, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take nickelous nitrate 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 40mL, boric acid 2g is after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper sheet substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 30.2%, Co is 7.1%, W is 58.2%, Cu is 3.2%, B is 1.3%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO
3Be light anode material (its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x), the anode illuminating area is 9cm2, and Ni-Co-W-Cu-B is cathode material, and ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.Produce the hydrogen curve as shown in Figure 2, its hydrogen-producing speed is 0.2125mmol/h, and under equal conditions, the hydrogen-producing speed of compacting carbon plate is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
1, the cleaning of copper sheet substrate: be 0.25mm with thickness, long is 8cm, wide is the copper sheet use sand papering surface of 2cm, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 40mL, boric acid 2g is after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper sheet substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 29.6%, Co is 6.9%, W is 58.6%, Cu is 3.7%, B is 1.2%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO
3Be light anode material (its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x), the anode illuminating area is 9cm
2, Ni-Co-W-Cu-B is cathode material, ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.Produce the hydrogen curve as shown in Figure 3, its hydrogen-producing speed is 0.2881mmol/h, and under equal conditions, the hydrogen-producing speed of compacting carbon plate is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
1, the cleaning of copper sheet substrate: be 0.25mm with thickness, long is 8cm, wide is the copper sheet use sand papering surface of 2cm, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g is after the solution dissolve complete, slowly add the 30g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper sheet substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, then adopt the different voltages of many groups to carry out galvanic deposit, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 26.5%, Co is 7.3%, W is 60.7%, Cu is 3.3%, B is 2.2%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO
3Be light anode material (its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x), the anode illuminating area is 9cm
2, Ni-Co-W-Cu-B is cathode material, ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.Produce the hydrogen curve as shown in Figure 4, its hydrogen-producing speed is that the hydrogen-producing speed of compacting carbon plate under the 0.3402mmol/h equal conditions is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
1, the cleaning of copper sheet substrate: be 0.25mm with thickness, long is 8cm, wide is the copper sheet use sand papering surface of 2cm, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g is after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper sheet substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, then adopt the different voltages of many groups to carry out galvanic deposit, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 30.2%, Co is 6.6%, W is 58.6%, Cu is 3.0%, B is 1.6%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO
3Be light anode material (its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x), the anode illuminating area is 9cm
2, Ni-Co-W-Cu-B is cathode material, ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.Produce the hydrogen curve as shown in Figure 5, its hydrogen-producing speed is 0.3116mmol/h, and under equal conditions, the hydrogen-producing speed of compacting carbon plate is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
1, the cleaning of copper sheet substrate: be 0.25mm with thickness, long is 8cm, wide is the copper sheet use sand papering surface of 2cm, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 20mL, boric acid 2g is after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper sheet substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, then adopt the different voltages of many groups to carry out galvanic deposit, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 29.6%, Co is 7.9%, W is 57.8%, Cu is 2.8%, B is 1.9%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO
3Be light anode material (its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x), the anode illuminating area is 9cm
2, Ni-Co-W-Cu-B is cathode material, ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.Produce the hydrogen curve as shown in Figure 6, its hydrogen-producing speed is 0.2816mmol/h, and under equal conditions, the hydrogen-producing speed of compacting carbon plate is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 7
1, the cleaning of copper sheet substrate: be 0.25mm with thickness, long is 8cm, wide is the copper sheet use sand papering surface of 2cm, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 80mL, boric acid 2g is after the solution dissolve complete, slowly add the 20g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper sheet substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, then adopt the different voltages of many groups to carry out galvanic deposit, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 35.6%, Co is 9.2%, W is 50.8%, Cu is 2.9%, B is 1.5%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: take WO3 as the light anode material (its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x), the anode illuminating area is 9cm2, Ni-Co-W-Cu-B is cathode material, ionogen is the 0.5M dilute sulphuric acid, be 100mW/cm2 in light intensity, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.Produce the hydrogen curve as shown in Figure 7, its hydrogen-producing speed is 0.2425mmol/h, and under equal conditions, the hydrogen-producing speed of compacting carbon plate is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
1, the cleaning of copper mesh substrate: be 1.0mm with thickness, long is 8cm, wide is the copper mesh deionized water rinsing of 2cm, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take single nickel salt 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g rose vitriol after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium sulfate 14.2g, ammonium sulfate 26.4g, Trisodium Citrate 89.3g, ammoniacal liquor 20mL, boric acid 2g is after the solution dissolve complete, slowly add the 20g sodium wolframate, stirring and dissolving can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper mesh substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, then adopt the different voltages of many groups to carry out galvanic deposit, be followed successively by 1.8V galvanic deposit 30min, 2.2V galvanic deposit 60min, 2.6V galvanic deposit 90min, 3.0V galvanic deposit 4h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu-B polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 33.7%, Co is 8.9%, W is 52.1%, Cu is 3.9%, B is 1.4%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO
3Be light anode material (its preparation is with reference to the people's such as fourth sky friend patent application 201010269960.x), the anode illuminating area is 9cm
2, Ni-Co-W-Cu-B is cathode material, ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2Bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, produce the hydrogen curve as shown in Figure 8, its hydrogen-producing speed is 0.4135mmol/h, under equal conditions, the hydrogen-producing speed of compacting carbon plate is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 9 (Comparative Examples)
1, the cleaning of copper sheet substrate: be 0.25mm with thickness, long is 8cm, wide is the copper sheet use sand papering surface of 2cm, then use deionized water rinsing, put into phosphate aqueous solution ultrasonic cleaning 30～60min of 30～65% after rinsing well, then use a large amount of deionized water rinsings, then put into deionized water for ultrasonic and clean 30～60min, with a large amount of washed with de-ionized water, then standby after removing.
2, take nickelous nitrate 30g and put into the beaker that fills the 700mL deionized water, and stir, add the 7.5g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES after dissolve complete, stir, and then add Salzburg vitriol 3.2g, after dissolve complete, add successively and dissolve sodium-chlor 11.68g, ammonium chloride 10.7g, Trisodium Citrate 89.3g, ammoniacal liquor 40mL, after the solution dissolve complete, slowly add the 25g sodium wolframate, stirring and dissolving, can obtain transparent blue solution after dissolve complete, and adding deionized water, to make overall solution volume be that 1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu (equipment used: the special CS of Instr Ltd. electrochemical workstation of Wuhan Cohan)
getting the plating solution 450mL for preparing pours in the 500mL beaker, with the Ag/AgCl electrode, the copper sheet substrate, platinized platinum respectively with the reference electrode of workstation, supporting electrode, working electrode is connected, and insert in plating solution, be followed successively by 1.6V galvanic deposit 45min, 2.0V galvanic deposit 75min, 2.4V galvanic deposit 105min, 2.8V galvanic deposit 6h, stopped reaction, after being taken out, sample uses deionized water rinsing, can obtain the Ni-Co-W-Cu polycomponent cathode material of surface metal gloss, the mass percentage content that adopts the inductively coupled plasma atomic emission spectrometry test to form, Ni is 29.6%, Co is 7.8%, W is 59.1%, Cu is 3.5%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu: with WO
3Be light anode material (its preparation is with reference to the people's such as fourth sky friend application for a patent for invention 201010269960.x), the anode illuminating area is 9cm
2, Ni-Co-W-Cu is cathode material, ionogen is the 0.5M dilute sulphuric acid, is 100mW/cm in light intensity
2, bias-voltage is test its Hydrogen Evolution Performance (equipment used is Agilent 6820 type gas-chromatographies) under the 1.2V condition, and the product hydrogen performance of the Ni-Co-W-Cu-B of itself and embodiment 2 is compared.Produce the hydrogen curve as shown in Figure 9, its hydrogen-producing speed is 0.1716mmol/h, and under equal conditions, the hydrogen-producing speed of the Ni-Co-W-Cu-B of embodiment 2 is 0.2125mmol/h.This explanation novel Ni-Co-W-Cu-B cathode material of the present invention has better hydrogen-producing speed, is more suitable in using in photoelectrocatalysis hydrogen production by water decomposition system.
Industrial applicability
The present invention the Ni-Co-W-Cu-B multi-component material be particularly suitable for using in photoelectrocatalysis hydrogen production by water decomposition system.
Claims (10)
1. Ni-Co-W-Cu-B polycomponent cathode material, comprise substrate and be formed on suprabasil Ni-Co-W-Cu-B alloy layer, wherein based on the total mass meter of described alloy layer, Ni is that 26.5 quality %～36.6 quality %, Co is that 6.6 quality %～9.2 quality %, W is that 50.8 quality %～60.7 quality %, Cu is 2.3～4.6 quality %, and B is 0.8～2.4 quality %.
2. Ni-Co-W-Cu-B polycomponent cathode material according to claim 1, wherein said substrate is copper sheet or copper mesh.
3. method for the preparation of Ni-Co-W-Cu-B polycomponent cathode material claimed in claim 1, described method comprises the steps:
Provide the metal that is adapted at using in the photoelectrocatalysis hydrogen production by water decomposition as substrate;
The plating solution that is suitable in the enterprising electroplating deposition of described substrate is provided, described plating solution contains Ni, Co, W, Cu and B, and the total mass based on the Ni in plating solution, Co, W, Cu and B, Ni is that 26.5 quality %～36.6 quality %, Co is that 6.6 quality %～9.2 quality %, W is that 50.8 quality %～60.7 quality %, Cu is 2.3～4.6 quality %, and B is 0.8～2.4 quality %;
Described substrate is placed in described electroplate liquid electroplates, can obtain Ni-Co-W-Cu-B polycomponent cathode material.
4. preparation method according to claim 3, wherein said substrate is copper mesh or copper sheet.
5. preparation method according to claim 3, wherein said plating is to carry out at least twice plating under the different voltages of at least two groups.
6. preparation method according to claim 5, wherein said plating comprises: successively at 1.4-1.8V galvanic deposit 30-60min, at 1.8-2.2V galvanic deposit 60-90min, at 2.2-2.6V galvanic deposit 90-120min and at 2.6-3.0V galvanic deposit 4-8h.
7. preparation method according to claim 3, the preparation process of wherein said plating solution is as follows:
Nickel salt in deionized water for stirring, is added cobalt salt after dissolving, stir, then add mantoquita, after dissolve complete, add successively the first sodium salt, then ammonium salt, the second sodium salt, ammoniacal liquor and boron-containing compound and make their dissolvings slowly add Tungstenic compound, then stirring and dissolving.
8. preparation method according to claim 7, wherein said the second sodium salt is Trisodium Citrate.
9. preparation method according to claim 7, wherein said the first sodium salt, nickel salt, cobalt salt and mantoquita are the salt that can be dissolved in the correspondence in deionized water.
A Ni-Co-W-Cu-B polycomponent cathode material according to claim 1 and 2 or by the Ni-Co-W-Cu-B polycomponent cathode material of the described method preparation of any one in claim 3-8 in the purposes aspect the photoelectrocatalysis hydrogen production by water decomposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110358963.5A CN103103562B (en) | 2011-11-14 | 2011-11-14 | A kind of Ni-Co-W-Cu-B multicomponent cathode material and its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110358963.5A CN103103562B (en) | 2011-11-14 | 2011-11-14 | A kind of Ni-Co-W-Cu-B multicomponent cathode material and its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103103562A true CN103103562A (en) | 2013-05-15 |
| CN103103562B CN103103562B (en) | 2016-05-18 |
Family
ID=48311744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110358963.5A Active CN103103562B (en) | 2011-11-14 | 2011-11-14 | A kind of Ni-Co-W-Cu-B multicomponent cathode material and its production and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103103562B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107268019A (en) * | 2017-06-16 | 2017-10-20 | 湘潭大学 | A kind of porous Ni-base alloy is electrolysed the preparation method of cathode material for hydrogen evolution |
| CN107988617A (en) * | 2017-11-24 | 2018-05-04 | 复旦大学 | Water electrolysis efficiently, double-function catalyzing electrode and preparation method thereof |
| CN108624907A (en) * | 2018-04-26 | 2018-10-09 | 复旦大学 | Nonmetal basal body efficient catalytic electrode and preparation method thereof |
| CN108722419A (en) * | 2015-03-05 | 2018-11-02 | 泰拉吉尼克有限公司 | The method of the hydrolysis and recycling of catalysis induction for metal borohydride solution |
| CN114808007A (en) * | 2022-03-14 | 2022-07-29 | 青岛科技大学 | Method for preparing Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by electrodeposition method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04365890A (en) * | 1991-06-12 | 1992-12-17 | Shimizu:Kk | Method of ni-w alloy plating |
| CN102216496A (en) * | 2008-12-02 | 2011-10-12 | 德诺拉工业有限公司 | Electrode suitable as hydrogen-evolving cathode |
-
2011
- 2011-11-14 CN CN201110358963.5A patent/CN103103562B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04365890A (en) * | 1991-06-12 | 1992-12-17 | Shimizu:Kk | Method of ni-w alloy plating |
| CN102216496A (en) * | 2008-12-02 | 2011-10-12 | 德诺拉工业有限公司 | Electrode suitable as hydrogen-evolving cathode |
