CN110156073B - Preparation of TiO by steam hot solution evaporation2Method (2) - Google Patents
Preparation of TiO by steam hot solution evaporation2Method (2) Download PDFInfo
- Publication number
- CN110156073B CN110156073B CN201810097645.XA CN201810097645A CN110156073B CN 110156073 B CN110156073 B CN 110156073B CN 201810097645 A CN201810097645 A CN 201810097645A CN 110156073 B CN110156073 B CN 110156073B
- Authority
- CN
- China
- Prior art keywords
- tio
- cup
- temperature
- reaction
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000010453 quartz Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 150000003608 titanium Chemical class 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000498 cooling water Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910000856 hastalloy Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 17
- -1 alcohol compound Chemical class 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 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 4
- 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 description 3
- 238000000926 separation method Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 35
- 239000002245 particle Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for preparing TiO by steam hot solution evaporation2The method of (1). Dripping titanium salt into organic solvent, magnetically stirring and mixing, and rotatingMoving the mixture into a high-foot quartz cup, adding an organic solvent into a Hastelloy reaction kettle, putting the high-foot quartz cup into the reaction kettle, carrying out steam hydrothermal reaction for 5 hours at the temperature of 240-500 ℃, after the reaction is finished, introducing cooling water into a condenser pipe in the reaction kettle to quickly reduce the temperature in the kettle, taking out a product in the cup after the temperature is cooled to room temperature, and levigating the product in the cup to obtain TiO when the product in the cup is in a solid state2The photocatalyst is prepared by separating solid from liquid when the product in the cup is in liquid state, washing with ethanol, and drying in a vacuum oven to obtain TiO2A photocatalyst. TiO obtained by the invention2The photocatalyst has excellent catalytic performance, simple and safe preparation process and good application prospect in the field of photocatalysis.
Description
Technical Field
The invention relates to a method for preparing TiO by steam hot solution evaporation2Belonging to the technical field of photocatalyst.
Background
TiO2Has wide application prospect in the field of photocatalytic degradation, and the TiO prepared by the conventional method2The crystal is generally exposed as the (101) crystal plane, and the (101) plane has disadvantages of low carrier mobility, few reactive sites, and the like.
The researchers found that TiO2The (001) plane of (A) has a higher density of active unsaturated Ti atoms and has a higher photocatalytic activity than the (101) plane. Thus (001) -face exposed TiO2Has great application potential in the field of photocatalysis. In order to expose the (001) plane during crystal growth, it is usually necessary to add F-ions such as strongly corrosive hydrofluoric acid, or strong oxidizers such as H during preparation2O2The addition of these substances poses certain safety hazards, which is not favorable for safe production.
Currently the most commonly used TiO2The preparation method is a hydrothermal method or a solvothermal method. The sample synthesized by the hydrothermal method has the advantages of few defects, high crystallinity of the product, uniform size and the like. However, there are also some disadvantages, firstly, in the conventional hydrothermal reaction for preparing TiO2In the process, water is used as a solvent, the hydrolysis reaction rate is high,therefore, the hydrolysis process is difficult to control, the prepared sample has large particles and small specific surface area, and the photocatalytic degradation performance is unfavorable, and in order to solve the problem, a dispersing agent is usually added into the reaction solution, and the problem of difficult cleaning is faced. Secondly, when a sample is prepared by a conventional hydrothermal method, the reaction temperature is generally below 220 ℃ due to the limitation of a reaction kettle, and because a polytetrafluoroethylene lining in the reaction kettle deforms seriously at 230 ℃, the sealing is poor, and the explosion danger is easy to occur. However, the lower reaction temperature can cause the crystallization degree of the sample to be low, and the subsequent heat treatment is needed for further crystallization.
Disclosure of Invention
In view of the above, the invention provides a method for preparing TiO by steam hot solution evaporation2By reaction in the supercritical state to give TiO2The photocatalyst has excellent catalytic performance, simple and safe preparation process and good application prospect in the field of photocatalysis.
