CN108097276A - A kind of preparation method of visible-light photocatalyst - Google Patents
A kind of preparation method of visible-light photocatalyst Download PDFInfo
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- CN108097276A CN108097276A CN201711121372.XA CN201711121372A CN108097276A CN 108097276 A CN108097276 A CN 108097276A CN 201711121372 A CN201711121372 A CN 201711121372A CN 108097276 A CN108097276 A CN 108097276A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 59
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 59
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 39
- 238000005342 ion exchange Methods 0.000 claims abstract description 22
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011240 wet gel Substances 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 18
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000013019 agitation Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 18
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000004847 absorption spectroscopy Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of visible-light photocatalyst, belong to optic catalytic composite material technical field.The method of the invention is combined with sol-gal process and hydro-thermal method using butyl titanate as titanium source and prepares white solid, and white solid grinds to obtain powder, which in Muffle furnace is sintered and obtains TiO2Powder；Then TiO2Powder is placed in ion exchange liquid, and adds in a small amount of inhibitor to prevent the hydrolysis of ion exchange liquid, is centrifuged after magnetic agitation, is dried to obtain area load ion Cl‑And Sn2+TiO2Powder；Above-mentioned powder is placed in AgNO3It in solution, is uniformly dispersed after being sufficiently stirred in no light conditions, Nano AgCl/TiO that photocatalytic activity is very strong2.AgCl/TiO prepared by the method for the present invention2Visible-light photocatalyst, Nano AgCl are distributed in TiO well2Surface, due to TiO2The roughness of powder surface makes the polymerization of nano-particle be effectively suppressed, thus makes AgCl/TiO2Visible light photocatalysis efficiency significantly improves.
Description
Technical field
The present invention relates to a kind of preparation methods of visible-light photocatalyst, belong to optic catalytic composite material technical field.
Background technology
With the rapid development of science and technology and modern industry, all trades and professions rhythm of production is constantly promoted, made thereupon
Into water pollution it is more serious.Photocatalysis oxidation technique is a kind of water pollutant treatment technology being concerned in recent years,
Extremely wide research is obtained.Detitanium-ore-type TiO2Because there is inexpensive, nontoxic, stronger chemical stability and in air and
Become the research hotspot of photocatalysis field for the degradation capability of organic pollution in water.But due to the TiO2Energy gap
About 3.2eV, absorbing wavelength are limited in ultraviolet region, and solar energy utilization rate is low, and the light in Photocatalytic Degradation Process
Raw electronics and photohole are easier to compound, and photo-generated carrier is less efficient, constrains photocatalytic activity.In order to make full use of the sun
Light, therefore to TiO2Photochemical catalyst is modified, it is made to absorb visible ray and increases substantially Photocatalytic oxidation activity.
In recent years, using metal ion to TiO2Be doped is considered as to obtain the photochemical catalyst with visible light activity
Effective means, metal ion is introduced into TiO2In lattice, make TiO2Forbidden energy gap in introduce impurity energy level and defect level,
It is excited required energy to become smaller, enhances efficiently separating for photo-generate electron-hole, widened ultraviolet region to a certain extent,
So as to improve the photocatalysis performance of visible ray.On TiO2There are many report of doping, the doping including single-element（［ 1 ］ it is yellow
Auspicious space, Luo Xuyan, Zhao Dongfang, Deng Jinmei, Zhu Ting Ag dopings titanium dioxide and its Photocatalytic Performance Study [J] are coloured
Metal science and engineering, 2016,7 (2): 67-72. ）And multi-element doping（［ 2 ］ Li Yi, Ni Lingfeng, Guo Yanfei wait
The nano-titanium dioxide visible light photocatalyst of zirconium, silver-colored codope: CN105170144A[P]. 2015）.However, to TiO2
It is usually not high to the utilization rate of noble metal when doped precious metal is to widen ultraviolet region and improve photocatalytic activity, such as use light
Reduction method prepares Ag/TiO2;The C doping TiO of carried metal Ag of the such as Zhao Jianwei a kind of;During Zhu Duanwei, to the utilization rate of Ag+
It is low（［ 3 ］ Liu Guanglong2Nano particle visible light catalyst and its application: CN104888770A[P]. 2015）.Meanwhile by reality
Issue after examination and approval existing, to be prepared with photoreduction met hod Ag/TiO2Photochemical catalyst makes absorption light that blue shift occur, light is urged when degrading rhodamine
It is unfavorable that change activity causes.Therefore, searching is a kind of can be by the Ag in solution+Deposit to TiO2Powder simultaneously makes what photocatalytic activity improved
Substance is the key issue for needing to solve in preparation process.
