CN104096577B - A kind of preparation method of water treatment nano material - Google Patents
A kind of preparation method of water treatment nano material Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of water treatment nano material.The method utilizes sol-gel process to prepare bismuth doping titanium dioxide nano particle, then adopt hydro-thermal method to prepare sulphur, rare earth, bismuth element codope titanate radical nanopipe, last ultrasonic microwave synergistic combination effect cuts off sulphur, rare earth, bismuth element codope titanate radical nanopipe.The inventive method adopts ultrasonic microwave synergistic combination effect to cut off sulphur, rare earth, bismuth element codope titanate radical nanopipe, and the sulphur of acquisition, rare earth, bismuth element codope metatitanic acid nanometer short tube uniform length, length is the shortest reaches 20nm.
Description
Technical field
The invention belongs to material for water treatment technical field, relate to a kind of preparation method of water treatment nano material, specifically the preparation method of a kind of sulphur, rare earth, bismuth element codope metatitanic acid nanometer short tube.
Background technology
The titanate radical nanopipe with architectural features such as large specific area, hollow duct and stratiforms is a kind of important inorganic functional semiconductor nano materials, there is good photoelectricity, photosensitive, air-sensitive, the characteristic such as pressure-sensitive, be widely used as the process of environmental wastewater photocatalytic degradation, various sensor, solar cell, organism plant the aspects such as people's material.The surface of titanate radical nanopipe usually can be electronegative, and this also makes titanate radical nanopipe become good substrate or the carrier of fixed catalyst particle.A kind of straightforward procedure usually preparing titanate radical nanopipe is that nano TiO 2 powder is carried out hydro-thermal reaction in highly basic, product can obtain titanate radical nanopipe through diluted acid ion-exchange, the titanate radical nanopipe caliber obtained is very little is about 10 nanometers, but the length of nanotube product is very long, the hollow duct of nanotube can not make full use of owing to transporting obstacle, sometimes unordered curling up is difficult to dispersion, and this brings very large restriction to their application.Simultaneously the forbidden band energy level of titanate radical nanopipe material is 3.3eV, can only by wavelength be less than the ultraviolet light of 387.5nm and black light excite, and ultraviolet light only accounts for 5 ﹪ of sunshine, and the 45 ﹪ visible rays contained in solar energy cannot utilize.In order to improve the utilization rate of visible ray, usually adopting element doping technology to reduce the energy gap of titanate radical nanopipe material, expanding spectral response range.Cheng-ChingHu etc. [Effectofnitrogendopingonthemicrostructureandvisiblelight photocatalysisoftitanatenanotubesbyafacilecohydrothermal synthesisviaureatreatment, AppliedSurfaceScience280 (2013) 171 – 178] are that nitrogenous source adopts hydrothermal method obtain nitrogen-doped titanic acid nanotube and have good photocatalysis performance with urea.Song Xuchun [preparation of Transition Element Substituted Titanic Acid Nanotubes and photocatalytic activity, Chinese Journal of Inorganic Chemistry, 2005,2l (12): 1897] prepared the titanate radical nanopipe of different doped transition metal ions, that wherein transition metal ions replaces is the Na of interlayer
+or H
+, and and Ti in non-substituted metatitanic acid lattice
4+,.The photocatalytic activity of Cr, Mn, Fe, Co, Ni, Cu doped transition metal ions titanate radical nanopipe obtained all is improved.V.C.Ferreira [SynthesisandpropertiesofCo-dopedtitanatenanotubesandthei ropticalsensitizationwithmethyleneblue, MaterialsChemistryandPhysics142 (2013) 355-362] with the titania-doped powder of Co for presoma, adopt hydrothermal method to obtain Co doped titanic acid nanotube, wherein Co element instead of the Ti in metatitanic acid lattice
4+, these Co doped titanic acid nanotubes present strong absworption peak at visible region.But these doped titanic acid nanotubes all belong to single-element doping, and the length Hen of the titanate radical nanopipe obtained is long.Uniform length, multi-element doping metatitanic acid nanometer short tube are not only because doping can reduce the utilization rate that energy gap improves visible ray, the obstacle that transports that simultaneously can reduce its hollow hole road due to short length makes hollow duct be fully used, in wastewater treatment, have more wide application prospect undoubtedly.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provides a kind of preparation method of water treatment nano material.