To achieve the above objects, the steam hot solution evaporation of the present invention is used to prepare TiO2The method comprises the steps of dripping titanium salt into an organic solvent, magnetically stirring and mixing to obtain clear liquid, transferring the clear liquid into a high-leg quartz cup, adding the organic solvent into a Hastelloy reaction kettle, putting the high-leg quartz cup into the reaction kettle, carrying out steam hydrothermal reaction for 5 hours at the temperature of 240 ℃ plus 500 ℃, introducing cooling water into a condenser pipe in the reaction kettle after the reaction is finished, rapidly reducing the temperature in the kettle, taking out a product in the cup after the reaction is cooled to room temperature, and grinding the product in the cup to obtain TiO when the product is in a solid state2Photocatalyst, when the product in the cup is in liquid state, the solid-liquid separation is carried out, then ethanol is added for washing for 4-5 times, the supernatant is poured off, and the mixture is put into a vacuum oven for drying to obtain TiO2A photocatalyst.
The titanium salt is at least one of isopropyl titanate, tetrabutyl titanate, titanium tetrachloride or titanium tetrafluoride.
The organic solvent is an alcohol compound with the supercritical temperature lower than 500 ℃.
The reaction is carried out under the supercritical condition, when the solvent is in the supercritical state, the vapor pressure is increased, the density, the surface tension and the viscosity are all lowered, the changes can accelerate the reaction among important ions, and the reaction which is difficult to occur under the normal state can be realized. Meanwhile, the reaction temperature is high, so that the prepared sample has high crystallization degree and does not need subsequent treatment.
The invention adopts non-aqueous liquid such as alcohols as solvent, heats the solvent to above supercritical temperature to make ethanol become steam, reacts in the steam to slowly generate water, reduces the hydrolysis speed of titanium source to prepare smaller TiO2Particles; because the reaction temperature is high, the crystallinity of the sample is good, and the subsequent crystallization treatment is not needed. After reacting for a period of time, the condensing tube is filled with water to rapidly cool the steam into liquid, the liquid is collected in the reaction kettle, so that the liquid in the quartz cup is reduced or disappears, and the TiO is obtained after treatment2Particles of TiO2The particle size is only 10-20nm, and is much smaller than that of the conventional hydrothermal synthesis; importantly, the TiO is promoted by a rapid cooling process2(001) Face exposed and TiO2Certain organic groups are adsorbed on the surface, so that the photoresponse range and the photocatalytic performance are improved, and the absorption of visible light is facilitated.
The method leads the evaporated solution to be quickly condensed on a condensing tube outside a quartz cup by a method of reaction in a supercritical state and then quick cooling, thereby promoting TiO2Exposed growth of (001) plane; meanwhile, the product in the quartz cup becomes dry powder and adsorbs a certain organic group, the two improve the photocatalytic performance, the photocatalytic performance of the prepared catalyst is far higher than that of industrial P25, and the catalyst does not need to be modified by expensive metals such as gold, silver, platinum and the like; the crystal face does not need to be regulated and controlled by harmful substances such as hydrofluoric acid and the like; the raw material is slowly hydrolyzed by the principle that alcohols are subjected to dehydration condensation at high temperature, and the generated particles are small and uniform.
The invention has the beneficial effects that: reaction under supercritical state to obtain TiO2The photocatalyst has excellent catalytic performance, simple and safe preparation process and good application prospect in the field of photocatalysis.
Drawings
FIG. 1 is a schematic view of a reaction apparatus.
FIG. 2 is TiO2XRD pattern of nanoparticles, according to TiO2Can determine TiO by using the standard PDF card (No.21-1272)2Is in a tetragonal anatase structure. Wherein, the abscissa is the diffraction angle, and the ordinate is the relative intensity.
FIG. 3 is TiO2Transmission Electron Microscopy (TEM) images of the nanoparticles.
FIG. 4 is TiO2UV-vis pattern of nanoparticles. Wherein the abscissa is the wavelength and the ordinate is the absorption intensity.
FIG. 5 is TiO2Infrared spectra of the nanoparticles. Wherein the abscissa is the wavelength and the ordinate is the absorption intensity.
FIG. 6 is TiO2Fluorescence spectra of the nanoparticles. Wherein the abscissa is the emission wavelength and the ordinate is the relative intensity of the emitted light.
