CN102976401A - Ultrasonic chemical preparation method for nitrogen-doped nano-titanium dioxide crystal - Google Patents
Ultrasonic chemical preparation method for nitrogen-doped nano-titanium dioxide crystal Download PDFInfo
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- CN102976401A CN102976401A CN2012104022053A CN201210402205A CN102976401A CN 102976401 A CN102976401 A CN 102976401A CN 2012104022053 A CN2012104022053 A CN 2012104022053A CN 201210402205 A CN201210402205 A CN 201210402205A CN 102976401 A CN102976401 A CN 102976401A
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Abstract
The invention relates to a preparation process for a nano-titanium dioxide crystal, and particularly discloses an ultrasonic chemical preparation method for a nitrogen-doped nano-titanium dioxide crystal. The ultrasonic chemical preparation method is characterized in that a white precipitate is obtained by the steps of mixing a tetravalent titanium salt, ammonia water or an ammonium salt and a dispersing agent into a reaction solution, wherein the tetravalent titanium salt is used as a titanium source; the ammonia water or the ammonium salt is used as a nitrogen source; and a reaction temperature is controlled to be 60-90 DEG C; performing ultrasonic treatment for 3-4 hours at a normal pressure; and obtaining a final product by separating the obtained precipitate via centrifugation, washing and vacuum drying the precipitate after the centrifugation. The preparation method has simple operational steps, reasonable design, low reaction temperature and concise process; the produced nano-titanium dioxide has the advantages of small particle size and narrow distribution range of the particle size; and the preparation method is suitable for wide popularization and application.
Description
(1) technical field
The present invention relates to the preparation technology of titanium dioxide nanocrystalline, particularly a kind of sonochemistry preparation method of nitrogen-doped titanium dioxide crystal.
(2) background technology
Nano-TiO
2As a kind of photocatalyst degradable water and airborne various organic pollutant of excellent property, also have the sterilization and disinfection effect simultaneously, and owing to self nontoxic pollution-free, it is had a good application prospect aspect environmental purification.But TiO
2Can only could produce electron-hole pair under less than the action of ultraviolet radiation of 387nm at wavelength, be converted into again hydroxyl radical free radical isoreactivity species and pollutent is played the degraded effect; And the energy of sunlight middle ultraviolet band part only accounts for about 5% of whole sun power, and the energy of most visible lights (about 45%) not yet is fully used.In order efficiently to utilize sunlight, must develop the novel photocatalyst with visible light catalysis activity.The theory and practice of Asahi etc. proves that it is TiO that non-metallic element N mixes
2Visible light photoactivated a kind of effective way, thus guided in the world wide based on N doped Ti O
2The research and development upsurge of photocatalyst.N doped Ti O
2The preparation method of photocatalyst is more, mainly contains roasting method, sol-gel method, liquid phase reaction method, hydrothermal method etc.Such as Asahi etc. with commodity TiO
2Do the titanium source, 600 ℃ of high-temperature roastings obtain TiO in the mixed atmosphere of NH3/Ar
2-xN
xPowder; Yang Honghui etc. are with TiCl
4Be raw material, ammoniacal liquor is that the neutralizing agent controlled hydrolysis is prepared colloid, then obtains Detitanium-ore-type TiO at 400 ℃ of lower roasting 4h
2-xN
xPhotocatalyst; T.Ihara etc. are with Ti (SO
4)
2The gel that the hydrolysis of solution and ammoniacal liquor makes makes N doped Ti O 400 ℃ of lower roastings
2Bao Nan etc. make layered titanic acid ammonium presoma take tetrabutyl titanate and ammoniacal liquor as raw material by hydrothermal method, carry out thermolysis under 400 ℃ again, have made the anatase octahedrite TiO that N mixes
2Nanocrystalline.The aforesaid method operational condition is different, but all needs the multistep operation, all be unable to do without pyroprocessing, thereby high consuming time, highly energy-consuming.
Sonochemistry has been proved to be a kind of highly effective technique means for preparing the specific performance nano material in recent years.Liquid can produce acoustic cavitation under ul-trasonic irradiation, i.e. the formation of microbubble in the liquid, growth and fast collapse, because adiabatic compression or the impact of gas phase in the bubble that subsides can produce part " focus ", its transient temperature is up to 5000K, and pressure can reach 5 * 10
7More than the Pa, simultaneously time of existing of this localized hyperthermia, high pressure very short, several microseconds are only arranged, so rate of temperature change is up to 10
9Ks
-1Thereby, cause series of physical, chemical transformation.Ultrasonic cavitation can greatly improve the speed of inhomogeneous reaction, realizes that Jie between the inhomogeneous reaction thing sees even mixing, and the diffusion process of accelerated reaction thing and product promotes the generation of solid cenotype, size and the distribution of control particle.Ultrasonic wave has obvious advantage and distinctive feature comparing with traditional method aspect the mass transfer of strengthening between the heterogeneous interface, is conducive to the formation of material special construction and performance.
