CN103601237B - 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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CN103601237B
CN103601237B CN201310549730.2A CN201310549730A CN103601237B CN 103601237 B CN103601237 B CN 103601237B CN 201310549730 A CN201310549730 A CN 201310549730A CN 103601237 B CN103601237 B CN 103601237B
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CN103601237A (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 nano particle 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 nano particle 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 of its have that the advantages such as nontoxic, spectrochemical property is stable, photocatalysis effect is good, reusable are widely used in low concentration wastewater process, noble metal reclaims, purification of air and the field such as coating surface is self-cleaning, this material can be degraded multiple environmental contaminants under ultraviolet light even radiation of visible light, also has the feature of Light induction.TiO 2mainly be present in occurring in nature with rutile-type, Detitanium-ore-type and brookite type three kinds of crystal structures, 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 preparing titania nanoparticles is a lot, and wherein chemical method mainly comprises vapor phase method and liquid phase method.Titanium dioxide nano-particle prepared by the vapor phase method of patent CN1736878A, CN1810653A report can realize its suitability for industrialized production, but device therefor is complicated, cost is high; Patent CN102320655A and CN101671052A adopts sol-gel process to prepare titanium dioxide nano-particle, and its cost of material is higher, and needs the processes such as secondary hydrolysis, high-temperature roasting, complex process; Patent CN103011273A adopts hydro-thermal method to prepare Nano flaky spherical anatase titanium dioxide, but needs to carry out crystallization at 160 ~ 200 DEG C; Patent CN102120612A reports a kind of and adds in the inorganic base dispersion soln containing anion surfactant by titanium source acid solution, after reaction, centrifugation obtains anatase titanium dioxide, and anion surfactant used is only the reunion in order to reduce 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 material diethylamine, triethylamine, propylamine etc. used, all to health toxic side effect, and solvent not easily reclaims, and causes harmful effect to environment.Although above technology all obtains structure or titanium dioxide of good performance, all do not provide the change of its surface electric charge.The TiO 2 particles for electrophoresis showed of patent CN102430370A report is in organic solvent by anionic surfactant sodium dodecylbenzene sulfonate or lauryl sodium sulfate, and the modification of cationic surfactant hexadecyltrimethylammonium chloride obtains, and is difficult in aqueous keep its charge.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of charge anatase titanium dioxide nano particle and low temperature preparation method thereof.
Charge anatase titanium dioxide nano particle provided by the invention and low temperature preparation method thereof realize based on the flow chart of accompanying drawing 1, comprises the following steps:
1) preparation of inorganic titanium salt/polyelectrolyte solution; 2) precipitation process; 3) peptization course; 4) purifying, dry run.
A kind of charge anatase titanium dioxide nano particle and low temperature preparation method thereof, realized by following concrete scheme:
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 makes it mix;
Step 2) precipitation process
Inorganic titanium salt/the polyelectrolyte solution of 2 ~ 5 mass parts step (1) obtained drops in 0.5 ~ 2.5wt% alkaline solution of 1 ~ 3 mass parts under agitation, and after precipitation reaction 30 ~ 120min, centrifugation, obtains white depositions;
Step 3) peptization course
The white depositions that step (2) obtains is scattered in the acid solution of 0.01 ~ 0.3mol/L, ultrasonic disperse 0.5 ~ 1.5h, then under agitation in 35 ~ 105 DEG C of backflow 1 ~ 5h;
Step 4) purifying, dry run
By the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven dry at 30 ~ 80 DEG C, namely obtains the anatase type nano TiO of charge 2.
Further, described cationic polyelectrolyte comprises poly-divinyl propyl ammonium chloride (PDDA), polymine (PEI), polyvinylamine (PVA), shitosan (CS); Described anionic polyelectrolyte comprises kayexalate (PSS), Sodium Polyacrylate (PAA), sodium lignin sulfonate (SLS), calcium lignosulfonate (CLS), sodium alginate (SA).Adopt cationic polyelectrolyte then product tape positive charge, according to anionic polyelectrolyte then product tape negative electrical charge.
Further, described inorganic titanium salt is the mixing of one or more in titanium sulfate, titanyl sulfate, titanium tetrachloride.
Further, described alkaline solution is the one in hexamethylenetetramine solution, ammonia spirit.
