CN102544431A - Composition slurry and method for preparing photoelectric catalytic tungsten trioxide thin film electrode - Google Patents
Composition slurry and method for preparing photoelectric catalytic tungsten trioxide thin film electrode Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 9
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title abstract description 24
- 239000002002 slurry Substances 0.000 title abstract description 20
- 239000010409 thin film Substances 0.000 title abstract description 10
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
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- 238000001035 drying Methods 0.000 claims abstract description 6
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- 239000012528 membrane Substances 0.000 claims description 46
- 239000011230 binding agent Substances 0.000 claims description 30
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052721 tungsten Inorganic materials 0.000 claims description 25
- 239000010937 tungsten Substances 0.000 claims description 25
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 12
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- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 claims description 8
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000126 substance Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention provides a composition slurry and a method for preparing a photoelectric catalytic tungsten trioxide thin film electrode. According to 100% of total mass of the composition slurry, the composition slurry comprises the following components in percentage by mass: 20-60% of tungsten trioxide, 1-10% of adhesive, and the balance of solvent and unavoidable impurity. The method comprises the steps of: preparing the composition slurry for preparing the photoelectric catalytic tungsten trioxide thin film electrode; coating the composition slurry for preparing the photoelectric catalytic tungsten trioxide thin film electrode on a clean conductive substrate to form a film; and drying the film, and placing the film in a vacuum oven for vacuumizing and drying . The invention provides the simple method for preparing the tungsten trioxide thin film electrode without using high-temperature calcining.
Description
Technical field
The present invention relates to a kind of combination pulp and method that is used to prepare WO 3 film, more specifically, relate to the combination pulp and the method that are used to prepare photoelectrocatalysis WO 3 film electrode.
Background technology
In the global situation of greenhouse effect that go from bad to worse and environmental pollution, utilize the abundant solar energy photocatalytic hydrogen manufacturing of nature as one of new forms of energy approach of sustainable development, receive showing great attention to of international community just day by day.Solar energy electrochemical cell hydrogen producing technology is based on solar energy and water, and these two kinds of materials all are reproducible, and this technology does not have byproduct; And can on the two poles of the earth, obtain hydrogen and oxygen respectively, can not bring pollution, show powerful advantage and development potentiality to environment; Both can small-scale application; Again can large-scale development, be directly to utilize the most attractive hydrogen manufacturing approach of solar hydrogen making, but its present efficient is also lower.The performance of forming the semi-conducting material of optoelectronic pole has determined the efficient of its photoelectricity hydrogen manufacturing, and therefore the semi-conducting material of low energy gap of exploitation and high corrosion resistance is present research emphasis.
Tungstic acid is compared with traditional titanium dioxide, zinc oxide semiconductor material, has narrower energy gap and lower price, and chemical property is stable, is not easy to corrode, and is a kind of good Application of Solar Energy semi-conducting material.WO 3 film preparation method commonly used at present has atomic layer deposition method, chemical vapour deposition technique, electrodeposition process and sol-gal process.Usually all comprise the process of carrying out high-temperature calcination (that is sintering) behind the plated film in these methods.Yet, need high-temperature calcination behind the plated film, cause the energy consumption of production technology higher, and high-temperature calcination process organic substance decompose and cause CO2 emission, unfriendly to environment.
For example, one Chinese patent application CN200910311691.6 discloses a kind of preparation method of nano tungsten trioxide thin film, particularly relates to a kind of preparation method of nano tungsten trioxide thin film of the semiconductor optical anode that is used for photocatalysis or photoelectrochemistrpool pool.It at first with water-soluble poly tungstates dissolving, adds dispersant and modifier and makes precursor liquid, adopts dip-coating method or spin-coating method to carry out plated film at substrate surface, and high-temperature calcination in air subsequently obtains nano tungsten trioxide thin film.The filming technology of this patent application is complicated, and the system film cycle is longer, and needs high-temperature calcination behind the plated film, and energy consumption is higher, and it is more that precursor liquid adds organic substance, and the decomposition of high-temperature calcination process organic substance causes CO2 emission.
In the prior art of preparation WO 3 film electrode, high-temperature calcination can probably be divided into two kinds of situation at present: a kind of is the reaction that need accomplish a kind of heating and decomposition after the presoma of tungsten is filmed through sintering.For example: ammonium tungstate is heated to uniform temperature can decompose generation tungstic acid and ammonia.Like this, original coating surplus tungstic acid only just in the substrate.Wherein the release of ammonia makes film internal layer generate the space.A kind ofly in addition be to use tungsten trioxide powder and other binding agent or pore creating material to be mixed and made into slurry to film.The method need be accomplished the removal of pore creating material or binding agent through sintering.These pore creating materials or binding agent generation carbon dioxide and water are discharged in the air behind the sintering, have stayed the tungstic acid rete with pore space structure.The loose structure that high temperature sintering forms can increase the specific area of film, makes it can absorb more light, thereby photoelectric current is increased to some extent.