(3) summary of the invention
The present invention is in order to remedy the deficiencies in the prior art, and a kind of sonochemistry preparation method of simple to operate, nitrogen-doped nanometer titanium dioxide crystal that temperature of reaction is low is provided.
The present invention is achieved through the following technical solutions:
A kind of sonochemistry preparation method of nitrogen-doped nanometer titanium dioxide crystal, it is characterized in that: take tetravalent salt of titanium as the titanium source, take ammoniacal liquor or ammonium salt as nitrogenous source, add dispersion agent, be mixed and made into reaction solution, the control reacting liquid temperature is 60 ~ 90 ℃, and supersound process is 3 ~ 4 hours under normal pressure, obtains white precipitate; With gained precipitation and centrifugal separation, washing, vacuum-drying, obtain at last product.
More excellent scheme of the present invention is:
During supersound process, ultrasonic frequency is greater than 20KHz, and intensity is greater than 20W/cm
2
Described dispersion agent is one or more in polyoxyethylene glycol, polyvinyl alcohol and the polypyrrole alkane ketone.
Described tetravalent salt of titanium is that concentration is the TiCl of 0.1 ~ 2.0mol/L
4Or Ti (SO
4)
2The aqueous solution.
Described nitrogenous source is ammoniacal liquor, ammonium chloride or ammonium sulfate.
The present invention is to different titaniums source under ul-trasonic irradiation and nitrogenous source synthesis of nano N-TiO
2Particle be studied.Experiment is found: take titanium sulfate as titanium source, NH
3H
2O or (NH
4)
2SO
4Be nitrogenous source, can directly obtain favorable dispersity N-TiO
2Particle, size is 8-15nm, and distribution range is narrower; By the control solution acidity, can obtain respectively Detitanium-ore-type and rutile-type N-TiO
2Crystal.In strong acid medium (pH<1), product is rutile crystal.Along with the rising of reaction medium pH value, rutile crystal grain reduces gradually in the product, and anatase crystal grain begins to occur.When reaction medium pH value is 1 ~ 3, generate simultaneously rutile-type and Detitanium-ore-type crystal grain in the product.With reaction medium pH>3, product mainly is anatase crystal grain, and reaction medium pH value is transferred to 5 ~ 7, and reaction product is pure Detitanium-ore-type crystal grain.Take titanium tetrachloride as titanium source, NH
4Cl or NH
3H
2O is nitrogenous source, can one the step directly synthesize Rutile Type-TiO
2Particle, its structure is that adhesion is gathered into the pinniform dendrite, the columnar-shaped particle size is 7 * 16nm (W/L).
Operation steps of the present invention is simple, and is reasonable in design, and temperature of reaction is low, and technique is succinct, and the nano titanium oxide of production has the advantage that product cut size is little, particle size distribution range is narrow, is suitable for wide popularization and application.
(4) description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is with Ti (SO
4)
2Be titanium source, (NH
4)
2SO
4For being nitrogenous source, under pH value 6.0,80 ℃ of conditions of temperature of reaction, the X-diffracting spectrum of differential responses stage product;
Fig. 2 is sample A plane of crystal x-ray photoelectron spectroscopy figure;
Fig. 3 is X-diffracting spectrum and the transmission electron microscope photo of sample B;
Fig. 4 is sample B plane of crystal x-ray photoelectron spectroscopy figure;
Fig. 5 is different crystal forms TiO
2Nucleus forms synoptic diagram;
Fig. 6 is nitrogen doped Ti O
2The uv-visible absorption spectra of sample A and sample B;
Fig. 7 be under the radiation of visible light methyl violet at different Ti O
2On degradation curve.
(5) embodiment
Can be found out that by accompanying drawing 1 ultrasonic reaction 1h, products therefrom illustrate that without obvious X-diffraction peak this moment, product was amorphous state; Ultrasonic reaction 2h begin to occur obvious X-diffraction peak, but the peak type is wider, illustrates that the product particle that forms is tiny; Ultrasonic reaction 3h, product produces 7 X-diffraction peaks, and consistent with JCPDS card 21-1272, illustrates that product is anatase type nano TiO
2Particle.The electromicroscopic photograph that inserts among Fig. 1 is ultrasonic reaction 3h gained Detitanium-ore-type N-TiO
2The photo of the TEM of (sample A) can be seen the N-TiO that makes
2Be columnar-shaped particle, particle size distribution range is narrower, and its size is 10 * 20nm (W/L).
Except the Ti2s and Ti2p characteristic peak of the O1s characteristic peak of O element, Ti element, also have obvious N1s characteristic peak at the 399.8eV place in the accompanying drawing 2, illustrate that the N element has entered TiO
2Lattice has formed the N-Ti key, has produced nitrogen-doped nanometer TiO2 crystal.
Accompanying drawing 3 is that the present invention is with TiCl
4Be titanium source, NH
4Cl is nitrogenous source, under pH value 0.5,70 ℃ of conditions of temperature of reaction, and ultrasonic reaction 3h, X-diffracting spectrum and the transmission electron microscope photo of products therefrom (sample B).Contrast TiO with JCPDS card 21-1276
2Be rutile-type, six stronger diffraction peaks of intensity that occur among the figure respectively with rutile TiO
2(110) face, (101) face, (111) face, (211) face, (002) face corresponding with (301), illustrate to generate
TiO2The crystal grain crystal formation is good.Calculate the median size D of crystal grain according to X-ray diffraction broadening analytical method
(111)=7.6nm.Can be found out by electromicroscopic photograph, with TiCl
4N-TiO for the raw material preparation
2, granularity is 7 * 16 nm, is long column shape, and intercrystalline is orientated adhesion mutually, assembles to form dendrite, and aggregate is pinniform, and its bearing of trend is consistent with the length direction of columnar grain.Be parallel to crystallographic axis C.
The N1s characteristic peak at 399.5eV place in the accompanying drawing 4 illustrates that the N element has entered TiO
2Lattice has formed the N-Ti key, has produced nitrogen-doped nanometer TiO
2Crystal.
As shown in Figure 5, solution acid alkalinity is to TiO
2The phase transformation of crystal has decisive influence, and rutile results from strong acid environment, at this moment Ti
4+Mainly with [TiO (H
2O)
5]
2+Single aggressiveness exists, and single aggressiveness is sloughed 2 water moleculess by " hydroxyl " effect, links to each other with the rib in the red plane, forms the polymer of straight chain, and forms thus the nucleus of rutile.Under weak acid and the neutrallty condition, Ti
4+Mainly with [Ti (OH)
2(H
2O)
4]
2+Single aggressiveness exists, and they can slough 2 water moleculess by " hydroxyl " effect, so that the slant edge on red plane is not continuous, form the nucleus of anatase octahedrite, and then form the Detitanium-ore-type crystal.
By accompanying drawing 6 as can be known, Degussa P-25 (dopen Nano TiO not
2) ABSORPTION EDGE is below 400nm, the photoresponse scope only limits to ultraviolet region.And the nitrogen doped Ti O of the present invention's preparation
2Obvious red shift occurs in sample A and sample B absorption spectrum, at visible region stronger absorption is arranged, and light abstraction width is extended to nearly 500nm always.The red shift of this absorption spectrum is from entering TiO
2Nitrogen element in the character.In the ultrasonic reaction process, the nitrogen element replaces TiO
2Oxygen element in the lattice enters TiO
2Structure cell makes TiO
2Valence band and conduction band between produce intermediate level, these intermediate level generation transition can be passed through in light induced electron and hole, therefore required excitation energy is reduced to visible-range, thereby makes nitrogen doped Ti O
2Obvious red shift occurs in absorption spectrum.The change of this absorbing properties makes it have good visible light catalysis activity.
Can be found out TiO after N mixes by accompanying drawing 7
2Visible light catalysis activity significantly improve, under 1000W xenon lamp irradiation, the degradation rate in a sample A, the sample B position photocatalyst, dye methyl violet 60min is respectively 81% and 99%, and the P-25 of the N that do not mix only has 42% to the degradation rate of methyl violet.Why the catalytic effect of sample A obviously is better than sample B, is because Detitanium-ore-type crystal catalytic performance is better than the event of rutile-type crystal.
