CN101619488B - Preparation method of single-crystal tungsten oxide with high specific surface area - Google Patents
Preparation method of single-crystal tungsten oxide with high specific surface area Download PDFInfo
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- CN101619488B CN101619488B CN2009100555023A CN200910055502A CN101619488B CN 101619488 B CN101619488 B CN 101619488B CN 2009100555023 A CN2009100555023 A CN 2009100555023A CN 200910055502 A CN200910055502 A CN 200910055502A CN 101619488 B CN101619488 B CN 101619488B
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Abstract
The invention relates to a single-crystal tungsten oxide material, in particular to a preparation method of single-crystal tungsten oxide with high specific surface area. The prior tungsten oxide materials applied to textile printing and dyeing industry and environment protection show low absorbability, unobvious processing effect of dye waste water and other defects. The method comprises the following steps: preparing a propodosoma solution; adding tungstate into water, wherein the mol ratio of the water to the tungstate is from 241 to 483; adjusting pH value; adding acid into the propodosoma solution, mixing the mixed solution, and adjusting the pH value of the solution to from 1 to 2; keeping the solution still for 0.5 to 3 days; after standing still, removing the solution into a polyfluortetraethylene water hot kettle for aging for 6 hours to 8 days at the temperature of 40 DGE.C to 180 DGE.C ; washing the sample obtained in step(4) after centrifugal separation by water for 3 times, and drying the sample put in a constant-temperature drying cabinet for 24 hours at the temperature of 100 DGE.C. The invention has the advantages of simple preparation process, large specific surface area of tungsten oxide, high dye absorbability and favorable processing effect of dye waste water.
Description
Technical field
The present invention relates to the single-crystal tungsten oxide material, specifically a kind of preparation method who dyestuff is had the single-crystal tungsten oxide with high specific surface area of strong absorption property.
Technical background
Tungsten oxide 99.999 is a kind of novel semiconductor material; Also be that a few is easy to one of oxide semiconductor of realizing quantum size effect; Have characteristics such as electrochromism, absorption, catalysis, be widely used in fields such as fuel cell, chemical sensor, photoelectric device.Owing to the development of nano material preparation technology, the efficient variable color and the proton transfer performance of tungsten oxide nanometer material come to light, and are widely used in a plurality of fields such as information storage, variable color window, big area information display screen, auto mirror in recent years.The structure that special performance and its had, pattern and the size of Tungsten oxide 99.999 have substantial connection.The Tungsten oxide 99.999 preparation of special construction and pattern is Tungsten oxide 99.999 and semiconductor material development key technical problem with property research.The preparation method of Tungsten oxide 99.999 is multiple at present; Like solid phase method, chemical deposition, sol-gel method, microemulsion method, hydrothermal synthesis method etc.; Adopt diverse ways can prepare the Tungsten oxide 99.999 particle of different structure, for example tetragonal system, hexagonal system, oblique system, rhombic system etc.
The tungsten oxide material of existing Tungsten oxide 99.999 technology preparation is applied to textile and dyeing industry and environment protection, shows shortcomings such as adsorptivity is not strong, dye wastewater treatment DeGrain.The present invention adopts hydrothermal technique to handle tungstenic precursor solution, obtains having high-specific surface area, six side's phases, single-crystal tungsten oxide material.In this way obtain tungsten oxide material owing to have the character that bigger serface and (1 ī 00) crystal face expose.Different crystal faces is with symbol of crystal face (hkil) difference expression, h wherein, and k, i, l representes the crystal indices, and is corresponding with different crystallographic axis respectively.Prepared single-crystal tungsten oxide material reveals stronger adsorptivity to dye sheets such as rhodamine B, methylene blues, and the processing of waste water from dyestuff is had good effect.
Summary of the invention
The purpose of this invention is to provide a kind of convenience controlled dyestuff is had the high specific surface area single-crystal WO of strong absorption property
3Preparation methods.
The objective of the invention is to realize like this:
The preparation method of single-crystal tungsten oxide with high specific surface area may further comprise the steps:
(1) preparation precursor solution: tungstate is added in the entry, and the mol ratio of water and tungstate is 241 to 483;
(2) regulate the pH value: add acid, stirring to precursor solution, regulator solution pH value 1～2;
(3) with above-mentioned solution left standstill 0.5 day～3 days;
(4) solution after leaving standstill moves in the tetrafluoroethylene water heating kettle, under 40 ℃～180 ℃ conditions of temperature, and ageing 6 hours～8 days;
(5) with after the spinning of step (4) gained sample with water washing 3 times, inserted in the thermostatic drying chamber 100 ℃ of dryings 24 hours, make bar-like single crystal WO
3Material.
Above-mentioned single-crystal tungsten oxide with high specific surface area preparation methods is characterised in that:
(1) tungstate in the step (1) is a kind of in ammonium tungstate or the sodium wolframate;
Main points of the present invention are: only need can obtain dyestuff is had the single-crystal tungsten oxide with high specific surface area WO of strong absorption property through simple hydrothermal method
3Material.Through modulation to material rate, digestion time and ageing temperature, controlled oxidation tungsten WO
3The size of monocrystalline, crystal plane structure and absorption property.Single crystal particle is more little, and (1 ī 00) face specific surface area is big more, and its absorption property to dyestuff is also strong more.
Technology of the present invention follows these steps to carry out:
At first; A certain amount of acid is joined in the precursor solution; Transfer in the tetrafluoroethylene water heating kettle after at room temperature leaving standstill for some time; Control ageing temperature and time with water washing 3 times, can obtain dyestuff is had the single-crystal tungsten oxide with high specific surface area WO of strong absorption property after the spinning of gained sample after the drying
3Material.
Advantage of the present invention is:
1, preparation technology is simple;
2, the Tungsten oxide 99.999 specific surface area is big, reaches 100-120m
2/ g, be existing Tungsten oxide 99.999 specific surface area 2-5 doubly;
3, strong to the strong absorption property of dyestuff;
4, dye wastewater treatment is effective.
Description of drawings
Fig. 1 is the transmission electron microscope figure of instance 1 sample;
Fig. 2 is the X ray polycrystalline diffractogram of instance 1 sample;
Fig. 3 is the sample that instance 1 makes, in the time of 25 ℃ to the adsorption isothermal line of rhodamine B.
Embodiment
Embodiment 1
Under the normal temperature, with 1.20g ammonium tungstate [5 (NH
4)
2O12WO
35H
2O] add in the 40mL water, under condition of stirring, drip sulfuric acid and equal 1.0 to pH, left standstill then 1 day, obtain intermediate solution A solution.A solution is transferred in the 50mL tetrafluoroethylene water heating kettle, kept 1 day at 180 ℃.After the spinning of gained sample with putting into 100 ℃ of thermostatic drying chambers after the water washing 3 times dry 24 hours, promptly making specific surface area is 101m
2The bar-shaped tungsten oxide material of/g.
Embodiment 2
Under the normal temperature, with 0.60g ammonium tungstate [5 (NH
4)
2O12WO
35H
2O] add in the 40mL water, stir, drip sulfuric acid and equal 1.0 to pH, left standstill then 0.5 day, obtain intermediate solution A solution.A solution is transferred in the 50mL tetrafluoroethylene water heating kettle, kept 6h at 180 ℃.After the spinning of gained sample with after the water washing 3 times in 100 ℃ of thermostatic drying chambers dry 24 hours, promptly making specific surface area is 116m
2The bar-like single crystal WO of/g
3Material.
Embodiment 3
Under the normal temperature, with 1.20g ammonium tungstate [5 (NH
4)
2O12WO
35H
2O] add in the 40mL water, under condition of stirring, drip sulfuric acid and equal 2.0 to pH, left standstill then 3 days, obtain intermediate solution A solution.A solution is transferred in the 50mL tetrafluoroethylene water heating kettle, kept 8 days at 40 ℃.After the spinning of gained sample with after the water washing 3 times in 100 ℃ of thermostatic drying chambers dry 24 hours, promptly making specific surface area is 120m
2The bar-like single crystal WO of/g
3Material.
Embodiment 4
Under the normal temperature, with 1.20g ammonium tungstate [5 (NH
4)
2O12WO
35H
2O] add in the 40mL water, under condition of stirring, drip sulfuric acid and equal 2.0 to pH, left standstill then 3 days, obtain intermediate solution A solution.A solution is transferred in the 50mL tetrafluoroethylene water heating kettle, kept 1 day at 180 ℃.After the spinning of gained sample with after the water washing 3 times in 100 ℃ of thermostatic drying chambers dry 24 hours, promptly make bar-like single crystal WO
3Material.
Embodiment 5
Under the normal temperature, with 1.5832g sodium wolframate (Na
2WO
4.2H
2O) add in the 40mL water, under condition of stirring, drip sulfuric acid and equal 1.0 to pH, left standstill then 1 day, obtain A solution.Intermediate solution A solution is transferred in the 50mL tetrafluoroethylene water heating kettle, kept 1 day at 100 ℃.After the spinning of gained sample with after the water washing 3 times in 100 ℃ of thermostatic drying chambers dry 24 hours, promptly make bar-like single crystal WO
3Material.
Embodiment 6
With the bar-like single crystal WO that obtains among the embodiment 1
3Material 0.07g, in the rhodamine B of the 100mg/L of 15.0mL ultrasonic 2 minutes, vibration 5 hours in 25 ℃ constant-temperature shaking appearance then; Get supernatant after centrifugal, survey its absorbancy, calculate adsorptive capacity at the 553nm place with ultraviolet spectrophotometer; The concentration of test rhodamine B of using the same method is respectively the adsorptive capacity of 40mg, 80mg, 120mg, 360mg, 460mg, 560mg; Draw the isothermal adsorption graphic representation, as shown in Figure 2, show prepared monocrystalline WO on the figure
3The absorption property of material will significantly be superior to by mesoporous SiO
2The SBA-15 material that constitutes.
The foregoing description is merely preference of the present invention, is not used for limiting the present invention, and is all within principle of the present invention, and any modification and the variation made are all within protection scope of the present invention.
Claims (1)
1. the preparation method of a single-crystal tungsten oxide with high specific surface area may further comprise the steps:
(1) preparation precursor solution: tungstate is added in the entry, and the mol ratio of water and tungstate is 241 to 483; Tungstate is a kind of in ammonium tungstate or the sodium wolframate;
(2) regulate the pH value: add acid, stirring to precursor solution, regulator solution pH value 1～2; Acid is a kind of in hydrochloric acid or the sulfuric acid
(3) with above-mentioned solution left standstill 0.5 day～3 days;
(4) solution after leaving standstill moves in the tetrafluoroethylene water heating kettle, under 40 ℃～180 ℃ conditions of temperature, and ageing 6 hours～8 days;
(5) with step (4) gained samples with water washing 3 times, inserted in the thermostatic drying chamber 100 ℃ of dryings 24 hours, making specific surface area is 100～120m
2The bar-like single crystal WO of/g
3Material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101845669B (en) * | 2010-05-31 | 2012-02-15 | 河南大学 | Hydrothermal synthesis method of monocrystal multilayer flaky WO3 |
| CN103420424B (en) * | 2013-05-21 | 2015-05-20 | 新疆大学 | Preparation of rod-shaped nano tungsten trioxide and technology of catalytic synthesis of adipic acid therethrough |
| CN105271421A (en) * | 2015-11-02 | 2016-01-27 | 哈尔滨工业大学 | Preparation method of tungsten-based nanosphere particle powder |
| CN106082344B (en) * | 2016-06-15 | 2017-10-31 | 中国科学技术大学 | A kind of preparation method of defect state tungstic acid for the aerobic coupling of photocatalysis |
| CN116143175B (en) * | 2023-04-23 | 2023-08-08 | 崇义章源钨业股份有限公司 | Nano tungsten oxide with high specific surface area and preparation method thereof |
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