FIG. 7 is TiO2And (3) a graph of the photocatalytic degradation efficiency of the nanoparticles to methylene blue. Wherein, the abscissa is the illumination time, and the ordinate is the degradation efficiency.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Preparation of TiO by steam hot solution evaporation2The method comprises the steps of dripping titanium salt into an organic solvent, magnetically stirring and mixing to obtain clear liquid, transferring the clear liquid into a high-leg quartz glass, adding the organic solvent into a Hastelloy reaction kettle, putting the high-leg quartz glass into the reaction kettle, carrying out steam hydrothermal reaction for 5 hours at the temperature of 240-500 ℃, introducing cooling water into a condenser pipe in the reaction kettle after the reaction is finished, rapidly reducing the temperature in the kettle, taking out a product in the glass after the reaction is cooled to room temperature, and finely grinding the product in the glass to obtain TiO when the product in the glass is in a solid state2Photocatalyst, when the product in the cup is in liquid state, the solid-liquid separation is carried out, then ethanol is added for washing for 4-5 times, the supernatant is poured out, and the obtained product is dried in a vacuum oven to obtain TiO2A photocatalyst.
The titanium salt is at least one of isopropyl titanate, tetrabutyl titanate, titanium tetrachloride or titanium tetrafluoride.
The organic solvent is an alcohol compound with the supercritical temperature lower than 500 ℃.
Example 1
(1) 4mL of isopropyl Titanate (TIP) was aspirated, dropped into 96mL of ethanol, and magnetically stirred for 30 min.
(2) The solution from step (1) was transferred to a 120mL quartz highleg.
(3) Weigh 200mL of ethanol into 1000mL of autoclave, and place the quartz cup in (2) into the autoclave. The following reactions were then carried out separately:
the reaction is carried out for 5 hours at 240 ℃. Cooling the solution, centrifuging to obtain a product, washing with anhydrous ethanol for 4-5 times, removing supernatant, drying at 60 deg.C for 12 hr to obtain TiO2Nano particles I;
the reaction is carried out for 5 hours at the temperature of 250 ℃. After the solution is cooled, the product in the cup is a dry light yellow solid, and TiO is obtained after grinding2Nano particles (II).
The resulting TiO2Nano particles (II) have very strong catalytic performance, and the degradation rate of the nano particles to methylene blue is nearly 3 times that of industrial P25.
Example 2
(1) TiO testing with X-ray polycrystal diffractometer (XRD; Smartlab9KW)2The X-ray diffraction pattern of the nanoparticles is shown in FIG. 2. From TiO in FIG. 22The comparison of the position and the relative intensity of the diffraction peak of the nano particle with the standard PDF card No.21-1272 shows that the TiO prepared by the method2The crystal structure of the nanoparticles is a tetragonal anatase phase.
(2) Characterization of TiO prepared in 240 ℃ Environment by Transmission Electron microscope (JEOLJEM-2100)2A Transmission Electron Microscope (TEM) image of the nanoparticle (i.e., particle (r)), see fig. 3 (a); characterise TiO at 250 ℃2Transmission Electron Micrograph (TEM) of the nanoparticles (i.e., particles), see fig. 3 (b); characterization of TiO at 250 ℃2High Resolution Transmission Electron Micrographs (HRTEM) of the nanoparticles, see FIG.3(c) and (d)
As can be seen from FIGS. 3(a) and 3(b), the prepared TiO was2The nanoparticles are nanoparticles having a particle size of about 10-20 nm. As shown in FIG. 3(c), the stripes with a pitch of 0.35 correspond to TiO2The (101) lattice fringes of (1). FIG. 3(d) shows a spectrum derived from TiO20.19nm and 0.35nm, respectively. Wherein the 0.19nm stripe corresponds to TiO2And 0.35nm of the stripe corresponds to TiO2The (101) plane of (1).
(3) Characterization of TiO by UV-visible near-IR Spectrophotometer (U-4100)2Nanoparticles of (i) and TiO2The ultraviolet and visible absorption spectrum of the nano particles is shown in figure 4. TiO 22The absorption edge of the nano particle is about 380nm, which shows that TiO2The band gap of the nano particles I is about 3.2eV, and the absorption capacity to visible light is insufficient; and TiO 22The nano particles (II) have obvious red shift phenomenon on the absorption edge and obvious absorption capacity to visible light.