Further, described acid solution is the one in nitric acid, glacial acetic acid.
Compared with prior art, the present invention has the following advantages:
The present invention is obtained anatase titanium dioxide nano particle under atmospheric low-temperature condition, and technique is simple, and energy consumption is low, and does not have organic solvent in preparation process, environmental friendliness.Adopt large molecule positive and negative cationic 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 electricity keeps better in aqueous.Meanwhile, the charge anatase titanium dioxide adopting the present invention to prepare also shows good photocatalysis performance, as shown in Figure 6, under the irradiation of ultraviolet light, makes 1.0 × 10 -4the rhodamine B solution of wt% concentration is degradable in 300 ~ 400min.Meanwhile, because the TiO 2 particles of patent of the present invention is charged, can not only and dye molecule between produce electrostatic adsorption power, and to be easily separated from light-catalyzed reaction system.
Accompanying drawing explanation
Fig. 1 is the flow chart of the technology of the present invention.
X-ray (XRD) figure of the nano-titanium dioxide powder that Fig. 2 the present invention obtains;
(a) embodiment 7, (b) embodiment 3, (c) embodiment 6);
ESEM (SEM) image of nano-titanium dioxide powder prepared by Fig. 3 embodiment 3.（）
The lotus positive electricity potential change of nano-titanium dioxide powder prepared by Fig. 4;
Embodiment 1, embodiment 2, embodiment 3, embodiment 7, embodiment 8;
The bear electric potential change of nano-titanium dioxide powder prepared by Fig. 5;
Embodiment 4, embodiment 5, embodiment 7, embodiment 9, embodiment 12;
Prepared by Fig. 6 embodiment 1, nano-titanium dioxide powder is to the degradation curve of rhodamine B.
Detailed description of the invention
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 stirring condition, 0.024g cationic polyelectrolyte polymine (PEI) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.01 with the mass ratio of polymine (PEI), continue to stir 0.5h and makes it mix;
2) Ti (SO of 2 parts of quality step (1) obtained 4) 2/ PEI solution drops in the hexamethylenetetramine solution of 1 part of quality 0.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.01mol/L, ultrasonic disperse 0.5h, then under agitation in 35 DEG C of backflow 5h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 30 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 3.86nm.Zeta potential measurement result this TiO known 2lotus positive electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.72g cationic polyelectrolyte polymine (PEI) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.15 with the mass ratio of polymine (PEI), continue to stir 0.5h and makes it mix;
2) Ti (SO of 5 parts of quality step (1) obtained 4) 2/ PEI solution drops in the hexamethylenetetramine solution of 3 parts of quality 2.5wt% under agitation, and after precipitation reaction 120min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.3mol/L, ultrasonic disperse 1.5h, then under agitation in 105 DEG C of backflow 1h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 80 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 6.88nm.Zeta potential measurement result this TiO known 2lotus positive electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.18g cationic polyelectrolyte polymine (PEI) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.05 with the mass ratio of polymine (PEI), continue to stir 0.5h and makes it mix;
2) Ti (SO of 3 parts of quality step (1) obtained 4) 2/ PEI solution drops in the hexamethylenetetramine solution of 2 parts of quality 1wt% under agitation, and after precipitation reaction 80min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.15mol/L, ultrasonic disperse 1h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation 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.Zeta potential measurement result this TiO known 2lotus positive electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.024g anionic polyelectrolyte kayexalate (PSS) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.01 with the mass ratio of kayexalate (PSS), continue to stir 0.5h and makes it mix;
2) Ti (SO of 2 parts of quality step (1) obtained 4) 2/ PSS solution drops in the hexamethylenetetramine solution of 1 part of quality 0.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.01mol/L, ultrasonic disperse 0.5h, then under agitation in 35 DEG C of backflow 5h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 30 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 4.9nm.Zeta potential measurement result this TiO known 2bear electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.72g anionic polyelectrolyte kayexalate (PSS) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.15 with the mass ratio of kayexalate (PSS), continue to stir 0.5h and makes it mix;