But because there is above-mentioned shortcoming in high temperature sintering, therefore expectation can have a kind of preparation method that can not use the easier WO 3 film electrode of high-temperature calcination.
Summary of the invention
Therefore, the present inventor has carried out deep research, and purpose is to seek a kind ofly can not use the sintering process of high-temperature calcination and don't sacrifice the preparation method of the WO 3 film electrode of its photoelectric properties.
For this reason, the invention provides following several aspect.
< 1>a kind of combination pulp that is used to prepare the photoelectrocatalysis membrane electrode; Gross mass based on said combination pulp is 100%; Said combination pulp comprises the tungstic acid of 20～60 quality %, the binding agent of 1～10 quality %, and balance solvent and unavoidable impurities.
< 2>according to < 1>described combination pulp that is used to prepare the photoelectrocatalysis membrane electrode, the amount of said binding agent is preferably 1～8 quality %, 2～6 quality % more preferably, and most preferably be 2.5～5 quality %.
< 3>according to < 1>or < 2>described combination pulp that is used to prepare the photoelectrocatalysis membrane electrode, said binding agent is to be selected from least a in polyvinylidene fluoride, ethyl cellulose, polytetrafluoroethylene and the CMC.
< 4>according to < 1>or < 2>described composition that is used to prepare the photoelectrocatalysis membrane electrode, said solvent is n-formyl sarcolysine base pyrrolidones, ethanol or deionized water.
< 5>a kind of method that is used to prepare the photoelectrocatalysis membrane electrode, said method comprises the steps:
The first step; Configuration < 1>described combination pulp that is used to prepare the photoelectrocatalysis membrane electrode; That is, the binding agent of 1～10 quality % is scattered in the solvent of 35～75 quality %, the tungstic acid with 20～60 quality % adds wherein again; And stir or be ground to evenly, obtain the said combination pulp that is used to prepare the photoelectrocatalysis membrane electrode;
In second step, the above-mentioned combination pulp that is used to prepare the photoelectrocatalysis membrane electrode that obtains is coated on the conductive substrates of cleaning to form film; And
In the 3rd step, the film oven dry with gained places vacuum drying oven to vacuumize after the drying then, obtains photoelectrocatalysis WO 3 film electrode.
< 6>according to < 5>described method that is used to prepare the photoelectrocatalysis membrane electrode, said the 3rd step is through after 1～12 hour, again it being inserted vacuum drying chamber 60～150 ℃ of oven dry, vacuumizes at 80～160 ℃ and carries out in dry 1～24 hour.
< 7>according to < 5>described method that is used to prepare the photoelectrocatalysis membrane electrode, the use amount of said binding agent is preferably 1～8 quality %, 2～6 quality % more preferably, and most preferably be 2.5～5 quality %.
< 8>according to < 5>described method that is used to prepare the photoelectrocatalysis membrane electrode, said binding agent is to be selected from least a in polyvinylidene fluoride, ethyl cellulose, polytetrafluoroethylene and the CMC.
< 9>according to < 5>described method that is used to prepare the photoelectrocatalysis membrane electrode, said solvent is n-formyl sarcolysine base pyrrolidones, ethanol or deionized water.
< 10>according to < 5>described method that is used to prepare the photoelectrocatalysis membrane electrode, said substrate is to be selected from a kind of in electro-conductive glass FTO, tungsten sheet, metal aluminium flake and the tungstic acid sintered electrode.
< 11>according to < 5>described method that is used to prepare the photoelectrocatalysis membrane electrode, stirring or grinding in the said first step comprise: stirred 1～24 hour or ground 10 minutes～2 hours.
< 12 >. according to < 5>or < 6>the described method that is used to prepare the photoelectrocatalysis membrane electrode, the vacuum degree in the described vacuum drying oven reaches-below the 0.1MPa.
Because prior art has the filming technology complicacy, system film cycle length and system film need high-temperature calcination, the shortcoming that energy consumption is high; Dry method had prepared tungstic acid photoelectrocatalysis membrane electrode after technology of the present invention had adopted tungstic acid, binding agent and organic solvent or other solvent slurry coating conductive substrates; This method need not high temperature sintering, has reduced cost and energy consumption, has simplified filming technology; Shorten the system film cycle, reached catalytic effect preferably.
Description of drawings
Fig. 1 is scanning electron microscopy (SEM) photo of the WO 3 film of preparation in accordance with the present invention acquisition;
Fig. 2 is the electron scanning micrograph according to the WO 3 film of preparation method's acquisition of contrast patent application 201010269963.3;
Fig. 3 is respectively the I-V test curve of an instance of method produced according to the present invention WO 3 film electrode that obtains and the WO 3 film electrode that obtains according to comparative example;
Fig. 4 is respectively the I-V test curve of another instance of method produced according to the present invention WO 3 film electrode that obtains and the WO 3 film electrode that obtains according to comparative example;
Fig. 5 is respectively the I-V test curve of another instance again the WO 3 film electrode that obtains and the WO 3 film electrode that obtains according to comparative example of method produced according to the present invention;
Fig. 6 is respectively the I-V test curve of another instance again the WO 3 film electrode that obtains and the WO 3 film electrode that obtains according to comparative example of method produced according to the present invention; And
Fig. 7 is respectively the I-V test curve of another instance again the WO 3 film electrode that obtains and the WO 3 film electrode that obtains according to comparative example of method produced according to the present invention.
Embodiment
Usually the problem that needs high temperature sintering when preparing the WO 3 film electrode in the prior art in order to solve; The inventor has found a kind of combination pulp that can be used for preparing photoelectrocatalysis WO 3 film electrode; And adopt in the process of this pulp preparation WO 3 film electrode and need not carry out sintering process, and obtained suitable with prior art even better photoelectric properties.
This combination pulp that is used to prepare photoelectrocatalysis WO 3 film electrode of the present invention generally includes: the tungstic acid of 20～60 quality %; The binding agent of 1～10 quality %; And balance solvent and unavoidable impurities, gross mass that said these mass ratioes all are based on said combination pulp is 100%.
In the present invention, employed binding agent mainly is the reagent that can play the effect on the conductive substrates that WO 3 film is adhered to, and condition is that the use of this reagent does not influence the conductivity between conductive substrates and the WO 3 film.Can be such as said binding agent for being selected from least a in polyvinylidene fluoride, ethyl cellulose, polytetrafluoroethylene and the CMC.And the use amount of binding agent can not be too big, because then possibly influence the conductivity between conductive substrates and the WO 3 film too greatly, and possibly influence bond effect very little.Therefore, on the basis of inventor's test of many times, draw the binding agent that can use 1～10 quality %.Preferably use the binding agent of 1～8 quality %, more preferably use the binding agent of 2～6 quality %, most preferably use the binding agent of 2.5～5 quality %.
The solvent that uses among the present invention such as adopting under the situation of polyvinylidene fluoride as binding agent, can use n-formyl sarcolysine base pyrrolidones or ethanol for disperseing the solvent of employed binding agent and tungstic acid.Such as, using under the situation of polytetrafluoroethylene as binding agent, can use deionized water.The use amount of said solvent need satisfy and can under the situation that stirs or grind, said binding agent and tungstic acid be prepared into uniform slurry, is beneficial to form the level and smooth relatively film in surface.Normally, be 100% by the gross mass of paste compound, the use amount of said solvent can be 35～75 quality %, is preferably 40～70 quality %, more preferably 45～65 quality % most preferably are 50～60 quality %.
In the present invention; The preparation process of the said combination pulp that is used for preparing photoelectrocatalysis WO 3 film electrode is following: the solvent that the binding agent of 1～10 quality % is scattered in 35～75 quality %; Tungstic acid with 20～60 quality % adds wherein again, and stirs 1～24 hour or ground 10 minutes～2 hours to form uniform slurry.The preparation process of slurry is simple, and does not relate to complex apparatus.
In addition, the present invention provides a kind of method that is used to prepare the photoelectrocatalysis membrane electrode, and said method comprises: the combination pulp that is used to prepare photoelectrocatalysis WO 3 film electrode of above-mentioned preparation is applied on the conductive substrates of cleaning to form film; With the film oven dry of gained, it is inserted vacuumize drying in the vacuum drying chamber again, particularly; For example 60～150 ℃ the oven dry 1～12 hour after; Again it is inserted vacuum drying chamber, after 80～160 ℃ vacuumize dry 1～24 hour, obtain photoelectrocatalysis WO 3 film electrode.In the present invention, it is inserted vacuumize dry purpose in the vacuum drying chamber when being to play desciccator diaphragm again, also play the effective adhesive that has that impels film and conductive substrates.Therefore, normally, vacuum degree is reached be approximately equal to or less than-0.1MPa.