Embodiment 1:
With 5.0gTi (SO
4)
2And 0.2g (NH
4)
2SO
4Be dissolved in the 50ml deionized water, regulate pH value to 6.0 with ammoniacal liquor, then supersound process is wherein carried out in the titanium alloy probe immersion of ultrasonic generator, ultrasonic frequency is 20KHz, and intensity is 25 W/cm
2, 80 ℃ of temperature of reaction of control, the reaction times is 3h, then adds 0.2g polypyrrole alkane ketone dispersion agent, behind the magnetic agitation 1h, centrifugation, the gained precipitation spends respectively ionized water washing secondary, absolute ethanol washing once, last vacuum-drying obtains N-TiO
2, size is 7 * 16nm, crystal formation is Detitanium-ore-type.
Embodiment 2:
With 6.0gTi (SO
4)
2Be dissolved in the 40ml deionized water, with 20ml2%NH
3H
2O splashes into Ti (SO
4)
2In the solution, then supersound process is wherein carried out in the titanium alloy probe immersion of ultrasonic generator, ultrasonic frequency is 380KHz, and intensity is 40W/cm
2, 70 ℃ of reacting liquid temperatures of control, the reaction times is 3h, then adds 0.1g polyvinyl alcohol dispersion agent, behind the magnetic agitation 1h, centrifugation, the gained precipitation spends respectively ionized water washing secondary, absolute ethanol washing once, last vacuum-drying.Products obtained therefrom is column, and size is 6 * 15nm (W/L), and crystal formation is Detitanium-ore-type.
Embodiment 3:
With 5.0 g titanium sulfate and 0.2gNH
4Cl is dissolved in the 50ml1M aqueous hydrochloric acid, then supersound process is wherein carried out in the titanium alloy probe immersion of ultrasonic generator, and ultrasonic frequency is 100KHz, and intensity is 35W/cm
260 ℃ of control temperature of reaction, the reaction times is 4h, then adds the mixed dispersant of 0.1g polyoxyethylene glycol (PEG) and 0.1g polypyrrole alkane ketone, behind the magnetic agitation 1h, centrifugation, gained precipitation spend respectively ionized water washing secondary, and absolute ethanol washing once, last vacuum-drying, products obtained therefrom is long column shape, and size is 5 * 20nm (W/L), and crystal formation is rutile-type.
Embodiment 4:
In ice-water bath, with 4mlTiCl
4Dropwise join 50ml and contain 0.2gNH
3Deionized water in, then the titanium alloy of ultrasonic generator probe is immersed and wherein carries out supersound process, ultrasonic frequency is 25KHz, intensity is 80W/cm
2, 90 ℃ of reacting liquid temperatures of control, the reaction times is 3h, then adds 0.1g polyoxyethylene glycol (PEG) dispersion agent, behind the magnetic agitation 1h, centrifugation, the gained precipitation spends respectively ionized water washing secondary, absolute ethanol washing once, last vacuum-drying.Gained is rutile-type, is the pinniform aggregate, for granularity is 7 * 16nm.
Claims (5)
1. the sonochemistry preparation method of a nitrogen-doped nanometer titanium dioxide crystal, it is characterized in that: take tetravalent salt of titanium as the titanium source, take ammoniacal liquor or ammonium salt as nitrogenous source, add dispersion agent, be mixed and made into reaction solution, the control reacting liquid temperature is 60 ~ 90 ℃, and supersound process is 3 ~ 4 hours under normal pressure, obtains white precipitate; With gained precipitation and centrifugal separation, washing, vacuum-drying, obtain at last product.
2. the sonochemistry preparation method of nitrogen-doped nanometer titanium dioxide crystal according to claim 1, it is characterized in that: during supersound process, ultrasonic frequency is greater than 20KHz, and intensity is greater than 20W/cm
2
3. the sonochemistry preparation method of nitrogen-doped nanometer titanium dioxide crystal according to claim 1, it is characterized in that: described dispersion agent is one or more in polyoxyethylene glycol, polyvinyl alcohol and the polypyrrole alkane ketone.
4. the sonochemistry preparation method of nitrogen-doped nanometer titanium dioxide crystal according to claim 1, it is characterized in that: described tetravalent salt of titanium is that concentration is the TiCl of 0.1 ~ 2.0mol/L
4Or Ti (SO
4)
2The aqueous solution.