2) Ti (SO of 5 parts of quality step (1) obtained 4) 2/ PSS solution drops in the hexamethylenetetramine solution of 3 parts of quality 2.5wt% under agitation, and after precipitation reaction 120min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.3mol/L, ultrasonic disperse 1.5h, then under agitation in 105 DEG C of backflow 1h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 80 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type, TiO 2size of microcrystal be about 6.4nm.Zeta potential measurement result this TiO known 2bear electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.18g anionic polyelectrolyte kayexalate (PSS) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.05 with the mass ratio of kayexalate (PSS), continue to stir 0.5h and makes it mix;
2) Ti (SO of 3 parts of quality step (1) obtained 4) 2/ PSS solution drops in the hexamethylenetetramine solution of 2 parts of quality 1wt% under agitation, and after precipitation reaction 80min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.15mol/L, ultrasonic disperse 1h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation 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.Zeta potential measurement result this TiO known 2bear electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, it is made to mix;
2) Ti (SO of 2 parts of quality step (1) obtained 4) 2solution drops in the hexamethylenetetramine solution of 1 part of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.3mol/L, ultrasonic disperse 1h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation 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 stirring condition, 0.24g cationic polyelectrolyte is gathered divinyl propyl ammonium chloride (PDDA) and be dissolved in this TiCl 4in solution, titanium tetrachloride TiCl 4be 1:0.10 with the mass ratio of poly-divinyl propyl ammonium chloride (PDDA), continue to stir 0.5h and makes it mix;
2) TiCl of 2 parts of quality step (1) obtained 4/ PDDA solution drops in the ammonia spirit of 1 part of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the glacial acetic acid solution of 0.3mol/L, ultrasonic disperse 0.5h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Zeta potential measurement result this TiO known 2lotus positive electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.12g anionic polyelectrolyte Sodium Polyacrylate (PAA) is dissolved in this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of Sodium Polyacrylate (PAA) be 1:0.05, continue stir 0.5h makes it mix;
2) TiOSO of 2 parts of quality step (1) obtained 4/ PAA solution drops in the ammonia spirit of 1 part of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the glacial acetic acid solution of 0.3mol/L, ultrasonic disperse 0.5h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Zeta potential measurement result this TiO known 2bear electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.18g cationic polyelectrolyte polymine (PVA) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.05 with the mass ratio of polyvinylamine (PVA), continue to stir 0.5h and makes it mix;
2) Ti (SO of 3 parts of quality step (1) obtained 4) 2/ PVA solution drops in the hexamethylenetetramine solution of 2 parts of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.15mol/L, ultrasonic disperse 1h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Zeta potential measurement result this TiO known 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 stirring condition, cationic polyelectrolyte shitosan (CS) is dissolved in this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of polyelectrolyte shitosan (CS) be 1:0.01, continue stir 0.5h makes it mix;
2) TiOSO of 2 parts of quality step (1) obtained 4/ CS solution drops in the ammonia spirit of 1 part of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the glacial acetic acid solution of 0.3mol/L, ultrasonic disperse 0.5h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Zeta potential measurement result this TiO known 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 stirring condition, 0.24g anionic polyelectrolyte sodium lignin sulfonate (SLS) is dissolved in this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of sodium lignin sulfonate (SLS) be 1:0.1, continue stir 0.5h makes it mix;
2) TiOSO of 2 parts of quality step (1) obtained 4/ SLS solution drops in the ammonia spirit of 1 part of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the glacial acetic acid solution of 0.3mol/L, ultrasonic disperse 0.5h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Zeta potential measurement result this TiO known 2bear electricity, works as TiO 2concentration is 2 × 10 in aqueous -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 stirring condition, 0.024g anionic polyelectrolyte calcium lignosulfonate (CLS) is dissolved in this TiOSO 4in solution, titanyl sulfate (TiOSO 4) and the mass ratio of calcium lignosulfonate (CLS) be 1:0.01, continue stir 0.5h makes it mix;
2) TiOSO of 2 parts of quality step (1) obtained 4/ CLS solution drops in the ammonia spirit of 1 part of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the glacial acetic acid solution of 0.3mol/L, ultrasonic disperse 0.5h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.