Ion-exchange is that a certain component ion in a solution has identical electricity with the another kind in a solid
The mutual reversing of position of ion of lotus, at this time the ion in solution go on solid, the method that the ion on solid is replaced.
Preparing AgCl/TiO2During photochemical catalyst, suitable ion-exchange liquids are selected by Ag+It makes full use of, makes Ag+It is attached to TiO2
On, so as to improve TiO2Photocatalysis performance.
The content of the invention
The technical problem to be solved in the present invention is：TiO2The problem of low to the utilization rate of visible ray low with photo-quantum efficiency.
It is an object of the invention to provide a kind of preparation method of visible-light photocatalyst, prepared Nano AgCl/
TiO2Visible-light photocatalyst particle size is small, specific surface area is high, there is good visible light-responded and photocatalysis performance, tool
Body comprises the following steps：
（1）It is 1 by volume:2~1:4 ratio takes butyl titanate to add in ethyl alcohol, and butyl titanate is obtained after being sufficiently mixed
Ethanol solution, be denoted as solution A；It is 1 by volume:4~1:8 ratio, which adds water to, obtains mixed solution in ethyl alcohol, be denoted as
Solution B；
（2）Solution B is added dropwise in solution A while stirring, is obtained after being stirred and evenly mixed after dripping on magnetic stirring apparatus molten
The volume ratio of glue, wherein solution B and solution A is 1:1~1:1.5；
（3）By step（2）Obtained colloidal sol pours into hydrothermal reaction kettle that reaction under high pressure 16-24h obtains TiO at 140-180 DEG C2
Wet gel obtains xerogel after dry, xerogel is ground to powder, sieving, and then calcining obtains TiO2Powder；
（4）By SnCl2▪2H20th, the molar ratio of HCl and water is 1:20:500-1:10:250 ratio by three after mixing
Ion exchange liquid is obtained, in the ratio of 10 ~ 15g/L by TiO2Powder is put into ion exchange liquid, is carried out after stirring 30 ~ 60min
Centrifugation, is dried to obtain area load Cl-And Sn2+TiO2Powder；
（5）In the ratio of 10 ~ 15g/L by step（4）Obtained TiO2Powder is added to the AgNO of 10 ~ 30mmol/L3Solution,
It centrifuged, dried to get Nano AgCl/TiO after 30 ~ 60min of stirring in no light conditions2Visible-light photocatalyst.
Preferably, step of the present invention（3）Middle drying condition is 80-100 DEG C, dry 20-24h.
Preferably, step of the present invention（3）Middle calcination condition is 400-600 DEG C, calcines 3 ~ 6h.
The beneficial effects of the invention are as follows：
（1）Preparation method condition provided by the invention is easily controllable, technological parameter is simple, with sol-gal process and hydro-thermal method knot
Symphysis is into TiO2During powder, TiO can be effectively improved2The roughness of powder surface is conducive to Nano AgCl in TiO2Surface Creation.
（2）Preparation method provided by the invention has stronger flexibility, and the doping of AgCl is easily controllable, can be to preparing
Nano AgCl/TiO2The photocatalysis performance of visible-light photocatalyst is regulated and controled.
（3）AgCl/TiO prepared by the method for the present invention2Visible-light photocatalyst, Nano AgCl are distributed in TiO well2Table
Face, due to TiO2The roughness of powder surface makes the polymerization of nano-particle be effectively suppressed, thus makes AgCl/TiO2Visible ray
Photocatalysis efficiency significantly improves.
(4) Nano AgCl/TiO of present invention gained2Visible-light photocatalyst grain size be 1-10nm.
Description of the drawings
Fig. 1 is Nano AgCl/TiO prepared by embodiment 12The TEM figures of 01 visible-light photocatalyst.
