CN108452847A - A kind of rear-earth-doped SnO2The synthetic method of the nano-photocatalyst material of/TS-1 and application - Google Patents
A kind of rear-earth-doped SnO2The synthetic method of the nano-photocatalyst material of/TS-1 and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 23
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 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 claims abstract description 16
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000010919 dye waste Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- -1 that is Chemical compound 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 28
- 230000015556 catabolic process Effects 0.000 abstract description 27
- 239000003054 catalyst Substances 0.000 abstract description 23
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 238000007146 photocatalysis Methods 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000007639 printing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 229910020785 La—Ce Inorganic materials 0.000 description 1
- XADCESSVHJOZHK-UHFFFAOYSA-N Meperidine Chemical compound C=1C=CC=CC=1C1(C(=O)OCC)CCN(C)CC1 XADCESSVHJOZHK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000280 vitalizing effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of rear-earth-doped SnO2The synthetic method of the nano-photocatalyst material of/TS 1 and application.The present invention is synthesized using stannic chloride pentahydrate and Titanium Sieve Molecular Sieve as primary raw material, and using lanthanum or/and cerium as rare earth doping elements using sol-gal process.The synthetic method of the present invention is simple, it is easily operated, and it is reproducible, after rear-earth-doped, the photocatalysis performance of gained catalysis material is promoted notable, especially after La, Ce codope, photocatalysis performance promotion becomes apparent, and gained photochemical catalyst LCST can reach 99.87% to the degradation rate of the rhodamine B in rhodamine B simulated wastewater；Also fine to the degradation effect of practical printing dye, LCST is to the acid blue in actual dye wastewater, active black, RGFL are yellow, acid red A 2BF degradation effect is respectively up to 99.85%, 99.78%, 96.15% and 94.65%, and it is good to reuse performance.
Description
Technical field
The present invention relates to catalysis materials, and in particular to a kind of rear-earth-doped SnO2The nano-photocatalyst material of/TS-1
Synthetic method and application.
Background technology
As environmental pollution is on the rise, photocatalysis technology because having the characteristics that degradation speed is fast, degradation is complete, energy saving,
Make to become most popular one of the research topic of processing environment pollution problem using photocatalysis degradation organic contaminant.Photocatalysis technology
Using light as the energy, conduction band is transitted to by valence-band electrons in vitalizing semiconductor, generates electron hole pair, and then generate free radicals,
And by a series of radical reaction, realize the degradation to organic matter.N-type semiconductor SnO2Energy gap is 3.6eV,
It is only capable of absorbing the ultraviolet light for accounting for about sunlight 5%, this characteristic seriously limits SnO2The industrial applications of nano-photocatalyst.
Many scholars study TiO2Photocatalysis behavior and application, but we are still keen to SnO2It is modified research, overcomes it certainly
The shortcomings that body, reduces its energy gap, to the degradation suitable for visible light.
Currently, SnO2Method of modifying have：Surface sensitizing, noble metal loading (are commonly used to modification SnO2The noble metal of catalyst
Have Pt, Pd, Ag, Au, Ru etc.), doping and semiconductors coupling etc..But stannic oxide is modified using rare earth doped
The research of research is few, be particularly applied to the photodegradative research of actual industrial waste water almost without.By adulterating and being made
Nano-particle, rare earth mixing with nano semiconductor SnO2From size, reach laser wave radius, forms quantum dot, conduction band meeting
To moving up, valence band can be to moving down, and originally continuous energy level can also become discrete.The result of these variations is exactly the band gap of quantum dot
It can be bigger than body phase semiconductor and selective to the absorption of the photon of different-energy.By rare earth mixing with nano semiconductor SnO2
Quantum dot is made, its energy gap will become larger, and move on to visible light region (450-650nm), while improve the inside and outside defect of lattice,
Once the energy for photon of coming in is just suitable, the electronics in valence band is absorbed by this photon and is transitted on conduction band from valence band, together
When in valence band original position generate a hole, attracted each other at this time by coulomb interaction power between electrons and holes, in this way
There have been an electron hole pair (exciton) on quantum dot, mechanism is as shown in Figure 1.
