CN101884939A - Controllable synthesis method of nonmetallic ion-doped nano titanium dioxide by phase separation-hydrolysis solvothermal method - Google Patents
Controllable synthesis method of nonmetallic ion-doped nano titanium dioxide by phase separation-hydrolysis solvothermal method Download PDFInfo
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- CN101884939A CN101884939A CN 201010246066 CN201010246066A CN101884939A CN 101884939 A CN101884939 A CN 101884939A CN 201010246066 CN201010246066 CN 201010246066 CN 201010246066 A CN201010246066 A CN 201010246066A CN 101884939 A CN101884939 A CN 101884939A
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Abstract
The invention relates a controllable synthesis method of nonmetallic ion-doped nano titanium dioxide by a phase separation-hydrolysis solvothermal method, in particular to a synthesis method of nonmetallic ion-doped nano titanium dioxide, which solves the problems of low doping efficiency, complicated process, high cost and poor universality of the existing nonmetallic ion doping method of the nano titanium dioxide. The synthesis method comprises the following steps: 1, mixing tetrabutyl titanate with methylbenzene and then stirring to obtain an organic phase; 2, adding nonmetallic ion aqueous solution to a high-pressure reaction kettle, placing the organic phase into a U-shaped groove, placing the groove into the nonmetallic ion aqueous solution, covering, carrying out solvothermal treatment, cooling and filtering; and 3, drying by oil bath and then roasting to obtain the nonmetallic ion-doped nano titanium dioxide. The synthesis method of the invention has simple process, high doping efficiency, low cost and wide applicability; and the obtained nano titanium dioxide has high crystallization degree and good visible light catalytic activity, thus the nano titanium dioxide can be applied to visible light catalytic degradation of organic pollutants.
Description
Technical field
The present invention relates to a kind of synthetic method of nonmetallic ion-doped nano titanium dioxide.
Background technology
The conductor photocatalysis technology is owing to easy and simple to handle, outstanding advantages such as reaction condition is gentle, non-secondary pollution come into one's own.In numerous semiconductor light-catalysts, titanium dioxide owing to active height, good stability, anti-photoetch by force, characteristics such as low price and safety non-toxic gain great popularity.When making titanium dioxide have high photocatalytic activity, the band gap of broad also its range of application is limited in the ultraviolet light range.Nonmetallic ion-doped is the effective ways of widening the titanium-dioxide photo response range, improving its visible light catalysis activity.At present the method for the synthetic non-metallic ion-doped nano titanium dioxide that adopts normally after titanium dioxide nano-particle obtains with the material mechanical agitation that contains nonmetalloid, and then carry out a reducing atmosphere under protecting high-temperature heat treatment and obtain product; Because nano particle produces, nonmetalloid is difficult to enter the titanium dioxide lattice and replaces oxygen element, so the doping efficiency of this method is low; High-temperature heat treatment process under need protecting through the building-up process of titanium dioxide, with material mechanical agitation process that contains nonmetalloid and reducing atmosphere, complex process, produce that equipment needed thereby is of a great variety, under the high temperature maintenance of reducing atmosphere equipment high temperature high voltage resistant and air-tightness are required high, so cost height; Existing process conditions can only realize a kind of nonmetal doping usually, so universality is poor.
Summary of the invention
The present invention seeks to the problem of, complex process low, cost height, universality difference, and provide a kind of utilization to be separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide for the method doping efficiency that solves existing synthetic non-metallic ion-doped nano titanium dioxide.
