CN103601237A - Charged anatase titania nanoparticles and low-temperature preparation method thereof - Google Patents

Charged anatase titania nanoparticles and low-temperature preparation method thereof Download PDF

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CN103601237A
CN103601237A CN201310549730.2A CN201310549730A CN103601237A CN 103601237 A CN103601237 A CN 103601237A CN 201310549730 A CN201310549730 A CN 201310549730A CN 103601237 A CN103601237 A CN 103601237A
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polyelectrolyte
titanium
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titanium dioxide
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CN103601237B (en
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秦振平
李叶
郭红霞
王乃鑫
纪树兰
张国俊
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Beijing University of Technology
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Abstract

The invention relates to charged anatase titania nanoparticles and a low-temperature preparation method thereof, belonging to the technical field of nanomaterials. The method comprises the steps of dissolving inorganic titanium salt and a cationic polyelectrolyte or anionic polyelectrolyte into water, mixing uniformly, dropwise adding to an alkaline solution, and reacting to obtain white precipitates; ultrasonically dispersing the precipitates into an acidic solution, refluxing, separating, washing by using anhydrous ethanol, and then drying. In an aqueous solution, the obtained product has relatively good electric quantity maintenance and shows good photocatalysis performance.

Description

A kind of charge anatase titanium dioxide nanoparticle and low temperature preparation method thereof
Technical field
The present invention relates to titanium dioxide nano-particle and preparation method thereof, be specifically related to a kind of anatase titanium dioxide nanoparticle and low temperature preparation method thereof of surface charge, belong to technical field of nano material.
Background technology
Nano-TiO 2material is a kind of energy-efficient Photocatalysis Function Material, because having the advantages such as nontoxic, spectrochemical property is stable, photocatalysis effect is good, reusable, it is widely used in the fields such as low concentration wastewater processing, precious metal recovery, purifying air and coating surface be self-cleaning, this material, at the UV-light multiple environmental pollutant of even can degrading under radiation of visible light, also has the hydrophilic feature of photoinduction.TiO 2mainly with rutile-type, Detitanium-ore-type and three kinds of crystalline structure of brookite type, be present in occurring in nature, wherein rutile-type and Detitanium-ore-type TiO 2there is higher catalytic activity, especially best with Detitanium-ore-type photocatalytic activity.
At present, the method for preparing titania nanoparticles is a lot, and wherein chemical process mainly comprises vapor phase process and liquid phase method.Titanium dioxide nano-particle prepared by the vapor phase process of patent CN1736878A, CN1810653A report can be realized its suitability for industrialized production, but equipment used is complicated, cost is high; Patent CN102320655A and CN101671052A adopt sol-gel method to prepare titanium dioxide nano-particle, and its raw materials cost is higher, and needs the processes such as secondary hydrolysis, high-temperature roasting, complex process; Patent CN103011273A adopts hydrothermal method to prepare the spherical anatase titania of nano-sheet, but need to carry out crystallization at 160～200 ℃; Patent CN102120612A has reported a kind of titanium source acid solution has been added in the mineral alkali dispersion soln containing anion surfactant, after reaction, centrifugation obtains anatase titanium dioxide, and anion surfactant used is only in order to reduce the reunion of titanium dioxide; Patent CN101890343A modifies TiO by excessive alkylamine compound 2nanocrystalline, do not need high-temperature roasting, its technique is simple, easy to operate, but coating materials diethylamine used, triethylamine, propylamine etc., and all to HUMAN HEALTH toxic side effect, and solvent is difficult for reclaiming, and environment is caused to detrimentally affect.Although above technology all obtains structure or well behaved titanium dioxide, all do not provide its surface electric charge and change.The TiO 2 particles for electrophoresis showed of patent CN102430370A report is by anionic surfactant sodium dodecylbenzene sulfonate or sodium lauryl sulphate at organic solvent, and cats product palmityl trimethyl ammonium chloride modifies and to obtain, in the aqueous solution, be difficult to keep its charge.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of charge anatase titanium dioxide nanoparticle and low temperature preparation method thereof.
Charge anatase titanium dioxide nanoparticle provided by the invention and low temperature preparation method thereof are that the schema based on accompanying drawing 1 is realized, and comprise the following steps:
1) preparation of inorganic titanium salt/polyelectrolyte solution; 2) precipitation process; 3) peptization course; 4) purifying, drying process.
Charge anatase titanium dioxide nanoparticle and a low temperature preparation method thereof, by following concrete scheme, realize:
Step 1) preparation of inorganic titanium salt/polyelectrolyte solution
Inorganic titanium salt is made into the aqueous solution of 0.2mol/L～0.4mol/L, under fully stirring, cationic polyelectrolyte or anionic polyelectrolyte is dissolved in this inorganic titanium solution.The mass ratio of inorganic titanium salt and polyelectrolyte is 1:0.01～1:0.15, continues fully to stir, and it is mixed;
Step 2) precipitation process
Inorganic titanium salt/the polyelectrolyte solution of 2～5 mass parts that step (1) is obtained drops in 0.5～2.5wt% basic solution of 1～3 mass parts under agitation condition, and after precipitin reaction 30～120min, centrifugation, obtains white depositions;
Step 3) peptization course
The white depositions that step (2) is obtained is scattered in the acid solution of 0.01～0.3mol/L, and ultrasonic dispersion 0.5～1.5h, then under agitation in 35～105 ℃ of 1～5h that reflux;
Step 4) purifying, drying process
The product centrifugation that step (3) is obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven dry at 30～80 ℃, obtains the anatase type nano TiO of charge 2.
Further, described cationic polyelectrolyte comprises poly-divinyl propyl ammonium chloride (PDDA), polymine (PEI), polyvinylamine (PVA), chitosan (CS); Described anionic polyelectrolyte comprises sodium polystyrene sulfonate (PSS), sodium polyacrylate (PAA), sodium lignosulfonate (SLS), calcium lignin sulphonate (CLS), sodium alginate (SA).Adopt product tape positive charge of cationic polyelectrolyte, if adopt product tape negative charge of anionic polyelectrolyte.
Further, described inorganic titanium salt is one or more the mixing in titanium sulfate, titanyl sulfate, titanium tetrachloride.
Further, described basic solution is a kind of in hexamethylenetetramine solution, ammonia soln.
Further, described acid solution is a kind of in nitric acid, glacial acetic acid.
Compared with prior art, the present invention has the following advantages:
The present invention makes anatase titanium dioxide nano particle under atmospheric low-temperature condition, and technique is simple, and energy consumption is low, and there is no organic solvent in preparation process, environmental friendliness.Adopt macromole positive and negative ion polyelectrolyte to make titanium dioxide nano-particle surface lotus positive electricity or bear electricity, as shown in accompanying drawing 4,5, its surface charge amount is higher, and its electric weight keeps better in the aqueous solution.Meanwhile, the charge anatase titanium dioxide that adopts the present invention to prepare also shows good photocatalysis performance, as shown in Figure 6, under the irradiation of UV-light, makes 1.0 * 10 -4the rhodamine B solution of wt% concentration is degradable in 300～400min.Meanwhile, because of the TiO 2 particles of patent of the present invention charged, can not only and dye molecule between produce electrostatic adsorption power, and easily separated from light-catalyzed reaction system.
Accompanying drawing explanation
Fig. 1 is the schema of the technology of the present invention.
The X ray of the nano-titanium dioxide powder that Fig. 2 the present invention obtains (XRD) figure;
(a) embodiment 7, and (b) embodiment 3, and (c) embodiment 6);
Scanning electron microscope (SEM) image of the nano-titanium dioxide powder of Fig. 3 embodiment 3 preparations.（）
The lotus positive electricity potential variation of the prepared nano-titanium dioxide powder of Fig. 4;
Embodiment 1, embodiment 2, embodiment 3, embodiment 7, embodiment 8;
The bear electric potential of the prepared nano-titanium dioxide powder of Fig. 5 changes;
Embodiment 4, embodiment 5, embodiment 7, embodiment 9, embodiment 12;
The degradation curve of the prepared nano-titanium dioxide powder of Fig. 6 embodiment 1 to rhodamine B.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
1) by the titanium sulfate Ti (SO of 2.4g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.2mol/L.Under abundant agitation condition, 0.024g cationic polyelectrolyte polymine (PEI) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of polymine (PEI) is 1:0.01, continues to stir 0.5h it is mixed;
2) Ti (SO of 2 parts of quality that step (1) obtained 4) 2/ PEI solution drops in the hexamethylenetetramine solution of 1 part of quality 0.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.01mol/L, and ultrasonic dispersion 0.5h, then under agitation in 35 ℃ of backflow 5h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 30 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 3.86nm.Known this TiO of Zeta potential measurement result 2lotus positive electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is 10.89mv.
Embodiment 2
1) by the titanium sulfate Ti (SO of 4.8g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.4mol/L.Under abundant agitation condition, 0.72g cationic polyelectrolyte polymine (PEI) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of polymine (PEI) is 1:0.15, continues to stir 0.5h it is mixed;
