CN103103562B - A kind of Ni-Co-W-Cu-B multicomponent cathode material and its production and use - Google Patents
A kind of Ni-Co-W-Cu-B multicomponent cathode material and its production and use Download PDFInfo
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Abstract
The invention provides a kind of Ni-Co-W-Cu-B multicomponent cathode material and its production and use. Described Ni-Co-W-Cu-B multicomponent cathode material comprises substrate and is formed on suprabasil Ni-Co-W-Cu-B alloy layer by electro-deposition, the wherein gross mass meter at suprabasil alloy layer based on electro-deposition, Ni is 26.5%～36.6%, Co is 6.6%～9.2%, W is 50.8%～60.7%, Cu is that 2.3～4.6%, B is 0.8～2.4%. Ni-Co-W-Cu-B multi-component material of the present invention has high hydrogen-producing speed and stability, is particularly suitable for applying in photoelectrocatalysis hydrogen production by water decomposition system.
Description
Technical field
The present invention relates to a kind of cathode material and its production and use, particularly, relate to one and existThe Ni-Co-W-Cu-B multicomponent cathode material using in photoelectrocatalysis hydrogen production by water decomposition system, andPreparation method.
Background technology
The energy, as the lifeblood of World Economics and the power of social development, has been subject to the height weight of various countriesDepending on. But, account for reserves that world energy sources supplies with 90% fossil fuel day by day exhausted. Meanwhile, withExpanding economy, production, conversion and the use of the energy have brought serious environmental pollution, ecosystemThe problems such as system destruction and climate change, have formed serious threat to mankind itself's the survival and development.Scientist thinks, Hydrogen Energy will become a kind of very important energy on 21 century energy stage. UtilizeHydrogen Energy is the effective way that solves energy problem of China and challenge, is also to realize China's sustainable development simultaneouslyThe important guarantee of exhibition, has bright prospect in China.
The method of preparing at present hydrogen is very many, and is both environmental protection by solar photolysis water hydrogenEconomic effective ways. Photoelectrocatalysis hydrogen production by water decomposition, has reduced the compound of electron-hole pair, makesThe separative efficiency that obtains electron-hole pair improves, and can on the two poles of the earth, obtain respectively hydrogen and oxygen, andCan effectively collect hydrogen. Photoelectrocatalysis hydrogen production by water decomposition utilizes solar energy and water to make hydrogen, does not haveByproduct, pollution-free, show powerful advantage and development potentiality.
In photoelectrocatalysis hydrogen production by water decomposition system, conventional anode material is WO3、Fe2O3、TiO2、(Ga1-xZnx)(N1-xOx)、Co-SrTiO3Deng, conventional cathode material is that platinized platinum, carbon carry platinum, palladium, rutheniumDeng noble metal, but commonly use the expensive of noble metal cathode material, and the material producing hydrogen effects such as graphitic carbonFruit is poor, has 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,There is very superior Hydrogen Evolution Performance. According to Brewer-Engel valence bond theory, electrode in liberation of hydrogen processSurface will have paired d electronics and d track in midair simultaneously, is so just conducive in liberation of hydrogen processThe transmission of electronics, and the adsorption and desorption of H, form so-called cooperative effect, obtains catalysis and liveThe coating that property is higher. From " volcano effect curve " figure, can find out, be in the gold of the ascent stage of curveBelong to, a little less than the absorption relatively of H, and it is stronger to be in the absorption of metal pair H of descending branch, researchShow, the alloy that the metal at curve two ends, office forms can demonstrate good cooperative effect, canObtain the good alloy electrode of Hydrogen Evolution Performance, as Ni-Mo alloy.
In the preparation of the alloy material for for photoelectrocatalysis hydrogen production by water decomposition technology, existing at presentMaterial has following classification: binary alloy (Ni-Mo, Ni-V, Ni-W, Ni-Mo, Fe-Mo, Co-MoSeveral alloys, wherein Ni-Mo alloy to do the overpotential of hydrogen evolution of negative electrode minimum), ternary alloy three-partalloy(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 sections of patents of CN200410061157 and CN200510018226 relate to titanium nickel and closingGold is substrate Electroless Plating Ni-Co-W alloy, but its purposes is medical carrier, not relevantThe purposes statement of photoelectrocatalysis hydrogen production by water decomposition. Document JournalofAlloysandCompounds489 (2010) 488-492, have reported the phase of synthesizing Ni-Co-W alloy taking Cu as substrate electro-deposition methodClose technique, and tested correlated performance, but also do not have in photoelectrocatalysis hydrogen production by water decomposition systemRelated application report.