(4) TiO is treated by Fourier infrared microscope system (Vertex80)2Nanoparticles of (i) and TiO2The infrared absorption of the nano particles is characterized, and the result is shown in figure 5. Comparative TiO2Nano particles (I) and TiO2Nanoparticles of TiO2The infrared spectrum of the nano particle (II) shows an absorption peak at 1731cm < -1 >, wherein the absorption peak is generated by stretching vibration of C ═ O double bonds, and the TiO is explained2Nanoparticles (C — O) adsorb a certain organic group.
(5) TiO is treated by fluorescence spectrophotometer (F-4500)2Nanoparticles of (i) and TiO2Nanometer particle is used for fluorescent characterization. The intensity of the emitted light of both samples excited by 300nm ultraviolet light was determined by scanning to be maximum, and the highest peaks appeared at emission wavelengths of 425nm and 475 nm. By comparison, TiO was found2The emitting light intensity of the nano particle is larger than that of TiO2The emitted light intensity of the nano-particles explains that of TiO2The nano particles (II) have lower electron-hole recombination rate, namely higher carrier service life.
(6) Respectively testing by using an ultraviolet visible spectrophotometer (UV-6100)TiO2Nano particles (I) and TiO2The nanometer particle and industrial P25 powder have photocatalytic degradation performance on methylene blue, and the result is shown in FIG. 7. After the illumination for 90min, the degradation efficiency of the three to methylene blue reaches more than 99 percent. Wherein the TiO is2The nano particles have excellent degrading capability to methylene blue, 99 percent of the methylene blue is degraded within about 30min and is faster than industrial P25 powder.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (3)
1. Preparation of TiO by steam hot solution evaporation2The method is characterized in that titanium salt is dripped into an organic solvent, the titanium salt is magnetically stirred and mixed to obtain clear liquid, the clear liquid is transferred into a high-leg quartz cup, the organic solvent is added into a Hastelloy reaction kettle, the high-leg quartz cup is placed into the reaction kettle, steam hydrothermal reaction is carried out for 5 hours at the temperature of 240-500 ℃, after the reaction is finished, cooling water is introduced into a condenser pipe in the reaction kettle to rapidly reduce the temperature in the kettle, products in the cup are taken out after the temperature is cooled to room temperature, and the products in the cup are ground to obtain TiO when the products in the cup are in a solid state2Photocatalyst, when the product in the cup is in liquid state, the solid-liquid separation is carried out, then ethanol is added for washing for 4-5 times, the supernatant is poured off, and the mixture is put into a vacuum oven for drying to obtain TiO2A photocatalyst.
2. The process for preparing TiO by evaporation of a hot solution according to claim 12The method of (1), wherein the titanium salt is at least one of isopropyl titanate, tetrabutyl titanate, titanium tetrachloride or titanium tetrafluoride.
3. The evaporative hot solution of claim 1Preparation of TiO2The method of (1), wherein the organic solvent is an alcohol compound having a supercritical temperature of less than 500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810097645.XA CN110156073B (en) | 2018-01-31 | 2018-01-31 | Preparation of TiO by steam hot solution evaporation2Method (2) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810097645.XA CN110156073B (en) | 2018-01-31 | 2018-01-31 | Preparation of TiO by steam hot solution evaporation2Method (2) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110156073A CN110156073A (en) | 2019-08-23 |
| CN110156073B true CN110156073B (en) | 2021-09-17 |
Family
ID=67641339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810097645.XA Expired - Fee Related CN110156073B (en) | 2018-01-31 | 2018-01-31 | Preparation of TiO by steam hot solution evaporation2Method (2) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110156073B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113333009B (en) * | 2021-05-29 | 2022-02-18 | 安徽大学 | Nitrogen-doped gamma-Bi2MoO6Method for preparing photocatalyst |
| CN113750928A (en) * | 2021-09-27 | 2021-12-07 | 合盛硅业（泸州）有限公司 | Shutdown forced drying process of dimethyl hydrolysis system |
