CN104894620A - Electroplating solution, IrO2/ZnO nano composite-structure film material and preparation method thereof - Google Patents
Electroplating solution, IrO2/ZnO nano composite-structure film material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electroplating solution, an IrO2/ZnO nano composite-structure film material and a preparation method thereof. The electroplating solution is composed of an iridium ion source, an electrolyte and a zinc ion source and can be used for preparation of a high-specific-surface-area precious metal oxide doped ZnO-carried composite nano structure IrO2/ZnO film photocatalytic material which is high in methylene blue photocatalytic degradation efficiency and excellent in methyl orange photodegradation and decoloration. The electroplating solution, the IrO2/ZnO nano composite-structure film material and the preparation method thereof have the advantages of technical simplicity, low cost and suitability for mass production.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, particularly relate to a kind of electroplate liquid, IrO
2/ ZnO nano composite structure thin-film material and preparation method thereof.
Background technology
Global environmental pollution and ecological damage make people give great concern to environmental improvement technology that is efficient, energy-conservation, non-secondary pollution.In recent years, photocatalysis oxidation technique and electro-catalytic oxidation technology cause as the treatment process of the organic pollutant of poisonous or difficult for biological degradation the concern that Chinese scholars continues.These two kinds of technology all have the advantages such as structure is simple, operational condition easily controls, oxidation capacity strong, non-secondary pollution, become two study hotspots the most active in current environment Environmental capacity field, and demonstrate wide application prospect.
Photocatalysis technology is under the effect of catalyzer, utilizes optical radiation pollutent to be decomposed into the process of nontoxic or that toxicity is lower material.Ultimate principle is: be greater than energy gap (E when semiconductor light-catalyst is subject to energy
g) rayed time, the electrode (e in its valence band
-) excited, cross forbidden band and enter conduction band, valence band stays the hole (h of positively charged
+).Photohole has extremely strong oxidisability, the electronics in water can be captured, the hydroxyl radical free radical (OH) that production oxidisability is very strong, OH can carry out the oxidation of non-selectivity to the organic pollutant near electrode surface, and organism exhaustive oxidation is CO by so-called " electrochemical combustion " process that can occur
2and water.ZnO nano-structure material is the Typical Representative of high efficiency semiconductor photocatalyst.ZnO has wider forbidden band (3.37 eV), and its weak point is the light (as ultraviolet) that wavelength can only be utilized very short; In semiconductor material, there is stronger " compound " tendency in electronics and hole in addition, and higher " electron-hole " concentration of maintenance is the prerequisite that light-catalyzed reaction is carried out.The semiconductor material making forbidden band little has competitive power in energy transformation, available optical band (as visible light wave range) will be expanded in other words, must manage to reduce the activation barrier potential needed for photoelectrochemistry reaction and reduction overpotential, and suppress the loss of interface " electron-hole compound ".The ZnO semiconductor material of doping can realize visible light catalytic, and this is confirmed.The method of ZnO light induced electron and hole-recombination is suppressed to have multiple, as semiconductors coupling, noble metal loading, semiconductor surface photosensitization, and the method such as ion doping.These methods can increase charge trap, promote that electronics and hole are to surface adsorption substance transfer, thus suppress the compound in electronics and hole.
From engineering viewpoint, photo catalytically treating waste water adopts two kinds of reactive systems usually:
One is suspended ZnO water treatment system, be scattered in sewage by powder shaped photocatalyst material, then apply optical radiation, because of photocatalyst and organic pollutant contact area large, show good photochemical catalytic oxidation efficiency, in most cases can by thorough for organism mineralising.But, suspending phase powder body material also exist be difficult to reclaim, the easy shortcoming such as poisoning.These shortcomings make this system be difficult to become a practical technology.
Another kind is immobilization system, is cured on suitable carrier, then applies with optical radiation by ZnO.This system also can improve light-catalyzed reaction efficiency by means of extra electric field.Its principle is: can produce a potential gradient in optoelectronic pole inside at photochemical catalysis system China and foreign countries added electric field, light induced electron is made to move to electrode under electric field action, current carrier is separated, reduce the compound again of " electron-hole ", so just can maintain higher hole concentration in the semiconductors, be conducive to the oxygenizement giving full play to photohole, thus improve the efficiency of light-catalyzed reaction.Immobilization technology overcomes the shortcoming that in suspending phase system, photocatalyst difficulty reclaims, and suppresses the simple composite of " electron-hole " by external electric field, and practicality is stronger comparatively speaking.The people such as Xu Feng (CN 102121130 A) disclose the ZnO nano sheet/nanowire composite structures and method for making with photocatalysis characteristic.They first with zinc nitrate and potassium chloride solution for electrolytic solution galvanic deposit making ZnO nanometer sheet, then with zinc nitrate and the vulkacit H aqueous solution for growth media, by chemistry of aqueous solution growth method at ZnO nanometer sheet surface second growth ZnO nano wire.Preparation process still seem complicated and preparation be simple ZnO photocatalyst, instead of noble metal support ZnO composite photocatalyst.Therefore the specific surface area of load rear catalyst reduce and the quantum effect brought and surface and interface effect the problem such as to weaken still undecided.
Therefore, be badly in need of developing simple, economic method to prepare the metal oxide containing precious metals loading ZnO composite nanostructure film photocatalyst of high-specific surface area.
Summary of the invention
The object of the present invention is to provide the IrO carrying ZnO composite nanostructure that a kind of technique is simple, cost is low, the metal oxide containing precious metals preparing high-specific surface area of applicable large-scale production adulterates
2/ ZnO film photocatalyst material.
For achieving the above object, the invention provides one for the preparation of IrO
2the electroplate liquid of/ZnO nano composite structure thin-film material, is characterized in that: described electrolytic solution comprises iridium ion source, ionogen and zinc ion source.
Further, in described electrolytic solution, iridium ion concentration is 0.05mg-1mg/L, preferred 0.1mg-1mg/L; More preferably 0.3-0.7 mg/L;
Optional, zinc ion concentration is 30-70g/L; Preferred 40-60 g/L;
Optional, electrolyte concentration is 40-120 g/L; Preferred 50-120 g/L.
Further, one or more in described ionogen particular certain cancers, sylvite or sulfuric acid.
Further, described iridium ion source is selected from one or more in chloro-iridic acid, iridic chloride, iridous chloride;
Optional, zinc ion source be selected from zinc sulfate, zinc chloride one or more.
The present invention also provides one to prepare IrO
2the method of/ZnO nano composite structure thin-film material, is characterized in that: preparation process is as follows,
The preparation of Ir/Zn codeposition coating: the negative electrode being used for deposition zinc is inserted in the electroplate liquid described in the arbitrary claim of claim 1-4, relative with the same anode inserting electroplate liquid, and the current density applying to be enough to deposit on negative electrode Ir/Zn codeposition coating is between a cathode and an anode electroplated, and obtains Ir/Zn codeposition coating;
The preparation of Ir/Zn thin-film material: stripped down from cathode surface by described Ir/Zn codeposition coating, after falling the electroplate liquid of attachment, obtains Ir/Zn thin-film material by clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: described Ir/Zn thin-film material is put into retort furnace, is oxidized and namely obtains IrO under air atmosphere or oxygen atmosphere
2/ ZnO nano composite structure thin-film material.
Further, described negative electrode is selected from titanium plate, titanium alloy sheet, aluminium sheet or aluminium alloy plate.
Further, described anode is selected from coating of metal oxides Ni―Ti anode, lead anode, alloy lead anode or metal foil electrodes.
Further, in the preparation process of described Ir/Zn codeposition coating, current density is 300 ~ 700A/m
2;
Optional, electroplating time is 1 ~ 4h;
Optional, described in obtain IrO
2in/ZnO nano composite structure thin-film material step, described oxidation is oxidized 2 ~ 4 hours at 300-400 DEG C.