Summary of the invention
In order to promote the development of photoelectrocatalysis hydrogen production by water decomposition technology, inventor is considering liberation of hydrogenIn performance, acid corrosion-resistant performance, the isoparametric situation of liberation of hydrogen stability, utilize alloy material, especiallyBe transition metal alloy, can reduce to a great extent the characteristic of overpotential of hydrogen evolution, design is syntheticA kind of Ni-Co-W-Cu-B multicomponent cathode material.
For this reason, the invention provides following several aspect:
<1>. a kind of Ni-Co-W-Cu-B multicomponent cathode material, wherein said Ni-Co-W-Cu-BMulticomponent cathode material comprises substrate and is formed on suprabasil Ni-Co-W-Cu-B alloy layer,The wherein gross mass meter based on described alloy layer, Ni is 26.5 quality %～36.6 quality %, CoBe that 6.6 quality %～9.2 quality %, W are that 50.8 quality %～60.7 quality %, Cu are 2.3～4.6Quality %, and B is 0.8～2.4 quality %.
<2>. according to<1>described Ni-Co-W-Cu-B multicomponent cathode material, wherein said substrateFor copper sheet or copper mesh.
<3>. a kind of for the preparation of<1>side of described Ni-Co-W-Cu-B multicomponent cathode materialMethod, described method comprises the steps:
Provide the metal that is adapted at using in photoelectrocatalysis hydrogen production by water decomposition as substrate;
The plating solution being suitable in the enterprising electroplating of described substrate deposition is provided, described plating solution contain Ni,Co, W, Cu and B, and the gross mass of Ni, Co, W, Cu and B based in plating solution, Ni is26.5 quality %～36.6 quality %, Co are that 6.6 quality %～9.2 quality %, W are 50.8 quality%～60.7 quality %, Cu are 2.3～4.6 quality %, and B is 0.8～2.4 quality %;
Described substrate is placed in to obtained electroplate liquid and electroplates, can obtainNi-Co-W-Cu-B multicomponent 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 at the different electricity of at least two groupsDepress and carry out at least twice plating.
<6>. according to<5>described preparation method, wherein said plating comprises: successively at 1.4-1.8VElectro-deposition 30-60min, at 1.8-2.2V electro-deposition 60-90min, in 2.2-2.6V electro-deposition90-120min and at 2.6-3.0V electro-deposition 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 to cobalt salt after dissolving, stirs, then add mantoquita,After dissolving completely, add successively the first sodium salt, ammonium salt, the second sodium salt, ammoniacal liquor and boron-containing compound are alsoAnd they are dissolved, then slowly add Tungstenic compound, then stirring and dissolving.
<8>. according to<7>described preparation method, wherein said the second sodium salt is natrium citricum.
<9>. according to<7>described preparation method, wherein said the first sodium salt, nickel salt, cobalt salt andMantoquita is the corresponding salt that can be dissolved in deionized water.
10. basis<1>or<2>described Ni-Co-W-Cu-B multicomponent cathode material or by<3>-<8>in the Ni-Co-W-Cu-B multicomponent cathode material prepared of method described in any one at lightThe purposes of electro-catalysis hydrogen production by water decomposition aspect.
The present invention has prepared a kind of Ni-Co-W-Cu-B multi-component material by the technique of electro-deposition first,And tested its performance performance in photoelectrocatalysis hydrogen production by water decomposition system, result shows that it has heightHydrogen-producing speed and stability, there is actual application value.
Brief description of the drawings
Fig. 1 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 1.
Fig. 2 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 2.
Fig. 3 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 3.
Fig. 4 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 4.
Fig. 5 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 5.
Fig. 6 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 6.
Fig. 7 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 7.
Fig. 8 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 8.
Fig. 9 is the product hydrogen curve map that is obtained Ni-Co-W-Cu-B multicomponent cathode material by embodiment 9.
Detailed description of the invention
The invention provides a kind of Ni-Co-W-Cu-B multicomponent cathode material and preparation method thereof andPurposes in photoelectrocatalysis hydrogen production by water decomposition system.
Ni-Co-W-Cu-B multicomponent cathode material of the present invention comprise substrate and by electro-deposition at baseThe Ni-Co-W-Cu-B alloy layer forming at the end. Described substrate adopts and is adapted at photoelectrocatalysis decompositionThe metal using as substrate in water hydrogen manufacturing system, for example copper sheet and copper mesh. Copper mesh is compared with copper sheet,Copper mesh can increase the surface area of material, the Ni-Co-W-Cu-B that therefore under equal conditions obtainedMulticomponent cathode material can produce better product hydrogen performance conventionally.
Ni-Co-W-Cu-B alloy layer tool in Ni-Co-W-Cu-B multicomponent cathode material of the present inventionHave metallic luster, and based on electro-deposition the gross mass meter at suprabasil alloy layer, Ni is 26.5Quality %～36.6 quality %, Co are that 6.6 quality %～9.2 quality %, W are 50.8 quality %～60.7Quality %, Cu are 2.3～4.6 quality %, and B is 0.8～2.4 quality %. Alloy layer of the present inventionComposition can adopt ICP-AES to measure. For example,, at alloy surfaceScrape gently 0.1g alloy-layer, then clear up with 10mL chloroazotic acid, after sample dissolves completely, surveyTry its component content.
Method at the Ni-Co-W-Cu-B of preparation multicomponent cathode material of the present invention comprises following stepRapid: to provide the metal that is adapted at using in photoelectrocatalysis hydrogen production by water decomposition as substrate; Provide and be suitable forAt the plating solution of the enterprising electroplating deposition of described substrate, described plating solution contains Ni, Co, W, Cu and B,And the gross mass of Ni, Co, W, Cu and B based in plating solution, Ni is 26.5 quality %～36.6Quality %, Co are that 6.6 quality %～9.2 quality %, W are 50.8 quality %～60.7 quality %, CuBe 2.3～4.6 quality %, B is 0.8～2.4 quality %; Described substrate is placed in to obtained electroplate liquidIn electroplate, can obtain Ni-Co-W-Cu-B multicomponent cathode material.
At this, described substrate is preferably copper sheet and copper mesh.
The described step that substrate is provided comprises the step of cleaning substrate. For example, be 0.25mm by thickness,Long is 8cm, the wide copper sheet for 2cm (or thickness is 1.0mm, and long is 8cm, and wide is 2cm'sCopper mesh) use sand papering surface, then use deionized water rinsing, after rinsing well, put into 30～65%Phosphate aqueous solution in ultrasonic cleaning 30～60min, then use a large amount of deionized water rinsings, then putEnter deionized water for ultrasonic and clean 30～60min, after removing, use a large amount of washed with de-ionized water, then standbyWith.
The described step that is suitable for the plating solution depositing at the enterprising electroplating of described substrate that provides comprises: will countThe nickel salt of calculation amount, in deionized water for stirring, adds the cobalt salt of amount of calculation after dissolving, stir, and then addsEnter the mantoquita of amount of calculation, after dissolving completely, add successively the first sodium salt of amount of calculation, ammonium salt, secondSodium salt, ammoniacal liquor and boron-containing compound and their are dissolved, then slowly add the tungstenic of amount of calculationCompound, then stirring and dissolving.
At this, wording " amount of calculation " refers to the Ni-Co-W-Cu-B finally obtaining according to neededIn multicomponent cathode material, the composition of Ni-Co-W-Cu-B alloy layer calculates, for example, and nickel saltAmount, or consider to calculate from the conductance or the cushioning effect plating solution that improve plating solutionAmount, for example amount of the first sodium salt, ammonium salt and the second sodium salt. At this, the first sodium salt can be sodium sulphateOr sodium chloride, preferably natrium citricum of the second sodium salt.
Nickel salt, cobalt salt and mantoquita should be all the salt that can be dissolved in deionized water, for example, can beNitrate, sulfate etc. For example, nickel salt can be nickelous sulfate, nickel nitrate, nickel chloride, acetic acidNickel, nickelous carbonate etc., cobalt salt can be cobaltous sulfate, cobalt nitrate, cobalt chloride etc., and mantoquita can be fiveHydrated copper sulfate, copper chloride, copper acetate etc. Ammonium salt can be ammonium chloride, ammonium sulfate, ammonium nitrate etc.Deng. Described boron-containing compound can be boric acid, and Tungstenic compound can be sodium tungstate and ammonium tungstate etc.
It is worthy of note, in plating solution of the present invention, metal ion and citric acid have certain complexingEffect, the effect of complexing agent is the cationic deposition potential that furthered, and metal ion can be realized altogetherDeposition, has strengthened bath stability, and for example ammonium chloride of ammoniacal liquor and ammonium salt has certain cushioning effect, dimensionHold plating solution pH value stable.
In order to understand better the preparation of the plating solution in the present invention, enumerate the concrete of plating solution 1-8 belowPreparation process, but these are not restrictive for example.
Plating solution 1: take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobaltous sulfate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum89.3g, ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate,Stirring and dissolving, can obtain transparent blue solution after dissolving completely, and adds deionized water and make solution overallAmass as 1000mL, place stand-by.
