CN107312532B - A kind of SiO2@TiO2:Sm3+The luminous and difunctional composite material and preparation method of photocatalysis - Google Patents
A kind of SiO2@TiO2:Sm3+The luminous and difunctional composite material and preparation method of photocatalysis Download PDFInfo
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- CN107312532B CN107312532B CN201710579465.0A CN201710579465A CN107312532B CN 107312532 B CN107312532 B CN 107312532B CN 201710579465 A CN201710579465 A CN 201710579465A CN 107312532 B CN107312532 B CN 107312532B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 91
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 63
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 63
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 63
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 63
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000003760 hair shine Effects 0.000 claims abstract description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 58
- 229910021641 deionized water Inorganic materials 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims description 16
- 239000012265 solid product Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 5
- 229940012189 methyl orange Drugs 0.000 abstract description 5
- 230000001588 bifunctional effect Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- -1 samarium ion Chemical class 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 16
- 239000012467 final product Substances 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005889 cellular cytotoxicity Effects 0.000 description 1
- 230000004700 cellular uptake Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000015788 innate immune response Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
- C09K11/7764—Aluminates; Silicates
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
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- 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
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- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- 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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Abstract
A kind of SiO of samarium ion doping2@TiO2:Sm3+The luminous and difunctional composite material and preparation method of photocatalysis, belongs to inorganic bifunctional field of material technology.It is to prepare SiO first2Powder, then prepare SiO2@TiO2:Sm3+Composite material, up to SiO after which is calcined2@TiO2:Sm3+It shines and the difunctional composite material of photocatalysis.With the reduction that water is added in reaction process, the hydrolysis rate of butyl titanate slows down, TiO2Nanoparticle can uniform coated Si O2On surface, therefore, luminous intensity is greatly improved, and sample shows orange light, and sample possesses good photocatalysis performance.After ultraviolet light 30min, the degradation rate of sample methyl orange reaches 73.3%.The present invention has simple process, production cost low, easily controllable, is suitble to the features such as producing in enormous quantities.Products obtained therefrom function admirable is applied to shine and photocatalysis field provides possibility for later rear-earth-doped composite material.
Description
Technical field
The invention belongs to inorganic bifunctional field of material technology, and in particular to a kind of SiO of samarium ion doping2@TiO2:
Sm3+The luminous and difunctional composite material and preparation method of photocatalysis.
Background technique
For titanium dioxide due to its special crystal structure, the features such as excellent thermodynamic property and environmental stability, is extensive
Be applied to catalysis, shine, the fields such as solar battery and rear-earth-doped host material.In recent years, rear-earth-doped TiO2Material
Expect to have become one of the hot spot of research in catalysis and the application of illumination field.But pure TiO2It is deposited in the application as main body
In some problems: easy to reunite, at high cost, easy in inactivation.If cheap SiO is added2Prepare SiO2With TiO2Composite material, then
It can be very good dispersion TiO2, while new catalytic site is generated, improve its application value.In addition, rare earth doped material due to
Unique 4f electron structure, becomes high performance luminescent material.Importantly, in catalytic field, rare earth ion
Presence inhibit the compound of light induced electron and hole, to improve the photocatalysis performance of sample while generating and shining.
Existing rare earth SiO2@TiO2The preparation method of composite material mainly include the following types:
(1) sol-gel method (1.Jin-Lin Hu, Hai-Sheng Qian, et al.Synthesis of
mesoporous SiO2@TiO2core/shell nanospheres with enhanced photocatalytic
properties[J].Particle&Particle Systems Characterization,2013,30(4): 306-310.
2.Li X,He J.Synthesis of raspberry-like SiO2–TiO2nanoparticles toward
antireflective and self-cleaning coatings[J].ACS applied materials&
interfaces, 2013,5(11):5282-5290.)；
(2) dissolution and resedimentation method (Oh W K, Kim S, Choi M, et al.Cellular uptake,
cytotoxicity,and innate immune response of silica-titania hollow
nanoparticles based on size and surface functionality[J].Acs Nano,2010,4(9):
5301-5313.)；
(3) collosol and gel and ultrasonic etching method (Lee J, Hwang S H, Yun J, et al.Fabrication of
SiO2/TiO2Double-Shelled Hollow Nanospheres with Controllable Size via Sol–Gel
Reaction and Sonication-Mediated Etching[J].ACS applied materials &
interfaces,2014,6(17):15420-15426.)。
But above method long preparation period, and cladding pattern is single, is unformed TiO2Gel layer, and need by
The effect of surfactant is by TiO2It is coated on SiO2On.In order to overcome disadvantage mentioned above, we use solvent-thermal method, appoint in nothing
Under conditions of what surfactant, by the TiO of the particle morphology of Anatase2: Sm3+It is coated on SiO2On surface, successfully prepare
SiO is gone out2@TiO2:Sm3+Composite material, sample shows the orange red light emitting of feature of samarium, and has good catalytic performance.And
And pass through the change of solvent ratio, the sample of available different-shape.