The present invention is prepared for La-Ce codopes using titanium-silicon molecular sieve TS-1 as carrier, using traditional sol-gal process and bears
Load type nano SnO2.The photocatalytic activity of four kinds of catalyst is compared, the LCST for selecting photocatalytic degradation effect best is carried out
The characterizations such as SEM, TEM, BET, UV-Vis, XPS.Photocatalytic degradation experiment is carried out with rhodamine B simulated wastewater, is probed into visible light
The feasibility of the lower practical printing dye of photocatalyst for degrading of irradiation；Electron capture agent ammonium persulfate, hole agent for capturing iodine are carried out
Change the influence experiment of potassium, free radical scavenger to photocatalytic degradation rhodamine B degradation rate and pre-test is carried out to LCST photocatalytic mechanisms.
Invention content
The purpose of the present invention is to provide a kind of rear-earth-doped SnO2The synthetic method of the nano-photocatalyst material of/TS-1 and
Using.
The technical scheme is that：
A kind of rear-earth-doped SnO2The synthetic method of the nano-photocatalyst material of/TS-1, includes the following steps：
(1) stannic chloride pentahydrate (SnCl is weighed4·5H2O), distilled water, lanthanum nitrate or/and cerous nitrate then is added to it
And concentrated hydrochloric acid, it is uniformly mixing to obtain solution；
(2) ammonium hydroxide is added into step (1) acquired solution, adjusts pH value of solution, then carries out ultrasonic disperse, it is molten to obtain white
Glue；
(3) Titanium Sieve Molecular Sieve, that is, TS-1 is added into leucosol obtained by step (2), it is still aging after stirring, then wash
It washs, is dried to obtain presoma；
(4) presoma is placed in Muffle furnace and is roasted, obtain rear-earth-doped SnO2The nano-photo catalytic material of/TS-1
Material, when it is rare earth doped be lanthanum (La) when, be named as LST；When it is rare earth doped be cerium (Ce) when, be named as CST；It is when rare earth doped
When lanthanum and cerium, it is named as LCST.
Further, SnCl4·5H2O, the mass ratio of TS-1, La or/and Ce are preferably 1：1~1.2：0.01~0.05,
More preferably 1：1~1.1：0.02~0.04, most preferably 1：1：0.03；When it is rare earth doped be La and Ce when, the quality of La, Ce
Than being preferably 1.5~2.5：1, more preferably 1.8~2.2：1, most preferably 2：1.
Further, in step (2), pH is preferably adjusted to 7~8.
Further, in step (2), preferably 1.5~4 hours, more preferable 2~2.5 hours time of ultrasonic disperse.
Further, in step (3), mixing time is preferably 2~6 hours, more preferably 2~3 hours.
Further, in step (3), digestion time is preferably 10~20 hours, more preferably 16~18 hours.
Further, in step (3), preferably 80~120 DEG C of drying temperature, preferably 4~12 hours drying time.
Further, in step (4), calcination temperature is preferably 350~600 DEG C, more preferably 400~550 DEG C, most preferably
It is 400 DEG C；Roasting time is 2~5 hours.
It is worth noting that when lanthanum nitrate and cerous nitrate are added, the two be added when can be different, and by therein one
Person is added simultaneously with Titanium Sieve Molecular Sieve.
Another object of the present invention is to the catalysis material obtained by above-mentioned preparation method is applied to industrial dye waste water
Degradation in.
Further, industrial dye waste water preferably contains rhodamine B, acid blue, active black, RGFL Huangs or acid red A-2BF
One or more of waste water.
The beneficial effects of the present invention are：
(1) present invention is with SnCl4·5H2O is raw material, and titanium-silicon molecular sieve TS-1 is carrier, and lanthanum and cerium are doped chemical, are adopted
With powder by supersonic sol-gel, rear-earth-doped loaded nano SnO is prepared2Catalysis material.The synthetic method letter of the present invention
Single, easily operated and reproducible, after rear-earth-doped, the photocatalysis performance of gained catalysis material has obtained highly significant
It is promoted, especially after La, Ce codope, photocatalysis performance promotion becomes apparent, and gained photochemical catalyst LCST simulates rhodamine B
The degradation rate of rhodamine B in waste water can reach 99.87%；It is also fine to the degradation effect of practical printing dye, LCST pairs
Acid blue, active black in actual dye wastewater, RGFL be yellow, acid red A-2BF degradation effect respectively up to 99.85%,
99.78%, 96.15% and 94.65%.