The inventive method comprises the following steps:
Step (1). sol-gel process prepares bismuth doping titanium dioxide nano particle:
Volume parts is that to join volume parts be in the absolute ethyl alcohol of 20 ~ 30 parts to the titanate esters of 10 parts by 1-1., stirs and forms titanate esters alcoholic solution;
Described titanate esters is the one in butyl titanate, isopropyl titanate or tetraethyl titanate;
It is in the polyethylene glycol-200 of 5 ~ 10 parts that bismuth salt is joined volume parts by 1-2., dissolves and forms bismuth salting liquid; Wherein bismuth salt is 0.03 ~ 0.3:10 with the molal volume ratio of titanate esters in step 1-1, and unit is mM/mL;
Described bismuth salt is the one in bismuth nitrate, bismuth chloride or bismuth acetate;
1-3. be the nitric acid of 1 ~ 2 part by volume parts, to be deionized water, the volume parts of 2 ~ 4 parts be volume parts that the absolute ethyl alcohol and stirring of 20 parts is even, forms acid solution;
The bismuth salting liquid that step 1-2 obtains by 1-4. and the titanate esters alcoholic solution that step 1-1 obtains are uniformly mixed, and then drip the acid solution that obtains of step 1-3, carry out stirring 2 ~ 5 hours under normal temperature, form gel, and then ageing 20 ~ 40 hours; The gel of ageing is dried in vacuum drying chamber and removes ethanol and moisture, calcine 4 ~ 6 hours at 500 ~ 600 DEG C in Muffle furnace after alcohol wash, washing, drying, pulverizing, obtain bismuth doping titanium dioxide nano particle;
Step (2). adopt hydro-thermal method to prepare sulphur, rare earth, bismuth element codope titanate radical nanopipe:
Bismuth doping titanium dioxide nano particle, sulfur-containing compound, rare earth compound are joined dispersed with stirring in the plastic containers that strong base solution is housed, obtains mixed liquor; Wherein the w/v of the titania-doped particle of bismuth, sulfur-containing compound, rare earth compound and strong base solution is 2 ~ 5g:0.01 ~ 0.05g:0.01 ~ 0.05g:100mL; Then proceeded to by mixed liquor in the stainless steel cauldron of inner liner polytetrafluoroethylene material and react, reaction temperature is 100 ~ 140 DEG C, 15 ~ 30 hours reaction time; Be cooled to normal temperature after reaction terminates, filter taking precipitate, wash with the diluted nitric acid aqueous solution of 0.1M, then spend deionized water, be then placed in vacuum drying chamber and dry, pulverize to obtain sulphur, rare earth, bismuth element codope titanate radical nanopipe;
Described sulfur-containing compound is the one in mercaptoethanol, dimercaprol dimercaptopropanol, sodium thioglycolate;
Described rare earth compound is the one in lanthanum chloride, lanthanum nitrate, cerium chloride, cerous nitrate;
Described strong base solution is sodium hydrate aqueous solution, and concentration is 8 ~ 15M;
Step (3). ultrasonic microwave synergistic combination effect cuts off sulphur, rare earth, bismuth element codope titanate radical nanopipe:
By sulphur, rare earth, the dispersion of bismuth element codope titanate radical nanopipe in aqueous, carry out cut-out process under being then placed in ultrasonic microwave composite reaction instrument normal temperature, precipitate and separate, drying obtain sulphur, rare earth, bismuth element codope metatitanic acid nanometer short tube; Wherein every 100mL aqueous dispersion has 2 ~ 5g sulphur, rare earth, bismuth element codope titanate radical nanopipe;
Described ultrasonic microwave composite reaction instrument condition is: ultrasonic frequency is 25KHz, and ultrasonic power control range is 10 ~ 100W; Microwave frequency is 2450MHz, and microwave power control range is 10 ~ 100W; The work for the treatment of time is 1 ~ 5 minute.