Fig. 2 is nano-TiO prepared by embodiment 22、AgCl/TiO202 and comparative example 3 prepare Nano AgCl/
TiO203 XRD diagram.
Fig. 3 is nano-TiO prepared by embodiment 22、AgCl/TiO2The 02 and AgCl/TiO of the preparation of comparative example 3203
Energy gap figure and luminescence generated by light figure.
Fig. 4 is nano-TiO prepared by embodiment 12To the ultraviolet-visible absorption spectroscopy figure of organic dyestuff rhodamine.
Fig. 5 is Nano AgCl/TiO prepared by embodiment 1 ~ 42To the ultraviolet-visible absorption spectroscopy of organic dyestuff rhodamine
Figure.
Fig. 6 is Nano AgCl/TiO prepared by embodiment 1 ~ 42, embodiment 1 prepare nano-TiO2It is right in itself with rhodamine
The degradation efficiency figure of organic dyestuff rhodamine.
Specific embodiment
The present invention is described in further detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
Pass through ion-exchange high-efficiency production of nano AgCl/TiO2Visible-light photocatalyst, be as follows：
（1）The butyl titanate of 10mL is taken to be added in 20mL ethyl alcohol, the ethanol solution of butyl titanate is obtained after being sufficiently mixed
A takes 5mL distilled water to be added in 25mL ethyl alcohol, and the ethanol solution B of admixture distilled water is obtained after being sufficiently mixed.
（2）It is 1 by volume:1 ratio solution B is added dropwise in the solution A being stirred continuously, after dripping solution B
Mixed solution is obtained into colloidal sol in magnetic agitation in stirring 5min.
（3）Above-mentioned colloidal sol is poured into hydrothermal reaction kettle reaction under high pressure at 140 DEG C and obtains TiO for 24 hours2Wet gel, wet solidifying
Glue drying in 80 DEG C of baking oven for 24 hours, obtains xerogel.
（4）Gained xerogel is ground to powder and is sieved under the sieve of 500 mesh, 6h is then calcined at 400 DEG C obtains
To TiO2Powder.
（5）By SnCl2▪2H20th, HCl, distilled water are 1 in molar ratio:10:250 ratio mixing, is uniformly mixing to obtain
40mL ion exchange liquids, in the ratio of 10g/L above-mentioned prepared TiO2Powder is put into ion exchange liquid, stirs 30min
Afterwards, cleaned with distilled water, in NaOH and TiO2 solution, and centrifuged under 5000r/min, dry 20h is obtained at 80 DEG C afterwards
To area load Cl-And Sn2+TiO2Powder.
（6）AgNO3It is dissolved in preparing in distilled water and obtains the AgNO of 10mmol/L3Solution.
（7）In the ratio of 10g/L by step（5）The TiO of the area load ion of gained2Powder is placed in AgNO3Solution,
30min is stirred in no light conditions, and takes the once solution through dark reaction every 10min and measures Ag therein with ICP+Content,
It is neutralized after stirring 30min, centrifuges, dries to get AgCl/TiO201 visible-light photocatalyst.
Fig. 1 is Nano AgCl/TiO prepared by embodiment 12The TEM figures of 01 visible-light photocatalyst, can be with from above-mentioned Fig. 1
Find out the AgCl/TiO prepared in embodiment 12The grain size of 01 visible-light photocatalyst is in 1-10nm, i.e., the visible ray that prepared by the method
Photochemical catalyst reaches Nano grade.
Embodiment 2
Pass through ion-exchange high-efficiency production of nano AgCl/TiO2Visible-light photocatalyst, be as follows：
（1）The butyl titanate of 10mL is taken to be added in 30mL ethyl alcohol, the ethanol solution of butyl titanate is obtained after being sufficiently mixed
A takes 5mL distilled water to be added in 30mL ethyl alcohol, and the ethanol solution B of admixture distilled water is obtained after being sufficiently mixed.
（2）It is 1 by volume:1.2 ratio solution B is added dropwise in the solution A being stirred continuously, and drips solution B
Mixed solution is obtained into colloidal sol in magnetic agitation in stirring 5min afterwards.
（3）Above-mentioned colloidal sol is poured into hydrothermal reaction kettle reaction under high pressure 18h at 160 DEG C and obtains TiO2Wet gel, wet solidifying
Glue dry 22h in 90 DEG C of baking oven, obtains xerogel.
