CN103121721A - Preparation method of pyrochlore tungsten oxide microtubes - Google Patents
Preparation method of pyrochlore tungsten oxide microtubes Download PDFInfo
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- CN103121721A CN103121721A CN2013100806850A CN201310080685A CN103121721A CN 103121721 A CN103121721 A CN 103121721A CN 2013100806850 A CN2013100806850 A CN 2013100806850A CN 201310080685 A CN201310080685 A CN 201310080685A CN 103121721 A CN103121721 A CN 103121721A
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Abstract
The invention belongs to preparation methods of pyrochlore tungsten oxide microtubes, and in particular relates to a preparation method of a pyrochlore tungsten oxide microtube. The method comprises the following steps of: adding 6-10mM thiourea and 3-13mM hydroxylamine hydrochloride into liquor of pyrochlore tungsten oxide by a hydrothermal method; adequately stirring with the pH value of 4-8; purging the mixed liquor to a reaction kettle for reaction for 18-30 hours; and after the temperature is naturally cooled to room temperature, taking out, centrifugalizing and vacuum drying. According to the preparation method provided by the invention, on the one hand, hydrogen bonds at the edge of a stratified structure of pyrochlore tungsten oxide are destroyed by thiourea, so that the stratified structure is unstable, the interlaminating effect of the pyrochlore tungsten oxide is weakened and the intrastratal effect is invariable, therefore, a tubular structure is generated by winding; on the other hand, the viscosity of the liquor is controlled by hydroxylamine hydrochloride so as to reduce agglomeration between the tubular structures. The preparation method is not only simple and feasible, simple to operate, but also the production cost is lowered, so that the preparation method is economical, practical and environment-friendly.
Description
Technical field
The invention belongs to burnt green stone type Tungsten oxide 99.999 preparation method class, be specifically related to the preparation method of the green stone type of a kind of Jiao tungsten oxide micron pipe, particularly a kind of preparation method who forms the burnt green stone type Tungsten oxide 99.999 tubular structure of stratiform by the interlayer hydrogen bonded.
Background technology
The discovery of carbon nanotube in 1991 is encouraging people to research and the exploration of tubular structure always.Scientists successfully synthesizes many tubulose mineral compound (as metal oxide, metallic sulfide, metal halide etc.) by various method.(normal note is H to burnt green stone type Tungsten oxide 99.999
2W
2O
7Or WO
30.5H
2O) same WO with distortion
6Octahedron is structural motif, constructs to form by the top, angle of tungsten oxygen rigid backbone to have the laminate structure in six-ring duct.Due to the reticulated structure with molecular sieve and the steady characteristic that is situated between, be used widely in fields such as catalysis, electrochromism, fuel cell, photosensitive gas sensors.
Tubular structure has the advantages that to provide the stability of additional space and self structure in hollow structure therein for the basic metal plasma, and this makes it obtain very large application at aspects such as rechargeable battery anode material and catalyzer.And owing to having larger specific surface area, tubular structure is also having very large application prospect aspect photosensitive and gas sensor.If so can synthesize the burnt green stone type Tungsten oxide 99.999 of this tubulose, the advantage of the green stone type of Jiao Tungsten oxide 99.999 can be combined with tubular structure, even produces some new character.
But different from general laminate structure is that its interlayer passes through hydrogen bonded, rather than general Van der Waals force.Because hydrogen bond belongs to secondary valence bond, bond energy is stronger than Van der Waals force, so WO30.5H
2The laminate structure that O(is relatively general) more difficult formation tubular structure.
At present, about the preparation method of the green stone type of Jiao Tungsten oxide 99.999, several different methods is arranged, but due to WO
30.5H
2The structural instability of O (typical temperature higher than 320 ℃ time its structure will be destroyed) is so the preparation method must carry out at a lower temperature.The people such as Coucou of France in 1988 (Solid.State.Ionics, 1988,28-30:1762-1765) adopt softening method to synthesize first burnt green stone type Tungsten oxide 99.999; The people (Mater.Res.Bull.1989,24:289-292) such as Amberg of Sweden in 1989 utilize hydrothermal method to prepare the burnt green stone type Tungsten oxide 99.999 of isometric system first; The people (Solid.State.Chem.1992,96:31-47) such as Kenneth had reported the preparation condition of Hydrothermal Synthesis Tungsten oxide 99.999 and the relation of crystal formation in more detail in 1992; The people such as nineteen ninety-five Guo (Power Sourcse, 1995,54:461-464) adopt Hydrothermal Synthesis and to utilize hydrochloric acid regulation system pH value be also to prepare the green stone type Tungsten oxide 99.999 that discharges of the coke at 6 o'clock.But the synthetic of the green stone type tungsten oxide micron pipe of focusing also do not reported.
Summary of the invention
For above problem, the purpose of this invention is to provide a kind of preparation method of simple burnt green stone type tungsten oxide micron pipe, the method can make burnt green stone type Tungsten oxide 99.999 form stratiform, pattern burnt green stone type tungsten oxide micron pipe uniformly with hydrogen bonded.
The present invention is achieved through the following technical solutions:
The preparation method of the green stone type of a kind of Jiao tungsten oxide micron pipe, it is characterized in that: add 6-10mM thiocarbamide and 3～13mM oxammonium hydrochloride in hydrothermal method prepares the solution of burnt green stone type Tungsten oxide 99.999, pH value is after fully stirring under 4～8 condition, mixing solutions was poured into reaction kettle for reaction 18-30 hour, when being down to room temperature naturally, temperature takes out, centrifugal, vacuum drying.
The concrete preparation process of the present invention is as follows:
A, adopt simple hydrothermal method, with Na
2WO
42H
2O adds in deionized water, stirs it is dissolved fully;
B, with CS (NH
2)
2Being dissolved in deionized water for stirring dissolves it fully;
C, above-mentioned two kinds of solution mix and blends are formed mixing solutions (a), and splash into wherein HCl and regulate pH value to 4-8, then at 50-80 ℃ of continuously stirring 25～70min;
D, with NH
2The OHHCl viscosity-controlling agent is dissolved in deionized water, adds after dissolving in the mixing solutions of step c gained in (a), continues to stir 1～2h at 80-120 ℃, forms mixing solutions (b);
E, solution (b) is transferred to reactor, reacts 18-30h under 150-250 ℃, after reaction finishes to be down to room temperature, take out centrifugal, dry 6-12h under 60-90 ℃ of vacuum condition.
The present invention prepares in the process of burnt green stone type Tungsten oxide 99.999 in hydrothermal method, add thiocarbamide and oxammonium hydrochloride in solution, what after centrifugal, oven dry realized under vacuum, namely add thiocarbamide and oxammonium hydrochloride to carry out pattern and structure regulating in the green stone type of Jiao Tungsten oxide 99.999 preparation process, be prepared into tubular structure.Utilize thiocarbamide to destroy the hydrogen bond of burnt green stone type Tungsten oxide 99.999 stratiform structural edge on the one hand, make laminate structure become unstable, at this moment WO
30.5H
2The interlaminar action of O weakens, and in layer, effect is constant, thereby coiling occurs produces tubular structure; On the other hand, utilize oxammonium hydrochloride to control solution viscosity, reduce the agglomeration between tubular structure.This preparation method is not only simple, and is easy and simple to handle, and reduced production cost, is the preparation method of a kind of not only economical and practical but also environmental protection.
Embodiment
In order to make the purpose, technical solutions and advantages of the present invention more clear, describe in detail below in conjunction with example:
Embodiment 1
With resistivity at the above deionized water of 15M Ω cm as solvent, take 2.8mMNa
2WO
42H
2O is dissolved in the 100ml deionized water, with hydrochloric acid conditioning solution pH value to 6,50 ℃ of continuously stirring 30 minutes, then solution is transferred in reactor, 180 ℃ of reactions 24 hours.When question response is completed temperature and naturally is down to room temperature, take out, centrifugal, obtain white precipitate, 80 ℃ of bakings are 10 hours in vacuum drying oven, namely obtain the white powder crystal.We carry out structural analysis to the sample that obtains, and comprise that X-ray diffraction (XRD) scanning, field emission scanning electron microscope (FESEM) are observed, high resolution transmission electron microscopy (HRTEM) is observed and the Raman spectrum test of 514nm.Wherein the XRD structural analysis shows that all diffraction peaks of sample are all corresponding to isometric system WO
30.5H
2O does not have other assorted peaks to occur.FESEM and HRTEM observe and find out that sample is a micron block materials, and the Raman spectrum test shows that the gained sample is the burnt green stone type Tungsten oxide 99.999 of isometric system.
The present embodiment adopts the standby burnt green stone type Tungsten oxide 99.999 of common hydro-thermal legal system, and the burnt green stone type Tungsten oxide 99.999 that makes is micron block isometric system.
Embodiment 2
As solvent, take 2.8mMNa with the deionized water of resistivity more than 15M Ω cm
2WO
42H
2O, 8mM CS (NH
2)
2Be dissolved in respectively in the 50ml deionized water, stir and solution to be mixed after making its dissolving, and with hydrochloric acid conditioning solution pH value to 7,60 ℃ of continuously stirring 40 minutes, then mixing solutions is poured in reactor, reacted 24 hours at 180 ℃.When question response is completed temperature and naturally is down to room temperature, take out, centrifugal, obtain white precipitate, 80 ℃ of bakings are 10 hours in vacuum drying oven, namely obtain the white powder crystal.We carry out structural analysis to the sample that obtains, and comprise that X-ray diffraction (XRD) scanning, field emission scanning electron microscope (FESEM) are observed, high resolution transmission electron microscopy (HRTEM) is observed and the Raman spectrum test of 514nm.Wherein the XRD structural analysis shows that all diffraction peaks of sample are all corresponding to WO
30.5H
2O does not have other assorted peaks.The FESEM test shows that sample is fine and close elongated micrometer structure, and its diameter is about 150nm, and length is about tens microns, observed the tubulose feature from some damaged micrometer structures, tube wall is about 40nm, but the micron tube dispersiveness is good not, exists the adhesion phenomenon between tube and tube.HRTEM observes and shows that further single micrometer structure is micron tube, and thickness of pipe is consistent with the FESEM observations.The Raman spectrum test shows that micron tube is burnt green stone type Tungsten oxide 99.999.
The present embodiment adopts in hydrothermal method and adds thiocarbamide to prepare burnt green stone type Tungsten oxide 99.999, and the burnt green stone type Tungsten oxide 99.999 that makes is fine and close elongated micrometer structure, and single micrometer structure is micron tube, but between micron tube, adhesion phenomenon is arranged.
Embodiment 3
As solvent, take 2.8mMNa with the deionized water of resistivity more than 15M Ω cm
2WO
42H
2O, 8mM CS (NH
2)
2Be dissolved in respectively 40 and the 30ml deionized water in, mix to form mixing solutions (a) after dissolving, with hydrochloric acid conditioning solution pH value to 6,60 ℃ of continuously stirring 30 minutes, then with 5mM NH
2OHHCl is dissolved in the 30ml deionized water, joins after dissolving in mixing solutions (a), stirs 1 hour at 90 ℃, forms mixing solutions (b).Then mixing solutions (b) is poured in reactor, 180 ℃ of reactions 24 hours.When the complete temperature of question response is down to room temperature naturally, take out, centrifugal, obtain white precipitate, 80 ℃ were toasted 10 hours in vacuum drying oven, namely obtained the white powder crystal.We carry out structural analysis to the sample that obtains, and comprise that X-ray diffraction (XRD) scanning, field emission scanning electron microscope (FESEM) are observed, high resolution transmission electron microscopy (HRTEM) is observed and the Raman spectrum test of 514nm.Wherein the XRD structural analysis show sample all diffraction peaks all corresponding to the green stone type of Jiao Tungsten oxide 99.999, do not have other dephasigns to occur.Observe from FESEM and HRTEM and find out that sample is the uniform tubular structure of pattern, dispersed relatively good between tube and tube, the distribution of whole viewing area pipe is also more even.Can clearly find out the coiling forming process of the structure of its tubulose from the defective structure of part.In the Raman spectrum that records and example 1, burnt green stone type Tungsten oxide 99.999 is compared also and is changed, and this variation can ascribe to and caused to the variation of tubular structure by laminate structure.
Embodiment 4
As solvent, take 2.8mMNa with the deionized water of resistivity more than 15M Ω cm
2WO
42H
2O, 8mM CS (NH
2)
2Be dissolved in respectively 40 and the 30ml deionized water in, mix to form mixing solutions (a) after dissolving, with hydrochloric acid conditioning solution pH value to 6,60 ℃ of continuously stirring 30 minutes, then with 7mM NH
2OHHCl is dissolved in the 30ml deionized water, joins after dissolving in mixing solutions (a), stirs 1 hour at 100 ℃, forms mixing solutions (b).Then mixing solutions (b) is poured in reactor, 210 ℃ of reactions 28 hours.When question response is completed temperature and naturally is down to room temperature, take out, centrifugal, obtain white precipitate, 80 ℃ of bakings are 10 hours in vacuum drying oven, namely obtain the white powder crystal.We carry out structural analysis to the sample that obtains, and comprise that X-ray diffraction (XRD) scanning, field emission scanning electron microscope (FESEM) are observed, high resolution transmission electron microscopy (HRTEM) is observed and the Raman spectrum test of 514nm.Wherein the XRD structural analysis shows that all diffraction peaks of sample are all corresponding to WO
30.5H
2O does not have other assorted peaks.The FESEM test shows that sample is fine and close elongated micrometer structure, its diameter is about 220nm, length is about tens microns, observed the tubulose feature from some damaged micrometer structures, tube wall is about 50nm, HRTEM observes and shows that further single micrometer structure is micron tube, and thickness of pipe is consistent with the FESEM observations.The Raman spectrum test shows that micron tube is burnt green stone type Tungsten oxide 99.999.
Embodiment 5
As solvent, take 2.8mMNa with the deionized water of resistivity more than 15M Ω cm
2WO
42H
2O, 8mM CS (NH
2)
2Be dissolved in respectively 40 and the 30ml deionized water in, mix to form mixing solutions (a) after dissolving, with hydrochloric acid conditioning solution pH value to 6,50 ℃ of continuously stirring 30 minutes, then with 10mM NH
2OHHCl is dissolved in the 30ml deionized water, joins after dissolving in mixing solutions (a), stirs 1.5 hours at 85 ℃, forms mixing solutions (b).Then mixing solutions (b) is poured in reactor, 210 ℃ of reactions 28 hours.When question response is completed temperature and naturally is down to room temperature, take out, centrifugal, obtain white precipitate, 80 ℃ of bakings are 10 hours in vacuum drying oven, namely obtain the white powder crystal.We carry out structural analysis to the sample that obtains, and comprise that X-ray diffraction (XRD) scanning, field emission scanning electron microscope (SEM) are observed, high resolution transmission electron microscopy (HRTEM) is observed and the Raman spectrum test of 514nm.Wherein the XRD structural analysis shows that all diffraction peaks of sample are all corresponding to WO
30.5H
2O。Find out that from FESEM and HRTEM observation sample is the mixed phase of tubular structure and a small amount of block structure.This is due to excessive NH
2OHHCl decomposes the generation by product, and reaction finishes rear and WO
30.5H
2O separates out together.This explanation CS (NH
2)
2Has important effect to forming tubular structure.
Embodiment 3-5 adopts in hydrothermal method and adds thiocarbamide and oxammonium hydrochloride to prepare burnt green stone type tungsten oxide micron pipe, has reduced the adhesion between micron tube, and the tubular structure pattern is even.
Claims (2)
1. the preparation method of the green stone type of a Jiao tungsten oxide micron pipe, it is characterized in that: add 6-10mM thiocarbamide and 3～13mM oxammonium hydrochloride in hydrothermal method prepares the solution of burnt green stone type Tungsten oxide 99.999, pH value is after fully stirring under 4～8 condition, mixing solutions was poured into reaction kettle for reaction 18-30 hour, when being down to room temperature naturally, temperature takes out, centrifugal, vacuum drying.
2. prepare according to claim 1 the method for burnt green stone type tungsten oxide micron pipe, preparation process is as follows:
A, adopt simple hydrothermal method, with Na
2WO
42H
2O adds in deionized water, stirs it is dissolved fully;
B, with CS (NH
2)
2Being dissolved in deionized water for stirring dissolves it fully;
C, above-mentioned two kinds of solution mix and blends are formed mixing solutions (a), and splash into wherein HCl and regulate pH value to 4-8, then at 50-80 ℃ of continuously stirring 25～70min;
D, with NH
2The OHHCl viscosity-controlling agent is dissolved in deionized water, adds after dissolving in the mixing solutions of step C gained in (a), continues to stir 1～2h at 80-120 ℃, forms mixing solutions (b);
E, solution (b) is transferred to reactor, reacts 18-30h under 150-250 ℃, after reaction finishes to be down to room temperature, take out centrifugal, dry 6-12h under 60-90 ℃ of vacuum condition.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741540A (en) * | 1996-01-16 | 1998-04-21 | Industrial Technology Research Institute | Method of forming solid state humidity sensor |
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2013
- 2013-03-14 CN CN201310080685.0A patent/CN103121721B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741540A (en) * | 1996-01-16 | 1998-04-21 | Industrial Technology Research Institute | Method of forming solid state humidity sensor |
Non-Patent Citations (6)
| Title |
|---|
| JINGDONG GUO ET AL.: "Hydrothermal synthesis of electrode materials Pyrochlore tungsten trioxide film", 《JOURNAL OF POWER SOURCES》 * |
| JONN R.GUNTER ET AL.: "1. Direct synthesis and single crystal structure determination of cubic pyrochlore-type tungsten trioxide hemihydeate, WO3•0.5H2O", 《MAT. RES. BULL.,》 * |
| JONN R.GUNTER ET AL.: "1. Direct synthesis and single crystal structure determination of cubic pyrochlore-type tungsten trioxide hemihydeate, WO3•0.5H2O", 《MAT. RES. BULL.,》, 31 December 1989 (1989-12-31) * |
| ZONGWEN LIU ET AL.: "Synthesis of tungsten oxide nanowires", 《CHEMICAL PHYSICS LETTERS》 * |
| 孙庆军: "水热与微波水热法合成形貌可控纳米氧化钨粉体", 《新疆大学硕士研究生论文》 * |
| ***: "焦绿石型氧化钨超细粉体的水热合成与机理研究", 《中南大学硕士学位论文》 * |
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