(2) the recycling performance of the rear-earth-doped catalyst of present invention gained is good, after LCST is reused 5 times, urges
Agent still maintains higher catalytic activity, remains able to reach 88.26% to the degradation rate of rhodamine B.
Description of the drawings
Fig. 1 is semiconductor light excitation process schematic diagram.
Fig. 2 is the XRD spectra and SnO of 1 gained ST of 3 gained LCST of embodiment and comparative example2(JSPDS41-1445)
Standard spectrogram.
Fig. 3 is that the SEM of carrier titanium-silicon molecular sieve TS-1 schemes.
The SEM that Fig. 4 is 3 gained LSCT of embodiment schemes.
The TEM that Fig. 5 is 3 gained LSCT of embodiment schemes.
Fig. 6 is high-resolution-ration transmission electric-lens (HRTEM) figure of the 3 spherical LCST of gained of embodiment.
Fig. 7 is nitrogen adsorption-desorption isotherm of 3 gained LCST of embodiment.
Fig. 8 is the graph of pore diameter distribution of 3 gained LCST of embodiment.
Fig. 9 is 3 gained LCST of embodiment and the UV-Vis spectrograms of 1 ST of the gained undoped with rare earth of comparative example.
Figure 10 is the full spectrograms of XPS of 3 gained LCST of embodiment.
Figure 11 is the La3d spectrograms of 3 gained LCST of embodiment.
Figure 12 is the Ce3d spectrograms of 3 gained LCST of embodiment.
Specific implementation mode
The present invention is described in further details with reference to specific embodiment, but the present invention is not limited thereto.
The preparation of 1 photochemical catalyst LST of embodiment
Weigh 3.0gSnCl4·5H2O is added 20ml distilled water, 0.06g lanthanum nitrates and the dense HCl of 0.1ml, is then added one
Quantitative ammonium hydroxide adjusts pH value of solution between 7.0-8.0, leucosol is obtained after ultrasonic wave dispersion 2h；It is added in colloidal sol
3.0g titanium-silicon molecular sieve TS-1s stir still aging 15h after 2h, are washed out, are dried to obtain presoma, presoma is placed in horse
Not in stove, in 500 DEG C of roasting temperature 2h, the loaded nano SnO of La doped is obtained2, it is named as LST.
The preparation of 2 photochemical catalyst CST of embodiment
Weigh 3.0gSnCl4·5H2O is added 20ml distilled water, 0.06g cerous nitrates and the dense HCl of 0.1ml, is then added one
Quantitative ammonium hydroxide adjusts pH value of solution between 7.0-8.0, leucosol is obtained after ultrasonic wave dispersion 2h；It is added in colloidal sol
3.0g titanium-silicon molecular sieve TS-1s stir still aging 15h after 2h, are washed out, are dried to obtain presoma, presoma is placed in horse
Not in stove, in 500 DEG C of roasting temperature 2h, rare earth metal cerium dopping loaded nano SnO is obtained2, it is named as CST.
The preparation of 3 photochemical catalyst LCST of embodiment
Weigh 3.0gSnCl4·5H220ml distilled water, 0.06g lanthanum nitrates and the dense HCl of 0.1ml, stirring to solution is added in O
Clarification, is then added a certain amount of ammonium hydroxide, adjusts pH value of solution between 7.0-8.0, leucosol is obtained after ultrasonic wave dispersion 2h；
3.0g titanium-silicon molecular sieve TS-1s and 0.03g cerous nitrates are added in colloidal sol, stirs still aging 15h after 2h, is washed out, dries
Presoma is obtained, presoma is placed in Muffle furnace, in 500 DEG C of roasting temperature 2h, obtains the loaded nano of lanthanum, cerium dopping
SnO2, it is named as LCST.
The preparation of 4 photochemical catalyst LCST of embodiment
Weigh 3.0gSnCl4·5H220ml distilled water, 0.08g lanthanum nitrates and the dense HCl of 0.1ml, stirring to solution is added in O
Clarification, is then added a certain amount of ammonium hydroxide, adjusts pH value of solution between 7.0-8.0, it is molten to obtain white after ultrasonic wave dispersion 1.5h
Glue；3.5g titanium-silicon molecular sieve TS-1s and 0.04g cerous nitrates are added in colloidal sol, stirs still aging 18h after 3h, be washed out,
It is dried to obtain presoma, presoma is placed in Muffle furnace, in 550 DEG C of roasting temperature 3h, obtains the support type of lanthanum, cerium dopping
Nano SnO2, it is named as LCST.