| CN114405404A (en) * | 2022-01-10 | 2022-04-29 | 南京工程学院 | Improved doping reaction device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234928C (en) * | 2004-06-11 | 2006-01-04 | 山东大学 | Preparing method for titanium dioxide fibre |
| RU2340558C2 (en) * | 2006-12-29 | 2008-12-10 | Марина Николаевна Данчевская | Method of obtaining fine crystalline alloyed lanthanum aluminate |
| CN100435940C (en) * | 2007-04-06 | 2008-11-26 | 武汉理工大学 | Steam heat method for preparing high-crystallized nanocrystalline titanium dioxide photocatalyst |
| CN101791545A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | Method for preparing (001) surface-exposed micrometer laminar titanium dioxide photocatalyst |
| CN103785371B (en) * | 2014-03-04 | 2016-01-13 | 湘潭大学 | A kind of porous carbon microspheres TiO 2composite and its preparation method and application |
-
2018
- 2018-01-31 CN CN201810097645.XA patent/CN110156073B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN110156073A (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tong et al. | Convenient fabrication of BiOBr ultrathin nanosheets with rich oxygen vacancies for photocatalytic selective oxidation of secondary amines | |
| AU2020102258A4 (en) | MIXED CRYSTAL TiO2/BiOBr COMPOSITE AND PREPARATION METHOD AND APPLICATION THEREOF | |
| Filippo et al. | Enhanced photocatalytic activity of pure anatase TiO 2 and Pt-TiO 2 nanoparticles synthesized by green microwave assisted route | |
| CN110156073B (en) | Preparation of TiO by steam hot solution evaporation2Method (2) | |
| CN110127722B (en) | Hydrophobic surface defect modified TiO2Preparation method of visible light nitrogen fixation catalyst | |
| CN112007632B (en) | Flower-shaped SnO 2 /g-C 3 N 4 Preparation method of heterojunction photocatalyst | |
| CN107952455A (en) | It is a kind of with the three-dimensional sheet BiOI catalysis materials of macroscopic frame and its preparation and application | |
| CN108993503B (en) | Cu/N codoped TiO prepared based on xerogel-hydrothermal method2Application of nano powder in degrading acetone in photocatalytic reaction | |
| CN108033432A (en) | A kind of cage structure material g-C3N4Preparation method and applications | |
| Sanjini et al. | Effect of precursors on the synthesis of CuO nanoparticles under microwave for photocatalytic activity towards methylene blue and rhodamine B dyes | |
| CN113663693A (en) | Preparation method of indium zinc sulfide-titanium dioxide composite material and application of indium zinc sulfide-titanium dioxide composite material in production of hydrogen peroxide for wastewater treatment | |
| Wu et al. | One‐pot hydrothermal synthesis and photocatalytic hydrogen evolution of pyrochlore type K2Nb2O6 | |
| CN111715265A (en) | Rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material and preparation method and application thereof | |
| CN107890861B (en) | Preparation method of titanium dioxide lamella/graphene composite film with {001} crystal face | |
| Mendoza-Mendoza et al. | A novel two-step route for synthesizing pure Ta2O5 nanoparticles with enhanced photocatalytic activity | |
| Xie et al. | Facile fabrication of TiO2-SiO2-C composite with anatase/rutile heterostructure via sol-gel process and its enhanced photocatalytic activity in the presence of H2O2 | |
| Shojaei et al. | Effect of microwave irradiation on morphology and size of anatase nano powder: Efficient photodegradation of 4-nitrophenol by W-doped titania | |
| Arul et al. | Visible light proven Si doped TiO2 nanocatalyst for the photodegradation of Organic dye | |
| CN112456556A (en) | Method for preparing tantalum oxide nanospheres | |
| CN110227517B (en) | CuBi2O4/BiPO4P-n type heterojunction photocatalyst, preparation method and application thereof | |
| Goulart-Gonçalves et al. | Direct synthesis of TiO2 nanoparticles without heat treatment: Effect of order of addition and precursor/reducing ratio | |
| CN101343043A (en) | Amphoteric metal compound nano-material and method of preparing the same | |
| CN110683518A (en) | Process for producing metal oxide | |
| Zhang et al. | Carbon-dot-modified TiO 2− x mesoporous single crystals with enhanced photocatalytic activity for degradation of phenol | |
| Yanchao et al. | La-doped titania nanocrystals with superior photocatalytic activity prepared by hydrothermal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210917 Termination date: 20220131 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |