阅读说明：本技术 一种wp-氢氧化镍反蛋白石复合微纳结构的电催化电极及其制备方法和析氢应用 (A kind of electro catalytic electrode of WP- nickel hydroxide counter opal composite micro-nano structure and preparation method thereof and liberation of hydrogen application ) 是由 孙志鹏 方路峻 张海峰 余锦超 吴方丹 史晓艳 邵涟漪 于 2019-08-05 设计创作，主要内容包括：本发明属于清洁能源材料技术领域,公开了一种WP-Ni(OH)<Sub>2</Sub>反蛋白石复合微纳结构的电催化电极及其制备方法和析氢应用。所述电催化电极是将预处理的基底垂直放入聚苯乙烯微球悬乳液中,在70～75℃恒温干燥,聚苯乙烯微球在基底表面形成多层模板；将该模板在90～100℃干燥后,浸泡在WO<Sub>3</Sub>前驱体溶液中,升温至500～550℃保温,得到WO<Sub>3</Sub>反蛋白石；在氩气下,升至600～800℃进行磷化,得到WP反蛋白石；将WP反蛋白石放入硫酸镍溶液中,加入过硫酸钾溶液和碱溶液中反应,在WP反蛋白石表面制备Ni(OH)<Sub>2</Sub>层制得。本发明方法简单,反蛋白石复合光子晶体结构在电催化析氢方面有广泛的应用潜力。(The invention belongs to clean energy resource field of material technology, disclose a kind of WP-Ni (OH) 2 Electro catalytic electrode of counter opal composite micro-nano structure and preparation method thereof and liberation of hydrogen application.The electro catalytic electrode is that pretreated substrate is vertically put into polystyrene microsphere suspended emulsion, and in 70~75 DEG C of freeze-day with constant temperature, polystyrene microsphere forms multilayer template in substrate surface；By the template after 90~100 DEG C dry, it is immersed in WO 3 In precursor solution, 500~550 DEG C of heat preservations are warming up to, WO is obtained 3 Counter opal；Under argon gas, 600~800 DEG C of progress phosphatizations are risen to, WP counter opal is obtained；WP counter opal is put into nickel sulfate solution, is added in potassium persulfate solution and aqueous slkali and reacts, prepares Ni (OH) on WP counter opal surface 2 Layer is made.The method of the present invention is simple, and counter opal composite photonic crystal structure is widely used potentiality in terms of electrocatalytic hydrogen evolution.)

1. a kind of electro catalytic electrode of WP- nickel hydroxide counter opal composite micro-nano structure, which is characterized in that the electro-catalysis electricity Pole is that the substrate for handling sulfuric acid and hydrogen peroxide mixed solution is vertically put into polystyrene microsphere suspended emulsion, in 70~75 DEG C of perseverances Temperature is dry, and polystyrene microsphere forms the multilayer template of close ordered arrangement in substrate surface；Multilayer template is taken out 90~ After 100 DEG C of dryings, which is immersed in WO₃It in precursor solution, is air-dried, is warming up to 500~550 DEG C of heat preservations, it is natural It is down to room temperature, obtains WO₃Counter opal；Then in argon atmosphere, 600~800 DEG C of heat preservations are warming up to, to WO₃Counter opal into Row phosphatization, is down to room temperature, obtains WP counter opal；WP counter opal is put into nickel sulfate solution, was added under stirring condition It is reacted in potassium sulfate solution and aqueous slkali, after washed and dry, prepares Ni (OH) on WP counter opal surface₂Layer is made.

2. WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 1, feature exist In the partial size of polystyrene microsphere is 400~500nm in the polystyrene microsphere suspended emulsion, and the polystyrene microsphere is outstanding The volume ratio of polystyrene microsphere and water is 1:(25~50 in lotion).

3. WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 1, feature exist In the volume ratio of the sulfuric acid and hydrogen peroxide is (3~4): (1~2).

4. WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 1, feature exist In the substrate is Ti piece, stainless steel substrates, FTO, quartz or silicon wafer.

5. WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 1, feature exist In the WO₃The concentration of precursor solution is 0.1~0.2mol/L.

6. WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 1, feature exist In the volume ratio of the quality and deionized water of nickel sulfate is (0.3~0.5) g:2ml in the nickel sulfate solution；The persulfuric acid The volume ratio of the quality and deionized water of potassium peroxydisulfate is (0.4~0.5) g:10ml in potassium solution；The nickel sulfate solution, mistake The volume ratio of potassium sulfate solution and aqueous slkali is 1:1:(0.15~0.25)；The aqueous slkali is ammonium hydroxide, sodium hydroxide or hydrogen-oxygen Change one or more of potassium.

7. WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 1-6 Preparation method, which is characterized in that comprise the following specific steps that:

S1. polystyrene microsphere is diluted with water, is ultrasonically treated, obtains uniform and stable suspended emulsion；By substrate be put into sulfuric acid and Hydrophilic treated is carried out in hydrogen peroxide mixed solution, is finally rinsed with deionized water, is dried with nitrogen；

S2. substrate is vertically put into polystyrene microsphere suspended emulsion, in 70~75 DEG C of freeze-day with constant temperature I, polystyrene microsphere with The form of self assembly forms the multilayer template of close ordered arrangement in substrate surface；Multilayer template is taken out, it is dry at 90~100 DEG C After dry, which is immersed in WO₃In precursor solution, it is air-dried II, 500~550 DEG C of heat preservations is warming up to, naturally rings to room Temperature obtains WO₃Counter opal；

S3. in argon atmosphere, 600~800 DEG C of heat preservations are warming up to, to WO₃Counter opal carries out phosphatization, naturally rings to room temperature, obtains To WP counter opal；

S4. the WP counter opal is put into nickel sulfate solution, potassium persulfate solution and aqueous slkali is added simultaneously while stirring Reaction, taking-up are rinsed with deionized water, drying at room temperature, prepare layer of Ni (OH) on WP counter opal surface₂, obtain WP-Ni (OH)₂The electro catalytic electrode of counter opal composite nanostructure.

8. the preparation method of WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 7, It is characterized in that, power ultrasonic described in step S1 is 20~25kHz, the time of the ultrasound is 20~30min.

9. the preparation method of WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode according to claim 7, It is characterized in that, dry I time described in step S2 is 10~12h；The time of the drying II is 3~5h；The heating Rate be 1~2 DEG C/min, time of the heat preservation is 3~5h；The rate of heating described in step S3 is 3~5 DEG C/min, The time of the heat preservation is 3~5h；The time of the reaction is 2~4min.

10. WP- nickel hydroxide counter opal composite micro-nano structure electro catalytic electrode described in any one of claims 1-6 is urged in electricity Change the application in evolving hydrogen reaction field.

Technical field

The invention belongs to clean energy resource field of material technology, more particularly, to a kind of WP- nickel hydroxide (Ni (OH)₂) Electro catalytic electrode of counter opal composite micro-nano structure and preparation method thereof and liberation of hydrogen application.

Background technique

Environmental pollution and energy crisis force people to develop the sustainable Hydrogen Energy (H of green₂) substitute conventional fossil fuel. In various H₂In production method, water is decomposed compared to photocatalysis and photoelectrocatalysis, electrolysis water has shown higher efficiency, Higher production purity (H₂) and lower carbon emission ratio.In H₂In O electrolysis system, determine whole device performance it is crucial because Element includes evolving hydrogen reaction (HER) and oxygen evolution reaction (OER) catalyst.Traditional noble metal catalyst, such as platinum, ruthenium, palladium, can have Effect ground improves its catalytic activity, however, the scarcity of these noble metals and high cost limit their application.In order to overcome this One problem, people have put into a large amount of energy in terms of developing base metal transition metal elctro-catalyst, such as carbide, vulcanization Object, boride, nitride etc..As alternative HER catalyst, the optimization of the elctro-catalyst of these earth rich reserves is set Meter and synthesis allow them to generate big cathode current under low overpotential.

Especially tungsten phosphide (WP₂And WP) have many advantages, such as that catalytic activity is high, overpotential is low, conductivity is high, in recent years at For the elctro-catalyst of great development prospect, although these WP nanostructures show excellent performance characteristics, they are only in acid Property medium in there is catalytic activity, typically, since the high-energy potential barrier caused by delay of response in alkaline medium, make its Overpotential with higher in alkaline solution, HER are generally divided into the progress of two steps: hydrogen intermediate is initially formed (H_abs,Volmer Step), and the H then generated₂(Heyrovsky and Tafel step).But in acidity (H₃O⁺) and alkalinity (H₂O/OH^-) be situated between In matter, Heyrovsky and Volmer step has different reactive species, and activation of most of catalyst in alkaline medium Dissociation steps are usually more much slower than in acid medium.The OH formed due to surface^-There is very strong absorption in alkaline solution The hydrolytic dissociation energy barrier of effect, the activation of WP marginal position becomes very high, and it is dynamic (dynamical) slow to result in HER.Therefore, it is urged in WP base Can promote the dissociation process of water in agent with good hydroxyl is vital to HER efficiency is improved.In recent years, interface engineering It is considered as the raising active effective way of elctro-catalyst alkalinity HER, in particular, recent research result indicate that, nickel hydroxide [Ni(OH)₂] by promote water dissociation, avoid hydroxyl from being adsorbed on its elctro-catalyst surface, to improve its in alkaline solution HER efficiency have synergistic effect.

Summary of the invention

In order to solve above-mentioned the shortcomings of the prior art and disadvantage, primary and foremost purpose of the present invention is to provide a kind of WP-Ni (OH)₂Counter opal composite micro-nano structure electro catalytic electrode.The composite micro-nano structure electro catalytic electrode have bigger serface and High conductivity.

Another object of the present invention is to provide above-mentioned WP-Ni (OH)₂Counter opal composite micro-nano structure electro catalytic electrode Preparation method.This method is suitable for preparing the counter opal structure of different pore size size, this method short preparation period, technique letter It is single.

A further object of the present invention is to provide above-mentioned WP-Ni (OH)₂Counter opal composite micro-nano structure electro catalytic electrode Application.

The purpose of the present invention is realized by following technical proposals:

A kind of WP-Ni (OH)₂The electro catalytic electrode of counter opal composite micro-nano structure, the electro catalytic electrode are by sulfuric acid It is vertically put into polystyrene microsphere suspended emulsion with the substrate of hydrogen peroxide mixed solution processing, in 70~75 DEG C of freeze-day with constant temperature, gathers Phenylethylene micro ball forms the multilayer template of close ordered arrangement in substrate surface；Multilayer template is taken out in 90~100 DEG C of dryings Afterwards, which is immersed in WO₃It in precursor solution, is air-dried, is warming up to 500~550 DEG C of heat preservations, is down to room temperature naturally, Obtain WO₃Counter opal；Then in argon atmosphere, 600~800 DEG C of heat preservations are warming up to, to WO₃Counter opal carries out phosphatization, drop To room temperature, WP counter opal is obtained；WP counter opal is put into nickel sulfate solution, potassium persulfate solution is added under stirring condition It is reacted in aqueous slkali, after washed and dry, prepares Ni (OH) on WP counter opal surface₂Layer is made.

Preferably, the partial size of polystyrene microsphere is 400~500nm in the polystyrene microsphere suspended emulsion, described poly- The volume ratio of polystyrene microsphere and water is 1:(25~50 in phenylethylene micro ball suspended emulsion).

Preferably, the volume ratio of the sulfuric acid and hydrogen peroxide is (3~4): (1~2).

Preferably, the substrate is Ti piece, stainless steel substrates, FTO, quartz or silicon wafer.

Preferably, the WO₃The concentration of precursor solution is 0.1~0.2mol/L.

Preferably, the volume ratio of the quality and deionized water of nickel sulfate is (0.3~0.5) g in the nickel sulfate solution: 2ml；The volume ratio of the quality and deionized water of potassium peroxydisulfate is (0.4~0.5) g:10ml in the potassium persulfate solution；It is described The volume ratio of nickel sulfate solution, potassium persulfate solution and aqueous slkali is 1:1:(0.15~0.25)；The aqueous slkali is ammonium hydroxide, hydrogen One or more of sodium oxide molybdena or potassium hydroxide.

The WP-Ni (OH)₂The preparation method of counter opal composite micro-nano structure electro catalytic electrode, including it is following specific Step:

S1. polystyrene microsphere is diluted with water, is ultrasonically treated, obtains uniform and stable suspended emulsion；Substrate is put into sulphur Hydrophilic treated is carried out in acid and hydrogen peroxide mixed solution, is finally rinsed, is dried with nitrogen with deionized water；

S2. substrate is vertically put into polystyrene microsphere suspended emulsion, in 70~75 DEG C of freeze-day with constant temperature I, polystyrene is micro- Ball forms the multilayer template of close ordered arrangement in the form of self assembly in substrate surface；Multilayer template is taken out, 90~100 After DEG C dry, which is immersed in WO₃In precursor solution, it is air-dried II, is warming up to 500~550 DEG C of heat preservations, is dropped naturally To room temperature, WO is obtained₃Counter opal；

S3. in argon atmosphere, 600~800 DEG C of heat preservations are warming up to, to WO₃Counter opal carries out phosphatization, naturally rings to room Temperature obtains WP counter opal；

S4. the WP counter opal is put into nickel sulfate solution, potassium persulfate solution and alkali is added simultaneously while stirring Solution reaction, taking-up are rinsed with deionized water, drying at room temperature, prepare layer of Ni (OH) on WP counter opal surface₂, obtain WP- Ni(OH)₂The electro catalytic electrode of counter opal composite nanostructure.

Preferably, power ultrasonic described in step S1 is 20~25kHz, and the time of the ultrasound is 20~30min.

Preferably, dry I time described in step S2 is 10~12h；The time of the drying II is 3~5h；It is described The rate of heating is 1~2 DEG C/min, and the time of the heat preservation is 3~5h；The rate of heating described in step S3 be 3~5 DEG C/ Min, the time of the heat preservation are 3~5h；The time of the reaction is 2~4min.

The WP-Ni (OH)₂Counter opal composite micro-nano structure electro catalytic electrode is in electrocatalytic hydrogen evolution reaction field Application.

The present invention is for the first time by WP counter opal and Ni (OH)₂In conjunction with due to the heterogeneous counter opal knot of the hydridization of unique structure Structure, it is intended that Ni (OH)₂Edge be capable of providing catalytic site, by water-splitting be H_ads, then H_adsAdsorb nigh WP Hydrogen molecule is generated on active site.We have synthesized WP counter opal in titanium sheet and then have coated layer of Ni (OH)₂, as one kind Novel composite nanostructure HER catalyst.The WP-Ni (OH) that we prepare₂Heterogeneous counter opal catalyst can expose more Active site, to promote the diffusion of electrolyte and gas.The combination of these effects results in it and opens up in alkaline medium Reveal the enhancing of catalytic activity, lower overpotential and excellent stability.The present invention is preparation interface hetero-junctions catalysis Agent improves its catalytic activity under the conditions of wide pH value and provides a kind of effective strategy.

The present invention can use electrochemical vapour deposition (EVD) technology and provide one layer of phosphate coating on counter opal surface.Electrochemistry gas Phase deposition technique has preferable control ability to the deposition uniformity of film.Activation of most of catalyst in alkaline medium Dissociation steps are usually more much slower than in acid medium.The OH formed due to surface^-There is very strong absorption in alkaline solution The hydrolytic dissociation energy barrier of effect, the activation of WP marginal position becomes very high, and it is dynamic (dynamical) slow to result in HER.Nearest research knot Fruit shows nickel hydroxide [Ni (OH)₂] by promoting the dissociation of water, avoid hydroxyl from being adsorbed on its elctro-catalyst surface, to mentioning Its high HER efficiency in alkaline solution has synergistic effect.

Synthetic route of the invention is that multilayer polystyrene microsphere template is prepared first with vertical deposition method, then in microballoon Gap is filled with presoma, and WO is prepared after calcining₃Counter opal, then to WO₃Counter opal carries out phosphatization, height in argon gas After temperature processing, by WO₃It is converted to WP, finally prepares layer of Ni (OH) on WP counter opal surface₂, obtain WP-Ni (OH)₂Anti- egg White stone composite micro-nano structure.Based on WP I/O fabric, a kind of elctro-catalyst of non precious metal has been synthesized in alkali.The invention Layout strategy are as follows: (1) I/O fabric of continuous conduction provides not only direct, quick electron transport route, and is electrification It learns reaction and provides more active sites, be conducive to the release of gas.(2)Ni(OH)₂By promoting the dissociation of water, hydrogen is avoided Oxygen root is adsorbed on its elctro-catalyst surface, has synergistic effect to its HER efficiency in alkaline solution is improved.

Compared with prior art, the invention has the following advantages:

1. WP counter opal of the invention has bigger serface and high conductivity, it is possible to provide quick direct electron-transport Path.

2. WP-Ni (OH) of the invention₂Counter opal composite micro-nano structure electro catalytic electrode has excellent Hydrogen Evolution Performance And outstanding stability, this is because the I/O fabric of continuous conduction provides not only direct, quick electron transport route, and And more active sites are provided for electrochemical reaction, be conducive to the release of gas.

3. the counter opal structure of method of the invention suitable for preparing different pore size size, this method short preparation period, Simple process.

4. the pore size of counter opal structure prepared by the present invention can by select polystyrene microsphere size come The type of accurate control, counter opal skin-material can be realized by selecting different electro-deposition presomas, in anti-albumen The selection of the resulting material in stone structure surface layer and structure is also than wide.

Detailed description of the invention

Fig. 1 is that (a) is three-dimensional WP counter opal in embodiment 1, (c) is WP-Ni (OH)₂Counter opal structure surface scan Electron microscopic picture (b) is three-dimensional WP counter opal, (d) is WP-Ni (OH)₂Counter opal structure cross-sectional scans electron microscopic picture.

Fig. 2 is WP-Ni (OH) in embodiment 1₂Counter opal, WO₃Counter opal, WP counter opal and business platinum carbon electrode The electrochemical property test in 1M KOH solution.

Specific embodiment

The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention. Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.