The preparation of 5 photochemical catalyst LCST of embodiment
Weigh 3.0gSnCl4·5H220ml distilled water, 0.04g lanthanum nitrates and the dense HCl of 0.1ml, stirring to solution is added in O
Clarification, is then added a certain amount of ammonium hydroxide, adjusts pH value of solution between 7.0-8.0, it is molten to obtain white after ultrasonic wave dispersion 2.5h
Glue；3.3g titanium-silicon molecular sieve TS-1s and 0.02g cerous nitrates are added in colloidal sol, stirs still aging 12h after 3h, be washed out,
It is dried to obtain presoma, presoma is placed in Muffle furnace, in 550 DEG C of roasting temperature 3h, obtains the support type of lanthanum, cerium dopping
Nano SnO2, it is named as LCST.
The preparation of 6 photochemical catalyst LCST of embodiment
Weigh 3.0gSnCl4·5H220ml distilled water, 0.04g lanthanum nitrates and the dense HCl of 0.1ml, stirring to solution is added in O
Clarification, is then added a certain amount of ammonium hydroxide, adjusts pH value of solution between 7.0-8.0, leucosol is obtained after ultrasonic wave dispersion 3h；
3.1g titanium-silicon molecular sieve TS-1s and 0.04g cerous nitrates are added in colloidal sol, stirs still aging 12h after 3h, is washed out, dries
Presoma is obtained, presoma is placed in Muffle furnace, in 550 DEG C of roasting temperature 3h, obtains the loaded nano of lanthanum, cerium dopping
SnO2, it is named as LCST.
The preparation of 1 photochemical catalyst ST of comparative example
Weigh 3.0gSnCl4·5H2O is added 20ml distilled water and the dense HCl of 0.1ml, a certain amount of ammonium hydroxide is then added, and adjusts
PH value of solution is saved between 7.0-8.0, leucosol is obtained after ultrasonic wave dispersion 1.5h；3.0g Titanium Sieve Molecular Sieve is added in colloidal sol
TS-1 stirs still aging 15h after 2h.It is washed out, is dried to obtain presoma, presoma is placed in Muffle furnace, at 500 DEG C
Roasting temperature 2h obtains loaded nano SnO2, it is named as ST.
7 photocatalysis performance of embodiment -- degradation property is tested
(1) rhodamine B is degradation object (simulation industrial dye waste water)
Select 20mg/L rhodamine B solutions as the light-catalysed degradation object of catalyst, accordingly, compound concentration is respectively
The rhodamine B solution of 1.25mg/L, 2.5mg/L, 5mg/L, 10mg/L, 15mg/L, 20mg/L, with 722S visible light light-splitting luminosity
Measure its absorbance.Experimentally determined, rhodamine B solution has maximum absorption band at λ=530nm, and when its concentration is relatively low
When in range, absorbance A and concentration C have the good linear dependence, fit standard curvilinear equation to be：
A=0.0005+0.00639C, regression coefficient R2=0.99972.
The test of photocatalysis performance is tested using the Phchem-III photo catalysis reactors of Beijing NewBide, by sieve 30ml
Red bright B simulated wastewaters (20mg/l) are placed in quartz test tube, with 722S visible spectrophotometers, in maximum absorption wavelength
Its initial absorbance A is measured under (530nm)0, add photochemical catalyst.After magnetic agitation 30min reaches adsorption equilibrium in dark,
Photocatalytic degradation is carried out by light source of 500W xenon lamps.After sampling is with 12500r/min high speed centrifugations, its absorbance A is measured530nm,.
It is denoted as A, utilizes (A0-A)/A0, the degradation rate D of rhodamine B is calculated, test result is as shown in table 1.
Degradation results of the different catalysis materials of table 1 to rhodamine B
(2) acid blue, active black, RGFL are yellow or acid red A-2BF is degradation object (actual industrial waste water from dyestuff)
Using the practical dyestuff of textile printing and dyeing factory as target degradation product, linear relationship and the degradation rate of TOC and COD are that evaluation is marked
Can standard, influence of the Study of Catalyst to degradation of dye effluent effect apply to miscellaneous rear stannic oxide after doping industrial practical
Degradation sewage is studied.The printing dye of actual use come from dolantin color additive Co., Ltd, be extracted respectively acid blue,
Active black, RGFL are yellow, tetra- kinds of dyestuffs of acid red A-2BF are studied；The TOC and COD of four kinds of dyestuffs have preferable linear pass
System, y=ax+b, a are respectively：0.307,0.301,0.412,0.503, b is respectively：24.877、24.687、16.450、
16.304 R is all higher than 0.98.
The experimental results showed that apparent better photocatalysis effect is presented in 3 gained LCST of embodiment, to acid blue, active black,
RGFL is yellow, acid red A-2BF degradation effect is respectively 99.85%, 99.78%, 96.15% and 94.65%.
Meanwhile also the performance that recycles of LCST is investigated.The experimental results showed that drops of the LCST to rhodamine B
Solution is in first time and secondary cycle, degradation rate 99.87%.And the catalyst photocatalysis performance after repeatedly recycling has one
Fixed reduction.After 5th time recycles, degradation rate 88.26% remains at higher level, illustrates the cycle of LSCT
Utility is good.
In addition, having carried out the multinomial characterization such as SEM, TEM, BET, UV-Vis, XPS to resulting materials, it is described as follows.
Fig. 2 is the XRD spectra and SnO of 1 gained ST of 3 gained LCST of embodiment and comparative example2(JSPDS41-1445)
Standard spectrogram.As shown in Figure 2, the catalyst LCST after the doping of catalyst ST and rare earth element La and Ce, 26.6 ° of the angle of diffraction,
There is diffraction maximum at 33.9 °, 38.1 °, 52.9 °, 62.3 ° and 65.9 °, it is corresponding with standard spectrogram JSPDS41-1445, it represents
Tetragonal structure SnO2, show molecular sieve TS-1 and rear-earth-doped processing without influencing SnO2The crystal form of particle.It is not examined in spectrogram
Measure oxide object phase corresponding with La, Ce, such as La2O3、Ce2O3, then illustrate La3+、Ce3+SnO is not entered into2In lattice simultaneously
Instead of Sn4+, it may be possible to due to La3+(0.115nm)、Ce3+The radius ratio Sn of (0.102nm)4+(0.069nm) is much bigger, so
La3+、Ce3+It is mainly dispersed in SnO2Surface.
Fig. 3 is that the SEM of carrier titanium-silicon molecular sieve TS-1 schemes.The SEM that Fig. 4 is 3 gained LSCT of embodiment schemes.3 He of comparison diagram
Fig. 4 is it is found that the LSCT patterns prepared using ultrasonic sol-gal process inherit the spherical morphology of carrier TS-1, good dispersion.Fig. 5
Scheme for the TEM of 3 gained LSCT of embodiment, as can be seen from Figure 5, spherical LCST is made of many nano-particles, and diameter of nano particles exists
Hole is formd between 10-20nm and nano-particle.This porous structure is conducive to the progress of photocatalytic degradation reaction.Fig. 6 is real
Apply high-resolution-ration transmission electric-lens (HRTEM) figure of the 3 spherical LCST of gained of example.Clearly lattice fringe is observed that from Fig. 6, into
One step shows spherical LSCT well-crystallized.It is 0.287nm and 0.469nm through measuring interplanar distance d values, lines is high-visible, into
One step shows that prepared LSCT powder purities are very high.
Fig. 7 and Fig. 8 is respectively nitrogen adsorption-desorption isotherm of 3 gained LCST of embodiment and corresponding graph of pore diameter distribution.
From figure 7 it can be seen that nitrogen adsorption curve and desorption curve form delay ring, further demonstrate that catalyst is porous structure.
As shown in Figure 8, the aperture of catalyst LCST is mainly distributed on 17.45nm and 37.07nm, average pore size 46.81nm, hole knot
Structure is mesoporous, large specific surface area.For catalyst, meso-hole structure has the characteristics that catalyst load capacity is high, is conducive to light
The progress of catalytic degradation reaction improves degradation efficiency.By calculating, the specific surface area of catalyst LCST is 270m2/g。
UV-vis can be good at characterizing the level structure and absorbing properties of material.Fig. 9 be 3 gained LCST of embodiment and
The UV-Vis spectrograms of 1 ST of the gained undoped with rare earth of comparative example.As seen from Figure 9, the absorbing boundary of LCST is 430.27nm,
Absorbing boundary undoped with rare earth element is 344.44nm, according to the estimation formula of the light absorption threshold value of semiconductor and band-gap energy,
It is 2.88eV that LCST band gap, which is calculated, and ST is then 3.47ev, and SnO2Energy gap 3.6eV, this shows La, Ce element
The visible light-responded range that material can be widened after doping, can absorb visible light, be conducive to improve photocatalytic activity.
XPS can determine La and Ce in the position of stannic oxide lattice.Figure 10 is that the XPS of 3 gained LCST of embodiment is composed entirely
Figure contains La, Ce, Sn, O element as shown in Figure 10 in sample.La and Ce has been doped to stannic oxide lattice or has been adsorbed
To stannic oxide surface.Figure 11 is the La3d spectrograms of 3 gained LCST of embodiment, as shown in Figure 11, the peak source at 835.08eV
In La, and La is the surface for being entrained in LCST.Figure 12 is the Ce3d spectrograms of 3 gained LCST of embodiment, is gone out in the peaks XPS of Ce3d
Show two basic change energy peak value, the peak at 736.98eV corresponds to Ce4+3d3/2, the peak at 727.48eV corresponds to Ce4+3d5/2, main
Ce-H is derived from, Ce-O is either adsorbed on stannic oxide surface, shows that Ce atoms have been doped in stannic oxide lattice.
Shown according to the characterize data of LCST：Use sol-gal process prepare spherical shape, porous structure, grain size 10-
20nm, high-purity powder；Specific surface area is about 270m2/ g, average pore size 46.81nm；Through the embedded codope of La, Ce, SnO2
Crystal form does not change；The apparent red shift of response wave length provides theoretical foundation for the follow-up research for carrying out Visible Light Induced Photocatalytic behavior.
In conclusion by rear-earth-doped gained SnO2The photocatalysis performance of the nano-photocatalyst material of/TS-1 is shown
It writes and is promoted, especially after the processing of La, Ce codope, photocatalysis performance promotion becomes apparent.
Claims (10)
1. a kind of rear-earth-doped SnO2The synthetic method of the nano-photocatalyst material of/TS-1, which is characterized in that include the following steps：
(1) stannic chloride pentahydrate is weighed, distilled water, lanthanum nitrate or/and cerous nitrate and concentrated hydrochloric acid then is added to it, stirs evenly
Obtain solution；
(2) ammonium hydroxide is added into step (1) acquired solution, adjusts pH value of solution, then carries out ultrasonic disperse, obtain leucosol；
(3) Titanium Sieve Molecular Sieve, that is, TS-1 is added into leucosol obtained by step (2), it is still aging after stirring, it is washed out, does
It is dry to obtain presoma；
(4) presoma is placed in Muffle furnace and is roasted, obtain rear-earth-doped SnO2The nano-photocatalyst material of/TS-1, when mixing
When miscellaneous rare earth is lanthanum, it is named as LST；When it is rare earth doped be cerium when, be named as CST；When it is rare earth doped be lanthanum and cerium when, be named as
LCST。
2. rear-earth-doped SnO according to claim 12The synthetic method of the nano-photocatalyst material of/TS-1, feature exist
In SnCl4.5H2O, the mass ratio of TS-1, La or/and Ce are 1：1~1.2：0.01~0.05.
3. rear-earth-doped SnO according to claim 12The synthetic method of the nano-photocatalyst material of/TS-1, feature exist
In in step (2), pH is adjusted to 7~8.
4. rear-earth-doped SnO according to claim 12The synthetic method of the nano-photocatalyst material of/TS-1, feature exist
In in step (2), the time of ultrasonic disperse is 1.5~4 hours.
5. rear-earth-doped SnO according to claim 12The synthetic method of the nano-photocatalyst material of/TS-1, feature exist
In in step (3), mixing time is 2~6 hours.
6. rear-earth-doped SnO according to claim 12The synthetic method of the nano-photocatalyst material of/TS-1, feature exist
In in step (3), digestion time is 10~20 hours.
7. rear-earth-doped SnO according to claim 12The synthetic method of the nano-photocatalyst material of/TS-1, feature exist
In in step (3), drying temperature is 80~120 DEG C, and drying time is 4~12 hours.
8. rear-earth-doped SnO according to claim 12The synthetic method of the nano-photocatalyst material of/TS-1, feature exist
In in step (4), calcination temperature is 350~600 DEG C, and roasting time is 2~5 hours.
9. the nano-photocatalyst material that claim 1 to 8 any one of them preparation method obtains is degraded in industrial dye waste water
In application.
10. application according to claim 9, which is characterized in that industrial dye waste water is containing rhodamine B, acid blue, activity
Black, RGFL is yellow or one or more of acid red A-2BF.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876767A (en) * | 2019-04-19 | 2019-06-14 | 闽江学院 | A kind of preparation and application of diatomite/lanthanum cerate composite material |
| CN113413888A (en) * | 2021-05-31 | 2021-09-21 | 重庆第二师范学院 | Photocatalyst and preparation method and application thereof |
| CN113559901A (en) * | 2021-08-06 | 2021-10-29 | 东北大学秦皇岛分校 | Silicon and rare earth modified Fe3Preparation method of C catalyst |
| CN113649066A (en) * | 2021-09-10 | 2021-11-16 | 四川大学 | Low-load rare earth doped nano photocatalyst and preparation method and application thereof |
| CN113683153A (en) * | 2021-08-06 | 2021-11-23 | 沈阳工业大学 | Device for treating waste water by utilizing photocatalytic reaction |
| CN113996329A (en) * | 2021-11-08 | 2022-02-01 | 常州市恒纶纺织有限公司 | Catalyst for degrading VOCs (volatile organic compounds), and preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01218635A (en) * | 1988-02-29 | 1989-08-31 | Hitachi Ltd | Deodorizing agent, its manufacturing method, deodorizing method, deodorizing apparatus and refrigeration cycle apparatus with said deodorizing apparatus |
| CN106391108A (en) * | 2016-10-30 | 2017-02-15 | 湖南工程学院 | Synthesis method and application of supported nano-SnO2/TS-1 (titanium silicalite-1) |
-
2018
- 2018-03-21 CN CN201810237889.3A patent/CN108452847A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01218635A (en) * | 1988-02-29 | 1989-08-31 | Hitachi Ltd | Deodorizing agent, its manufacturing method, deodorizing method, deodorizing apparatus and refrigeration cycle apparatus with said deodorizing apparatus |
| CN106391108A (en) * | 2016-10-30 | 2017-02-15 | 湖南工程学院 | Synthesis method and application of supported nano-SnO2/TS-1 (titanium silicalite-1) |
Non-Patent Citations (2)
| Title |
|---|
| ABDULLAH M. AL-HAMDI • MIKA SILLANPǍǍ ET AL.: "Photocatalytic degradation of phenol in aqueous solution by rare earth-doped SnO2 nanoparticles", 《J MATER SCI》 * |
| 王进贤等: "《静电纺丝技术与无机纳米材料合成》", 31 August 2012, 北京：国防工业出版社 * |
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| CN109876767B (en) * | 2019-04-19 | 2021-09-28 | 闽江学院 | Preparation and application of diatomite/lanthanum cerate composite material |
| CN113413888A (en) * | 2021-05-31 | 2021-09-21 | 重庆第二师范学院 | Photocatalyst and preparation method and application thereof |
| CN113413888B (en) * | 2021-05-31 | 2023-04-18 | 重庆第二师范学院 | Photocatalyst and preparation method and application thereof |
| CN113559901A (en) * | 2021-08-06 | 2021-10-29 | 东北大学秦皇岛分校 | Silicon and rare earth modified Fe3Preparation method of C catalyst |
| CN113683153A (en) * | 2021-08-06 | 2021-11-23 | 沈阳工业大学 | Device for treating waste water by utilizing photocatalytic reaction |
| CN113649066A (en) * | 2021-09-10 | 2021-11-16 | 四川大学 | Low-load rare earth doped nano photocatalyst and preparation method and application thereof |
| CN113996329A (en) * | 2021-11-08 | 2022-02-01 | 常州市恒纶纺织有限公司 | Catalyst for degrading VOCs (volatile organic compounds), and preparation method and application thereof |
| CN115196617A (en) * | 2022-08-04 | 2022-10-18 | 亳州市亚珠新材料有限公司 | Preparation method of boron-doped porous carbon rod-shaped material |
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