Utilization is separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide, it is characterized in that utilizing being separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide realizes according to the following steps: one, butyl titanate mixed the back with toluene by the volume ratio of 1:3 and stirs 20 ~ 40min, obtain organic facies; Two, be that the aqueous solution of the nonmetallic ion of 1.5 ~ 2.0mol/L joins in the autoclave with concentration, the U-lag of again organic facies being packed into is placed in the aqueous solution of nonmetallic ion, the aqueous solution liquid level of nonmetallic ion is positioned under the U-lag top end face, cover kettle cover then, then at 140 ~ 180 ℃ of following solvent thermal reaction 5 ~ 7h, be cooled to room temperature, filter; Three, will be under 100 ~ 140 ℃ of conditions, step 2 filtered the sediment that obtains with the dry 1h of dimethicone oil bath, grind, be warming up to 300 ~ 400 ℃ with the heating rate of 5 ~ 15 ℃/min, insulation 1 ~ 3h cools off with stove; Promptly obtain nonmetallic ion-doped nano titanium dioxide.
The present invention carries out solvent thermal reaction by introduce nonionics such as ammoniacal liquor, thiocarbamide or vulcanized sodium at aqueous phase in autoclave, prepared different nonmetallic ion-doped nano titanium oxides.Degree of crystallization height, visible light catalysis activity that the inventive method prepares nonmetallic ion-doped nano titanium oxide are good, are used for visible light photocatalytic degradation of organic pollutants.The crystalline phase that the inventive method prepares nonmetallic ion-doped nano titanium dioxide is the anatase phase, and its photoresponse scope is wideer, can reach 700nm.Compare with the pure sample product without overdoping, the nonmetallic ion-doped nano titanium dioxide light absorption that the present invention obtains is stronger, and visible light catalysis activity improves, and the efficient height that mixes is described.The inventive method technology is simple, and the reaction condition gentleness is low for equipment requirements, thereby has reduced production cost; Can obtain multiple nonmetallic ion-doped nano titanium oxide by changing the nonmetallic substance that adds, widely applicable, be suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the synthesizer schematic diagram, 1 expression kettle cover among Fig. 1,2 expression autoclaves, 3 expression U-lags, 4 expression organic facies, 5 expression waters; Fig. 2 is the XRD figure of the prepared nonmetallic ion-doped nano titanium dioxide of the specific embodiment ten, a represents the XRD figure with the nonmetallic ion-doped nano titanium dioxide of ammonia spirit preparation, b represents that c represents the XRD figure with the nonmetallic ion-doped nano titanium dioxide of vulcanized sodium with the XRD figure of the nonmetallic ion-doped nano titanium dioxide of thiourea solution preparation; Fig. 3 is the DRS figure of the prepared nonmetallic ion-doped nano titanium dioxide of the specific embodiment ten, 1 expression is without the pure anatase-phase nano titanium dioxide of nonmetallic ion-doped (other synthesis condition unanimities) among Fig. 3, the 2 expressions nonmetallic ion-doped nano titanium dioxide of vulcanized sodium, the nonmetallic ion-doped nano titanium dioxide that 3 expressions prepare with ammonia spirit, the nonmetallic ion-doped nano titanium dioxide that 4 expressions prepare with thiourea solution; Fig. 4 is the visible light catalysis activity figure of the prepared nonmetallic ion-doped nano titanium dioxide of the specific embodiment ten, the nonmetallic ion-doped nano titanium dioxide that 5 expressions prepare with ammonia spirit among Fig. 4, the nonmetallic ion-doped nano titanium dioxide that 6 expressions prepare with thiourea solution, the 7 expressions nonmetallic ion-doped nano titanium dioxide of vulcanized sodium, 8 expression titanium dioxide (commodity P25), 9 pure anatase-phase nano titanium dioxides without nonmetallic ion-doped (other synthesis condition unanimities).