5. the sonochemistry preparation method of nitrogen-doped nanometer titanium dioxide crystal according to claim 1, it is characterized in that: described nitrogenous source is ammoniacal liquor, ammonium chloride or ammonium sulfate.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104069843A (en) * | 2014-07-22 | 2014-10-01 | 苏州志佳电子科技有限公司 | Preparation method of titanium dioxide nanometer photocatalyst |
CN104998690A (en) * | 2015-06-28 | 2015-10-28 | 渤海大学 | Preparation method of composite titanium dioxide nanoparticles |
CN105478151A (en) * | 2014-09-15 | 2016-04-13 | 中国科学院大连化学物理研究所 | Crystal phase controllable nitrogen-doped titanium dioxide preparation method |
CN106334574A (en) * | 2016-09-26 | 2017-01-18 | 广西科技大学 | Preparation method of high-water-dispersibility nitrogen-doped nano-titanium dioxide |
CN109206339A (en) * | 2017-06-29 | 2019-01-15 | 湘潭大学 | A kind of method that cyclohexylamine oxidation prepares cyclohexanone oxime |
CN110504112A (en) * | 2019-08-12 | 2019-11-26 | 三峡大学 | A kind of preparation method of polypyrrole cladding nitrogen-doped titanium dioxide ultra micro ball electrode |
CN113582226A (en) * | 2021-08-09 | 2021-11-02 | 吉林建筑大学 | Preparation method of optical nano material for treating black and odorous water body |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1431153A (en) * | 2003-01-20 | 2003-07-23 | 济南大学 | Ultrasonic and chemical method for preparing nano crystals of titanium dioxide |
CN1506154A (en) * | 2002-12-06 | 2004-06-23 | 中国科学院化学研究所 | Prepn of nitrogen-doped titania powder |
-
2012
- 2012-10-22 CN CN2012104022053A patent/CN102976401A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1506154A (en) * | 2002-12-06 | 2004-06-23 | 中国科学院化学研究所 | Prepn of nitrogen-doped titania powder |
CN1431153A (en) * | 2003-01-20 | 2003-07-23 | 济南大学 | Ultrasonic and chemical method for preparing nano crystals of titanium dioxide |
Non-Patent Citations (5)
Title |
---|
包南等: "介孔纳米TiO2的超声化学法合成及其表征", 《环境化学》, vol. 24, no. 2, 31 March 2005 (2005-03-31), pages 150 - 152 * |
吴建懿: "纳米二氧化钛可控制备及合成工艺的研究", 《中国优秀博硕士论文全文数据库(硕士) 工程科技I辑》, no. 01, 15 March 2005 (2005-03-15), pages 27 * |
张惠芳等: "超声条件下制备氮掺杂TiO2及其光催化活性研究", 《徐州工程学院学报》, vol. 22, no. 10, 31 October 2007 (2007-10-31), pages 14 - 18 * |
李桂芹: "pH值对TiO2相结构的影响", 《贵州科学》, vol. 23, no. 1, 31 March 2005 (2005-03-31), pages 30 - 32 * |
詹志洁等: "Sol-Gel法中pH值对TiO2纳米微粒晶型的影响", 《过程工程学报》, vol. 6, 31 December 2006 (2006-12-31), pages 325 - 328 * |
Cited By (10)
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CN104069843A (en) * | 2014-07-22 | 2014-10-01 | 苏州志佳电子科技有限公司 | Preparation method of titanium dioxide nanometer photocatalyst |
CN105478151A (en) * | 2014-09-15 | 2016-04-13 | 中国科学院大连化学物理研究所 | Crystal phase controllable nitrogen-doped titanium dioxide preparation method |
CN105478151B (en) * | 2014-09-15 | 2018-12-07 | 中国科学院大连化学物理研究所 | A kind of preparation method for the nitrogen-doped titanium dioxide that crystal phase is controllable |
CN104998690A (en) * | 2015-06-28 | 2015-10-28 | 渤海大学 | Preparation method of composite titanium dioxide nanoparticles |
CN106334574A (en) * | 2016-09-26 | 2017-01-18 | 广西科技大学 | Preparation method of high-water-dispersibility nitrogen-doped nano-titanium dioxide |
CN109206339A (en) * | 2017-06-29 | 2019-01-15 | 湘潭大学 | A kind of method that cyclohexylamine oxidation prepares cyclohexanone oxime |
CN109206339B (en) * | 2017-06-29 | 2021-04-27 | 湘潭大学 | Method for preparing cyclohexanone oxime by oxidizing cyclohexylamine |
CN110504112A (en) * | 2019-08-12 | 2019-11-26 | 三峡大学 | A kind of preparation method of polypyrrole cladding nitrogen-doped titanium dioxide ultra micro ball electrode |
CN110504112B (en) * | 2019-08-12 | 2021-06-18 | 三峡大学 | Preparation method of polypyrrole-coated nitrogen-doped titanium dioxide super-microsphere electrode |
CN113582226A (en) * | 2021-08-09 | 2021-11-02 | 吉林建筑大学 | Preparation method of optical nano material for treating black and odorous water body |
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