In this article, said conductive substrates has no particular limits, and normally used in the art conductive substrates all can be used.Especially, in this article, said conductive substrates can comprise electro-conductive glass (FTO), tungsten sheet, metal aluminium flake and the tungstic acid sintering basal electrode for preparing in preceding one Chinese patent application 200910157787.1 disclosed methods according to the applicant.Wherein the conductivity of FTO is than the poorly conductive of tungsten; And used in the present invention according to the applicant under the situation of tungstic acid sintering basal electrode as substrate of the disclosed methods preparation of preceding one Chinese patent application 200910157787.1; Being actually with tungsten is the substrate conduction, so conductivity is suitable with the tungsten substrate.In addition, the conductivity of metallic aluminium is also close with tungsten.
Electro-conductive glass (FTO) promptly is the fin oxide condutire glass that fluorine mixes.
The preparation process that the concrete preparation process of above-mentioned tungstic acid sintering basal electrode as conductive substrates is put down in writing in can the embodiment 2 referring to the application.
The method that is used to prepare the photoelectrocatalysis membrane electrode of the present invention comprises also that with said conductive substrates with absolute ethyl alcohol, deionized water respectively after the ultrasonic cleaning, for example ultrasonic cleaning dried up subsequent use after 10 minutes with nitrogen.Such cleaning helps improving the bonding of conductive substrates and WO 3 film.
The thickness of the formed WO 3 film of preparation method of the present invention usually can be in 1～100 micron scope, preferably at 10～90 microns, more preferably at 20～80 microns, most preferably at 30～60 microns.If film is too thin such as less than 10 microns, then effectively photoproduction to separate the hole less, cause photoelectric current not high, its catalytic performance is not good.If too thickness rate is as greater than 90 microns for film, it is oversize through the path to separate back institute at both hole and electron, separates the hole and does not also have enough time to arrive material surface just by electron recombination, causes photoelectric current also not high, and photocatalysis performance also can decrease.
In the present invention, be used to apply the not special restriction of method of WO 3 film slurry, for example can adopt that rod is coated with, blade coating, spin coating and dip-coating etc.In theory, can make combination pulp of the present invention form level and smooth relatively film on the surface on the conductive substrates as long as be used to apply the method for WO 3 film slurry.
The inventor uses scanning electron microscopy (SEM) to investigate the surface texture of the formed WO 3 film electrode of combination pulp of the present invention, and is as shown in Figure 1.Fig. 2 is the surface texture by the prepared photoelectricity hydrogen manufacturing WO 3 film electrode of the preparation method of prior art (applicant's the disclosed method for preparing photoelectricity hydrogen manufacturing WO 3 film electrode in preceding one Chinese patent application 201010269963.3).Particularly, one Chinese patent application 201010269963.3 (among this paper, being called for short the contrast patent sometimes) adopts simple knife coating and through high temperature sintering, has for example prepared cheap oxidate nano perforated membrane such as WO on the tungsten sheet in metallic substrates
3Membrane structure.Can find out that from the comparison of Fig. 1 and Fig. 2 the hole of the film that preparation method of the present invention is prepared is less relatively,, also not adopt the cause of pore creating material because preparation method of the present invention does not have high-temperature sintering process.Although the loose structure on tungsten trioxide film surface can increase the specific area of film; Make it can absorb more light; Thereby photoelectric current is increased to some extent; But under the situation of not accepting the opinion constraint, we think does not have the WO 3 film of hole surface may help the conduction of electronics, thereby causes the increase of photoelectric current yet.
In order to investigate the photoelectric current effect of the photoelectrocatalysis WO 3 film electrode that preparation method of the present invention obtains; Adopted according to the applicant and prepared the tungstic acid membrane electrode as comparing in preceding one Chinese patent application 201010269963.3 methods; Electrochemical workstation (CS350) with Koster Instr Ltd. in Wuhan produces has been tested their current-voltage (I-V) curve respectively, and has investigated the value that photoelectric current can reach when voltage is 1.2V.The comparison of the value that photoelectric current can reach when voltage is 1.2V can find out, the photoelectric property of the prepared photoelectrocatalysis WO 3 film electrode that goes out of preparation method of the present invention can with the performance of the comparative example that uses sintering process quite or even slightly improve.
Therefore, of the present inventionly be used to prepare the method for photoelectrocatalysis membrane electrode and other preparation method of prior art compares, have following advantage:
(1) to prepare WO 3 film all be through on conductive substrates, filming to other coating method, and after super-dry and calcining film forming, use.The inventive method only needs after filming on the conductive substrates, can directly use through super-dry.Manufacturing cycle is shorter, and preparation technology is simpler.
(2) other coating method later stage need be passed through calcining and removed organic substance, and the inventive method need not the later stage calcining, has reduced energy consumption on the one hand, has also reduced emission of carbon-dioxide on the other hand.
(3) organic substance all is removed after other coating method later stage calcining, stays loose and porous structure, although increased specific area, has also reduced the conductivity of film itself simultaneously.Preparation method of the present invention need not only to need can use after the drying through calcination process.Film is through a spot of polymeric binder the tungstic acid material to be bonded in the substrate, add the effect that vacuumizes and promoted tungstic acid better to combine with substrate, and film itself does not have too much pore structure, and this may help the conduction of electronics.
To be described in more detail the present invention through embodiment below, but these embodiment are not limitation of the scope of the invention that scope of the present invention should be defined by the claims.
Embodiment
Pharmaceutical raw material: tungsten trioxide powder, produce by East China, Tianjin chemical reagent work; Absolute ethyl alcohol is produced by East China, Tianjin chemical reagent work; Polyvinylidene fluoride (PVDF) is produced by Alpha; N-formyl sarcolysine base pyrrolidones (NMP) is produced by East China, Tianjin chemical reagent work.
Experimental facilities: the hot blast baking oven that Koster Instr Ltd. in Wuhan makes; The vacuum drying chamber that Wuhan Koster Instr Ltd. makes; The electrochemical workstation (CS350) that Wuhan Koster Instr Ltd. makes, the high-precision spiral mircrometer gauge (294-340) that Mitutoyo makes
Embodiment 1:
To after 10 minutes, dry up subsequent use with absolute ethyl alcohol, the ultrasonic cleaning of deionized water difference with nitrogen as the FTO electro-conductive glass of conductive substrates.5 gram polyvinylidene fluoride (PVDF) are scattered in 45 grams n-formyl sarcolysine base pyrrolidones (NMP) obtain A, again 50 gram tungstic acids are put into A magnetic agitation 4 hours to slurry B uniformly.Stick 8 layers of 60um invisible tape in the conductive substrates FTO both sides of cleaning, expose mid portion FTO, with the glass bar knife coating slurry B is coated in the middle FTO substrate of adhesive tape and obtains film C.After film C inserted 150 ℃ in hot blast baking oven oven dry 24h, again it is inserted vacuum drying chamber, vacuumize dry 24h at about 160 ℃, vacuum degree can reach below the pact-0.1MPa, obtains required membrane electrode.Film thickness test:, be about 50 microns with high-precision spiral mircrometer gauge MEASUREMENTS OF THIN thickness.
Photoelectric current test process: room temperature, light intensity 100mW/cm
2, electrolyte 0.5M H
2SO
4, electrochemical workstation, scanning step 5mV/s is a platinum electrode to electrode.All membrane electrode sheet areas are 9cm
2, electrode is used 4cm
2The Pt sheet, sample is connected the work electrode of electrochemical workstation, electrode Pt sheet is connected auxiliary electrode and reference electrode, adopt the 500W xenon lamp to do light source, install filter disc additional and filter out the ultraviolet light below the 380nm, light intensity is adjusted to 100mW/cm
2, utilize electrochemical workstation to carry out the scanning of photoelectric current, measure photocurrent response intensity.Solid line among measured current-voltage (I-V) curve such as Fig. 1 is represented, can know that from Fig. 1 photoelectric current reaches 1.55mA/cm when 1.2V
2
Comparative example 1:
Application reference people prepares the tungstic acid membrane electrode in preceding one Chinese patent application 201010269963.3 methods, and this method needs high-sintering process:
(1) with 1g WO
3Nano-powder (celebrating of commercially available Beijing is contained and reached chemical industry technology Co., Ltd) is (commercially available with the 3g terpinol; The Beijing Chemical Plant; Analyze pure), the ethanolic solution (10wt%) and the 100ml absolute ethyl alcohol of 5g ethyl cellulose (Beijing Chemical Plant analyzes pure) mix in the 250mL beaker.
(2) with behind the magneton stirring 10min; Use cell pulverization machine (the new root of Dahurian angelica biotech inc in Ningbo again; JY92-IIN) ultrasonic 10min, (EYELA OSB-2000) steams 1h at 50 ℃ of underspins to adopt vacuum to revolve steaming device then; Be transferred to slurry in the 100mL beaker after accomplishing, thereby prepare stabilized uniform WO
3Slurry, for use.
(3) employing 10mm * 30mm * 0.2mm purity is 99.9% tungsten sheet (Beijing Non-Ferrous Metal Research General Academy), uses 360 orders, 600 orders and 1000 purpose sand paperings respectively, every kind of sand papering 1min.
(4) the tungsten sheet after will polishing is in ethanol with the ultrasonic cleaning machine ultrasonic 30 minutes, dries at 90 ℃ again.
(5) the tungsten sheet is put into tube furnace, logical oxygen, flow is 80 μ L/min, is warming up to 750 ℃ and at 750 ℃ of sintering 15min with the speed of 10 ℃ of per minutes, naturally cools to room temperature.
(6) 8 layer of 60 μ m invisible tape sticked in the tungsten sheet both sides behind sintering, exposes the tungsten sheet of mid portion, gets WO
3Slurry is filmed on the tungsten sheet in the middle of the adhesive tape with the method for blade coating.
(7) the tungsten sheet after will filming is put into baking oven, at 120 ℃ of oven dry 15min.
(8) in tube furnace, place the tungsten sheet of filming, logical oxygen waits when oxygen pressure is 1 atmospheric pressure in the stove; Make tube furnace and atmosphere, the adjustment oxygen flow is 100 μ L/min, is warming up to 750 ℃ with the speed of 1 ℃ of per minute; Insulation 15min naturally cools to room temperature.Obtain WO
3Film.
Thickness records and is about 50 microns.
I-V curve test process can be known from test result with embodiment 1, reach 1.2mA/cm at the 1.2V photoelectric current
2
Can be known by Fig. 3: the prepared tungstic acid membrane electrode of the inventive method has shown photoelectric respone preferably, and when voltage 1.2V, photoelectric current can reach 1.55mA/cm
2, need the 1.2mA/cm of the contrast patent of high temperature sintering
2Improve about 29%.It is thus clear that, not only can realize omission through adopting preparation method of the present invention to high-sintering process, make technical process simplify more, reduced cost, and reduced pollution, but also can make the photoelectric current effect obtain suitable raising environment.
Embodiment 2:
4 gram polyvinylidene fluoride (PVDF) are scattered in 58 grams n-formyl sarcolysine base pyrrolidones (NMP) obtain A, again 38 gram tungstic acids are put into A magnetic agitation 12h and obtain uniform slurry B.Stick 4 layers of 60um invisible tape in tungstic acid conductive substrates (according to the open method preparation of CN200910157787.1) both sides; Expose mid portion tungstic acid conductive substrates; With the glass bar knife coating slurry B is coated on the tungstic acid conductive substrates in the middle of the adhesive tape and forms thin film, obtain film C.After film C inserted 100 ℃ in hot blast baking oven oven dry 4h, again it is inserted vacuum drying chamber, vacuumize dry 4h at about 140 ℃, vacuum degree can reach below the pact-0.1MPa, obtains required membrane electrode.Its thickness is measured as 20 microns.
Trioxide substrate as conductive substrates; According to the applicant in 200910157787.1 preparations of preceding one Chinese patent application as follows: employing purity is 99.9% tungsten sheet (Beijing Non-Ferrous Metal Research General Academy); Use 360 orders, 600 orders and 1000 purpose sand paperings respectively, every kind of sand papering 1min.With the tungsten sheet after the polishing in ethanol ultrasonic 30 minutes, dry at 90 ℃ again with the ultrasonic cleaning machine.In tube furnace, place the tungsten sheet after the oven dry, logical oxygen, flow is 100 μ L/min, is warming up to 800 ℃ with the speed of 10 ℃ of per minutes, insulation 10min naturally cools to room temperature, obtains the tungstic acid basal electrode of tungsten sheet sintering.
The I-V test process is with embodiment 1, and test result is found out at the 1.2V photoelectric current to reach 1.27mA/cm from this Fig. 4 referring to the represented curve of the solid line among Fig. 4
2It is thus clear that; Through adopting preparation method of the present invention not only can realize omission to high-sintering process, make technical process simplify more, reduced cost; And reduced pollution, but also can make the photoelectric current effect of photoelectric current effect and prior art (comparative example) suitable to environment.
Embodiment 3
To after 10 minutes, dry up subsequent use with absolute ethyl alcohol, the ultrasonic cleaning of deionized water difference with nitrogen as the electro-conductive glass of conductive substrates.10 gram polytetrafluoroethylene (PTFE)s are scattered in 35 grams obtain A in the deionized waters, again 55 gram tungstic acids are put into A and grind 1h and obtain uniform slurry B.Stick 12 layers of 60um invisible tape in the electro-conductive glass both sides, expose mid portion FTO, with the glass bar knife coating slurry B is coated on the middle electro-conductive glass of adhesive tape and forms thin film, obtain film C.After film C inserted 80 ℃ in hot blast baking oven oven dry 2h, again it is inserted vacuum drying chamber, 100 ℃ vacuumize dry 4h, and vacuum degree can reach-below the 0.1MPa, obtain required membrane electrode.The film thickness test: with high-precision spiral mircrometer gauge MEASUREMENTS OF THIN thickness, thickness is measured as 62 microns.
The I-V test process is with embodiment 1.Test result can be found out at the 1.2V photoelectric current to reach 1.22mA/cm from this Fig. 5 referring to the curve shown in the solid line in the accompanying drawing 5
2This has also explained; Through adopting preparation method of the present invention not only can realize omission to high-sintering process; Make technical process simplify more; Reduced cost, and reduced pollution, but also can make the photoelectric current effect of photoelectric current effect and prior art (comparative example) suitable environment.
Embodiment 4:
After 10 minutes, dry up subsequent use with absolute ethyl alcohol, the ultrasonic cleaning of deionized water difference with nitrogen the substrate of tungsten sheet.5 gram ethyl celluloses are scattered in 45 grams obtain A in the ethanol, again 50 gram tungstic acids are put into A magnetic agitation 4h and obtain uniform slurry B.Stick 8 layers of 60um invisible tape in tungsten sheet substrate both sides, expose mid portion tungsten sheet, with the glass bar knife coating slurry B is coated on the middle tungsten sheet of adhesive tape and obtains film C.After film C inserted 150 ℃ in hot blast baking oven oven dry 4h, again it is inserted vacuum drying chamber, vacuumize dry 4h at about 140 ℃, vacuum degree can reach below the pact-0.1MPa, obtains required membrane electrode.Film thickness test:, be about 48 microns with high-precision spiral mircrometer gauge MEASUREMENTS OF THIN thickness.
The I-V test process is with embodiment 1.Test result can be found out at the 1.2V photoelectric current to reach 1.17mA/cm from this Fig. 6 referring to the curve shown in the solid line in the accompanying drawing 6
2This has also explained; Through adopting preparation method of the present invention not only can realize omission to high-sintering process; Make technical process simplify more; Reduced cost, and reduced pollution, but also can make the photoelectric current effect similar with the photoelectric current effect of prior art (comparative example) to environment.
Embodiment 5:
To after 10 minutes, dry up subsequent use with absolute ethyl alcohol, the ultrasonic cleaning of deionized water difference with nitrogen as the metal aluminium flake of conductive substrates.1 gram CMC is scattered in 49 grams obtains A in the deionized waters, again 50 gram tungstic acids are put into A magnetic agitation 2h, obtain uniform slurry B.In the substrate of metal aluminium flake, obtain film C with dip coating.After film C inserted 150 ℃ in hot blast baking oven oven dry 6h, again it is inserted vacuum drying chamber, vacuumize dry 6h at about 140 ℃, vacuum degree can reach below the pact-0.1MPa, obtains required membrane electrode.Film thickness test:, be about 10 microns with high-precision spiral mircrometer gauge MEASUREMENTS OF THIN thickness.
The I-V test process is with embodiment 1.Test result can be found out at the 1.2V photoelectric current to reach 1.19mA/cm from this figure referring to the curve shown in the solid line in the accompanying drawing 7
2This has also explained; Through adopting preparation method of the present invention not only can realize omission to high-sintering process; Make technical process simplify more; Reduced cost, and reduced pollution, but also can make the photoelectric current effect of photoelectric current effect and prior art (comparative example) suitable environment.
Industrial applicability
Because preparation method of the present invention need not high temperature sintering when preparation tungstic acid photoelectrocatalysis membrane electrode; Therefore reduce technology cost and energy consumption, simplified filming technology, shortened the system film cycle; Also reach photoelectricity effect preferably simultaneously, thereby be particularly suitable for commercial Application.
Claims (12)
1. combination pulp that is used to prepare the photoelectrocatalysis membrane electrode; Gross mass based on said combination pulp is 100%; Said combination pulp comprises the tungstic acid of 20-60 quality %, the binding agent of 1～10 quality %, and balance solvent and unavoidable impurities.
2. the combination pulp that is used to prepare the photoelectrocatalysis membrane electrode according to claim 1, the amount of said binding agent are preferably 1～8 quality %, 2～6 quality % more preferably, and most preferably be 2.5～5 quality %.
3. the combination pulp that is used to prepare the photoelectrocatalysis membrane electrode according to claim 1 and 2, said binding agent are to be selected from least a in polyvinylidene fluoride, ethyl cellulose, polytetrafluoroethylene and the CMC.
4. the composition that is used to prepare the photoelectrocatalysis membrane electrode according to claim 1 and 2, said solvent are n-formyl sarcolysine base pyrrolidones, ethanol or deionized water.
5. method that is used to prepare the photoelectrocatalysis membrane electrode, said method comprises the steps:
The first step; The described combination pulp that is used to prepare the photoelectrocatalysis membrane electrode of configuration claim 1; That is, the binding agent of 1～10 quality % is scattered in the solvent of 35～75 quality %, the tungstic acid with 20～60 quality % adds wherein again; And stir or be ground to evenly, obtain the said combination pulp that is used to prepare the photoelectrocatalysis membrane electrode;
In second step, the above-mentioned combination pulp that is used to prepare the photoelectrocatalysis membrane electrode that obtains is coated on the conductive substrates of cleaning to form film;
In the 3rd step, the film oven dry with gained places vacuum drying oven to vacuumize after the drying then, obtains photoelectrocatalysis WO 3 film electrode.
6. the method that is used to prepare the photoelectrocatalysis membrane electrode according to claim 5, said the 3rd step is through after 1-12 hour, again it being inserted vacuum drying chamber 60～150 ℃ of oven dry, vacuumizes at 80～160 ℃ and carries out in dry 1～24 hour.
7. the method that is used to prepare the photoelectrocatalysis membrane electrode according to claim 5, the use amount of said binding agent are preferably 1～8 quality %, 2～6 quality % more preferably, and most preferably be 2.5～5 quality %.
8. the method that is used to prepare the photoelectrocatalysis membrane electrode according to claim 5, said binding agent are to be selected from least a in polyvinylidene fluoride, ethyl cellulose, polytetrafluoroethylene and the CMC.
9. the method that is used to prepare the photoelectrocatalysis membrane electrode according to claim 5, said solvent are n-formyl sarcolysine base pyrrolidones, ethanol or deionized water.
10. the method that is used to prepare the photoelectrocatalysis membrane electrode according to claim 5, said substrate are to be selected from a kind of in electro-conductive glass FTO, tungsten sheet, metal aluminium flake and the tungstic acid sintered electrode.
11. the method that is used to prepare the photoelectrocatalysis membrane electrode according to claim 5, stirring or grinding in the said first step comprise: stirred 1～24 hour or ground 10 minutes～2 hours.
12. according to claim 5 or the 6 described methods that are used to prepare the photoelectrocatalysis membrane electrode, the vacuum degree in the said vacuum drying oven reaches-below the 0.1MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324389A (en) * | 2017-06-17 | 2017-11-07 | 常州新区金利宝塑料制品有限公司 | A kind of preparation method of molybdenum doping tungstic trioxide nano-film material |
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| WO2023177433A1 (en) * | 2022-03-17 | 2023-09-21 | W.R. Grace & Co.-Conn. | Process for producing heat treated supported aluminoxanes in an aliphatic solvent using solid aluminoxanes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999067181A1 (en) * | 1998-06-22 | 1999-12-29 | Universite De Geneve | Method for making an electrode comprising a tungsten oxide film |
| CN1616142A (en) * | 2003-11-11 | 2005-05-18 | 中国科学院物理研究所 | Method for preparing slurry and its use |
| US20090192032A1 (en) * | 2008-01-29 | 2009-07-30 | Seoul National University Industry Foundation | Visible light-responsive photocatalyst composition containing tungsten-based oxides and method of producing the same |
| CN101906642A (en) * | 2010-08-30 | 2010-12-08 | 新奥科技发展有限公司 | Method for making photoelectric hydrogen production electrode and photoelectric hydrogen production electrode |
-
2010
- 2010-12-20 CN CN201010600723.7A patent/CN102544431B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999067181A1 (en) * | 1998-06-22 | 1999-12-29 | Universite De Geneve | Method for making an electrode comprising a tungsten oxide film |
| CN1616142A (en) * | 2003-11-11 | 2005-05-18 | 中国科学院物理研究所 | Method for preparing slurry and its use |
| US20090192032A1 (en) * | 2008-01-29 | 2009-07-30 | Seoul National University Industry Foundation | Visible light-responsive photocatalyst composition containing tungsten-based oxides and method of producing the same |
| CN101906642A (en) * | 2010-08-30 | 2010-12-08 | 新奥科技发展有限公司 | Method for making photoelectric hydrogen production electrode and photoelectric hydrogen production electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324389A (en) * | 2017-06-17 | 2017-11-07 | 常州新区金利宝塑料制品有限公司 | A kind of preparation method of molybdenum doping tungstic trioxide nano-film material |
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