The specific embodiment
The specific embodiment one: utilize in the present embodiment to be separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide realizes according to the following steps: one, butyl titanate mixed stirring 20 ~ 40min afterwards with toluene by the volume ratio of 1:3, obtains organic facies; Two, be that the aqueous solution of the nonmetallic ion of 1.5 ~ 2.0mol/L joins in the autoclave with concentration, the U-lag of again organic facies being packed into is placed in the aqueous solution (water) of nonmetallic ion, the aqueous solution liquid level of nonmetallic ion is positioned under the U-lag top end face, cover kettle cover then, then at 140 ~ 180 ℃ of following solvent thermal reaction 5 ~ 7h, be cooled to room temperature, filter; Three, will be under 100 ~ 140 ℃ of conditions, step 2 filtered the sediment that obtains with the dry 1h of dimethicone oil bath, grind, be warming up to 300 ~ 400 ℃ with the heating rate of 5 ~ 15 ℃/min, insulation 1 ~ 3h cools off with stove; Promptly obtain nonmetallic ion-doped nano titanium dioxide.
The crystalline phase that the present embodiment method prepares nonmetallic ion-doped nano titanium dioxide is the anatase phase, and its photoresponse scope is wideer, can reach 700nm.
The specific embodiment two: present embodiment is implemented one and different is with concrete: the mixing time described in the step 1 is 30min.Other step is identical with the specific embodiment one with parameter.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is: the described nonmetallic ion aqueous solution of step 2 is ammonia spirit, thiourea solution or sodium sulfide solution.Other step is identical with the specific embodiment one or two with parameter.
The specific embodiment four: what present embodiment was different with one of specific embodiment one to three is: the concentration of the aqueous solution of the described nonmetallic ion of step 2 is 1.8mol/L.Other step is identical with one of parameter and specific embodiment one to three.
The specific embodiment five: what present embodiment was different with one of specific embodiment one to four is: the described solvent thermal reaction temperature of step 2 is 160 ℃.Other step is identical with one of parameter and specific embodiment one to four.
The specific embodiment six: what present embodiment was different with one of specific embodiment one to five is: the described solvent thermal reaction of the step 2 time is 6h.Other step is identical with one of parameter and specific embodiment one to five.
The specific embodiment seven: what present embodiment was different with one of specific embodiment one to six is: the described baking temperature of step 3 is that 120 ℃, time are 1h.Other step is identical with one of parameter and specific embodiment one to six.
The specific embodiment eight: what present embodiment was different with one of specific embodiment one to seven is: 10 ℃/min of the described heating rate of step 3.Other step is identical with one of parameter and specific embodiment one to seven.
The specific embodiment nine: what present embodiment was different with one of specific embodiment one to eight is: step 3 is described to be incubated 2h under 350 ℃ of conditions.Other step is identical with one of parameter and specific embodiment one to eight.
The specific embodiment ten: present embodiment utilizes the method for two hydrolysis that are separated-solvent-thermal method controlledly synthesis nonmetallic ion-doped nano titanium dioxide to realize by the following method: one, butyl titanate is mixed the back with toluene by the volume ratio of 1:3 and stir 30min, obtain organic facies; Two, be that the aqueous solution, thiourea solution or the sodium sulfide solution of the ammoniacal liquor of 1.8mol/L joins in the autoclave as water with concentration, the U-lag of again organic facies being packed into is placed in the aqueous solution (water) of nonmetallic ion, the aqueous solution liquid level of nonmetallic ion is positioned under the U-lag top end face, cover kettle cover then, then at 160 ℃ of following solvent thermal reaction 6h, be cooled to room temperature, filter; Three, will be under 120 ℃ of conditions, step 2 filtered the sediment that obtains with the dry 1h of dimethicone oil bath, grind, be warming up to 350 ℃ with the heating rate of 10 ℃/min, insulation 2h cools off with stove; Promptly obtain nonmetallic ion-doped nano titanium dioxide.
Adopt XRD, DRS that the present embodiment product is detected, and use rhodamine B degraded and verify effect of the present invention, the result is as described in Fig. 2 ~ 4.