The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Zeta potential measurement result this TiO known 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 stirring condition, 0.18g anionic polyelectrolyte sodium alginate (SA) is dissolved in this Ti (SO 4) 2in solution, titanium sulfate Ti (SO 4) 2be 1:0.05 with the mass ratio of sodium alginate (SA), continue to stir 0.5h and makes it mix;
2) Ti (SO of 3 parts of quality step (1) obtained 4) 2/ SA solution drops in the hexamethylenetetramine solution of 2 parts of quality 2.5wt% under agitation, and after precipitation reaction 30min, centrifugation, obtains white depositions;
3) white depositions that step (2) obtains is scattered in the salpeter solution of 0.15mol/L, ultrasonic disperse 1h, then under agitation in 50 DEG C of backflow 2h;
4) by the product centrifugation that step (3) obtains, fully wash with absolute ethyl alcohol, then this sediment is placed in baking oven, dry at 50 DEG C, obtain white titania powder.The crystal formation being analyzed this titania powder by X-ray diffraction is Detitanium-ore-type.Zeta potential measurement result this TiO known 2bear electricity.

Claims (5)

1. a low temperature preparation method for charge anatase titanium dioxide nano particle, 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 salting liquid; The mass ratio of inorganic titanium salt and polyelectrolyte is 1:0.01 ~ 1:0.15, continues fully to stir, and makes it mix;
Step 2) precipitation process
By step 1) the inorganic titanium salt/polyelectrolyte solution of 2 ~ 5 mass parts that obtains drops in 0.5 ~ 2.5wt% alkaline solution of 1 ~ 3 mass parts under agitation, and after precipitation reaction 30 ~ 120min, centrifugation, obtains white depositions;
Step 3) peptization course
By step 2) white depositions that obtains is scattered in the acid solution of 0.01 ~ 0.3mol/L, and ultrasonic disperse 0.5 ~ 1.5h, then under agitation in 35 ~ 105 DEG C of backflow 1 ~ 5h;
Step 4) purifying, dry run
By step 3) the product centrifugation that obtains, fully wash with absolute ethyl alcohol, then sediment is placed in baking oven dry at 30 ~ 80 DEG C, namely 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, polymine, polyvinylamine, shitosan; Described anionic polyelectrolyte is kayexalate, Sodium Polyacrylate, sodium lignin sulfonate, calcium lignosulfonate, sodium alginate.
3. according to the method for claim 1, it is characterized in that, inorganic titanium salt is the mixing of one or more in titanium sulfate, titanyl sulfate, titanium tetrachloride.
4. according to the method for claim 1, it is characterized in that, described alkaline solution is the one in hexamethylenetetramine solution, ammonia spirit.
5. according to the method for claim 1, it is characterized in that, described acid solution is the one in nitric acid, glacial acetic acid.
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CN104785124B (en) * 2015-03-30 2017-11-17 北京工业大学 A kind of charged TiO2/ polyelectrolyte composite nanometer filtering film and preparation method and application
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102120612A (en) * 2011-01-27 2011-07-13 洛阳师范学院 Preparation method of anatase type titanium dioxide nanoparticles
CN102408758A (en) * 2011-09-13 2012-04-11 天津大学 Electrophoretic particles having titanium dioxide/cationic polymer core-shell structure and preparation method thereof
CN103354179A (en) * 2013-04-07 2013-10-16 东华大学 Method for preparing bifunctional DSSC (dye-sensitized solar cell) photo-anode scattering particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102120612A (en) * 2011-01-27 2011-07-13 洛阳师范学院 Preparation method of anatase type titanium dioxide nanoparticles
CN102408758A (en) * 2011-09-13 2012-04-11 天津大学 Electrophoretic particles having titanium dioxide/cationic polymer core-shell structure and preparation method thereof
CN103354179A (en) * 2013-04-07 2013-10-16 东华大学 Method for preparing bifunctional DSSC (dye-sensitized solar cell) photo-anode scattering particles

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Electrophoretic TiO2 nanoparticle modified with poly(methyl methacrylate);Bong Jun Park et al.;《J Electroceram》;20061231;第17卷;第1031-1033页 *
Granulating Titania Powder by Colloidal Route Using Polyelectrolytes;Antoine Pringuet et al.;《Langmuir》;20080906;第24卷(第19期);第10702-10708页 *
Molecular Self-Assembly of TiO2/Polymer Nanocomposite Films;Yanjing Liu et al.;《J. Phys. Chem. B》;19970220;第101卷(第8期);第1385-1388页 *

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