（4）Gained xerogel is ground to powder and is sieved under the sieve of 300 mesh, then calcines 4.5h at 500 DEG C
Obtain TiO2Powder.
（5）By SnCl2▪2H20th, HCl, distilled water are 1 in molar ratio:15:350 ratio mixing, be uniformly mixing to obtain from
Son exchanges liquid, in the ratio of 12.5g/L above-mentioned prepared TiO2Powder is put into ion exchange liquid, after stirring 30min, is used
Distilled water cleans, in NaOH and TiO2Solution, and centrifuged under 5000r/min, dry 22h obtains surface at 90 DEG C afterwards
Load C l-And Sn2+TiO2Powder.
（6）Take AgNO3It is dissolved in preparing in distilled water and obtains the AgNO of 20mmol/L3Solution.
（7）In the ratio of 12.5g/L by step（5）The TiO of the area load ion of gained2Powder is placed in AgNO3Solution,
After stirring 30min in no light conditions, and take the once solution through dark reaction every 10min and measure Ag+ therein with ICP and contain
It measures, is neutralized after stirring 30min, centrifuge, dry to get AgCl/TiO202 visible-light photocatalyst.
Comparative example 3
（1）The butyl titanate of 10mL is taken to be added in 30mL ethyl alcohol, the ethanol solution of butyl titanate is obtained after being sufficiently mixed
A takes 5mL distilled water to be added in 30mL ethyl alcohol, and the ethanol solution B of admixture distilled water is obtained after being sufficiently mixed.
（2）It is 1 by volume:1.2 ratio solution B is added dropwise in the solution A being stirred continuously, and drips solution B
Mixed solution is obtained into colloidal sol in magnetic agitation in stirring 5min afterwards.
（3）Above-mentioned colloidal sol is poured into hydrothermal reaction kettle reaction under high pressure 18h at 160 DEG C and obtains TiO2Wet gel, wet solidifying
Glue dry 22h in 90 DEG C of baking oven, obtains xerogel.
（4）Gained xerogel is ground to powder and is sieved under the sieve of 500 mesh, then calcines 4.5h at 500 DEG C
Obtain TiO2 powders.
（5）Take AgNO3It is dissolved in preparing in distilled water and obtains the AgNO of 20mmol/L3Solution.
（6）In the ratio of 12.5g/L by step（5）Prepared 0.5gTiO2Powder is placed in AgNO3Solution, in 300W xenons
30min is stirred under lamp stabilized current supply, and takes the once solution after xenon lamp irradiates every 10min and measures Ag therein with ICP+
Content is centrifuged, dried to get AgCl/TiO after stirring 30min203 visible-light photocatalyst.
Table 1 is AgCl/TiO prepared by embodiment 22The 02 and AgCl/TiO of the preparation of comparative example 3203 aqueous solution with
Light application time Ag+The ICP charts of concentration variation.
Table 1
。
Embodiment 4
Pass through ion-exchange high-efficiency production of nano AgCl/TiO2Visible-light photocatalyst, be as follows：
（1）The butyl titanate of 10mL is taken to be added in 50mL ethyl alcohol, the ethanol solution of butyl titanate is obtained after being sufficiently mixed
A takes 5mL distilled water to be added in 35mL ethyl alcohol, and the ethanol solution B of admixture distilled water is obtained after being sufficiently mixed.
（2）It is 1 by volume:1.5 ratio solution B is added dropwise in the solution A being stirred continuously, and drips solution B
Mixed solution is obtained into colloidal sol in magnetic agitation in stirring 5min afterwards.
（3）Above-mentioned colloidal sol is poured into hydrothermal reaction kettle reaction under high pressure 16h at 180 DEG C and obtains TiO2Wet gel, wet solidifying
Glue dry 20h in 100 DEG C of baking oven, obtains xerogel.
（4）Gained xerogel is ground to powder and is sieved under the sieve of 500 mesh, 3h is then calcined at 600 DEG C obtains
To TiO2Powder.
