CN1321738C - Production of nitrogen-doped anatase-type nanometer titanium dioxide - Google Patents
Production of nitrogen-doped anatase-type nanometer titanium dioxide Download PDFInfo
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- CN1321738C CN1321738C CNB2005100116653A CN200510011665A CN1321738C CN 1321738 C CN1321738 C CN 1321738C CN B2005100116653 A CNB2005100116653 A CN B2005100116653A CN 200510011665 A CN200510011665 A CN 200510011665A CN 1321738 C CN1321738 C CN 1321738C
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004408 titanium dioxide Substances 0.000 title abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims abstract 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 3
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 3
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 238000001556 precipitation Methods 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 19
- 238000001035 drying Methods 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000000802 nitrating effect Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- -1 is provided Chemical compound 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
本发明提供了一种氮掺杂锐钛矿型纳米二氧化钛的制备方法，属于二氧化钛粉体制备技术领域。采用水热合成法，将钛源、沉淀剂、掺杂氮源和水按一定比例混合制成混合溶液系统，然后转入带聚四氟乙烯内衬的高压釜中进行水热合成反应，最后经过醇洗、水洗至中性，经过干燥，得到锐钛矿型氮掺杂纳米二氧化钛粉体。水热合成条件为：温度为80℃～200℃，保温时间为：1～24小时，压力为0.1MPa～15MPa，搅拌速度200～1000转/分钟。本发明的优点在于：所制备纳米TiO2粉体晶粒度可控、比表面积高并且均为锐钛矿相。
The invention provides a method for preparing nitrogen-doped anatase nanometer titanium dioxide, which belongs to the technical field of titanium dioxide powder preparation. Using the hydrothermal synthesis method, the titanium source, precipitant, doping nitrogen source and water are mixed in a certain proportion to form a mixed solution system, and then transferred to a polytetrafluoroethylene-lined autoclave for hydrothermal synthesis reaction, and finally Washing with alcohol and water until neutral, and drying to obtain anatase-type nitrogen-doped nano-titanium dioxide powder. The hydrothermal synthesis conditions are as follows: the temperature is 80°C-200°C, the holding time is 1-24 hours, the pressure is 0.1MPa-15MPa, and the stirring speed is 200-1000 rpm. The invention has the advantages that the prepared nano TiO 2 powder has a controllable crystal grain size, a high specific surface area and all are in anatase phase.
Description
Technical field
The invention belongs to the titanium dioxide powder preparing technical field, a kind of preparation method of nitrogen-doped anatase-type nanometer titanium dioxide particularly is provided, be applicable to and do photocatalyst material.
Background technology
1972, Japanese scholar A.Fujishima and K.Honda were at n type semiconductor TiO
2Found the photoelectrocatalysis decomposition of water on the electrode.From that time, nano-TiO
2As a kind of semiconductor light-catalyst, caused research interest more and more widely in solar energy conversion and aspects such as storage, harmful complicated organic matter degradation.Photochemical catalyst is exactly in beche-de-mer without spike and the following catalyst for reaction that takes place, and works as TiO
2Be subjected to greater than TiO
2When the light of energy gap width shone, internal electron will be energized, and has an effect with the oxygen and the hydrone of air, produces the hole of electronegative electronics and positively charged.Electronics makes the hydrogen reduction in air or the water, generate hydrogen peroxide, then work to the direction of oxidized surface hydrone in the hole, produce negative oxygen ion and (hydroxyl) basic atomic group, these all are active oxygens, powerful oxidative decomposition capacity is arranged, produce strong redox reaction thus, the organic matter that is attached to the surface is resolved into water and carbon dioxide.Titanium dioxide not only has powerful oxidative decomposition capacity, and the advantages such as light of self not decomposing, almost can permanently work and can utilize sunlight and fluorescent lamp in addition.Nano-TiO
2As the function catalysis material of excellent performance, carried out the degraded of formaldehyde in indoor air, ammonia, benzene class pernicious gas etc., performance purifies air, the function of organic pollution, antibacterial and mouldproof in the degradation water.Nano-TiO
2Belong to non-dissolution type photochemical catalyst, safety non-toxic own, content of beary metal is few.So use this nano-TiO
2During the photochemical catalyst functional stuffing, there are not any medicine stripping or volatilization, nontoxic to environment, human body is not produced harmful effect, be the environment-friendly materials of safe and reliable antibiotic scrubbing.
But, TiO
2Energy gap broad (Eg=3.2ev), have only ultraviolet ray to be absorbed as wavelength 1＜387.5nm, but this part ultraviolet ray in the sunshine (300～400nm) only account for and reach 4～6% of solar energy on the ground, and the sunshine utilization rate is low.In addition, from antibiotic mechanism, the number of free radical that antimicrobial efficiency and antibacterial ability and system produce is closely related, and number of free radical is then relevant with photoproduction carrier concentration.Promptly can separate after electronics and hole produce with compound, the high more photocatalysis influence to titanium dioxide of its recombination rate is big more.Therefore, improve the photocatalytic activity of titanium dioxide, most important two aspects are exactly the forbidden band and suppress right compound of electrons/of narrowing.One of main path that solves these two problems is exactly to mix at present.People are carrying out a large amount of research aspect the optically catalytic TiO 2 doping, the transition metal that mixed, rare earth metal etc., and these catalyst are reducing band gap, expansion TiO
2The aspect of photoresponse scope certain progress has been arranged.The TiO of metal/metal oxide or metal ion mixing
2Though, can significantly reduce the band gap energy level, realized exciting of visible light, because the characteristic of metal/metal oxide no matter these doped chemicals are as interstitial atom, is still replaced lattice atoms, in fact all be at TiO
2Crystal grain in set up good electron/hole-recombination point position, in most cases carrier is separating, is catching, moving and is being diffused in the surface process, almost most of acted on by these some positions compound, though TiO
2Visible light activity has been arranged, but significantly reduced TiO simultaneously
2In the activity of ultraviolet light photocatalysis, and there are some researches show that the bad ultraviolet light photocatalysis activity that causes of heat endurance of cation doping reduces.Asahi is at Science (R.Asahi, T.Morikawa, T.Ohwahi, K.Aoki, Y.Taga.Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides, Science, 2001,293:269～217.) reported the Lattice Oxygen that nitrogen substitutes a small amount of (0.75%) on and can make TiO
2Band gap narrow down, not reducing the photoactive while of ultraviolet, make TiO
2Has visible light activity.But technology such as the doping that Asahi mentions employing ion injection are carried out at titanium dioxide film materials.Songwang Yang (Songwang Yang, et al.NewMethod to Prepare Nitrogen-Doped Titanium Dioxide and Its Photocatalytic ActivitiesIrradiated by Visible Light.J.Am.Ceram.Soc., 2004 (87): 1803-1805.) wait with doping process and TiO
2Crystallization process is simultaneously at NH
3Carry out in the atmosphere, effectively nitrogen-atoms is incorporated into TiO
2In the lattice.They with the mixed liquor of butyl titanate, thiocarbamide and ethanol behind drying and dehydrating under the reducing atmosphere at NH
3After the temperature of hundreds of Celsius is heat-treated under the atmosphere, obtain nitrating TiO
2Powder.But this technology exists and reunites and inhomogeneity problem because will experience pyroprocess.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nitrogen-doped anatase-type nanometer titanium dioxide, the technical problem of solution is synthetic preparation and the nitrogen doping method that proposes a kind of synchronous anatase-type nanometer titanium dioxide.
The present invention adopts hydrothermal synthesis method, titanium source, precipitating reagent, doping nitrogen source and water are mixed and made into the mixed solution system by a certain percentage, change over to then in the band teflon-lined autoclave and carry out hydrothermal synthesis reaction, obtain Detitanium-ore-type nitrogen-doped nanometer titanium dioxide powder.