The inventive method adopts ultrasonic microwave synergistic combination effect to cut off sulphur, rare earth, bismuth element codope titanate radical nanopipe, and the sulphur of acquisition, rare earth, bismuth element codope metatitanic acid nanometer short tube uniform length, length is the shortest reaches 20nm.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further analyzed.
Embodiment 1.
Step (1). sol-gel process prepares bismuth doping titanium dioxide nano particle:
10mL butyl titanate joins in 20mL absolute ethyl alcohol by 1-1., stirs and forms 30mL butyl titanate alcoholic solution;
0.03mM bismuth nitrate joins in 5mL polyethylene glycol-200 by 1-2., dissolves and forms bismuth nitrate solution;
1-3. by 1mL nitric acid, 2mL deionized water, 20mL absolute ethyl alcohol and stirring evenly, forms 23mL acid solution;
The bismuth nitrate solution that step 1-2 obtains by 1-4. and the butyl titanate alcoholic solution that step 1-1 obtains are uniformly mixed, and then drip the acid solution that obtains of step 1-3, stir 2 hours under normal temperature, form gel, and then ageing 20 hours; The gel of ageing is dried in vacuum drying chamber and removes ethanol and moisture, calcine 6 hours at 500 DEG C in Muffle furnace after alcohol wash, washing, drying, pulverizing, obtain bismuth doping titanium dioxide nano particle;
Step (2). adopt hydro-thermal method to prepare sulphur, rare earth, bismuth element codope titanate radical nanopipe:
2g bismuth doping titanium dioxide nano particle, 0.01g mercaptoethanol, 0.01g lanthanum chloride are joined dispersed with stirring in the plastic containers that 100mL8M sodium hydrate aqueous solution is housed, obtains mixed liquor; Then proceeded to by mixed liquor in the stainless steel cauldron of inner liner polytetrafluoroethylene material and react, reaction temperature is 100 DEG C, 30 hours reaction time; Be cooled to normal temperature after reaction terminates, filter taking precipitate, wash with the diluted nitric acid aqueous solution of 0.1M, then spend deionized water, be then placed in vacuum drying chamber and dry, pulverize to obtain sulphur, rare earth, bismuth element codope titanate radical nanopipe;
Step (3). ultrasonic microwave synergistic combination effect cuts off sulphur, rare earth, bismuth element codope titanate radical nanopipe:
2g sulphur step (2) obtained, rare earth, bismuth element codope titanate radical nanopipe are dispersed in the 100mL aqueous solution, then cut-out process is carried out under being placed in ultrasonic microwave composite reaction instrument normal temperature, ultrasonic microwave composite reaction instrument condition is: ultrasonic frequency is 25KHz, ultrasonic power control range is 10W, microwave frequency is 2450MHz, microwave power control range is 10W, and the work for the treatment of time is 5 minutes; Precipitate and separate, drying obtain sulphur, rare earth, bismuth element codope metatitanic acid nanometer short tube.
Embodiment 2.