（5）By SnCl2▪2H20th, HCl distilled water presses 1:20:500 mixed in molar ratio, is uniformly mixing to obtain ion exchange
Liquid, will be above-mentioned prepared TiO in the ratio of 15g/L2Powder is put into ion exchange liquid, after stirring 30min, uses distilled water
Cleaning, in NaOH and TiO2Solution, and centrifuged under 5000r/min, dry 20h obtains area load at 100 DEG C afterwards
Cl-And Sn2+TiO2Powder.
（6）Take AgNO3It is dissolved in preparing in distilled water and obtains the AgNO of 30mmol/L3Solution.
（7）In the ratio of 15g/L by step（5）The TiO of the area load ion of gained2Powder is placed in AgNO3Solution,
30min is stirred in no light conditions, and takes the once solution through dark reaction every 10min and measures Ag therein with ICP+Content,
It is neutralized after stirring 30min, centrifuges, dries to get AgCl/TiO204 visible-light photocatalyst.
Fig. 2 is nano-TiO prepared by embodiment 22、AgCl/TiO202 and comparative example 3 prepare Nano AgCl/
TiO203 XRD diagram, as can be seen that Nano AgCl/TiO from the XRD diagram in Fig. 22The peak of AgCl compares AgCl/TiO in 02203
By force, i.e., the Nano AgCl/TiO prepared by ion-exchange2Ag in 02+Content higher.
Table 1 is AgCl/TiO prepared by embodiment 22The 02 and AgCl/TiO of the preparation of comparative example 3203 aqueous solution with
Light application time Ag+The ICP charts of concentration variation.As can be seen that changing to 30min from 0min in table 1, pass through ion-exchange
Nano AgCl/TiO of preparation202 visible-light photocatalyst, which is higher than under steady current source for xenon lamp the utilization rate of Ag+ in solution, to be prepared
Visible-light photocatalyst so that table 1 is corresponding with Fig. 2, therefore the Nano AgCl/TiO prepared by ion-exchange202 tool
There is higher photocatalysis efficiency.
Fig. 3 (a) and (b) are nano-TiO prepared by embodiment 22、AgCl/TiO2The 02 and AgCl/ of the preparation of comparative example 3
TiO203 energy gap figure and luminescence generated by light figure；From the graph as can be seen that the AgCl/ prepared by ion-exchange in 3 (a)
TiO202 passes through Ag+Modification after, energy gap value reduces to 3.23eV, AgCl/TiO in the value and Fig. 3 (b)202 peak intensity
Reduce corresponding, illustrate Ag+Admixture be conducive to TiO2Middle electronics and the separation in hole, make Nano AgCl/TiO202 has more
High photocatalysis efficiency.
Fig. 4 is nano-TiO prepared by embodiment 12To the ultraviolet-visible absorption spectroscopy figure of organic dyestuff rhodamine.From figure
(4) find out, as light application time from 0min increases to 60min, peak intensity of the rhodamine at λ=553nm dies down, illustrate with light
According to the increase of intensity, TiO2 nano-powders constantly enhance the degradation efficiency of rhodamine.
Fig. 5 (a-d) is respectively AgCl/TiO prepared by embodiment 1201, Nano AgCl/TiO prepared by embodiment 2202、
Nano AgCl/TiO prepared by embodiment 4 is implemented in comparison203 and Nano AgCl/TiO of the preparation of embodiment 4204 pair of organic dyestuff sieve
Red bright ultraviolet-visible absorption spectroscopy figure.It was found from Fig. 5 (a-d), there is Ag+The nano-TiO of admixture2Compared to individual nanometer
TiO2Possesses higher photocatalysis efficiency；The AgCl/TiO prepared by ion-exchange is understood by upper figure simultaneously2It is steady compared to xenon lamp
The visible-light photocatalyst prepared under galvanic electricity source has higher photocatalysis efficiency.
Fig. 6 be rhodamine in itself, embodiment 1 prepare nano-TiO2、AgCl/TiO201, nanometer prepared by embodiment 2
AgCl/TiO202nd, Nano AgCl/TiO prepared by comparative example 3203 and Nano AgCl/TiO of the preparation of embodiment 4204 pair has
The degradation efficiency figure of machine dye, rhodamine.Above-mentioned Fig. 6 corresponds respectively to degradation of each powder to rhodamine in Fig. 4 and Fig. 5 (a-d)
Efficiency is compared, the Nano AgCl/TiO prepared by embodiment 2 by upper figure202 possess higher photocatalysis efficiency and
Stability is the optimal selection of this experiment more preferably.