Plating solution 2: take nickel nitrate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobalt nitrate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum89.3g, ammoniacal liquor 40mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate,Stirring and dissolving, can obtain transparent blue solution after dissolving completely, and adds deionized water and make solution overallAmass as 1000mL, place stand-by.
Plating solution 3: take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobaltous sulfate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum89.3g, ammoniacal liquor 40mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate,Stirring and dissolving, can obtain transparent blue solution after dissolving completely, and adds deionized water and make solution overallAmass as 1000mL, place stand-by.
Plating solution 4: take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobaltous sulfate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum89.3g, ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 30g sodium tungstate,Stirring and dissolving, can obtain transparent blue solution after dissolving completely, and adds deionized water and make solution overallAmass as 1000mL, place stand-by.
Plating solution 5: take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobaltous sulfate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum89.3g, ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate,Stirring and dissolving, can obtain transparent blue solution after dissolving completely, and adds deionized water and make solution overallAmass as 1000mL, place stand-by.
Plating solution 6: take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobaltous sulfate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum89.3g, ammoniacal liquor 20mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate,Stirring and dissolving, can obtain transparent blue solution after dissolving completely, and adds deionized water and make solution overallAmass as 1000mL, place stand-by.
Plating solution 7: take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobaltous sulfate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum89.3g, ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 20g sodium tungstate,Stirring and dissolving, can obtain transparent blue solution after dissolving completely, and adds deionized water and make solution overallAmass as 1000mL, place stand-by.
Plating solution 8: take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stirMix, to be dissolvedly add 7.5g cobaltous sulfate after completely, stir, and then add Salzburg vitriol 3.2g,After dissolving completely, add successively and dissolve sodium sulphate 14.2g, ammonium sulfate 26.4g, natrium citricum 89.3g,Ammoniacal liquor 20mL, boric acid 2g, after solution dissolves completely, slowly adds 20g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL, places stand-by.
Need to use electrification described substrate being placed in to the step that obtained electroplate liquid electroplatesLearn work station, for example CS of Wuhan Gastec Instrument Ltd. electrochemical workstation. Described platingJourney comprises: get the plating solution preparing and pour in beaker, by Ag/AgCl electrode, copper sheet substrate (or copperNet substrate), platinized platinum respectively with reference electrode, auxiliary electrode, the working electrode phase of electrochemical workstationConnect, and insert in plating solution, then adopt the different voltage of at least two groups to carry out at least twice electro-deposition, exampleAs, be followed successively by 1.4-1.8V electro-deposition 30-60min, 1.8-2.2V electro-deposition 60-90min,At 2.2-2.6V electro-deposition 90-120min and at 2.6-3.0V electro-deposition 4-8h, can obtain thisThe electro-deposition of invention is at described suprabasil Ni-Co-W-Cu-B alloy layer.
It is worthy of note, described employing at least two groups different voltages carry out at least twice electro-depositionAdvantage is: the object of selecting low-voltage in the time that electroplating reaction starts is to reduce reaction rate, makes coatingTight with substrate contact, the later stage increases voltage gradually, and sedimentation rate is improved, and serving has certainGas porosity, has increased specific 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, testsJourney is as follows: with WO3For light anode material, (its preparation is with reference to the people's such as fourth sky friend patent application201010269960.x carry out), taking Ni-Co-W-Cu-B of the present invention as cathode material, electrolyteUsing 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2, bias-voltage is to test it under 1.2V conditionHydrogen Evolution Performance, and the product hydrogen performance of platinized platinum under itself and equal conditions is compared.
In addition, the present invention has investigated the kinds of processes ginsengs such as base type, ammonia volume, sodium tungstate consumptionSeveral impacts on material property, draw to draw a conclusion: the impact of the amount of different ammoniacal liquor, embodiment 3,Embodiment 5, embodiment 6 contrast, and illustrate that 80mL ammoniacal liquor content is better; Different sodium tungstate content is realExecute example 4, embodiment 5, embodiment 7 comparative illustration 30g sodium tungstate content better; Embodiment 2 HesEmbodiment 9 comparative illustration add boron element, improved material property; Embodiment 1 and embodiment 5Ratio, illustrates that copper mesh substrate is better than copper sheet substrate. , and optimized preparation technology, thus finally obtainThe Ni-Co-W-Cu-B multicomponent cathode material of the high and stable performance of hydrogen-producing speed.
To be described in more detail the present invention by embodiment below, but these embodiment are notLimit the scope of the present invention, scope of the present invention should be defined by the claims.