As shown in Figure 1, the crystalline phase of the nonmetallic ion-doped nano titanium dioxide that obtains of present embodiment is the anatase phase.As shown in Figure 3, compare with the pure sample product without overdoping, the photoresponse scope of the nonmetallic ion-doped nano titanium dioxide that present embodiment obtains is wideer, absorption is stronger.As shown in Figure 4, (the rhodamine B solution concentration is 20mg/L at the visible light photocatalytic degradation to the rhodamine B aqueous solution, liquor capacity is 100ml, add catalyst 0.2g, light source is the 150W xenon lamp, the distance of lamp and catalytic unit is 10cm) in, the nonmetallic ion-doped nano titanium dioxide that present embodiment obtains has shown high visible light catalysis activity, considerably beyond pure anatase-phase nano titanium dioxide and commodity P25 titanium dioxide without nonmetallic ion-doped (other synthesis condition unanimities), it is good to illustrate that the present embodiment mode obtains the nonmetallic ion-doped nano titanium dioxide visible light catalysis activity.
Claims (9)
1. utilize to be separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide, it is characterized in that utilizing being separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide realizes according to the following steps: one, butyl titanate mixed the back with toluene by the volume ratio of 1:3 and stirs 20 ~ 40min, obtain organic facies; Two, be that the aqueous solution of the nonmetallic ion of 1.5 ~ 2.0mol/L joins in the autoclave with concentration, the U-lag of again organic facies being packed into is placed in the aqueous solution of nonmetallic ion, the aqueous solution liquid level of nonmetallic ion is positioned under the U-lag top end face, cover kettle cover then, then at 140 ~ 180 ℃ of following solvent thermal reaction 5 ~ 7h, be cooled to room temperature, filter; Three, will be under 100 ~ 140 ℃ of conditions, step 2 filtered the sediment that obtains with the dry 1h of dimethicone oil bath, grind, be warming up to 300 ~ 400 ℃ with the heating rate of 5 ~ 15 ℃/min, insulation 1 ~ 3h cools off with stove; Promptly obtain nonmetallic ion-doped nano titanium dioxide.
2. utilization according to claim 1 is separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide, it is characterized in that the mixing time described in the step 1 is 30min.
3. utilization according to claim 1 and 2 is separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide, it is characterized in that the described nonmetallic ion aqueous solution of step 2 is ammonia spirit, thiourea solution or sodium sulfide solution.
4. utilization according to claim 3 is separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide, and the concentration that it is characterized in that the aqueous solution of the described nonmetallic ion of step 2 is 1.8mol/L.
5. be separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide according to claim 1,2 or 4 described utilizations, it is characterized in that the described solvent thermal reaction temperature of step 2 is 160 ℃.
6. utilization according to claim 5 is separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide, it is characterized in that the described solvent thermal reaction time of step 2 is 6h.
7. be separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide according to claim 1,2,4 or 6 described utilizations, it is characterized in that the described baking temperature of step 3 is 120 ℃.
8. utilization according to claim 7 is separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide, it is characterized in that 10 ℃/min of the described heating rate of step 3.
9. be separated-method of the hot method controlledly synthesis of hydrolysising solvent nonmetallic ion-doped nano titanium dioxide according to claim 1,2,4,7 or 8 described utilizations, it is characterized in that step 3 is described under 350 ℃ of conditions, to be incubated 2h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935668A (en) * | 2006-09-30 | 2007-03-28 | 华南理工大学 | Nitrogen-doped titanium dioxide solvent thermal preparation method |
| CN1986907A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Process of preparing oil soluble nano titania line |
| CN101760171A (en) * | 2008-12-25 | 2010-06-30 | 西北工业大学 | Optical resonance composite material in noble metal/titanium dioxide micro-nano structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986907A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Process of preparing oil soluble nano titania line |
| CN1935668A (en) * | 2006-09-30 | 2007-03-28 | 华南理工大学 | Nitrogen-doped titanium dioxide solvent thermal preparation method |
| CN101760171A (en) * | 2008-12-25 | 2010-06-30 | 西北工业大学 | Optical resonance composite material in noble metal/titanium dioxide micro-nano structure |
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