Step (1). sol-gel process prepares bismuth doping titanium dioxide nano particle:
10mL isopropyl titanate joins in 30mL absolute ethyl alcohol by 1-1., stirs and forms 40mL isopropyl titanate alcoholic solution;
0.3mM bismuth chloride joins in 10mL polyethylene glycol-200 by 1-2., dissolves and forms bismuth chloride solution;
1-3. by 2mL nitric acid, 4mL deionized water, 20mL absolute ethyl alcohol and stirring evenly, forms 26mL acid solution;
The bismuth chloride solution that step 1-2 obtains by 1-4. and the isopropyl titanate alcoholic solution that step 1-1 obtains are uniformly mixed, and then drip the acid solution that obtains of step 1-3, stir 5 hours under normal temperature, form gel, and then ageing 40 hours; The gel of ageing is dried in vacuum drying chamber and removes ethanol and moisture, calcine 4 hours at 600 DEG C in Muffle furnace after alcohol wash, washing, drying, pulverizing, obtain bismuth doping titanium dioxide nano particle;
Step (2). adopt hydro-thermal method to prepare sulphur, rare earth, bismuth element codope titanate radical nanopipe:
5g bismuth doping titanium dioxide nano particle, 0.05g dimercaprol dimercaptopropanol, 0.05g lanthanum nitrate are joined dispersed with stirring in the plastic containers that 100mL15M sodium hydrate aqueous solution is housed, obtains mixed liquor; Then proceeded to by mixed liquor in the stainless steel cauldron of inner liner polytetrafluoroethylene material and react, reaction temperature is 140 DEG C, 15 hours reaction time; Be cooled to normal temperature after reaction terminates, filter taking precipitate, wash with the diluted nitric acid aqueous solution of 0.1M, then spend deionized water, be then placed in vacuum drying chamber and dry, pulverize to obtain sulphur, rare earth, bismuth element codope titanate radical nanopipe;
Step (3). ultrasonic microwave synergistic combination effect cuts off sulphur, rare earth, bismuth element codope titanate radical nanopipe:
5g sulphur step (2) obtained, rare earth, bismuth element codope titanate radical nanopipe are dispersed in the 100mL aqueous solution, then cut-out process is carried out under being placed in ultrasonic microwave composite reaction instrument normal temperature, ultrasonic microwave composite reaction instrument condition is: ultrasonic frequency is 25KHz, ultrasonic power control range is 100W, microwave frequency is 2450MHz, microwave power control range is 100W, and the work for the treatment of time is 1 minute; Precipitate and separate, drying obtain sulphur, rare earth, bismuth element codope metatitanic acid nanometer short tube.
Embodiment 3.
Step (1). sol-gel process prepares bismuth doping titanium dioxide nano particle:
10mL tetraethyl titanate joins in 25mL absolute ethyl alcohol by 1-1., stirs and forms tetraethyl titanate alcoholic solution;
0.1mM bismuth acetate joins in 8mL polyethylene glycol-200 by 1-2., dissolves and forms bismuth acetate solution; Wherein bismuth salt is 0.03 ~ 0.3:10 with the molal volume ratio of titanate esters in step 1-1, and unit is mM/mL,
1-3. by 1.5mL nitric acid, 3mL deionized water, 20mL absolute ethyl alcohol and stirring evenly, forms 24.5mL acid solution;
The bismuth acetate solution that step 1-2 obtains by 1-4. and the tetraethyl titanate alcoholic solution that step 1-1 obtains are uniformly mixed, and then drip the acid solution that obtains of step 1-3, stir 4 hours under normal temperature, form gel, and then ageing 30 hours; The gel of ageing is dried in vacuum drying chamber and removes ethanol and moisture, calcine 5 hours at 550 DEG C in Muffle furnace after alcohol wash, washing, drying, pulverizing, obtain bismuth doping titanium dioxide nano particle;
Step (2). adopt hydro-thermal method to prepare sulphur, rare earth, bismuth element codope titanate radical nanopipe:
3g bismuth doping titanium dioxide nano particle, 0.03g sodium thioglycolate, 0.03g cerium chloride are joined dispersed with stirring in the plastic containers that 100mL10M sodium hydrate aqueous solution is housed, obtains mixed liquor; Then proceeded to by mixed liquor in the stainless steel cauldron of inner liner polytetrafluoroethylene material and react, reaction temperature is 120 DEG C, 22 hours reaction time; Be cooled to normal temperature after reaction terminates, filter taking precipitate, wash with the diluted nitric acid aqueous solution of 0.1M, then spend deionized water, be then placed in vacuum drying chamber and dry, pulverize to obtain sulphur, rare earth, bismuth element codope titanate radical nanopipe.
Step (3). ultrasonic microwave synergistic combination effect cuts off sulphur, rare earth, bismuth element codope titanate radical nanopipe:
3g sulphur step (2) obtained, rare earth, bismuth element codope titanate radical nanopipe are dispersed in the 100mL aqueous solution, then cut-out process is carried out under being placed in ultrasonic microwave composite reaction instrument normal temperature, ultrasonic microwave composite reaction instrument condition is: ultrasonic frequency is 25KHz, ultrasonic power control range is 50W, microwave frequency is 2450MHz, microwave power control range is 50W, and the work for the treatment of time is 4 minutes; Precipitate and separate, drying obtain sulphur, rare earth, bismuth element codope metatitanic acid nanometer short tube.
Embodiment 4.
Step (1). sol-gel process prepares bismuth doping titanium dioxide nano particle:
10mL tetraethyl titanate joins in 22mL absolute ethyl alcohol by 1-1., stirs and forms tetraethyl titanate alcoholic solution;
0.2mM bismuth acetate joins in 6mL polyethylene glycol-200 by 1-2., dissolves and forms bismuth acetate solution;
1-3. by 2mL nitric acid, 3mL deionized water, 20mL absolute ethyl alcohol and stirring evenly, forms 25mL acid solution;
The bismuth acetate solution that step 1-2 obtains by 1-4. and the tetraethyl titanate alcoholic solution that step 1-1 obtains are uniformly mixed, and then drip the acid solution that obtains of step 1-3, stir 3 hours under normal temperature, form gel, and then ageing 35 hours; The gel of ageing is dried in vacuum drying chamber and removes ethanol and moisture, calcine 4.5 hours at 570 DEG C in Muffle furnace after alcohol wash, washing, drying, pulverizing, obtain bismuth doping titanium dioxide nano particle;
Step (2). adopt hydro-thermal method to prepare sulphur, rare earth, bismuth element codope titanate radical nanopipe:
4g bismuth doping titanium dioxide nano particle, 0.04g sodium thioglycolate, 0.02g cerous nitrate are joined dispersed with stirring in the plastic containers that 100mL12M sodium hydrate aqueous solution is housed, obtains mixed liquor; Then proceeded to by mixed liquor in the stainless steel cauldron of inner liner polytetrafluoroethylene material and react, reaction temperature is 130 DEG C, 20 hours reaction time; Be cooled to normal temperature after reaction terminates, filter taking precipitate, wash with the diluted nitric acid aqueous solution of 0.1M, then spend deionized water, be then placed in vacuum drying chamber and dry, pulverize to obtain sulphur, rare earth, bismuth element codope titanate radical nanopipe.
Step (3). ultrasonic microwave synergistic combination effect cuts off sulphur, rare earth, bismuth element codope titanate radical nanopipe:
4g sulphur step (2) obtained, rare earth, bismuth element codope titanate radical nanopipe are dispersed in the 100mL aqueous solution, then cut-out process is carried out under being placed in ultrasonic microwave composite reaction instrument normal temperature, ultrasonic microwave composite reaction instrument condition is: ultrasonic frequency is 25KHz, ultrasonic power control range is 60W, microwave frequency is 2450MHz, microwave power control range is 60W, and the work for the treatment of time is 3 minutes; Precipitate and separate, drying obtain sulphur, rare earth, bismuth element codope metatitanic acid nanometer short tube.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.
Claims (5)
1. a preparation method for water treatment nano material, is characterized in that the method comprises the following steps:
Step (1). sol-gel process prepares bismuth doping titanium dioxide nano particle:
Volume parts is that to join volume parts be in the absolute ethyl alcohol of 20 ~ 30 parts to the titanate esters of 10 parts by 1-1., stirs and forms titanate esters alcoholic solution;
It is in the polyethylene glycol-200 of 5 ~ 10 parts that bismuth salt is joined volume parts by 1-2., dissolves and forms bismuth salting liquid; Wherein bismuth salt is 0.03 ~ 0.3:10 with the molal volume ratio of titanate esters in step 1-1, and unit is mM/mL;
1-3. be the nitric acid of 1 ~ 2 part by volume parts, to be deionized water, the volume parts of 2 ~ 4 parts be volume parts that the absolute ethyl alcohol and stirring of 20 parts is even, forms acid solution;
The bismuth salting liquid that step 1-2 obtains by 1-4. and the titanate esters alcoholic solution that step 1-1 obtains are uniformly mixed, and then drip the acid solution that obtains of step 1-3, carry out stirring 2 ~ 5 hours under normal temperature, form gel, and then ageing 20 ~ 40 hours; The gel of ageing is dried in vacuum drying chamber and removes ethanol and moisture, calcine 4 ~ 6 hours at 500 ~ 600 DEG C in Muffle furnace after alcohol wash, washing, drying, pulverizing, obtain bismuth doping titanium dioxide nano particle;
Step (2). adopt hydro-thermal method to prepare sulphur, rare earth, bismuth element codope titanate radical nanopipe:
Bismuth doping titanium dioxide nano particle, sulfur-containing compound, rare earth compound are joined dispersed with stirring in the plastic containers that strong base solution is housed, obtains mixed liquor; Wherein the w/v of the titania-doped particle of bismuth, sulfur-containing compound, rare earth compound and strong base solution is 2 ~ 5g:0.01 ~ 0.05g:0.01 ~ 0.05g:100mL; Then proceeded to by mixed liquor in the stainless steel cauldron of inner liner polytetrafluoroethylene material and react, reaction temperature is 100 ~ 140 DEG C, 15 ~ 30 hours reaction time; Be cooled to normal temperature after reaction terminates, filter taking precipitate, wash with the diluted nitric acid aqueous solution of 0.1M, then spend deionized water, be then placed in vacuum drying chamber and dry, pulverize to obtain sulphur, rare earth, bismuth element codope titanate radical nanopipe;
Described rare earth compound is the one in lanthanum chloride, lanthanum nitrate, cerium chloride, cerous nitrate;
Step (3). ultrasonic microwave synergistic combination effect cuts off sulphur, rare earth, bismuth element codope titanate radical nanopipe:
By sulphur, rare earth, the dispersion of bismuth element codope titanate radical nanopipe in aqueous, carry out cut-out process under being then placed in ultrasonic microwave composite reaction instrument normal temperature, precipitate and separate, drying obtain sulphur, rare earth, bismuth element codope metatitanic acid nanometer short tube; Wherein every 100mL aqueous dispersion has 2 ~ 5g sulphur, rare earth, bismuth element codope titanate radical nanopipe;
Described ultrasonic microwave composite reaction instrument condition is: ultrasonic frequency is 25KHz, and ultrasonic power control range is 10 ~ 100W; Microwave frequency is 2450MHz, and microwave power control range is 10 ~ 100W; The work for the treatment of time is 1 ~ 5 minute.
2. the preparation method of a kind of water treatment nano material as claimed in claim 1, the titanate esters that it is characterized in that described in step (1) is the one in butyl titanate, isopropyl titanate or tetraethyl titanate.
3. the preparation method of a kind of water treatment nano material as claimed in claim 1, the bismuth salt that it is characterized in that described in step (1) is the one in bismuth nitrate, bismuth chloride or bismuth acetate.
4. the preparation method of a kind of water treatment nano material as claimed in claim 1, the sulfur-containing compound that it is characterized in that described in step (2) is the one in mercaptoethanol, dimercaprol dimercaptopropanol, sodium thioglycolate.
5. the preparation method of a kind of water treatment nano material as claimed in claim 1, it is characterized in that the strong base solution described in step (2) is sodium hydrate aqueous solution, concentration is 8 ~ 15M.
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| CN101279767A (en) * | 2008-04-28 | 2008-10-08 | 哈尔滨工业大学 | Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube |
| CN101602483A (en) * | 2009-07-10 | 2009-12-16 | 杭州电子科技大学 | The method for cutting of sodium titanate nanotubes |
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| CN101279767A (en) * | 2008-04-28 | 2008-10-08 | 哈尔滨工业大学 | Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube |
| CN101602483A (en) * | 2009-07-10 | 2009-12-16 | 杭州电子科技大学 | The method for cutting of sodium titanate nanotubes |
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