Hydrothermal synthesizing condition is: temperature is 80 ℃～200 ℃, and temperature retention time is: 1～24 hour, pressure was 0.1MPa～15MPa, 200～1000 rev/mins of mixing speeds.
It is synthetic that this law is carried out hydro-thermal under these conditions, washes, is washed to neutrality through alcohol at last, through super-dry, promptly obtains polymolecularity nitrogen-doped nanometer titanium dioxide powder.
Water of the present invention is deionized water.Described titanium source is: one or both in titanyl sulfate, titanium sulfate, butyl titanate, titanium tetrachloride, metatitanic acid methyl esters, tetraethyl titanate, the isopropyl titanate and above combination thereof.The molar concentration in titanium source is 0.05M～2M, is preferably 0.5～1M.Described precipitating reagent is urea, ammoniacal liquor, NaOH, (NH
4))
2SO
4The atomic ratio of precipitating reagent and titanium ion is 0.5: 1～8: 1, is preferably 1: 1～4: 1.Described nitrogenous source is: one or both in ethamine, thiocarbamide, methylamine, guanidine hydrochloride, urea, the ammonium carbonate and above combination thereof.The molar concentration of nitrogenous source is 0.5M～6M, preferred 1M～3M.
The performance characterization of prepared nitrogen-doped nanometer titanium dioxide comprises: X-ray diffraction (XRD) is measured phase structure, thing phase composition and grain size size.Adopt photoelectron spectroscopy (XPS) to measure nitrogen doping situation.Adopt the specific area of determination of nitrogen adsorption titanium dioxide.Adopt ultraviolet-visible spectrophotometer to measure absorption spectrum.
The invention has the advantages that: prepared nano-TiO
2The powder grain size is controlled, specific area is high and be the anatase phase.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 prepared powder.Wherein, abscissa is an angle of diffraction, and ordinate is a diffracted intensity.
Fig. 2 is the TEM photo of the powder due to the embodiment 3.
Fig. 3 is the XRD figure spectrum of embodiment 10.Wherein, abscissa is an angle of diffraction, and ordinate is a diffracted intensity.
Fig. 4 is the ultraviolet-visible light reflectogram of embodiment 8.Wherein, abscissa is a wavelength, and ordinate is a reflectivity.
The specific embodiment
Embodiment 1
With 1.3L deionization water as solvent, the technical grade TiOSO of 0.25M
4Solution is made presoma, and the urea that adds 0.5M is made precipitating reagent, adds the 1.3L deionized water down at 25 ℃, make their dissolvings with mechanical agitation, at initial pressure 6MPa, mixing speed is under the 300r/min condition in autoclave, be incubated 2h down at 110 ℃, the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO
4 2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 2
With deionized water be] solvent, with the technical grade TiOSO of 0.25M
4Solution is made presoma, and the urea that adds 0.5M is made precipitating reagent, liquor capacity 1.3L, make their dissolvings with mechanical agitation under 25 ℃, at initial pressure 6MPa, mixing speed is under the 300r/min condition in autoclave, be incubated 24h down at 110 ℃, the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO
4 2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 3
Presoma technical grade TiOSO
4Be respectively 0.25M and 0.5M with the concentration of precipitating reagent urea, adding deionized water makes liquor capacity 1.3L add deionized water down at 25 ℃, make their dissolvings with mechanical agitation, in the autoclave of 2L at initial pressure 6MPa, mixing speed is under the 300r/min condition, be incubated 8h down at 110 ℃, the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO
4 2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 4
Ti (SO with 1M
4)
2Solution is made presoma, and the ammoniacal liquor that adds 2M is made precipitating reagent, adds the 1.3L deionized water down at 25 ℃, make their dissolvings with mechanical agitation, at initial pressure 6MPa, mixing speed is under the 300r/min condition in autoclave, be incubated 8h down at 150 ℃, the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO
4 2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 5
TiCl with 1M
4Solution is made presoma, and the ammonium sulfate that adds 2M is made precipitating reagent, adds the 1.3L deionized water down at 25 ℃, make their dissolvings with mechanical agitation, at initial pressure 6MPa, mixing speed is under the 300r/min condition in autoclave, be incubated 4h down at 150 ℃, the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO
4 2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 6
Technical grade TiOSO with 1M
4Solution is made presoma, and the ammoniacal liquor that adds 2M is made precipitating reagent, adds the 1.3L deionized water down at 25 ℃, makes their dissolvings with mechanical agitation, regulates pH value to 2 with NaOH.At initial pressure 6MPa, mixing speed is under the 300r/min condition in autoclave, is incubated 8h down at 180 ℃, and the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO
4 2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 7
TiOSO with 1M
4Solution is made presoma, and the ammoniacal liquor that adds 2M is made precipitating reagent, adds the 1.3L deionized water down at 25 ℃, makes their dissolvings with mechanical agitation, regulates pH value to 2 with NaOH.At initial pressure 6MPa, mixing speed is under the 900r/min condition in autoclave, is incubated 24h down at 180 ℃, and the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO
4 2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 8: nitrating
Respectively with the TiCl of 1M
4Make titanium source and nitrogenous source with the 2M ethylamine solution, the urea that adds 2M is made precipitating reagent, adding appropriate amount of deionized water, to make the mixed liquor cumulative volume be 1.3L (autoclave inner bag volume 75%), adopt mechanical agitation that mixed liquor is mixed under the room temperature, in autoclave at initial pressure 6MPa, mixing speed is under the 300r/min condition, is incubated 10h down at 100 ℃, and the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO4
2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 12 hours with absolute ethyl alcohol.
Embodiment 9: nitrating
Respectively with the TiOSO of 1M
4Make titanium source and nitrogenous source with the 2M thiourea solution, the urea that adds 2M is made precipitating reagent, adding appropriate amount of deionized water, to make the mixed liquor cumulative volume be 1.3L (autoclave inner bag volume 75%), adopt mechanical agitation that mixed liquor is mixed under the room temperature, in autoclave at initial pressure 4MPa, mixing speed is under the 500r/min condition, is incubated 3h down at 180 ℃, and the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO4
2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 16 hours with absolute ethyl alcohol.
Embodiment 10: nitrating
Respectively with the TiOSO of 1M
4Make titanium source and nitrogenous source with the 3M guanidine hydrochloride solution, the urea that adds 1.5M is made precipitating reagent, adding appropriate amount of deionized water, to make the mixed liquor cumulative volume be 1.3L (autoclave inner bag volume 75%), adopt mechanical agitation that mixed liquor is mixed under the room temperature, in autoclave at initial pressure 8MPa, mixing speed is under the 600r/min condition, is incubated 3h down at 140 ℃, and the back uses the distilled water suction filtration extremely with Ba (NO
3)
2Solution detects less than SO4
2-Behind the ion, wash 5-8 time, then 60 ℃ of following drying with water baths 10 hours with absolute ethyl alcohol.
The specific area of table 1: embodiment 1 and embodiment 3 gained powders is by its equivalent diameter of calculating
| Example 1 | Example 5 | Example 9 | Example 8 | Example 10 | |
| Specific area (m 2/ g) equivalent spherical diameter (nm) | 226.6 6.9 | 124.7 12.5 | 122.071 12.8 | 205.835 205.835 | 144.915 10.8 |
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| CN109746020A (en) * | 2019-01-16 | 2019-05-14 | 浙江理工大学 | A kind of preparation method of nitrogen-doped titanium dioxide with high-energy crystal face on the surface |
| CN109821524B (en) * | 2019-03-22 | 2021-12-10 | 南京森之语新材料科技有限公司 | Preparation method of photo-degradable organic toxic gas multistage nano composite material |
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