CN105948103A - Preparation method of bowl-shaped indium hydroxide/indium oxide micro-nano material - Google Patents

Preparation method of bowl-shaped indium hydroxide/indium oxide micro-nano material Download PDF

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Publication number
CN105948103A
CN105948103A CN201610291565.9A CN201610291565A CN105948103A CN 105948103 A CN105948103 A CN 105948103A CN 201610291565 A CN201610291565 A CN 201610291565A CN 105948103 A CN105948103 A CN 105948103A
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indium
bowl
nano material
micro
preparation
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沈明
邵美玲
王文书
蒋坤
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Yangzhou University
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Yangzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a preparation method of a bowl-shaped indium hydroxide/indium oxide micro-nano material, and relates to the technical field of preparation of semiconductor materials. Urea is adopted as a precipitating agent to provide hydroxyl radicals, a composite soft template formed by cetyl trimethyl ammonium bromide and trimellitic acid is adopted for the first time, and the indium hydroxide/indium oxide micro-nano material with controlled morphology can be synthesized through calcining after a reaction under hydrothermal conditions.

Description

A kind of preparation method of bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material
Technical field
The present invention relates to the synthetic method of the micro-nano material of the preparing technical field of semi-conducting material, particularly indium hydroxide and Indium sesquioxide..
Background technology
Indium sesquioxide. (In2O3) it is a kind of N-type semiconductor material, up to now, the method of the Indium sesquioxide. preparing pattern and size uniformity relates only to simple template, such as carbon bead, aluminum oxide porous film, oxalic acid, glycerol, sodium lauryl sulphate, Triton X-100 etc., and during using the surfactant such as cetyl trimethylammonium bromide of cationic as dispersant, because repulsive interaction interionic with indium metal, typically can only limit particle size and the effect of control indium hydroxide/Indium sesquioxide. pattern cannot be played.
Summary of the invention
The present invention seeks to propose the preparation method of the bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material of a kind of morphology controllable.
The present invention comprises the following steps:
1) trimellitic acid, cetyl trimethylammonium bromide, indium salts and carbamide are dissolved in deionized water, form mixture；
2) mixture is placed in the environment of 100～130 DEG C and carries out insulation reaction, then obtain the solid that reaction generates；
3) with distilled water and washing with alcohol solid, then solid is vacuum dried；
4) solid after vacuum drying is placed in the environment of 400～600 DEG C calcining, obtains bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material.
The present invention provides hydroxyl using carbamide as precipitant, use the compound soft template that cetyl trimethylammonium bromide is collectively forming with trimellitic acid first, first react under hydrothermal conditions, after calcining, reached the purpose of indium hydroxide/Indium sesquioxide. micro-nano material morphology control synthesis.
The particularly temperature of insulation reaction is 100～130 DEG C, slow less than the speed that this temperature hydroxyl produces, fast higher than the speed that this temperature hydroxyl produces, it is impossible to control product morphology well.
Further, the mass ratio that feeds intake of trimellitic acid of the present invention, cetyl trimethylammonium bromide, indium salts and carbamide is 1: 1～2: 1～2: 12～15.Preferably, the mass ratio that feeds intake of described trimellitic acid, cetyl trimethylammonium bromide, indium salts and carbamide is 1: 1.74: 1.43: 14.30.This rate of charge can preferably generate bowl-shape indium hydroxide micro-nano material.
Step 2) in the insulation reaction time be 10～12 hours.Time is too short not to reach little particle packing and becomes the bowl-shape required time.Higher than the 12 hours waste energy.
In step 3), vacuum drying temperature conditions is 50～70 DEG C, and the time is 12～14 hours.Exceed this temperature then product to reunite, be then dried not exclusively less than this temperature.Can guarantee that the abundant drying and dehydrating of sample in this drying time, and sample will not be reunited.
In step 4), calcination time is 3～5 hours.Less than this calcining heat and time, presoma can not be fully converted to Indium sesquioxide..Higher than this calcining heat and time, then waste the energy.
Described indium salts is indium acetate, indium nitrate or indium sulfate.This three classes indium salts is general chemical raw material readily soluble, that be easy to get, and preparation cost is low, effective.
Accompanying drawing explanation
Fig. 1 is prepared bowl-shape In (OH)3The FE-SEM photo of micro-nano material.
Fig. 2 is prepared bowl-shape In (OH)3The HR-TEM photo of micro-nano material.
Fig. 3 is the partial enlarged drawing of Fig. 2.
Fig. 4 is the partial enlarged drawing of Fig. 3.
Fig. 5 is the bowl-shape In of gained after calcining2O3The FE-SEM photo of micro-nano material.
Fig. 6 is the bowl-shape In of gained after calcining2O3The HR-TEM photo of micro-nano material.
Fig. 7 is the partial enlarged drawing of Fig. 6.
Fig. 8 is the partial enlarged drawing of Fig. 7.
Fig. 9 is the XRD figure spectrum of bowl-shape Indium sesquioxide. micro-nano material (b) after the bowl-shape indium hydroxide (a) of presoma and calcining.
Figure 10 is gained In (OH) in CTAB micelle volume3FE-SEM Photo.
Figure 11 is gained In (OH) in trimellitic acid aqueous solution3FE-SEM Photo.
Detailed description of the invention
One, the preparation of bowl-shape indium hydroxide micro-nano material:
The trimellitic acid of 1g, the cetyl trimethylammonium bromide of 1.74g, the indium nitrate (or indium acetate or indium sulfate) of 1.43g and the carbamide of 14.30g are dissolved in the deionized water of 452.38g, mixture obtains solid through centrifugal sedimentation after 100～130 DEG C of hydro-thermals are incubated 10～12 hours, with after distilled water and washing with alcohol, solid is dried 12～14 hours in 50～70 DEG C of vacuum drying ovens respectively, obtains bowl-shape indium hydroxide micro-nano material.
Two, product is identified:
Fig. 1 gives prepared bowl-shape In (OH)3Field emission scanning electron microscope (FE-SEM) photo of micro-nano material.This photo absolutely proves that obtained indium hydroxide micro-nano material is bowl structure.
Fig. 2,3,4 give prepared bowl-shape In (OH)3High-resolution-ration transmission electric-lens (HR-TEM) photo of micro-nano material.Illustrated that obtained indium hydroxide micro-nano material is bowl structure by Fig. 2.Fig. 3 is the partial enlarged drawing of Fig. 2, it is seen that: the bowl-shape micro-nano structure of indium hydroxide is that the indium hydroxide granule of size about 10～20nm " in order " under compound soft template assists assembles.Fig. 4 is the partial enlarged drawing of Fig. 3, it is seen that: the interplanar distance of indium hydroxide granule is 0.290nm, corresponding to C-In (OH)3(220) crystal face of structure, proves that this material is indium hydroxide further.
Three, the preparation of bowl-shape Indium sesquioxide. micro-nano material:
The In (OH) that above-mentioned purification is crossed3Powder loads corundum crucible and is placed in Muffle furnace, obtains bowl-shape Indium sesquioxide. micro-nano material after 400～600 ° of C calcine 3～5 h.
Four, product is identified:
Fig. 5 gives the bowl-shape In of gained after calcining2O3The FE-SEM photo of micro-nano material.It can be seen that obtained Indium sesquioxide. micro-nano material is bowl structure in figure.
Fig. 6,7,8 give the bowl-shape In of gained after calcining2O3The HR-TEM photo of micro-nano material.Illustrated that obtained Indium sesquioxide. micro-nano material is bowl structure by Fig. 6.Fig. 7 is the partial enlarged drawing of Fig. 6, it is seen that: the bowl-shape micro-nano structure of Indium sesquioxide. is that the indium oxide particles of size about 10 ~ 20nm is piled up and formed.Fig. 8 is the partial enlarged drawing of Fig. 7, it is seen that: the interplanar distance of indium oxide particles is 0.291nm, corresponding to C-In2O3(222) crystal face of structure, after proving further to calcine, resulting materials is Indium sesquioxide..
Fig. 9 gives the XRD figure spectrum of bowl-shape Indium sesquioxide. micro-nano material (b) after the bowl-shape indium hydroxide (a) of presoma and calcining, curve (a) therein display precursor In (OH)3With In (OH)3XRD standard diagram (the JCPDS of crystal No. 76-1464) consistent, curve (b) shows the bowl-shape In after calcining2O3With In2O3XRD standard diagram (the JCPDS of crystal No. 71-2194) consistent.Bowl-shape In after calcining2O3Diffraction peak intensity and the change of peak position show C-In (OH) after calcining3It is changed into C-In2O3。
Five, CTAB trimellitic acid is combined soft template to indium hydroxide micro-nano structure size and the regulation and control of pattern:
Constant in other conditions and without in the system of trimellitic acid, in the presence of the most only CTAB, gained indium hydroxide is rod-shpaed particle, and length is about 450nm, as shown in Figure 10.
And keep other conditions constant and without CTAB, the most only in the presence of trimellitic acid, gained indium hydroxide is hollow spheres structure, particle diameter is about 1.5 mm, examining this hollow spheres granule visible is that the accumulation of graininess indium hydroxide forms, and its packed structures is the most loose, as shown in Figure 11.
When system exists CTAB and trimellitic acid simultaneously, bowl-shape indium hydroxide micro-nano structure (see figure 1) can be obtained by this experimental technique.Trace it to its cause and be because to form positively charged rod-shaped micelle in certain density CTAB aqueous solution, and after containing the trimellitic acid molecule addition system of three carboxyls, can be adsorbed in around CTAB globular micelle by electrostatic interaction and form electronegative globular micelle (being i.e. combined soft template), the carboxyl being now in outer layer can be to the In in solution3+Ion plays enrichment and fixation, and makes In3+Ion forms Concentraton gradient around micelle.When the carbamide in system decomposes in reflux course and hydrolyzes generation OH-During ion, first indium hydroxide precipitation produces around rod-shaped micelle and is protected by surfactant molecule, so that the particle size generated is controlled, thereafter along with OH-The further increase of ion concentration, newly-generated indium hydroxide nano granule will assemble along electronegative globular micelle " in order " to be piled up, unsymmetry yet with trimellitic acid molecule, make it the tightst in the arrangement of CTAB electropositive micellar surface, thus the hollow spheres indium hydroxide that obtains is the finest and close, at reflux along with the convection current of compound soft template molecule so that hollow sphere opening is relatively big and forms crimping at opening part, ultimately forms bowl-shape indium hydroxide micro-nano material.

Claims (7)

1. the preparation method of bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material, it is characterised in that comprise the following steps:
1) trimellitic acid, cetyl trimethylammonium bromide (CTAB), indium salts and carbamide are dissolved in deionized water, form mixture；
2) mixture is placed in the environment of 100～130 DEG C and carries out insulation reaction, then obtain the solid that reaction generates；
3) with distilled water and washing with alcohol solid, then solid is vacuum dried；
4) solid after vacuum drying is placed in the environment of 400～600 DEG C calcining, obtains bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material.
The preparation method of the most bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material, it is characterised in that: the mass ratio that feeds intake of described trimellitic acid, cetyl trimethylammonium bromide, indium salts and carbamide is 1: 1～2: 1～2: 12～15.
The preparation method of the most bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material, it is characterised in that: the mass ratio that feeds intake of described trimellitic acid, cetyl trimethylammonium bromide, indium salts and carbamide is 1: 1.74: 1.43: 14.30.
The preparation method of the most bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material, it is characterised in that: described step 2) in the insulation reaction time be 10～12 hours.
The preparation method of the most bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material, it is characterised in that: in described step 3), vacuum drying temperature conditions is 50～70 DEG C, and the time is 12～14 hours.
The preparation method of the most bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material, it is characterised in that: in described step 4), calcination time is 3～5 hours.
7. according to the preparation method of bowl-shape indium hydroxide/Indium sesquioxide. micro-nano material described in claim 1 or 2 or 3 or 4 or 5 or 6, it is characterised in that: described indium salts is indium acetate, indium nitrate or indium sulfate.
CN201610291565.9A 2016-05-05 2016-05-05 Preparation method of bowl-shaped indium hydroxide/indium oxide micro-nano material Pending CN105948103A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108455659A (en) * 2018-04-28 2018-08-28 电子科技大学 A kind of preparation method of nano bar-shape indium oxide gas sensitive

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CN101559977A (en) * 2009-05-31 2009-10-21 淮北煤炭师范学院 Hydro-thermal synthesis method of polypod structure In(OH)* microcrystal
JP2010156893A (en) * 2008-12-29 2010-07-15 Sony Corp Optical device, method of manufacturing the same and display apparatus
CN101857263A (en) * 2010-06-23 2010-10-13 东华大学 Method for preparing nano indium oxide with controllable appearance by hydrothermal method
CN102826593A (en) * 2012-09-11 2012-12-19 电子科技大学 Preparation method for indium oxide nanometer material
CN103183374A (en) * 2013-03-13 2013-07-03 济南大学 Method for preparing monodisperse indium oxide nanometer porous microsphere

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010156893A (en) * 2008-12-29 2010-07-15 Sony Corp Optical device, method of manufacturing the same and display apparatus
CN101559977A (en) * 2009-05-31 2009-10-21 淮北煤炭师范学院 Hydro-thermal synthesis method of polypod structure In(OH)* microcrystal
CN101857263A (en) * 2010-06-23 2010-10-13 东华大学 Method for preparing nano indium oxide with controllable appearance by hydrothermal method
CN102826593A (en) * 2012-09-11 2012-12-19 电子科技大学 Preparation method for indium oxide nanometer material
CN103183374A (en) * 2013-03-13 2013-07-03 济南大学 Method for preparing monodisperse indium oxide nanometer porous microsphere

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强金凤等: "碗状In2O3纳米材料可控合成及其光催化性能", 《中国化学会第十三届胶体与界面化学会议论文集》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108455659A (en) * 2018-04-28 2018-08-28 电子科技大学 A kind of preparation method of nano bar-shape indium oxide gas sensitive

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