Understand there is Ag by the attached drawing in specification+The nano-TiO of modification2Compared to individual nano-TiO2Possesses higher
Photocatalysis efficiency；And understand the AgCl/TiO prepared by ion-exchange2It can compared to what is prepared under steady current source for xenon lamp
See that light photochemical catalyst has higher photocatalysis efficiency.
Claims (3)
1. a kind of preparation method of visible-light photocatalyst, which is characterized in that specifically include following steps：
（1）It is 1 by volume:2~1:4 ratio takes butyl titanate to add in ethyl alcohol, and butyl titanate is obtained after being sufficiently mixed
Ethanol solution, be denoted as solution A；It is 1 by volume:4~1:8 ratio, which adds water to, obtains mixed solution in ethyl alcohol, be denoted as
Solution B；
（2）Solution B is added dropwise in solution A while stirring, is obtained after being stirred and evenly mixed after dripping on magnetic stirring apparatus molten
The volume ratio of glue, wherein solution B and solution A is 1:1~1:1.5；
（3）By step（2）Obtained colloidal sol pours into hydrothermal reaction kettle that reaction under high pressure 16-24h obtains TiO at 140-180 DEG C2
Wet gel obtains xerogel after dry, xerogel is ground to powder, sieving, and then calcining obtains TiO2Powder；
（4）By SnCl2▪2H20th, the molar ratio of HCl and water is 1:20:500-1:10:250 ratio obtains three after mixing
To ion exchange liquid, in the ratio of 10 ~ 15g/L by TiO2Powder is put into ion exchange liquid, stir 30 ~ 60min after carry out from
The heart is dried to obtain area load Cl-And Sn2+TiO2Powder；
（5）In the ratio of 10 ~ 15g/L by step（4）Obtained TiO2Powder is added to the AgNO of 10 ~ 30mmol/L3Solution,
It centrifuged in no light conditions after 30 ~ 60min of stirring, be drying to obtain Nano AgCl/TiO2Visible-light photocatalyst.
2. the preparation method of visible-light photocatalyst according to claim 1, it is characterised in that：Step（3）Middle dried strip
Part is 80-100 DEG C, dry 20-24h.
3. the preparation method of visible-light photocatalyst according to claim 1, it is characterised in that：Step（3）Middle calcining item
Part is 400-600 DEG C, calcines 3 ~ 6h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109019754A (en) * | 2018-07-12 | 2018-12-18 | 昆明理工大学 | A kind of preparation method of chlorination modified by silver boron nitride composite photo-catalyst |
| CN110026170A (en) * | 2019-05-23 | 2019-07-19 | 乐山师范学院 | A kind of TiO of photocatalytic degradation rhodamine B2Photochemical catalyst and preparation method thereof |
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| CN1230917A (en) * | 1996-09-20 | 1999-10-06 | 株式会社日立制作所 | Thin photocatalytic film and articles provided with the same |
| CN104941615A (en) * | 2015-06-01 | 2015-09-30 | 天津工业大学 | Preparation method of Ag/AgCl/TiO2 nanotube |
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| US3280167A (en) * | 1959-07-18 | 1966-10-18 | Bayer Ag | Process for the production of aliphatic nitriles from olefins using solid acid reacting boron phosphate or titanium phosphate catalysts |
| US3250728A (en) * | 1962-07-16 | 1966-05-10 | Socony Mobil Oil Co Inc | Hydrocarbon conversion catalyst and method of preparation thereof |
| CN1230917A (en) * | 1996-09-20 | 1999-10-06 | 株式会社日立制作所 | Thin photocatalytic film and articles provided with the same |
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| CN109019754A (en) * | 2018-07-12 | 2018-12-18 | 昆明理工大学 | A kind of preparation method of chlorination modified by silver boron nitride composite photo-catalyst |
| CN110026170A (en) * | 2019-05-23 | 2019-07-19 | 乐山师范学院 | A kind of TiO of photocatalytic degradation rhodamine B2Photochemical catalyst and preparation method thereof |
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