The present invention also protects described preparation IrO
2the IrO that the method of/ZnO nano composite structure thin-film material prepares
2/ ZnO nano composite structure thin-film material.
The IrO prepared described in the present invention also protects
2/ ZnO nano composite structure thin-film material is used for the purposes of photocatalytic degradation organic waste water; The purposes of preferred light catalyzed degradation textile dyestuff waste water.
Containing iridium ion source and zinc ion source in electroplate liquid, therefore itself possesses certain electroconductibility; And electrolytical effect is the electroconductibility in order to strengthen electroplate liquid, not forming impact to the structure of electroplated film disk, just can affect galvanic deposit power consumption, therefore electrolytical consumption can be optional and unrestricted within the specific limits.
In electroplate liquid, the effect of iridium ion has two: one to be and zinc codeposition obtain the thin-film material containing iridium and zinc; Two is the appearance structure regulating and controlling film, iridium is good liberation of hydrogen catalyzer, after iridium and zinc are deposited on cathode surface simultaneously, iridium surface is preferential separates out hydrogen instead of zinc, therefore can form wide aperture porous film material, the existence of iridium and liberation of hydrogen have also been changed the deposition growing mode of zinc, and the growth pattern of zinc changes into and presents nano-sheet growth pattern, and also have certain space between nanometer sheet and nanometer sheet, form small-bore three-dimensional porous structure.
The compliance test result test-results of the embodiment of the present invention shows, after ultraviolet light irradiation 90min, the degradation rate of methylene blue is 5.03%.The IrO of the embodiment of the present invention 1 ~ 3
2the degradation rate of/ZnO nano composite structure film to methylene blue is respectively 98.52%, 81.23% and 85.45%.Its degradation rate all will far above blank assay result.This illustrates IrO
2the light-catalyzed reaction of/ZnO nano composite structure film to methylene blue occupies absolute advantage.The mode of simple photoirradiation can not carry out light-catalyzed reaction.Wherein, the IrO of embodiment 1 preparation
2the photocatalytic degradation efficiency of/ZnO nano composite structure film to methylene blue reaches 98.52%, and this is ideal degradation effect.
Adopt the IrO that preparation method of the present invention prepares
2/ ZnO nano composite structure thin-film material, shows the ability of excellent degradation of methylene blue, the IrO of especially embodiment 1 preparation
2/ ZnO nano composite structure film.This and the present invention are preparing IrO
2the preparation method adopted during/ZnO nano composite structure film is inseparable, and this is also that beneficial effect of the present invention embodies:
The first, adopt codeposition mode, this mode can obtain Ir/Zn codeposition film, and the deposition of iridium can bring a large amount of liberations of hydrogen, and liberation of hydrogen causes zinc not deposit thereon, thus forms macroporous structure, as shown in Figure 1; The existence of iridium and the liberation of hydrogen process change growth pattern of zinc, thus finally obtain the film of three-dimensional porous nano composite structure, as described in Figure 2.Aperture is conducive to the diffusion circulation of methylene blue solution, and the micropore of small-bore is conducive to increasing specific surface area, and structural macroscopical wide aperture adds microcosmic small-bore, makes it have structural advantage when degradation of methylene blue.Traditional high surface area thin-film material is based on microcosmic aperture, and the film of this type is actually imperfect, because there is the attraction power to solution in aperture on microcosmic, and our capillarity of knowing.This can cause the diffusion of liquid to slow down, especially the solution at deep hole place, is difficult to rapid diffusion.This just causes the methylene blue feed speed in solution to slow down, and affects speed of response.Film of the present invention is except micropore, and also have the through hole that aperture is very large, these apertures do not have capillary and manifest, and can accelerate the Convention diffusion of solution.By solution supply to film depths.Therefore carrying out fast of reaction is contributed to.This also embodies IrO prepared by the present invention
2the structural advantage of/ZnO nano composite structure thin-film material.
The second, usual precious metal doping metal oxide semiconductor material is have best photocatalytic activity between 0.2 ~ 0.5% in precious metal doping concentration, as can be seen from Figure 3, and IrO
2in/ZnO nano composite structure film, Ir atomic ratio is that 0.36%, Ir atomic ratio is just in time within the scope of this.This and suitable iridium ion concentration and zinc ion concentration are arranged in pairs or groups and are undivided, and illustrate that the present invention is very rational on iridium ion and zinc ion concentration collocation.IrO
2effect major embodiment both ways: one is the energy band structure affecting ZnO, and two is affect redox reaction process.Due to IrO
2existence, light induced electron is to IrO
2flowing, IrO
2the light induced electron of catching has stronger mobility, can be rapidly to IrO
2/ ZnO transmits, with the H of surface adsorption on surface
+or O
2reaction, thus decrease light induced electron at IrO
2the inner probability with hole-recombination of/ZnO, so more photohole can with H
2o or OH-reaction generates the hydroxyl radical free radical of Strong oxdiative performance, and hydroxyl radical free radical reacts with methylene blue further, and methylene blue is resolved into CO
2and H
2o.This also embodies IrO prepared by the present invention
2the Composition Design advantage in composition collocation of/ZnO nano composite structure thin-film material.
The technique of preparation method of the present invention is simple, workable, is applicable to large-scale production, and the cheap and thin-film material finally made of cost of manufacture is the IrO without the need to carrier
2/ ZnO nano composite structure thin-film material.
Accompanying drawing explanation
Fig. 1 is IrO prepared by the embodiment of the present invention 1
2the SEM figure of/ZnO nano composite structure thin-film material under low power is amplified.
Fig. 2 is IrO prepared by the embodiment of the present invention 1
2the SEM figure of/ZnO nano composite structure thin-film material under magnification at high multiple.
Fig. 3 is IrO prepared by the embodiment of the present invention 1
2/ ZnO nano composite structure thin-film material surface composition energy spectrogram.
Fig. 4 is IrO prepared by the embodiment of the present invention 3
2the SEM figure of/ZnO nano composite structure thin-film material under low height amplifies.
Fig. 5 is IrO prepared by the embodiment of the present invention 1 ~ 3
2/ ZnO nano composite structure thin-film material is to the change curve of the photocatalytic activity-time of methylene blue solution.
Fig. 6 is IrO prepared by the embodiment of the present invention 5
2/ ZnO nano composite structure thin-film material is to absorbance curve before and after methyl orange solution degraded.
Fig. 7 is IrO prepared by the embodiment of the present invention 6
2/ ZnO nano composite structure thin-film material is to absorbance curve before and after methyl orange solution degraded.
Fig. 8 is IrO prepared by the embodiment of the present invention 7
2/ ZnO nano composite structure thin-film material is to absorbance curve before and after methyl orange solution degraded.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Be exemplary below by the embodiment be described with reference to the drawings, be intended to for explaining the present invention, and can not limitation of the present invention be interpreted as.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
embodiment 1:IrO
2
the preparation of/ZnO nano composite structure thin-film material
Electroplate liquid: preparation iridium ion concentration is 0.5mg/L, zinc ion concentration is 60g/L, electrolyte sulfuric acid concentration is 100g/L mixed aqueous solution, i.e. electroplate liquid.Iridium ion source adopts chloro-iridic acid, zinc ion source to adopt zinc sulfate.
Ir/Zn codeposition preparation of coatings: be negative electrode with aluminium sheet, take lead alloy as anode, by parallel with anode for negative electrode insertion electroplate liquid, applies direct current between a cathode and an anode, and cathode current density controls as 500A/m
2, electroplate 2 hours, obtain Ir/Zn codeposition coating;
Prepared by Ir/Zn thin-film material: stripped down from cathode surface by Ir/Zn codeposition coating, falls to be attached to the electroplate liquid on surface, then dry, obtain Ir/Zn thin-film material by a large amount of clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: Ir/Zn thin-film material is put into retort furnace, is oxidized 2 hours in air atmosphere and at 350 DEG C, namely obtains the IrO with photocatalysis characteristic
2/ ZnO nano composite structure thin-film material.See Fig. 1-Fig. 2.As shown in Figure 1, the deposition of iridium can bring a large amount of liberations of hydrogen, and liberation of hydrogen causes zinc not deposit thereon, thus forms macroporous structure; Depositing and the liberation of hydrogen process change growth pattern of zinc of iridium, thus finally obtain the film of three-dimensional porous nano composite structure, as shown in Figure 2.
Fig. 3 is the energy spectrogram of thin-film material surface, can be obtained the atomic composition ratios of thin-film material by energy spectrogram.As can be seen from Figure 3, IrO
2in/ZnO nano composite structure film, Ir atomic ratio is that 0.36%, Ir atomic ratio is just in time within the scope of this.This and suitable iridium ion concentration and zinc ion concentration are arranged in pairs or groups and are undivided, and illustrate that the present invention is very rational on iridium ion and zinc ion concentration collocation.IrO
2effect be mainly reflected in two each side: one is the energy band structure affecting ZnO, and two is affect redox reaction process.Due to IrO
2existence, light induced electron item IrO
2flowing, IrO
2the light induced electron of catching has stronger mobility, can be rapidly to IrO
2/ ZnO transmits, with H+ or O of surface adsorption on surface
2reaction, thus decrease light induced electron at IrO
2the probability of/ZnO inside and hole-recombination, so more photohole can H
2o or OH-reaction generates the hydroxyl radical free radical of Strong oxdiative performance, and hydroxyl radical free radical reacts with methylene blue further, and methylene blue is resolved into CO
2and H
2o.This also embodies IrO prepared by the present invention
2the Composition Design advantage in composition collocation of/ZnO nano composite structure thin-film material.
embodiment 2:IrO
2
the preparation of/ZnO nano composite structure thin-film material
Electroplate liquid: preparation iridium ion concentration is 0.05mg/L, zinc ion concentration is 30g/L, sodium chloride electrolysis matter concentration is the mixed aqueous solution of 100g/L, i.e. electroplate liquid.Iridium ion source adopts iridic chloride, zinc ion source to adopt zinc chloride
Ir/Zn codeposition preparation of coatings: be negative electrode with aluminium sheet, take lead alloy as anode, by parallel with anode for negative electrode insertion electroplate liquid, applies direct current between a cathode and an anode, and cathode current density controls as 350A/m
2, electroplate 4 hours, obtain Ir/Zn codeposition coating;
Prepared by Ir/Zn thin-film material: stripped down from cathode surface by Ir/Zn codeposition coating, falls to be attached to the electroplate liquid on surface, then dry, obtain Ir/Zn thin-film material by a large amount of clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: Ir/Zn thin-film material is put into retort furnace, is oxidized 4 hours in air atmosphere and at 300 DEG C, namely obtains the IrO with photocatalysis characteristic
2/ ZnO nano composite structure thin-film material.
embodiment 3:IrO
2
the preparation of/ZnO nano composite structure thin-film material
Electroplate liquid: preparation iridium ion concentration is 1 mg/L, zinc ion concentration is 70g/L, potassium sulfate electrolyte concentration is 50g/L mixed aqueous solution, i.e. electroplate liquid.Iridium ion source adopts chloro-iridic acid, zinc ion source to adopt zinc sulfate.
Ir/Zn codeposition preparation of coatings: with titanium plate for negative electrode, with coating of metal oxides Ni―Ti anode for anode, by parallel with anode for negative electrode insertion electroplate liquid, applies direct current between a cathode and an anode, and cathode current density controls as 450A/m
2, electroplate 3 hours, obtain Ir/Zn codeposition coating;
Prepared by Ir/Zn thin-film material: stripped down from cathode surface by Ir/Zn codeposition coating, falls to be attached to the electroplate liquid on surface, then dry, obtain Ir/Zn thin-film material by a large amount of clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: Ir/Zn thin-film material is put into retort furnace, is oxidized 2 hours in air atmosphere and at 350 DEG C, namely obtains the IrO with photocatalysis characteristic
2/ ZnO nano composite structure thin-film material.See Fig. 4, as can be seen from the figure, thin-film material presents nano flower-like structure, has very high specific surface area.
embodiment 4:IrO
2
the compliance test result test of/ZnO nano composite structure thin-film material
With the IrO prepared by embodiment 1 ~ 3
2/ ZnO nano compound structure film carries out photodegradation experiment to methylene blue: get four quartz glass wares, and loading 50 mL concentration is the methylene blue solution of 20mg/L; Then by the IrO of embodiment 1 ~ 3 preparation
2/ ZnO nano composite structure film is cut into the sheet of 2cm*2cm respectively, puts into first three quartz glass ware successively.4th quartz apparatus is used for contrast as blank assay.With ultraviolet source, illumination is carried out to reaction system, additional magnetic agitation.Every 15 minutes, UV-Visible absorption test is carried out to methylene blue solution.Degradation rate is by formulae discovery below:
Degradation rate=(A
0-A
t)/A
0
In formula, A
0for initial soln is in the absorbancy at 664nm place, A
tfor the absorbancy at 664nm place of solution when degradation time is t.Fig. 5 is embodiment 1 ~ 3 gained IrO
2/ ZnO nano composite structure film is to the change curve of the photocatalytic activity-time of methylene blue.Wherein X-coordinate is the ultraviolet light irradiation time, and ordinate zou is the degradation rate of methylene blue solution.Give in Fig. 5 and do not put into photocatalyst, just by the blank test result of ultraviolet light irradiation.
Result shows, after ultraviolet light irradiation 90min, the degradation rate of methylene blue is 5.03%.The IrO of the embodiment of the present invention 1 ~ 3
2the degradation rate of/ZnO nano composite structure film to methylene blue is respectively 98.52%, 81.23% and 85.45%.Its degradation rate all will far above blank assay result.This illustrates IrO
2the light-catalyzed reaction of/ZnO nano composite structure film to methylene blue occupies absolute advantage.The mode of simple photoirradiation can not carry out light-catalyzed reaction.Wherein, the IrO of embodiment 1 preparation
2the photocatalytic degradation efficiency of/ZnO nano composite structure film to methylene blue reaches 98.52%, and this is ideal degradation effect.
embodiment 5:IrO
2
the preparation of/ZnO nano composite structure thin-film material
Electroplate liquid: join that iridium ion concentration is 0.1mg/L, zinc ion concentration is 40g/L, electrolyte sulfuric acid concentration is the mixed aqueous solution of 120g/L, i.e. electroplate liquid.Iridium ion source adopts iridous chloride, zinc ion source to adopt zinc chloride
Ir/Zn codeposition preparation of coatings: be negative electrode with aluminium sheet, take lead alloy as anode, by parallel with anode for negative electrode insertion electroplate liquid, applies direct current between a cathode and an anode, and cathode current density controls as 700A/m
2, electroplate 1 hour, obtain Ir/Zn codeposition coating;
Prepared by Ir/Zn thin-film material: stripped down from cathode surface by Ir/Zn codeposition coating, falls to be attached to the electroplate liquid on surface, then dry, obtain Ir/Zn thin-film material by a large amount of clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: Ir/Zn thin-film material is put into retort furnace, is oxidized 2 hours in air atmosphere and at 400 DEG C, namely obtains the IrO with photocatalysis characteristic
2/ ZnO nano composite structure thin-film material.
embodiment 6:IrO
2
the preparation of/ZnO nano composite structure thin-film material
Electroplate liquid: join that iridium ion concentration is 0.3mg/L, zinc ion concentration is 50g/L, sodium sulfate electrolyte concentration is 40g/L, electrolyte sulfuric acid concentration is the mixed aqueous solution of 40g/L, i.e. electroplate liquid.Iridium ion source adopts iridic chloride, zinc ion source to adopt zinc sulfate (contribution 25g/L Zn
2+) and zinc chloride (contribution 25g/L Zn
2+).
Ir/Zn codeposition preparation of coatings: be negative electrode with aluminium sheet, take lead alloy as anode, by parallel with anode for negative electrode insertion electroplate liquid, applies direct current between a cathode and an anode, and cathode current density controls as 300A/m
2, electroplate 4 hours, obtain Ir/Zn codeposition coating;
Prepared by Ir/Zn thin-film material: stripped down from cathode surface by Ir/Zn codeposition coating, falls to be attached to the electroplate liquid on surface, then dry, obtain Ir/Zn thin-film material by a large amount of clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: Ir/Zn thin-film material is put into retort furnace, is oxidized 3 hours in air atmosphere and at 335 DEG C, namely obtains the IrO with photocatalysis characteristic
2/ ZnO nano composite structure thin-film material.
embodiment 7:IrO
2
the preparation of/ZnO nano composite structure thin-film material
Electroplate liquid: join that iridium ion concentration is 0.7g/L, zinc ion concentration is 60g/L, Repone K electrolyte concentration is 50g/L, sodium chloride electrolysis matter concentration is the mixed aqueous solution of 50g/L, i.e. electroplate liquid.Iridium ion source adopts chloro-iridic acid contribution 0.3mg/L Ir
4+), iridic chloride (contribution 0.2mg/L Ir
4+) and iridous chloride (contribution 0.2mg/L Ir
3+); Zinc ion source adopts zinc sulfate.
Ir/Zn codeposition preparation of coatings: be negative electrode with aluminium sheet, take lead alloy as anode, by parallel with anode for negative electrode insertion electroplate liquid, applies direct current between a cathode and an anode, and cathode current density controls as 300A/m
2, electroplate 4 hours, obtain Ir/Zn codeposition coating;
Prepared by Ir/Zn thin-film material: stripped down from cathode surface by Ir/Zn codeposition coating, falls to be attached to the electroplate liquid on surface, then dry, obtain Ir/Zn thin-film material by a large amount of clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: Ir/Zn thin-film material is put into retort furnace, is oxidized 3 hours in air atmosphere and at 335 DEG C, namely obtains the IrO with photocatalysis characteristic
2/ ZnO nano composite structure thin-film material.
embodiment 8:IrO
2
the compliance test result test of/ZnO nano composite structure thin-film material
With the IrO prepared by embodiment 5 ~ 7
2/ ZnO nano compound structure film carries out photodegradation experiment to tropeolin-D: get three quartz glass wares, and loading 50 mL concentration is the methyl orange solution of 20mg/L; Then by the IrO of embodiment 5 ~ 7 preparation
2/ ZnO nano composite structure film is cut into the sheet of 2cm*2cm respectively, puts into quartz glass ware successively.With ultraviolet source, illumination is carried out to reaction system, additional magnetic agitation.Every 15 minutes, UV-Visible absorption test is carried out to methyl orange solution.
Fig. 6 ~ 8 are respectively IrO prepared by the embodiment of the present invention 5 ~ 7
2/ ZnO nano composite structure thin-film material is to absorbance curve before and after methyl orange solution degraded.Can find out, after degrading through the photochemical catalysis of 120min, methyl orange solution will be nearly all zero in the absorbancy of visible light wave range.Formulae discovery by below:
Degradation rate=(A
0-A
t)/A
0
In formula, A
0for the absorbancy of initial orange solution at 462nm place, A
tfor methyl orange solution when degradation time is t is in the absorbancy at 462nm place.The degradation rate of sample prepared by embodiment 5 reaches 98.6%; Embodiment 6 and 7 is 100%.IrO prepared by the embodiment of the present invention 5 ~ 7 is described
2the photodegradation of/ZnO nano compound structure film to tropeolin-D is respond well, and decoloring ability is strong.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention when not departing from principle of the present invention and aim, revising, replacing and modification.
Claims (10)
1. one kind for the preparation of IrO
2the electroplate liquid of/ZnO nano composite structure thin-film material, is characterized in that: described electrolytic solution comprises iridium ion source, ionogen and zinc ion source.
2. described in claim 1 for the preparation of IrO
2the electroplate liquid of/ZnO nano composite structure thin-film material, is characterized in that: in described electrolytic solution, iridium ion concentration is 0.05mg-1mg/L, preferred 0.1mg-1mg/L; More preferably 0.3-0.7 mg/L;
Optional, zinc ion concentration is 30-70g/L; Preferred 40-60 g/L;
Optional, electrolyte concentration is 40-120 g/L; Preferred 50-120 g/L.
3. described in claim 1 for the preparation of IrO
2the electroplate liquid of/ZnO nano composite structure thin-film material, is characterized in that: one or more in described ionogen particular certain cancers, sylvite or sulfuric acid.
4. described in claim 1 for the preparation of IrO
2the electroplate liquid of/ZnO nano composite structure thin-film material, is characterized in that: described iridium ion source be selected from chloro-iridic acid, iridic chloride, iridous chloride one or more;
Optional, zinc ion source be selected from zinc sulfate, zinc chloride one or more.
5. prepare IrO for one kind
2the method of/ZnO nano composite structure thin-film material, is characterized in that: preparation process is as follows,
The preparation of Ir/Zn codeposition coating: the negative electrode being used for deposition zinc is inserted in the electroplate liquid described in the arbitrary claim of claim 1-4, relative with the same anode inserting electroplate liquid, and the current density applying to be enough to deposit on negative electrode Ir/Zn codeposition coating is between a cathode and an anode electroplated, and obtains Ir/Zn codeposition coating;
The preparation of Ir/Zn thin-film material: stripped down from cathode surface by described Ir/Zn codeposition coating, after falling the electroplate liquid of attachment, obtains Ir/Zn thin-film material by clean water;
Obtain IrO
2/ ZnO nano composite structure thin-film material: described Ir/Zn thin-film material is put into retort furnace, is oxidized and namely obtains IrO under air atmosphere or oxygen atmosphere
2/ ZnO nano composite structure thin-film material.
6. prepare IrO described in claim 5
2the method of/ZnO nano composite structure thin-film material, is characterized in that: described negative electrode is selected from titanium plate, titanium alloy sheet, aluminium sheet or aluminium alloy plate.
7. prepare IrO described in claim 5
2the method of/ZnO nano composite structure thin-film material, is characterized in that: described anode is selected from coating of metal oxides Ni―Ti anode, lead anode, alloy lead anode or metal foil electrodes.
8. prepare IrO described in claim 5
2the method of/ZnO nano composite structure thin-film material, is characterized in that: in the preparation process of described Ir/Zn codeposition coating, current density is 300 ~ 700A/m
2;
Optional, electroplating time is 1 ~ 4h;
Optional, described in obtain IrO
2in/ZnO nano composite structure thin-film material step, described oxidation is oxidized 2 ~ 4 hours at 300-400 DEG C.
9. the arbitrary described preparation IrO of claim 5-8
2the IrO that the method of/ZnO nano composite structure thin-film material prepares
2/ ZnO nano composite structure thin-film material.
10. the IrO prepared described in claim 9
2/ ZnO nano composite structure thin-film material is used for the purposes of photocatalytic degradation organic waste water; The purposes of preferred light catalyzed degradation textile dyestuff waste water.
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