Embodiment
Embodiment 1
1, the cleaning of copper mesh substrate: be 1.0mm by thickness, long is 8cm, and wide is the copper mesh of 2cmWith deionized water rinsing, after rinsing well, put into 30～65% phosphate aqueous solution ultrasonic cleaning30～60min, then uses a large amount of deionized water rinsings, then puts into deionized water for ultrasonic and cleans30～60min, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobaltous sulfate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper meshSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, then adopt the different voltage of many groups to carry out electro-deposition, be followed successively by 1.6V electro-deposition 45min,2.0V electro-deposition 75min, 2.4V electro-deposition 105min, 2.8V electro-deposition 6h, stops reaction,After being taken out, sample with deionized water rinsing, can obtain surface metal glossNi-Co-W-Cu-B multicomponent cathode material, adopts ICP-AESThe mass percentage content of test composition, Ni is 29.8%, Co is 6.9%, W is 58.8%,Cu is that 3.1%, B is 1.4%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO3For light anode material, its preparationWith reference to the people's such as fourth sky friend patent application 201010269960.x, anode illuminating area is 9cm2，Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), and the product hydrogen performance of platinized platinum under itself and equal conditions is compared. Produce hydrogen curve as shown in Figure 1,Wherein the x in Fig. 1 and y represent respectively corresponding abscissa and ordinate, and R2Represent degree of fitting (thisA little explanations are suitable for following Fig. 2-Fig. 9 equally). As can be seen from Figure 1, the Ni-Co-W-Cu-B of gainedThe hydrogen-producing speed of cathode material be 0.4846mmol/h, and under equal conditions, suppress the product hydrogen of carbon plateSpeed is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 2
1, the cleaning of copper sheet substrate: be 0.25mm by thickness, long is 8cm, and wide is the copper of 2cmSheet is used sand papering surface, then uses deionized water rinsing, puts into 30～65% phosphorus after rinsing wellUltrasonic cleaning 30～60min in aqueous acid, then uses a large amount of deionized water rinsings, then puts intoUltrasonic cleaning 30～60min in ionized water, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickel nitrate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobalt nitrate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 40mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper sheetSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, be followed successively by 1.6V electro-deposition 45min, 2.0V electro-deposition 75min, 2.4V electro-deposition105min, 2.8V electro-deposition 6h, stops reaction, uses deionized water rinsing, after sample is taken outCan obtain the Ni-Co-W-Cu-B multicomponent cathode material of surface metal gloss, adopt inductance coupling highThe mass percentage content of plasma atomic emission spectrometry test composition, Ni is 30.2%, CoBe 7.1%, W is 58.2%, Cu is that 3.2%, B is 1.3%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO3For (its preparation of light anode materialWith reference to the people's such as fourth sky friend patent application 201010269960.x), anode illuminating area is 9cm2,Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), and the product hydrogen performance of platinized platinum under itself and equal conditions is compared. Produce hydrogen curve as shown in Figure 2,Its hydrogen-producing speed is 0.2125mmol/h, and the hydrogen-producing speed of suppressing carbon plate under equal conditions is0.086mmol/h, the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 3
1, the cleaning of copper sheet substrate: be 0.25mm by thickness, long is 8cm, and wide is the copper of 2cmSheet is used sand papering surface, then uses deionized water rinsing, puts into 30～65% phosphorus after rinsing wellUltrasonic cleaning 30～60min in aqueous acid, then uses a large amount of deionized water rinsings, then puts intoUltrasonic cleaning 30～60min in ionized water, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobaltous sulfate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 40mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper sheetSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, be followed successively by 1.6V electro-deposition 45min, 2.0V electro-deposition 75min, 2.4V electro-deposition105min, 2.8V electro-deposition 6h, stops reaction, uses deionized water rinsing, after sample is taken outCan obtain the Ni-Co-W-Cu-B multicomponent cathode material of surface metal gloss, adopt inductance coupling highThe mass percentage content of plasma atomic emission spectrometry test composition, Ni is 29.6%, CoBe 6.9%, W is 58.6%, Cu is that 3.7%, B is 1.2%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO3For (its preparation of light anode materialWith reference to the people's such as fourth sky friend patent application 201010269960.x), anode illuminating area is 9cm2，Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), and the product hydrogen performance of platinized platinum under itself and equal conditions is compared. Produce hydrogen curve as shown in Figure 3,Its hydrogen-producing speed is 0.2881mmol/h, and the hydrogen-producing speed of suppressing carbon plate under equal conditions is0.086mmol/h, the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 4
1, the cleaning of copper sheet substrate: be 0.25mm by thickness, long is 8cm, and wide is the copper of 2cmSheet is used sand papering surface, then uses deionized water rinsing, puts into 30～65% phosphorus after rinsing wellUltrasonic cleaning 30～60min in aqueous acid, then uses a large amount of deionized water rinsings, then puts intoUltrasonic cleaning 30～60min in ionized water, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobaltous sulfate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 30g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper sheetSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, then adopt the different voltage of many groups to carry out electro-deposition, be followed successively by 1.6V electro-deposition 45min,2.0V electro-deposition 75min, 2.4V electro-deposition 105min, 2.8V electro-deposition 6h, stops reaction,After being taken out, sample with deionized water rinsing, can obtain surface metal glossNi-Co-W-Cu-B multicomponent cathode material, adopts ICP-AESThe mass percentage content of test composition, Ni is 26.5%, Co is 7.3%, W is 60.7%,Cu is that 3.3%, B is 2.2%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO3For (its preparation of light anode materialWith reference to the people's such as fourth sky friend patent application 201010269960.x), anode illuminating area is 9cm2，Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), and the product hydrogen performance of platinized platinum under itself and equal conditions is compared. Produce hydrogen curve as shown in Figure 4,Its hydrogen-producing speed is that the hydrogen-producing speed of suppressing carbon plate under 0.3402mmol/h equal conditions is0.086mmol/h, the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 5
1, the cleaning of copper sheet substrate: be 0.25mm by thickness, long is 8cm, and wide is the copper of 2cmSheet is used sand papering surface, then uses deionized water rinsing, puts into 30～65% phosphorus after rinsing wellUltrasonic cleaning 30～60min in aqueous acid, then uses a large amount of deionized water rinsings, then puts intoUltrasonic cleaning 30～60min in ionized water, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobaltous sulfate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper sheetSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, then adopt the different voltage of many groups to carry out electro-deposition, be followed successively by 1.6V electro-deposition 45min,2.0V electro-deposition 75min, 2.4V electro-deposition 105min, 2.8V electro-deposition 6h, stops reaction,After being taken out, sample with deionized water rinsing, can obtain surface metal glossNi-Co-W-Cu-B multicomponent cathode material, adopts ICP-AESThe mass percentage content of test composition, Ni is 30.2%, Co is 6.6%, W is 58.6%,Cu is that 3.0%, B is 1.6%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO3For (its preparation of light anode materialWith reference to the people's such as fourth sky friend patent application 201010269960.x), anode illuminating area is 9cm2，Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), and the product hydrogen performance of platinized platinum under itself and equal conditions is compared. Produce hydrogen curve as shown in Figure 5,Its hydrogen-producing speed is 0.3116mmol/h, and the hydrogen-producing speed of suppressing carbon plate under equal conditions is0.086mmol/h, the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 6
1, the cleaning of copper sheet substrate: be 0.25mm by thickness, long is 8cm, and wide is the copper of 2cmSheet is used sand papering surface, then uses deionized water rinsing, puts into 30～65% phosphorus after rinsing wellUltrasonic cleaning 30～60min in aqueous acid, then uses a large amount of deionized water rinsings, then puts intoUltrasonic cleaning 30～60min in ionized water, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobaltous sulfate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 20mL, boric acid 2g, after solution dissolves completely, slowly adds 25g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper sheetSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, then adopt the different voltage of many groups to carry out electro-deposition, be followed successively by 1.6V electro-deposition 45min,2.0V electro-deposition 75min, 2.4V electro-deposition 105min, 2.8V electro-deposition 6h, stops reaction,After being taken out, sample with deionized water rinsing, can obtain surface metal glossNi-Co-W-Cu-B multicomponent cathode material, adopts ICP-AESThe mass percentage content of test composition, Ni is 29.6%, Co is 7.9%, W is 57.8%,Cu is that 2.8%, B is 1.9%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO3For (its preparation of light anode materialWith reference to the people's such as fourth sky friend patent application 201010269960.x), anode illuminating area is 9cm2，Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), and the product hydrogen performance of platinized platinum under itself and equal conditions is compared. Produce hydrogen curve as shown in Figure 6,Its hydrogen-producing speed is 0.2816mmol/h, and the hydrogen-producing speed of suppressing carbon plate under equal conditions is0.086mmol/h, the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 7
1, the cleaning of copper sheet substrate: be 0.25mm by thickness, long is 8cm, and wide is the copper of 2cmSheet is used sand papering surface, then uses deionized water rinsing, puts into 30～65% phosphorus after rinsing wellUltrasonic cleaning 30～60min in aqueous acid, then uses a large amount of deionized water rinsings, then puts intoUltrasonic cleaning 30～60min in ionized water, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobaltous sulfate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 80mL, boric acid 2g, after solution dissolves completely, slowly adds 20g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper sheetSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, then adopt the different voltage of many groups to carry out electro-deposition, be followed successively by 1.6V electro-deposition 45min,2.0V electro-deposition 75min, 2.4V electro-deposition 105min, 2.8V electro-deposition 6h, stops reaction,After being taken out, sample with deionized water rinsing, can obtain surface metal glossNi-Co-W-Cu-B multicomponent cathode material, adopts ICP-AESThe mass percentage content of test composition, Ni is 35.6%, Co is 9.2%, W is 50.8%,Cu is that 2.9%, B is 1.5%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: taking WO3 as (its preparation of light anode materialWith reference to the people's such as fourth sky friend patent application 201010269960.x), anode illuminating area is 9cm2,Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, in light intensity is100mW/cm2, bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent6820 type gas-chromatographies), and the product hydrogen performance of platinized platinum under itself and equal conditions is compared. Produce hydrogenAs shown in Figure 7, its hydrogen-producing speed is 0.2425mmol/h to curve, suppresses carbon plate under equal conditionsHydrogen-producing speed is 0.086mmol/h, and the hydrogen-producing speed of platinized platinum is 0.2248mmol/h.
Embodiment 8
1, the cleaning of copper mesh substrate: be 1.0mm by thickness, long is 8cm, and wide is the copper mesh of 2cmWith deionized water rinsing, after rinsing well, put into 30～65% phosphate aqueous solution ultrasonic cleaning30～60min, then uses a large amount of deionized water rinsings, then puts into deionized water for ultrasonic and cleans30～60min, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickelous sulfate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobaltous sulfate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium sulphate 14.2g, ammonium sulfate 26.4g, natrium citricum 89.3g,Ammoniacal liquor 20mL, boric acid 2g, after solution dissolves completely, slowly adds 20g sodium tungstate, stirs moltenSeparate, can obtain transparent blue solution after dissolving completely, and add deionized water and make overall solution volume be1000mL places stand-by.
3, the preparation of Ni-Co-W-Cu-B (device therefor: the CS of Wuhan Gastec Instrument Ltd.Electrochemical workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper meshSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, then adopt the different voltage of many groups to carry out electro-deposition, be followed successively by 1.8V electro-deposition 30min,2.2V electro-deposition 60min, 2.6V electro-deposition 90min, 3.0V electro-deposition 4h, stops reaction, willAfter taking out, sample with deionized water rinsing, can obtain the Ni-Co-W-Cu-B of surface metal glossMulticomponent cathode material, the quality that adopts ICP-AES test to formDegree, Ni is 33.7%, Co is 8.9%, W is 52.1%, Cu is that 3.9%, B is1.4％。
4, the hydrogen-producing speed of test Ni-Co-W-Cu-B: with WO3For (its preparation of light anode materialWith reference to the people's such as fourth sky friend patent application 201010269960.x), anode illuminating area is 9cm2，Ni-Co-W-Cu-B is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), produce hydrogen curve as shown in Figure 8, its hydrogen-producing speed is 0.4135mmol/h, under equal conditionsThe 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 example)
1, the cleaning of copper sheet substrate: be 0.25mm by thickness, long is 8cm, and wide is the copper of 2cmSheet is used sand papering surface, then uses deionized water rinsing, puts into 30～65% phosphorus after rinsing wellUltrasonic cleaning 30～60min in aqueous acid, then uses a large amount of deionized water rinsings, then puts intoUltrasonic cleaning 30～60min in ionized water, with a large amount of washed with de-ionized water, then for subsequent use after removing.
2, take nickel nitrate 30g and put into the beaker that fills 700mL deionized water, and stir, treatAfter dissolving completely, add 7.5g cobalt nitrate, stir, and then add Salzburg vitriol 3.2g, moltenAfter separating completely, add successively and dissolve sodium chloride 11.68g, ammonium chloride 10.7g, natrium citricum 89.3g,Ammoniacal liquor 40mL, after solution dissolves completely, slowly adds 25g sodium tungstate, and stirring and dissolving, dissolvesCompletely, can obtain transparent blue solution, and adding deionized water, to make overall solution volume be that 1000mL is putPut stand-by.
3, the preparation of Ni-Co-W-Cu (device therefor: the Wuhan CS of Gastec Instrument Ltd. electricityChem workstation)
Get the plating solution 450mL preparing and pour in 500mL beaker, by Ag/AgCl electrode, copper sheetSubstrate, platinized platinum are connected with reference electrode, auxiliary electrode, the working electrode of work station respectively, and insertIn plating solution, be followed successively by 1.6V electro-deposition 45min, 2.0V electro-deposition 75min, 2.4V electro-deposition105min, 2.8V electro-deposition 6h, stops reaction, uses deionized water rinsing, after sample is taken outCan obtain the Ni-Co-W-Cu multicomponent cathode material of surface metal gloss, adopt inductance coupling high etc.The mass percentage content of gas ions atomic emission spectrometry test composition, Ni is 29.6%, Co is7.8%, W is 59.1%, Cu is 3.5%.
4, the hydrogen-producing speed of test Ni-Co-W-Cu: with WO3For light anode material, (it prepares ginsengExamine the people's such as Ding Tianpeng application for a patent for invention 201010269960.x), anode illuminating area is 9cm2，Ni-Co-W-Cu is cathode material, and electrolyte is 0.5M dilute sulfuric acid, is 100mW/cm in light intensity2，Bias-voltage is under 1.2V condition, to test its Hydrogen Evolution Performance (device therefor is Agilent 6820 type gas phase looksSpectrum), and the product hydrogen performance of the Ni-Co-W-Cu-B of itself and embodiment 2 is compared. Produce hydrogen curveAs shown in Figure 9, its hydrogen-producing speed is 0.1716mmol/h, embodiment 2 under equal conditionsThe hydrogen-producing speed of Ni-Co-W-Cu-B is 0.2125mmol/h. This explanation is of the present invention novelNi-Co-W-Cu-B cathode material has better hydrogen-producing speed, is more suitable in decomposing at photoelectrocatalysisIn water hydrogen manufacturing system, apply.
Industrial applicability
The present invention Ni-Co-W-Cu-B multi-component material be particularly suitable for decomposing at photoelectrocatalysisIn water hydrogen manufacturing system, apply.
Claims (10)
1. a Ni-Co-W-Cu-B multicomponent cathode material, comprises substrate and is formed in substrateNi-Co-W-Cu-B alloy layer, the wherein gross mass meter based on described alloy layer, Ni is 26.5Quality %～36.6 quality %, Co are that 6.6 quality %～9.2 quality %, W are 50.8 quality %～60.7Quality %, Cu are 2.3～4.6 quality %, and B is 0.8～2.4 quality %.
2. Ni-Co-W-Cu-B multicomponent cathode material according to claim 1, wherein saidSubstrate is copper sheet or copper mesh.
3. one kind for the preparation of Ni-Co-W-Cu-B multicomponent cathode material claimed in claim 1Method, described method comprises the steps:
Provide the metal that is adapted at using in photoelectrocatalysis hydrogen production by water decomposition as substrate;
The plating solution being suitable in the enterprising electroplating of described substrate deposition is provided, described plating solution contain Ni,Co, W, Cu and B, and the gross mass of Ni, Co, W, Cu and B based in plating solution, Ni is26.5 quality %～36.6 quality %, Co are that 6.6 quality %～9.2 quality %, W are 50.8 quality%～60.7 quality %, Cu are 2.3～4.6 quality %, and B is 0.8～2.4 quality %;
Described substrate is placed in to described electroplate liquid and electroplates, can obtain Ni-Co-W-Cu-B manyComponent 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 at least two groups notWith carrying out at least twice plating under voltage.
6. preparation method according to claim 5, wherein said plating comprises: exist successively1.4-1.8V electro-deposition 30-60min, at 1.8-2.2V electro-deposition 60-90min, at 2.2-2.6V electricityDeposition 90-120min and at 2.6-3.0V electro-deposition 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 to cobalt salt after dissolving, stirs, then add mantoquita,After dissolving completely, add successively the first sodium salt, ammonium salt, the second sodium salt, ammoniacal liquor and boron-containing compound are alsoAnd they are dissolved, then slowly add Tungstenic compound, then stirring and dissolving.
8. preparation method according to claim 7, wherein said the second sodium salt is natrium citricum.
9. preparation method according to claim 7, wherein said the first sodium salt, nickel salt, cobaltSalt and mantoquita are the corresponding salt that can be dissolved in deionized water.
10. a Ni-Co-W-Cu-B multicomponent cathode material according to claim 1 and 2Or the Ni-Co-W-Cu-B multicomponent negative electrode of being prepared by the method described in any one in claim 3-8The purposes of material aspect photoelectrocatalysis hydrogen production by water decomposition.
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