CN102390862A - Liquid-phase precipitation preparation method of zinc oxide porous hollow balls - Google Patents
Liquid-phase precipitation preparation method of zinc oxide porous hollow balls Download PDFInfo
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- CN102390862A CN102390862A CN2011102322557A CN201110232255A CN102390862A CN 102390862 A CN102390862 A CN 102390862A CN 2011102322557 A CN2011102322557 A CN 2011102322557A CN 201110232255 A CN201110232255 A CN 201110232255A CN 102390862 A CN102390862 A CN 102390862A
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- porous hollow
- zinc oxide
- sodium citrate
- hexamethylenetetramine
- zno
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 35
- 238000001556 precipitation Methods 0.000 title claims abstract description 12
- 239000007791 liquid phase Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 28
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000001509 sodium citrate Substances 0.000 claims abstract description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract 6
- 239000004094 surface-active agent Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000008092 positive effect Effects 0.000 abstract 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 8
- 229940038773 trisodium citrate Drugs 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
一种液相沉淀法制备氧化锌多孔空心球的方法，以六次甲基四胺和硝酸锌为原料，以柠檬酸钠为表面活性剂，在水中进行沉淀反应，步骤如下：1）将六次甲基四胺溶于去离子水中，溶解后加入硝酸锌和柠檬酸钠，制成反应液；2）将反应液置于80～95℃水浴槽中反应3-7h后抽滤，得到白色沉淀物，将沉淀物充分洗涤，过滤后将沉淀物烘干，即可制得粉末状氧化锌多孔空心球。本发明的优点和积极效果：1)液相沉淀法制备ZnO多孔空心球的制备方法与其他方法相比，工艺简单、成本低；2)该方法可以获得均匀分布的ZnO多孔空心球，比表面积较大，多孔结构使其气体充分接触，这特别有利于基于ZnO纳米材料的气敏器件的制造。
A liquid-phase precipitation method for preparing porous hollow spheres of zinc oxide , using hexamethylenetetramine and zinc nitrate as raw materials, using sodium citrate as a surfactant, and carrying out precipitation reaction in water, the steps are as follows: 1) adding six Dissolve methylenetetramine in deionized water, add zinc nitrate and sodium citrate after dissolving to make a reaction solution; 2) place the reaction solution in a water bath at 80-95°C for 3-7 hours and then filter it with suction to obtain a white For the precipitate, the precipitate is fully washed, filtered and then dried to obtain a powdery porous hollow sphere of zinc oxide. Advantages and positive effects of the present invention: 1) Compared with other methods, the preparation method of ZnO porous hollow spheres prepared by liquid phase precipitation method has simple process and low cost; 2) the method can obtain evenly distributed ZnO porous hollow spheres, and the specific surface area The larger, porous structure makes it fully accessible to gases, which is particularly beneficial for the fabrication of gas-sensing devices based on ZnO nanomaterials.
Description
Technical field
The invention belongs to the preparation that belongs to gas sensitive, particularly a kind of liquid-phase precipitation method prepares the method for ZnO porous hollow sphere.
Background technology
Zinc oxide is a kind of important wide bandgap compound semiconductors, has important use in fields such as chemical sensor, piezoelectricity, photochemical catalysis, opto-electronic conversion, blue green LED and laser apparatus and is worth.In chemical sensor, piezoelectricity, photochemical catalysis, opto-electronic conversion application process, increase the zinc oxide specific surface area is to promote its performance effective ways always.The method for preparing zinc oxide commonly used at present; Like template, sol-gel method, microemulsion method etc.; The common only outside surface of material capable of using; Do not give full play to the performance of material as yet, the zinc oxide porous hollow sphere that this patent proposed passes the internal surface and the outside surface that can make full use of material, might realize improving the above-mentioned application performance of material.
Summary of the invention
The objective of the invention is according to above-mentioned technical Analysis, the method that provides a kind of liquid-phase precipitation method to prepare the zinc oxide porous hollow sphere, this preparing method's technology is simple, cost is low, and can obtain equally distributed ZnO nanoporous hollow ball, and specific surface area is bigger; This material is used to prepare the heater-type gas sensor, can fully contact with monitoring gas.
Technical scheme of the present invention:
A kind of liquid-phase precipitation method prepares the method for zinc oxide porous hollow sphere
,With hexamethylenetetramine and zinc nitrate is raw material, is tensio-active agent with the Trisodium Citrate, in water, carries out precipitin reaction, and step is following:
1) hexamethylenetetramine is dissolved in the deionized water, ultrasonic it is dissolved fully, add zinc nitrate and fully after the dissolving, add Trisodium Citrate again, process reaction solution;
2) reaction solution is placed suction filtration behind 80～95 ℃ of water baths reaction 3-7h; Obtain white depositions; Throw out is used deionized water, absolute ethyl alcohol thorough washing respectively, after the filtration throw out is dried under 50～80 ℃ of temperature, can make the powdered zinc oxide porous hollow sphere.
The amount ratio of said hexamethylenetetramine, zinc nitrate, Trisodium Citrate and deionized water is that hexamethylenetetramine is that 0.1-0.4g, zinc nitrate are that 0.5-0.8 g, Trisodium Citrate are 0.1-0.2g in the 100 ml deionized waters.
Reaction principle of the present invention: when no Trisodium Citrate exists; Zinc oxide is easy to form club shaped structure; But owing to there is Trisodium Citrate; Regular chain-like structure makes it be easy to be adsorbed on its process of growth of ZnO surface of seed change, causes the formation of sheet structure, and the continuous gathering of sheet structure has finally formed the surface and has been the ZnO porous hollow sphere of porous laminated structure.The surface of ZnO porous hollow sphere is to combine porous laminated structure by many particles, and the space is arranged again between the particle, and some ball surface does not have complete closed; Part is opened wide, and the diameter of ball is about 2 μ m, and gas molecule can get into; Inside and outsidely all can contact simultaneously with gas; Thereby the adsorb oxygen amount that has improved nano zine oxide reaches the contact area with gas, and it is had good air-sensitive performance as gas sensitive, can be used as gas sensitive and is applied to gas sensing unit.
Advantage of the present invention and positively effect:
1) liquid-phase precipitation method prepares the preparation method and the data by MoM and MEI of ZnO porous hollow sphere, and technology is simple, cost is low; 2) this method can obtain equally distributed ZnO porous hollow sphere, and specific surface area is bigger, and vesicular structure fully contacts its gas, and this is particularly conducive to the manufacturing based on the gas sensitive device of ZnO nano material.
[description of drawings]
Fig. 1 is a ZnO porous hollow sphere ball wall SEM photo, and illustration is a porous hollow sphere SEM photo.
Fig. 2 is the XRD figure of ZnO porous hollow sphere.
Fig. 3 is the nitrogen adsorption/desorption isothermal curve of ZnO porous hollow sphere.
Fig. 4 is the sensitivity curve of ZnO porous hollow sphere to different concentration ethanol.
[embodiment]
Embodiment:
A kind of liquid-phase precipitation method prepares the method for zinc oxide porous hollow sphere
,With hexamethylenetetramine and zinc nitrate is raw material, is tensio-active agent with the Trisodium Citrate, in water, carries out precipitin reaction, and step is following:
1) the 0.7g hexamethylenetetramine is dissolved in the 200ml deionized water, ultrasonic it is dissolved fully, add the 1.49g zinc nitrate again, after the dissolving, take by weighing the 0.24g Trisodium Citrate again and add above-mentioned solution fully, it is dissolved fully.
2) this mixing solutions is placed 95 ℃ of water baths, reaction back suction filtration gets white precipitate, for observing its process of growth, has set 3 reaction times, is respectively 3h, 5h and 7h.After reaction finishes respectively with throw out with deionized water, absolute ethyl alcohol thorough washing, after the filtration throw out is placed 60 ℃ of baking ovens dryings, make Powdered ZnO porous hollow sphere.Whether can influence product structure for observing annealing process, the product that makes was calcined 2 hours in 400 ℃ of retort furnaces.
Fig. 1, Fig. 2 and Fig. 3 are respectively to be ZnO porous hollow sphere SEM, XRD, the nitrogen adsorption/desorption isothermal curve of 5h in the reaction times.Can know that by Fig. 1 the surface of ball is to combine porous laminated structure by many particles, thickness is about about 10nm, and the space is arranged between the particle.Can know the wurtzite structure that is of ZnO porous hollow sphere through the preparation of this method by Fig. 2, crystallization degree is very high.The specific surface area that is obtained product by nitrogen adsorption/desorption isothermal curve of Fig. 3 is 41.84 m
2/ g.Fig. 4 ZnO differential responses time porous hollow sphere is to alcoholic acid sensitivity curve figure, and 5h is the suitable reactions time, and sensitivity is 51.4 to product to the 500ppm alcoholic acid at this moment.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897825A (en) * | 2012-09-25 | 2013-01-30 | 江苏大学 | Method for preparing nano-hollow spherical shell zinc oxide by hydrothermal-calcinating method |
| CN103943838A (en) * | 2014-04-21 | 2014-07-23 | 西安交通大学 | Preparation method of metal oxide nanosheet and carbon nanotube composite energy-storage material |
| CN104128159A (en) * | 2014-08-13 | 2014-11-05 | 陕西科技大学 | Wastewater treatment material with photocatalysis and heavy metal adsorption functions and capable of being recycled and preparation method thereof |
| CN104164176A (en) * | 2014-08-04 | 2014-11-26 | 陕西科技大学 | Method for enhancing water resistance of water-based polyurethane for synthetic leather by using zinc oxide |
| CN105600815A (en) * | 2014-11-12 | 2016-05-25 | 天津科技大学 | Doped nanometer zinc oxide light conversion agent preparation method |
| CN107572578A (en) * | 2017-09-07 | 2018-01-12 | 东南大学 | A kind of method that no template prepares zinc oxide spherical shell |
| CN109174092A (en) * | 2018-09-21 | 2019-01-11 | 东华大学 | A kind of zinc oxide/platinum composite material microballoon and its preparation method and application |
| CN110002511A (en) * | 2019-04-18 | 2019-07-12 | 郑州轻工业学院 | A kind of Co of hollow structure3O4Nano material and preparation method thereof |
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| CN101311119B (en) * | 2007-05-25 | 2010-09-08 | 中国科学院合肥物质科学研究院 | Reticular nanoporous zinc oxide micron hollow sphere and preparation method thereof |
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2011
- 2011-08-15 CN CN2011102322557A patent/CN102390862A/en active Pending
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| CN101311119B (en) * | 2007-05-25 | 2010-09-08 | 中国科学院合肥物质科学研究院 | Reticular nanoporous zinc oxide micron hollow sphere and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897825B (en) * | 2012-09-25 | 2014-05-28 | 江苏大学 | Method for preparing nano-hollow spherical shell zinc oxide by hydrothermal-calcinating method |
| CN102897825A (en) * | 2012-09-25 | 2013-01-30 | 江苏大学 | Method for preparing nano-hollow spherical shell zinc oxide by hydrothermal-calcinating method |
| CN103943838B (en) * | 2014-04-21 | 2016-07-20 | 西安交通大学 | The preparation method of metal oxide nano-sheet and CNT composite energy-storage material |
| CN103943838A (en) * | 2014-04-21 | 2014-07-23 | 西安交通大学 | Preparation method of metal oxide nanosheet and carbon nanotube composite energy-storage material |
| CN104164176A (en) * | 2014-08-04 | 2014-11-26 | 陕西科技大学 | Method for enhancing water resistance of water-based polyurethane for synthetic leather by using zinc oxide |
| CN104128159A (en) * | 2014-08-13 | 2014-11-05 | 陕西科技大学 | Wastewater treatment material with photocatalysis and heavy metal adsorption functions and capable of being recycled and preparation method thereof |
| CN104128159B (en) * | 2014-08-13 | 2016-04-20 | 陕西科技大学 | There is wastewater treatment material that photocatalysis and heavy metal adsorption function can be recycled and preparation method thereof |
| CN105600815A (en) * | 2014-11-12 | 2016-05-25 | 天津科技大学 | Doped nanometer zinc oxide light conversion agent preparation method |
| CN105600815B (en) * | 2014-11-12 | 2018-04-20 | 天津科技大学 | A kind of preparation method of doped nano zinc oxide light conversion agent |
| CN107572578A (en) * | 2017-09-07 | 2018-01-12 | 东南大学 | A kind of method that no template prepares zinc oxide spherical shell |
| CN109174092A (en) * | 2018-09-21 | 2019-01-11 | 东华大学 | A kind of zinc oxide/platinum composite material microballoon and its preparation method and application |
| CN109174092B (en) * | 2018-09-21 | 2021-07-20 | 东华大学 | A kind of zinc oxide/platinum composite material microsphere and its preparation method and application |
| CN110002511A (en) * | 2019-04-18 | 2019-07-12 | 郑州轻工业学院 | A kind of Co of hollow structure3O4Nano material and preparation method thereof |
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Application publication date: 20120328 |