2) Ti (SO of 5 parts of quality that step (1) obtained 4) 2/ PEI solution drops in the hexamethylenetetramine solution of 3 parts of quality 2.5wt% under agitation condition, and after precipitin reaction 120min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.3mol/L, and ultrasonic dispersion 1.5h, then under agitation in 105 ℃ of backflow 1h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 80 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 6.88nm.Known this TiO of Zeta potential measurement result 2lotus positive electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is 25.10mv.
Embodiment 3
1) by the titanium sulfate Ti (SO of 3.6g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.3mol/L.Under abundant agitation condition, 0.18g cationic polyelectrolyte polymine (PEI) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of polymine (PEI) is 1:0.05, continues to stir 0.5h it is mixed;
2) Ti (SO of 3 parts of quality that step (1) obtained 4) 2/ PEI solution drops in the hexamethylenetetramine solution of 2 parts of quality 1wt% under agitation condition, and after precipitin reaction 80min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.15mol/L, and ultrasonic dispersion 1h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, as shown in Fig. 2 (b), and TiO 2size of microcrystal be about 5nm.Known this TiO of Zeta potential measurement result 2lotus positive electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is 15.05mv
Embodiment 4
1) by the titanium sulfate Ti (SO of 2.4g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.2mol/L.Under abundant agitation condition, 0.024g anionic polyelectrolyte sodium polystyrene sulfonate (PSS) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of sodium polystyrene sulfonate (PSS) is 1:0.01, continues to stir 0.5h it is mixed;
2) Ti (SO of 2 parts of quality that step (1) obtained 4) 2/ PSS solution drops in the hexamethylenetetramine solution of 1 part of quality 0.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.01mol/L, and ultrasonic dispersion 0.5h, then under agitation in 35 ℃ of backflow 5h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 30 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 4.9nm.Known this TiO of Zeta potential measurement result 2bear electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is-18.84mv.
Embodiment 5
1) by the titanium sulfate Ti (SO of 4.8g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.4mol/L.Under abundant agitation condition, 0.72g anionic polyelectrolyte sodium polystyrene sulfonate (PSS) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of sodium polystyrene sulfonate (PSS) is 1:0.15, continues to stir 0.5h it is mixed;
2) Ti (SO of 5 parts of quality that step (1) obtained 4) 2/ PSS solution drops in the hexamethylenetetramine solution of 3 parts of quality 2.5wt% under agitation condition, and after precipitin reaction 120min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.3mol/L, and ultrasonic dispersion 1.5h, then under agitation in 105 ℃ of backflow 1h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 80 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 6.4nm.Known this TiO of Zeta potential measurement result 2bear electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is-39.81mv.
Embodiment 6
1) by the titanium sulfate Ti (SO of 3.6g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.3mol/L.Under abundant agitation condition, 0.18g anionic polyelectrolyte sodium polystyrene sulfonate (PSS) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of sodium polystyrene sulfonate (PSS) is 1:0.05, continues to stir 0.5h it is mixed;
2) Ti (SO of 3 parts of quality that step (1) obtained 4) 2/ PSS solution drops in the hexamethylenetetramine solution of 2 parts of quality 1wt% under agitation condition, and after precipitin reaction 80min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.15mol/L, and ultrasonic dispersion 1h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, as shown in Figure 2 (c), and TiO 2size of microcrystal be about 5.1nm.Known this TiO of Zeta potential measurement result 2bear electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is-23.91mv
Embodiment 7(comparative example)
1) by the titanium sulfate Ti (SO of 2.4g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.2mol/L.Under abundant agitation condition, it is mixed;
2) Ti (SO of 2 parts of quality that step (1) obtained 4) 2solution drops in the hexamethylenetetramine solution of 1 part of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.3mol/L, and ultrasonic dispersion 1h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, as shown in Figure 2 (a) shows, and TiO 2size of microcrystal be about 4.4nm.
Embodiment 8
1) by the titanium tetrachloride (TiCl of 2.4g 4) be dissolved in 50mL water, be made into the titanium tetrachloride solution of 0.2mol/L.Under abundant agitation condition, the poly-divinyl propyl ammonium chloride (PDDA) of 0.24g cationic polyelectrolyte is dissolved in to this TiCl 4in solution, titanium tetrachloride TiCl 4with the mass ratio of poly-divinyl propyl ammonium chloride (PDDA) be 1:0.10, continue to stir 0.5h it mixed;
2) TiCl of 2 parts of quality that step (1) obtained 4/ PDDA solution drops in the ammonia soln of 1 part of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the glacial acetic acid solution of 0.3mol/L, and ultrasonic dispersion 0.5h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Known this TiO of Zeta potential measurement result 2lotus positive electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is 19.84mv.
Embodiment 9
1) by the titanyl sulfate (TiOSO of 2.4g 4) be dissolved in 50mL water, be made into the titanyl sulfate solution of 0.2mol/L.Under abundant agitation condition, 0.12g anionic polyelectrolyte sodium polyacrylate (PAA) is dissolved in to this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of sodium polyacrylate (PAA) be 1:0.05, continue to stir 0.5h it mixed;
2) TiOSO of 2 parts of quality that step (1) obtained 4/ PAA solution drops in the ammonia soln of 1 part of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the glacial acetic acid solution of 0.3mol/L, and ultrasonic dispersion 0.5h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Known this TiO of Zeta potential measurement result 2bear electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is-23.91mv.
Embodiment 10
1) by the titanium sulfate Ti (SO of 3.6g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.3mol/L.Under abundant agitation condition, 0.18g cationic polyelectrolyte polymine (PVA) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of polyvinylamine (PVA) is 1:0.05, continues to stir 0.5h it is mixed;
2) Ti (SO of 3 parts of quality that step (1) obtained 4) 2/ PVA solution drops in the hexamethylenetetramine solution of 2 parts of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.15mol/L, and ultrasonic dispersion 1h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Known this TiO of Zeta potential measurement result 2lotus positive electricity.
Embodiment 11
1) by the titanyl sulfate (TiOSO of 2.4g 4) be dissolved in 50mL water, be made into the titanyl sulfate solution of 0.2mol/L.Under abundant agitation condition, cationic polyelectrolyte chitosan (CS) is dissolved in to this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of polyelectrolyte chitosan (CS) be 1:0.01, continue to stir 0.5h it mixed;
2) TiOSO of 2 parts of quality that step (1) obtained 4/ CS solution drops in the ammonia soln of 1 part of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the glacial acetic acid solution of 0.3mol/L, and ultrasonic dispersion 0.5h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Known this TiO of Zeta potential measurement result 2lotus positive electricity.
Embodiment 12
1) by the titanyl sulfate (TiOSO of 2.4g 4) be dissolved in 50mL water, be made into the titanyl sulfate solution of 0.2mol/L.Under abundant agitation condition, 0.24g anionic polyelectrolyte sodium lignosulfonate (SLS) is dissolved in to this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of sodium lignosulfonate (SLS) be 1:0.1, continue to stir 0.5h it mixed;
2) TiOSO of 2 parts of quality that step (1) obtained 4/ SLS solution drops in the ammonia soln of 1 part of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the glacial acetic acid solution of 0.3mol/L, and ultrasonic dispersion 0.5h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Known this TiO of Zeta potential measurement result 2bear electricity, works as TiO 2in the aqueous solution, concentration is 2 * 10 -4during g/L, Zeta potential is-25.55mv.
Embodiment 13
1) by the titanyl sulfate (TiOSO of 2.4g 4) be dissolved in 50mL water, be made into the titanyl sulfate solution of 0.2mol/L.Under abundant agitation condition, 0.024g anionic polyelectrolyte calcium lignin sulphonate (CLS) is dissolved in to this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of calcium lignin sulphonate (CLS) be 1:0.01, continue to stir 0.5h it mixed;
2) TiOSO of 2 parts of quality that step (1) obtained 4/ CLS solution drops in the ammonia soln of 1 part of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the glacial acetic acid solution of 0.3mol/L, and ultrasonic dispersion 0.5h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.
The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Known this TiO of Zeta potential measurement result 2bear electricity.
Embodiment 14
1) by the titanium sulfate Ti (SO of 3.6g 4) 2be dissolved in 50mL water, be made into the titanium sulfate solution of 0.3mol/L.Under abundant agitation condition, 0.18g anionic polyelectrolyte sodium alginate (SA) is dissolved in to this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2with the mass ratio of sodium alginate (SA) is 1:0.05, continues to stir 0.5h it is mixed;
2) Ti (SO of 3 parts of quality that step (1) obtained 4) 2/ SA solution drops in the hexamethylenetetramine solution of 2 parts of quality 2.5wt% under agitation condition, and after precipitin reaction 30min, centrifugation, obtains white depositions;
3) white depositions step (2) being obtained is scattered in the salpeter solution of 0.15mol/L, and ultrasonic dispersion 1h, then under agitation in 50 ℃ of backflow 2h;
4) product centrifugation step (3) being obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven, dry at 50 ℃, obtains white titanium dioxide powder.The crystal formation of being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Known this TiO of Zeta potential measurement result 2bear electricity.

Claims (6)

1. a low temperature preparation method for charge anatase titanium dioxide nanoparticle, is characterized in that, comprises the following steps:
Step 1) preparation of inorganic titanium salt/polyelectrolyte solution
Inorganic titanium salt is made into the aqueous solution of 0.2mol/L～0.4mol/L, under fully stirring, cationic polyelectrolyte or anionic polyelectrolyte is dissolved in this inorganic titanium solution.The mass ratio of inorganic titanium salt and polyelectrolyte is 1:0.01～1:0.15, continues fully to stir, and it is mixed;
Step 2) precipitation process
Inorganic titanium salt/the polyelectrolyte solution of 2～5 mass parts that step (1) is obtained drops in 0.5～2.5wt% basic solution of 1～3 mass parts under agitation condition, and after precipitin reaction 30～120min, centrifugation, obtains white depositions;
Step 3) peptization course
The white depositions that step (2) is obtained is scattered in the acid solution of 0.01～0.3mol/L, and ultrasonic dispersion 0.5～1.5h, then under agitation in 35～105 ℃ of 1～5h that reflux;
Step 4) purifying, drying process
The product centrifugation that step (3) is obtained, fully washs with dehydrated alcohol, then this throw out is placed in to baking oven dry at 30～80 ℃, obtains the anatase type nano TiO of charge 2.
2. according to the method for claim 1, it is characterized in that, cationic polyelectrolyte is poly-divinyl propyl ammonium chloride (PDDA), polymine (PEI), polyvinylamine (PVA), chitosan (CS); Described anionic polyelectrolyte is sodium polystyrene sulfonate (PSS), sodium polyacrylate (PAA), sodium lignosulfonate (SLS), calcium lignin sulphonate (CLS), sodium alginate (SA).
3. according to the method for claim 1, it is characterized in that, inorganic titanium salt is one or more the mixing in titanium sulfate, titanyl sulfate, titanium tetrachloride.
4. according to the method for claim 1, it is characterized in that, described basic solution is a kind of in hexamethylenetetramine solution, ammonia soln.
5. according to the method for claim 1, it is characterized in that, described acid solution is a kind of in nitric acid, glacial acetic acid.
6. the charge anatase titanium dioxide nanoparticle preparing according to the either method described in claim 1-5.
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CN110339864A (en) * 2019-07-25 2019-10-18 河南嘉利美环保材料有限公司 One kind containing TiO2The spheric granules of purification factor
CN114164511A (en) * 2021-03-23 2022-03-11 耐酷时(北京)科技有限公司 Preparation method of porous titanium dioxide mixed polyacrylonitrile fiber

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Publication number Priority date Publication date Assignee Title
CN104118906A (en) * 2014-08-05 2014-10-29 苏州巨联环保科研有限公司 Method for preparing porous titanium dioxide by polymer-assisted deposition
CN104118906B (en) * 2014-08-05 2016-06-29 苏州巨联环保科研有限公司 A kind of method that polymer assistant depositing prepares poriferous titanium dioxide
CN104785124A (en) * 2015-03-30 2015-07-22 北京工业大学 Charged TiO2/polyelectrolyte composite nanofiltration membrane as well as preparation method and application thereof
CN110339864A (en) * 2019-07-25 2019-10-18 河南嘉利美环保材料有限公司 One kind containing TiO2The spheric granules of purification factor
CN114164511A (en) * 2021-03-23 2022-03-11 耐酷时(北京)科技有限公司 Preparation method of porous titanium dioxide mixed polyacrylonitrile fiber
CN114164511B (en) * 2021-03-23 2024-02-09 耐酷时(北京)科技有限公司 Preparation method of porous titanium dioxide mixed polyacrylonitrile fiber

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