Non-Patent Citations (2)
| Title |
|---|
| 邹勇进: "低析氢超电势镍-钴基多元合金功能电极材料电化学性能的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, 15 September 2005 (2005-09-15), pages 020 - 45 * |
| 韩庆等: "镍合金用作电解水析氢阴极的发展现状", 《中国有色金属学报》, vol. 11, 31 May 2001 (2001-05-31), pages 158 - 162 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722419A (en) * | 2015-03-05 | 2018-11-02 | 泰拉吉尼克有限公司 | The method of the hydrolysis and recycling of catalysis induction for metal borohydride solution |
| US10919763B2 (en) | 2015-03-05 | 2021-02-16 | Electriq-Global Energy Solutions Ltd | Method for catalytically induced hydrolysis and recycling of metal borohydride solutions |
| CN107268019A (en) * | 2017-06-16 | 2017-10-20 | 湘潭大学 | A kind of porous Ni-base alloy is electrolysed the preparation method of cathode material for hydrogen evolution |
| CN107988617A (en) * | 2017-11-24 | 2018-05-04 | 复旦大学 | Water electrolysis efficiently, double-function catalyzing electrode and preparation method thereof |
| CN108624907A (en) * | 2018-04-26 | 2018-10-09 | 复旦大学 | Nonmetal basal body efficient catalytic electrode and preparation method thereof |
| CN114808007A (en) * | 2022-03-14 | 2022-07-29 | 青岛科技大学 | Method for preparing Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by electrodeposition method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103103562B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102127776A (en) | Amorphous plating layer with high hydrogen evolution catalytic activity and preparation method thereof | |
| CN102352524B (en) | Metal oxide modified TiO2 nanometer tube array electrode and preparation method thereof | |
| CN101748426B (en) | Preparation method of foam electrode for water electrolysis | |
| CN107081163B (en) | Preparation and application of NiWP electrocatalyst material with three-dimensional structure | |
| CN105483751A (en) | Efficient Ni-S-Mo hydrogen evolution electrode and preparation method thereof | |
| CN102787329A (en) | Preparation method of efficient Ni-Mo-P/Ni hydrogen evolution electrode | |
| CN104923268A (en) | Self-support transition metal selenide catalyst as well as preparation method and application thereof | |
| CN103924260A (en) | Composite hydrogen evolution electrode with copper and cobalt loaded on three-dimensional foamed nickel and preparation method thereof | |
| CN105013512A (en) | Self-supporting transitional metal sulfide catalyst and preparation methods and applications thereof | |
| CN110129825B (en) | High-efficiency Ni/Ni (OH)2Hydrogen evolution electrode and preparation method thereof | |
| CN103103562B (en) | A kind of Ni-Co-W-Cu-B multicomponent cathode material and its production and use | |
| CN103996547B (en) | Manganese-contained transition metal composite oxide electrode and preparing method and application thereof | |
| CN102899681A (en) | Porous nickel composite electrode, electroplating solution and preparation method of porous nickel composite electrode | |
| CN106967986A (en) | A kind of nickel hydroxide/nickel/graphene with hierarchy is combined the preparation method of hydrogen-precipitating electrode | |
| CN103227057B (en) | A kind of method preparing manganese dioxide electrode of super capacitor | |
| CN108607586B (en) | Nickel phosphide, preparation method thereof and method for producing hydrogen by electrolyzing water | |
| CN106807349A (en) | A kind of nano metal simple substance modification transition metal hydroxide array catalyst and its preparation method and application | |
| CN105148920A (en) | Self-supporting transition metal-metal alloy catalyst as well as preparation method and application of self-supporting transition metal-metal alloy catalyst | |
| CN108070878A (en) | A kind of porous Ni-S/TiO2Compound hydrogen-precipitating electrode and preparation method thereof | |
| CN106319558B (en) | A kind of MoS of high-efficiency multiple2- Zn hydrogen-precipitating electrodes and preparation method thereof | |
| CN107419290B (en) | A kind of electrolytic brine prepares the system and method for pure hydrogen, oxygen | |
| CN107326395B (en) | A kind of preparation method of the compound hydrogen-precipitating electrode of carbosphere of nickel/N doping | |
| CN104022289B (en) | A kind of DMFC RuNi/TiO2nanotube electrode and preparation method | |
| CN111250102A (en) | TiO22Preparation method of NiMo alloy catalyst supported by nanotube array | |
| CN113279010B (en) | Fe-Se hydrogen evolution electrode with high catalytic activity and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |