CN102134092B - Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application - Google Patents
Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application Download PDFInfo
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- CN102134092B CN102134092B CN 201110039341 CN201110039341A CN102134092B CN 102134092 B CN102134092 B CN 102134092B CN 201110039341 CN201110039341 CN 201110039341 CN 201110039341 A CN201110039341 A CN 201110039341A CN 102134092 B CN102134092 B CN 102134092B
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Abstract
The invention provides a preparation method of indium oxide with new appearance, belonging to the technical field of synthesis and nano material of the indium oxide. The preparation method comprises the following steps: taking inorganic salt solution of the indium as an indium source, adopting N, N-dimethyl formamide (DMF) as an alkali source and anion active agents such as sodium dodecyl sulfate (SDS) and the like as an additive, using hydrothermal synthesis to prepare the novel hollow-microspherical and flower-shaped indium oxide with the secondary structure under the condition without adding any hard template, and controlling the appearance of the secondary structure by chemical means. In the preparation method provided by the invention, the technical process is simple, the promotion is easy, the selected reagent is low in price and environment-friendly, and the need on low-cost, large-scale and green production is met.
Description
Technical field
The present invention relates to a kind of prepare hollow ball with secondary structure and simple and easy method and the application thereof of flower-shaped Indium sesquioxide, belong to the synthetic and Application Areas of micrometer/nanometer control of material.
Background technology
As everyone knows, inorganic micrometer/nanometer material character is relevant with size and the shape of particle.Present extensive work concentrates on the control of the micrometer/nanometer material of different shapes, size, dimension and structure and synthesizes.Especially to by nano structured unit; such as nano particle; nanometer rod/line/band or nanometer sheet make up the 3D micrometer/nanometer structured material with level time or complex construction that forms research oneself through becoming one of study hotspot of material; this is because the secondary structure of material can produce more excellent overall coordination character usually; the characteristic that not only can have structural unit; the coupling effect that also may have the nano structured unit combination results; thereby synergistic effect etc. have made these materials shows is different from the physics and chemistry character of the uniqueness of its construction unit and block materials, and this is the further novel Nano/micron dimension transducer of design design; device provides solid basis.Recently, people oneself through having reported many Nano/micron materials with level aggregated(particle) structure of different-shape, and set forth they catalysis, Conversion of energy and storage, environmental purification, sensor and biological aspect potential application.（a)H.?Jiang,?J.?Q.?Hu,?F.?Gu,?W.?Shao?and?C.Z.?Li,?
Chem.?Commun.,?2009,?3618,?b)K.I.?Choi,?H.R.?Kim,?J.H.?Lee,?
Sens.?Actuators?B，2009,?138,?497.）
Indium sesquioxide is a kind of N-type semiconductor, belongs to III-VI family, has the direct band gap of 3.55 –, 3.75 eV, has high conductivity and visible light transmissivity.Nanostructure or the Indium sesquioxide with secondary structure that is made up by nano structured unit, show the electricity of many novelties owing to the quantum confined effect with current carrier, optical property, can be used for solar cell, transparent conductor, the window well heater, opto-electronic device, flat-panel monitor, UV, visible light (ultraviolet ray) laser apparatus, detector, the field such as Organic Light Emitting Diode and gas sensor has uses (a) I. Hamberg and C. G. Granqvist very widely
J. Appl. Phys., 1986,60,123; B) H. Zhou, W. Cai and L. Zhang,
Appl. Phys. Lett., 1999,26,495; C) N. Pinna, G. Neri, M. Antonietti and M. Niederberger,
Angew. Chem., Int. Ed., 2004,43,4345).It is used widely so that the control of Indium sesquioxide is synthesized important Research Significance, so the micrometer/nanometer Indium sesquioxide with secondary structure that is made up by nano structured unit is in the news successively.For example use sucrose as the synthetic hollow ball Indium sesquioxide with needle-like or shaft-like secondary structure of hard template (H. Jiang, J. Q. Hu, F. Gu, W. Shao and C.Z. Li,
Chem. Commun., 2009,3618) and synthesize the hollow ball Indium sesquioxide with nano particle secondary structure as additive with amino acid, (K.I. Choi, H.R. Kim, J.H. Lee,
Sens. Actuators B, 2009,138,497) and use urea synthesis to have the flower-shaped microballoon Indium sesquioxide of shaft-like secondary structure, (H.Z., X.L. Wang, F. Yang, and X.R. Yang,
Crystal Growth ﹠amp; Design, 2008,8,950.) add the synthetic flower-shaped ball Indium sesquioxide with porous nano-sheet secondary structure of thiocarbamide (J.Y. Liu, T. Luo, F.L. Meng, K. Qian, Y.T. Wan, and J.H. Liu,
J. Phys. Chem. C2010
, 114,4887) etc.But above-mentioned synthetic method existence condition is harsh, and cost is higher, complicated operation, and the problems such as Indium sesquioxide that can only synthesizing single shape, what have can not large batch of synthetic putting into production.
Summary of the invention
The objective of the invention is to solve in the above-mentioned Indium sesquioxide preparation process that production cost is high, the technological deficiencies such as experiment condition is harsh, complicated operation, a kind of simple method for preparing with secondary structure hollow spheres and flower-shaped Indium sesquioxide is provided, and with the sensitive material of synthetic material as gas sensor gas.
For achieving the above object, the present invention is by the following technical solutions:
(1) first a certain amount of indium salt and anion surfactant are added in the corresponding beaker that deionized water is housed, then mix to dissolving, again with a certain amount of N, dinethylformamide (DMF) adds in the middle of the mentioned solution, continue to stir and make its dissolving, then changing the respective volume liner over to is in the stainless steel autoclave of tetrafluoroethylene, and control autoclave temperature was 140～180 ℃ of hydro-thermal reactions 1～10 hour after the sealing;
(2) after reaction finished, collecting reaction product obtained white precipitate, then repeatedly cleans the precursor of dry washed product Indium sesquioxide through deionized water, dehydrated alcohol;
(3) change precursor over to crucible and place retort furnace, under the certain temperature condition, calcine and namely obtained Indium sesquioxide in 2～6 hours;
(4) with the sensitive material of synthetic Indium sesquioxide as the catalytic luminescence sensor, hydrogen sulfide is tested.
Thereby wherein regularly can obtain by the amount control of control anion surfactant the pattern of Indium sesquioxide when these experiment conditions one of consumption, temperature of reaction and the hydro-thermal reaction time of indium salt; Thereby regularly can obtain by the control of control hydro-thermal reaction time the pattern of Indium sesquioxide when these experiment conditions one of consumption, temperature of reaction and anion surfactant consumption of indium salt.
A kind of in the inorganic salt that described indium salt is the indiums such as indium chloride, indium sulfate and indium nitrate; Described anion surfactant is sodium laurylsulfonate (SDS) or Sodium dodecylbenzene sulfonate (SDBS).
Calcining obtains described step (3) hollow spheres Indium sesquioxide under 600 ℃ the condition being not less than 400 ℃, flower-shaped Indium sesquioxide and being not less than.
Compared with prior art, the present invention has following beneficial effect:
A) raw material sources of the present invention are extensive, and experimental technique is simple, and preparation method's cost is low;
B) preparation method of the present invention does not need to add in addition hard template, and is simple to operation;
C) method provided by the present invention is synthesized by the control that two kinds of new patterns of reaction times realization of regulating and control different anion surfactant consumptions or system have the Indium sesquioxide of secondary structure;
D) can be as the sensitive material of catalytic luminescence gas sensor.
Description of drawings
Fig. 1 is scanning electronic microscope (SEM) figure of Indium sesquioxide of the present invention and precursor thereof, wherein schemes a and be to have the SEM figure of precursor of the hollow microsphere Indium sesquioxide of secondary structure; Figure b is the SEM figure with hollow microsphere Indium sesquioxide of secondary structure; Figure c is the SEM figure of the precursor of flower-shaped Indium sesquioxide; Figure d is the SEM figure of flower-shaped Indium sesquioxide;
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of Indium sesquioxide of the present invention.Wherein, a is the XRD figure with hollow microsphere Indium sesquioxide of secondary structure; Figure b is the XRD figure of flower-shaped Indium sesquioxide;
Fig. 3 is X-ray diffraction (XRD) figure of the precursor of Indium sesquioxide of the present invention.A has the XRD figure of precursor of the hollow microsphere Indium sesquioxide of secondary structure; Figure b is the XRD figure of the precursor of flower-shaped Indium sesquioxide;
Fig. 4 is transmission electron microscope (TEM), high-resolution-ration transmission electric-lens (HRTEM) and selected diffraction (SAED) figure of Indium sesquioxide of the present invention.Wherein, figure a, b are the TEM figure with hollow microsphere Indium sesquioxide of secondary structure; Figure c has the HRTEM figure of the hollow microsphere Indium sesquioxide of secondary structure; Figure d is the SAED figure with hollow microsphere Indium sesquioxide of secondary structure.Figure e is the TEM figure of flower-shaped Indium sesquioxide; Figure f is that the XRD figure of flower-shaped Indium sesquioxide is the HRTEM figure of flower-shaped Indium sesquioxide; Figure g is the SAED figure of flower-shaped Indium sesquioxide;
Fig. 5 be adopt hollow ball Indium sesquioxide that method of the present invention synthesizes as the catalytic luminescence sensitive material respectively to the response of the hydrogen sulfide of 2 ppm and 4 ppm.
Embodiment
Has the hollow spheres Indium sesquioxide of secondary structure and simple method for preparing and the application thereof of flower-shaped Indium sesquioxide is described further below by embodiment to of the present invention.The present embodiment is implemented under take the present invention program as prerequisite, has provided detailed embodiment and concrete operating process.
Embodiment 1:
A) first 2 mmol indium chlorides, 4g SDS are added in the 50mL beaker that the 40mL deionized water is housed, then mix and blend is approximately 20 minutes.Again 4 mL DMF are added in the middle of the mentioned solution, continued stir about 10 minutes.This solution is changed in the 60mL teflon-lined autoclave, after the sealing autoclave is placed 160 ℃ of lower maintenances 10 hours.After 10 hours autoclave is taken out, to be cooled to the room temperature the opening high pressure still, product is transferred in the beaker;
B) above-mentioned product is cleaned repeatedly with deionized water and dehydrated alcohol.Last white precipitate is placed 60 ℃ of lower oven dry.White precipitate is precursor.And prepared white precursor carried out XRD, the sign of SEM;
C) precursor after will drying is transferred in the crucible, with crucible put into retort furnace 400 ℃ lower keep 5 hours after, take out, be cooled to room temperature.The yellow final product that obtains has at last been carried out XRD, SEM, the sign of TEM.
Embodiment 2:
A) first 2 mmol indium chlorides, 6g SDS are added in the 50mL beaker that the 40mL deionized water is housed, then mix and blend is approximately 20 minutes.Again 4 mL DMF are added in the middle of the mentioned solution, continued stir about 10 minutes.This solution is changed in the 60mL teflon-lined autoclave, after the sealing autoclave is placed 160 ℃ of lower maintenances 10 hours.After 10 hours autoclave is taken out, to be cooled to the room temperature the opening high pressure still, product is transferred in the beaker;
B) above-mentioned product is cleaned repeatedly with deionized water and dehydrated alcohol.Last white precipitate is placed 60 ℃ of lower oven dry.White precipitate is precursor.And prepared white precursor carried out XRD, the sign of SEM;
C) precursor after will drying is transferred in the crucible, with crucible put into retort furnace 600 ℃ lower keep 5 hours after, take out, be cooled to room temperature.The yellow final product that obtains has at last been carried out XRD, SEM, the sign of TEM.
Embodiment 3:
A) first 2 mmol indium chlorides, 1g SDS are added in the 50mL beaker that the 40mL deionized water is housed, then mix and blend is approximately 20 minutes.Again 4 mL DMF are added in the middle of the mentioned solution, continued stir about 10 minutes.This solution is changed in the 60mL teflon-lined autoclave, after the sealing autoclave is placed 160 ℃ of lower maintenances 10 hours.After 10 hours autoclave is taken out, to be cooled to the room temperature the opening high pressure still, product is transferred in the beaker;
B) above-mentioned product is cleaned repeatedly with deionized water and dehydrated alcohol.Last white precipitate is placed 60 ℃ of lower oven dry.White precipitate is precursor.And prepared white precursor carried out XRD, the sign of SEM;
C) precursor after will drying is transferred in the crucible, with crucible put into retort furnace 400 ℃ lower keep 5 hours after, take out, be cooled to room temperature.
Embodiment 4:
The present embodiment is mainly in order to investigate in the above-mentioned Indium sesquioxide process of preparation the experiment condition such as the concentration of SDS and hydro-thermal reaction time to the impact of Indium sesquioxide pattern.Concrete preparation method's method is with implementing 1, and difference is amount, hydrothermal temperature and the reaction times that changes respectively SDS in the reaction process.The concrete quadrature form (table 1) of pressing is implemented.The SDS amount is more as can be known by experimental result, and the time, longer then product tended to generate flower-shaped Indium sesquioxide; When SDS amount longer then product of fewer time tends to generate the hollow microsphere Indium sesquioxide with secondary structure.And the secondary structure of hollow ball also can be along with the variation of the amount of SDS and reaction times length and is changed.
The hydro-thermal reaction experiment condition of the above-mentioned Indium sesquioxide of table 1 preparation
Embodiment 5:
The present embodiment is for adopting the prepared Indium sesquioxide of the present invention to be used for the catalytic luminescence gas sensor test experiment that the gas sensor sensitive material carries out.Concrete steps are as follows:
A) with the synthetic hollow microsphere Indium sesquioxide dip-coating about 0.05g on ceramic heating bar.Will be with Indium sesquioxide after the oven dry
Ceramic heating bar is put into a silica tube good seal, and connects temperature regulator, inlet mouth, gives vent to anger, and puts into the illuminated chamber of catalytic luminescence detector;
B) with air as carrier gas, speed is 600 mL min
– 1, Heating temperature is 400 C.About the blowing air 10min of elder generation
Get rid of the interference of other foreign gases, treat that baseline stability begins the hydrogen sulfide of sample introduction 12ppm later, after signal is got back to baseline, continue the hydrogen sulfide of sample introduction 12ppm, sample introduction 3 times, the record experimental data, the result is as shown in Figure 5.
Experimental result shows, the hollow spheres Indium sesquioxide with secondary structure of the present invention can be used as the gas sensor sensitive material.
Claims (1)
1. have the hollow spheres of secondary structure or the preparation method of flower-shaped Indium sesquioxide, it is characterized in that processing step is as follows successively:
(a) first a certain amount of indium salt and anion surfactant are added in the corresponding beaker that deionized water is housed, then mix to dissolving, again with a certain amount of N, dinethylformamide adds in the middle of the mentioned solution, continue to stir and make its dissolving, then changing the respective volume liner over to is in the stainless steel autoclave of tetrafluoroethylene, and control autoclave temperature was 140～180 ℃ of hydro-thermal reactions 1～10 hour after the sealing;
(b) after reaction finished, collecting reaction product obtained white precipitate, then repeatedly cleans the precursor of dry washed product Indium sesquioxide through deionized water, dehydrated alcohol;
(c) change precursor over to crucible and place retort furnace, under the certain temperature condition, calcine and namely obtained Indium sesquioxide in 2～6 hours;
Indium salt is a kind of in indium chloride, indium sulfate and the indium nitrate; Anion surfactant is sodium laurylsulfonate or Sodium dodecylbenzene sulfonate;
Calcining obtains step (c) hollow spheres Indium sesquioxide under 600 ℃ the condition being not less than 400 ℃, flower-shaped Indium sesquioxide and being not less than;
Its pattern of hollow spheres is the sphere of comparison rule, outside diameter 1.5～3 μ m, inner hollow, surperficial secondary structure be the length of side 100～500nm cube, flower-shaped it is characterized in that being clustered round by the lamella between multi-layered thickness 100～300nm form diameter 8～20 μ m.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102503834B (en) * | 2011-09-29 | 2013-11-13 | 苏州大学 | Preparation method for porous sulfo-indium salt |
| CN102557114B (en) * | 2011-12-29 | 2014-06-25 | 中国科学院上海光学精密机械研究所 | Preparation method of indium oxide-based gas-sensitive material with three-dimensional hollow multi-stage structure and application thereof |
| KR101358098B1 (en) * | 2012-07-13 | 2014-02-05 | 재단법인 멀티스케일 에너지시스템 연구단 | 3-dimensional nanoparticle structure and gas sensor using same |
| CN103334179B (en) * | 2013-04-27 | 2015-07-22 | 青岛大学 | Hollow structure indium oxide nanometer fiber preparation method |
| CN104229871A (en) * | 2014-06-24 | 2014-12-24 | 济南大学 | Preparation method of flower type indium oxide gas-sensitive material with hierarchical structure |
| CN106006719B (en) * | 2016-07-20 | 2017-08-04 | 济南大学 | A kind of preparation method of the hierarchy indium oxide microballoon of nano particle composition |
| CN107140682B (en) * | 2017-06-12 | 2019-03-01 | 吉林大学 | A kind of the indium oxide powder and its low-temperature hydro-thermal synthesis of morphology controllable |
| CN110642287B (en) * | 2019-10-08 | 2022-01-07 | 济南大学 | Cubic phase In2O3Method for synthesizing micro/nano sphere structure |
| CN112811461B (en) * | 2021-03-12 | 2022-07-12 | 济南大学 | Chain bead-shaped particle self-assembled In2O3Synthetic method of hollow cage and obtained product |
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| CN101508462A (en) * | 2009-03-11 | 2009-08-19 | 长沙理工大学 | Process for producing flower shaped indium hydroxide powder having high specific surface area |
| CN101857263A (en) * | 2010-06-23 | 2010-10-13 | 东华大学 | Method for preparing nano indium oxide with controllable appearance by hydrothermal method |
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Patent Citations (2)
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|---|---|---|---|---|
| CN101508462A (en) * | 2009-03-11 | 2009-08-19 | 长沙理工大学 | Process for producing flower shaped indium hydroxide powder having high specific surface area |
| CN101857263A (en) * | 2010-06-23 | 2010-10-13 | 东华大学 | Method for preparing nano indium oxide with controllable appearance by hydrothermal method |
Non-Patent Citations (2)
| Title |
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| Hui Zhu et al..Self-Assembled 3D Microflowery In(OH)3 Architecture and Its Conversion to In2O3.《 J. Phys. Chem. C》.2008,第112卷(第39期),15285-15292. * |
| Li-Yong Chen et al..Tunable Synthesis of Various Hierarchical Structures of In(OH)3 and In2O3 Assembled by Nanocubes.《Eur. J. Inorg. Chem》.2008,1445-1451. * |
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