CN103060872B - Method for preparing lignin sulfonate-doped nano-zinc oxide composite film by electrochemical deposition method - Google Patents
Method for preparing lignin sulfonate-doped nano-zinc oxide composite film by electrochemical deposition method Download PDFInfo
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- CN103060872B CN103060872B CN201210517096.XA CN201210517096A CN103060872B CN 103060872 B CN103060872 B CN 103060872B CN 201210517096 A CN201210517096 A CN 201210517096A CN 103060872 B CN103060872 B CN 103060872B
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Abstract
The invention belongs to the technical field of nano-material preparation, and relates to a preparation method of a nano-zinc oxide composite film, especially to a method for preparing a lignin sulfonate-doped nano-zinc oxide composite film by an electrochemical deposition method. The method provided by the invention comprises preparing a precursor solution containing zinc, adding the lignin sulfonate as a surfactant, transferring the precursor solution into a three-electrode system for the electrochemical deposition, and finally calcining the obtained products and treating to obtain the product. The method uses the lignin sulfonate as a template and the surfactant, and prepares the nano-zinc oxide compound through the electrochemical deposition method. During a calcining process, part groups of the lignin sulfonate are burnt and thus gaps are left, thereby obtaining the porous zinc oxide composite film. The lignin sulfonate, as wastes, is recycled, and thus a cost is low. The prepared product is white, and has a lead-zinc structure of a hexagonal system and an average particle size of 18-25 nm. The method has advantages of easy control, low cost and simple technology and process, and is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, relate to the preparation method of nano zine oxide laminated film, particularly a kind of electrochemical deposition method prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film.
Background technology
Nano zine oxide is as a kind of important photoelectric semiconductor material, there is wider energy gap, larger exciton bind energy, and there is excellent piezoelectric property, pyroelecthc properties, photoelectric response characteristic, be subject to people to pay close attention to widely, its application has related to all many-sides such as opto-electronic device, gas sensor, feds, anti-biotic material, photochemical catalysis always.
The preparation method of nano zine oxide is a lot, is divided into vapor phase process, liquid phase method, solid phase method etc.Wherein liquid phase method is divided into again electrochemical process, the precipitator method, sol-gel method and hydrothermal method etc.Wherein to have sedimentation rate high for electrochemical deposition method; Material growth temperature is low, can operate at normal temperatures and pressures; Be adapted at complicated Grown; The film of the different photoelectric property of different thickness can be obtained by changing electrochemical parameter; Device simple, easily operation, cost are low, environmental friendliness; Be applicable to the advantages such as scale operation.The electrolytic solution of galvanic deposit ZnO film has two types, i.e. the aqueous solution and non-aqueous solution (mainly dimethyl sulfoxide (DMSO)).It is higher that non-aqueous solution makes electrolytic solution cost, and the ZnO film particle diameter usually prepared for electrolytic solution with the single aqueous solution is for micron order, and membrane quality is poor.Nearest research finds, can significantly improve the quality of galvanic deposit ZnO film, refining grain size by adding proper amount of surfactant in aqueous.
Tensio-active agents a lot of is at present as somewhat expensive in the price such as sodium laurylsulfonate, hexadecyl trimethyl ammonium bromide, and cost compare is high.Xylogen is natural high moleculer eompound, it is the main component of black liquid, sulfonated lignin (sodium salt, calcium salt etc.) are the by products of paper industry, there is natural reticulated structure, anion surfactant can be done, xylogen as waste utilization have inexpensive, nontoxic, the feature such as be easy to get, reaction cost can be reduced to the utilization of xylogen, and new pollution can not be caused to environment.
Summary of the invention
The object of this invention is to provide a kind of preparation method utilizing electrochemical deposition method to prepare xylogen nanometer doped zinc oxide, technical scheme disclosed by the invention is as follows:
A kind of electrochemical deposition method prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film, first prepare the precursor solution containing zinc, adding ligninsulfonate is tensio-active agent, then precursor solution is proceeded to three-electrode system and carry out electrochemical deposition, finally products therefrom is calcined aftertreatment and obtain.
In a more excellent disclosed example of the present invention, described preparation containing the precursor solution step of zinc is, add in zinc solution under room temperature after sulfonated lignin stir and leave standstill, the volumetric molar concentration of described zinc solution is 0.05 ~ 0.1M, described sulfonated lignin mass concentration is 1%, and described zinc solution and the volume ratio of lignosulfonate solutions are 100:1 ~ 10.
In a more excellent disclosed example of the present invention, described electrochemical-deposition step is, above-mentioned precursor solution is proceeded in three-electrode system and deposits, wherein, described three-electrode system is using conductive substrates as working electrode, and platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, depositing temperature 25 ~ 60 DEG C, depositing time 5 ~ 25min, sedimentation potential-1.1 ~-2.5V.
In a more excellent disclosed example of the present invention, described calcining post-processing step is by through the product deionized water rinsing of electrochemical deposition gained, drying, is placed in retort furnace in 500 DEG C of calcining 2 ~ 3h, is cooled to room temperature.
In a more excellent disclosed example of the present invention, described conductive substrates is ITO conductive glass, and described sedimentation potential is-2.0V, the preferred 15min of depositing time preferably.
In a more excellent disclosed example of the present invention, described zinc salt is any one in zinc nitrate, zinc chloride, zinc sulfate.
In a more excellent disclosed example of the present invention, described sulfonated lignin are any one in calcium lignin sulphonate or sodium lignosulfonate.
According to sulfonated lignin nanometer doped zinc oxide laminated film prepared by above-mentioned either method disclosed by the invention, it is polycrystalline hexagonal wurtzite structure.
According to sulfonated lignin nanometer doped zinc oxide laminated film prepared by above-mentioned either method disclosed by the invention, the particle diameter of zinc oxide is 18 ~ 25nm.
Sulfonated lignin nanometer doped zinc oxide laminated film prepared by the present invention, can do sensor, anti-biotic material, photocatalyst etc.
The present invention's reagent zinc nitrate used, zinc chloride, zinc sulfate are analytical pure; Calcium lignin sulphonate, sodium lignosulfonate are technical grade, are commercially available.
beneficial effect
The present invention utilizes sulfonated lignin for template and tensio-active agent, prepares nano-zinc oxide compound by electrochemical deposition method, and in calcination process, the moieties of sulfonated lignin is burnt, and leaves space, and what obtain is porous zinc bloom composite membrane.The present invention have be easy to control, cost is low, the advantage of technique and simple flow, be applicable to suitability for industrialized production.
Accompanying drawing explanation
The Electron micrographs Electronic Speculum figure (SEM) of the sulfonated lignin nanometer doped zinc oxide laminated film that Fig. 1 embodiment 1 is obtained.
The X ray diffracting spectrum (XRD) of the sulfonated lignin nanometer doped zinc oxide laminated film that Fig. 2 obtains, wherein a is that embodiment 1 obtains, and b is that embodiment 2 obtains, and c is that embodiment 3 obtains.
Embodiment
Below in conjunction with concrete embodiment, the present invention will be further described, and to make those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
embodiment 1
1, prepare precursor solution, zinc source is zinc nitrate, and calcium lignin sulphonate is tensio-active agent, zinc nitrate concentration 0.1M, and lignosulfonic acid calcium concn 1%, according to the ratio of volume ratio 100:4, drips calcium lignosulfonate solution in zinc nitrate solution;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 25 DEG C, depositing time 15min, sedimentation potential-2.0V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C calcining 2h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 18nm, and Electron micrographs Electronic Speculum figure (SEM) is shown in Fig. 1, XRD as Fig. 2 a,
embodiment 2
1, prepare precursor solution, zinc source is zinc nitrate, and sodium lignosulfonate is tensio-active agent, zinc nitrate concentration 0.05M, lignosulfonic acid na concn 1%, according to the ratio of volume ratio 100:1, drips lignosulfonic acid sodium solution in zinc nitrate solution;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 30 DEG C, depositing time 15min, sedimentation potential-1.5V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C of calcining 2h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 20nm, and XRD is as Fig. 2 b.
embodiment 3
1, prepare precursor solution, zinc source is zinc chloride, and calcium lignin sulphonate is tensio-active agent, zinc oxide concentration 0.1M, and lignosulfonic acid calcium concn 1%, according to the ratio of volume ratio 100:2, drips calcium lignosulfonate solution in liquor zinci chloridi;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 30 DEG C, depositing time 15min, sedimentation potential-2.5V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C of calcining 2h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 19nm, and XRD is as Fig. 2 c.
The Electron micrographs Electronic Speculum figure (SEM) of Fig. 1 embodiment 1.
The X ray diffracting spectrum (XRD) of Fig. 2 embodiment, wherein a is embodiment 1, b be embodiment 2, c is embodiment 3.As can be seen from the figure, a, b, c have the charateristic avsorption band of zinc oxide, and wherein a peak is capable the strongest, and c peak is capable the most weak, and illustrate that a crystalline substance row is the most complete, and particle diameter is minimum, main powered position influence is comparatively large, and-2.0 is preferred current potential.Following examples choosing is preferred current potential-2.0V then.
embodiment 4
1, prepare precursor solution, zinc source is zinc sulfate, and calcium lignin sulphonate is tensio-active agent, zinc sulfate concentration 0.1M, and lignosulfonic acid calcium concn 1%, according to the ratio of volume ratio 100:1, drips calcium lignosulfonate solution in solution of zinc sulfate;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 30 DEG C, depositing time 5min, sedimentation potential-2.0V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C of calcining 2h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 20nm.
embodiment 5
1, prepare precursor solution, zinc source is zinc nitrate, and calcium lignin sulphonate is tensio-active agent, zinc nitrate concentration 0.1M, and lignosulfonic acid calcium concn 1%, according to the ratio of volume ratio 100:10, drips calcium lignosulfonate solution in zinc nitrate solution;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 60 DEG C, depositing time 25min, sedimentation potential-2.0V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C of calcining 3h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 25nm.
embodiment 6
1, prepare precursor solution, zinc source is zinc chloride, and sodium lignosulfonate is tensio-active agent, zinc oxide concentration 0.1M, lignosulfonic acid na concn 1%, according to the ratio of volume ratio 100:1, drips lignosulfonic acid sodium solution in liquor zinci chloridi;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 25 DEG C, depositing time 15min, sedimentation potential-2.0V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C of calcining 2h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 18nm.
embodiment 7
1, prepare precursor solution, zinc source is zinc chloride, and sodium lignosulfonate is tensio-active agent, zinc oxide concentration 0.1M, lignosulfonic acid na concn 1%, according to the ratio of volume ratio 100:10, drips lignosulfonic acid sodium solution in liquor zinci chloridi;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 30 DEG C, depositing time 10min, sedimentation potential-2.0V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C of calcining 2h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 24nm.
embodiment 8
1, prepare precursor solution, zinc source is zinc sulfate, and sodium lignosulfonate is tensio-active agent, zinc sulfate concentration 0.1M, lignosulfonic acid na concn 1%, according to the ratio of volume ratio 100:10, drips lignosulfonic acid sodium solution in solution of zinc sulfate;
2, electrochemical deposition, proceeds to three-electrode system by precursor solution, wherein using ITO conductive glass as working electrode, platinum electrode as supporting electrode, saturated calomel electrode as reference electrode, depositing temperature 30 DEG C, depositing time 25min, sedimentation potential-2.0V;
3, aftertreatment, by product deionized water rinsing, drying repeatedly, 500 DEG C of calcining 2h, obtain zinc-oxide nano composite membrane, product is polycrystalline hexagonal wurtzite structure, and median size is about 25nm.
Claims (8)
1. an electrochemical deposition method prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film, first preparation is containing the precursor solution of zinc, adding ligninsulfonate is tensio-active agent, then precursor solution is proceeded to three-electrode system and carry out electrochemical deposition, finally products therefrom is calcined aftertreatment to obtain, it is characterized in that
Described preparation containing the precursor solution step of zinc is: add in zinc solution under room temperature after sulfonated lignin stir and leave standstill, the volumetric molar concentration of described zinc solution is 0.05 ~ 0.1M, described sulfonated lignin mass concentration is 1%, and described zinc solution and the volume ratio of lignosulfonate solutions are 100:1 ~ 10;
Described electrochemical-deposition step is: proceeded in three-electrode system by above-mentioned precursor solution and deposit, wherein, described three-electrode system is using conductive substrates as working electrode, platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, depositing temperature 25 ~ 60 DEG C, depositing time 5 ~ 25min, sedimentation potential-1.1 ~-2.5V;
Described calcining post-processing step is by through the product deionized water rinsing of electrochemical deposition gained, drying, is placed in retort furnace in 500 DEG C of calcining 2 ~ 3h, is cooled to room temperature.
2. electrochemical deposition method according to claim 1 prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film, it is characterized in that, described zinc salt is any one in zinc nitrate, zinc chloride, zinc sulfate.
3. electrochemical deposition method according to claim 1 prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film, it is characterized in that, described sulfonated lignin are any one in calcium lignin sulphonate or sodium lignosulfonate.
4. electrochemical deposition method according to claim 1 prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film, it is characterized in that, described conductive substrates is ITO conductive glass.
5. electrochemical deposition method according to claim 1 prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film, it is characterized in that, described sedimentation potential is-2.0V.
6. electrochemical deposition method according to claim 1 prepares the method for sulfonated lignin nanometer doped zinc oxide laminated film, it is characterized in that, described depositing time is 15min.
7. according to sulfonated lignin nanometer doped zinc oxide laminated film prepared by claim 1 ~ 6 either method.
8. sulfonated lignin nanometer doped zinc oxide laminated film according to claim 7, is characterized in that, the particle diameter of zinc oxide is 18 ~ 25nm.
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| CN103320828B (en) * | 2013-06-14 | 2015-12-09 | 江苏大学 | A kind of electrochemical preparation method of hexamethylenetetramine nanometer doped zinc oxide film |
| CN105738416B (en) * | 2016-02-25 | 2018-11-09 | 华南师范大学 | A kind of method of surfactant induction electro-deposition processing ZnO gas sensors |
| CN111289580A (en) * | 2018-06-27 | 2020-06-16 | 成都新柯力化工科技有限公司 | Film sensing material for detecting atmosphere hydrogen sulfide gas and preparation method thereof |
| CN109103027A (en) * | 2018-07-09 | 2018-12-28 | 江苏大学 | Solvent-thermal method prepares the method and its application of cobalt acid copper combination electrode material |
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| JPS6362895A (en) * | 1986-09-03 | 1988-03-19 | Kao Corp | Organic polymer-zinc alloy composite electroplating bath |
| CN87106993A (en) * | 1986-10-17 | 1988-08-31 | 花王株式会社 | Composition coating of zinc and organic polymer |
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