Summary of the invention
The object of the invention is that making up above-mentioned the deficiencies in the prior art, a kind of SiO is provided2@TiO2:Sm3+Shine and
It is catalyzed bifunctional material and preparation method thereof.And its luminous and photocatalysis performance and solvent are than closely related.This method operation letter
Anatase TiO can be obtained in single, favorable reproducibility, the presence of surfactant-free2For the composite material of shell, composite wood is being prepared
Material field is worth with important research.
SiO of the present invention2@TiO2:Sm3+The preparation method of bifunctional material is shone and is catalyzed, its step are as follows:
(1)SiO2The preparation of powder
By 3~6mL ethyl orthosilicate (TEOS) be added to 2~10mL deionized water, 18~23mL isopropanol, 0.1~
In the mixed solution of 0.5mL ammonium hydroxide (mass fraction 25%~28%), 8~10h is stirred at room temperature, then by centrifuge washing, uses
Dehydrated alcohol and deionized water alternately washing 3~5 times, dry 5~8h obtains SiO at 50~80 DEG C2Powder；
(2)SiO2@TiO2:Sm3+The preparation of composite material
0.1~0.3g SiO that step (1) is obtained2Powder ultrasonic disperse to 36~38mL dehydrated alcohol and 0.5~
Be added in the mixed solution of 2mL deionized water, after stirring 1~1.4mL butyl titanate and 0.01~0.48mL, 0.3~
0.8mol/L samaric nitrate aqueous solution, above-mentioned solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, in temperature 100~150
It is reacted 1~4 hour under the conditions of DEG C；Cooled to room temperature later, the solid product dehydrated alcohol and deionized water that will be obtained
Alternating centrifugal washs 3~5 times, and dry 5~8h, obtains SiO at 50~80 DEG C2@TiO2:Sm3+Composite material powder；
(3) product postprocessing
By above-mentioned SiO2@TiO2:Sm3+Powder calcines 2~4h at 700 DEG C~900 DEG C, and heating rate is 1~2 DEG C/
Min, up to SiO after calcining2@TiO2:Sm3+It shines and the difunctional composite material of photocatalysis.
Beneficial effect
Preparation method of the invention is not required to that any surfactant is added, by simple solvent-thermal method, without calcining
Under conditions of be obtained with anatase TiO2Particle morphology is the composite material of shell, size uniformity, good dispersion.And it originally grinds
Study carefully and shows that solvent compares shining for material and has a major impact with photocatalysis performance, if water is big, the hydrolysis speed of butyl titanate
Rate quickly, TiO2Meeting independent nucleation, and serious agglomeration.With the reduction of rate of water added, the hydrolysis rate of butyl titanate slows down, TiO2
Nanoparticle can uniform coated Si O2On surface, therefore, luminous intensity is greatly improved, and sample shows orange light.And sample
Possess good photocatalysis performance.After ultraviolet light 30min, the degradation rate of sample methyl orange reaches 73.3% (such as attached drawing 5
It is shown).
The present invention has simple process, production cost low, easily controllable, is suitble to the features such as producing in enormous quantities.Products obtained therefrom
Function admirable is applied to shine and photocatalysis field provides possibility for later rear-earth-doped composite material.
Detailed description of the invention
Fig. 1: SiO in the embodiment of the present invention 1,2,32@TiO2:Sm3+The XRD comparison diagram of composite material.
The SiO as prepared by the present invention2For amorphous state, so SiO2@TiO2:Sm3+The crystal phase of composite material be by
TiO2What crystal phase determined.As shown, prepared sample is pure anatase phase (JCPDS No.72-1272).
Fig. 2: SiO in the embodiment of the present invention 1,2,32@TiO2:Sm3+SEM of the composite material under 50000 times of amplification shines
Piece.
The prepared SiO of SEM photograph (a, b, c) display2@TiO2:Sm3+Composite material is with SiO2For core, TiO2For shell
SiO2@TiO2:Sm3+Spherical structure material, about 0.8~1.1 μm of diameter.However, photo (a) shows TiO2Nanoparticle cladding
Uniformly, (b) and the TiO of (c)2The independent nucleations of nanoparticle all showed differents and reunion, this is because the increase of water, promotees
Caused by too fast hydrolysis into TBOT.
Fig. 3: SiO in the embodiment of the present invention 12@TiO2:Sm3+(a) excitation spectrum of composite material and (b) emission spectrum.
Excitation spectrum is located at the broadband of 359nm by a main peak and some weaker excitation peaks form, and is respectively belonging to sharp
Titanium ore phase TiO2The absorption of matrix and Sm3+The f-f transition of ion.The absorption of matrix further proves TiO2Main body and Sm3+Between
There are effective energy transfer processes.Emission spectrum is made of a series of emission peaks, and main peak is located at 610nm, shows as orange light
Transmitting.
Fig. 4: SiO in the embodiment of the present invention 1,2,32@TiO2:Sm3+The emission spectrum comparison diagram of composite material.
As shown, emission spectrum is by Sm3+Series of features emission peak composition, however SiO prepared by embodiment 12@
TiO2:Sm3+The luminous intensity of composite material is best.Show that covered effect can have a significant impact to luminous intensity, covered effect is got over
It is good, it shines stronger.
Fig. 5: the SiO in the embodiment of the present invention 12@TiO2:Sm3+In the presence of composite material, the methyl orange of different irradiation times
The absorption spectrum of solution.
As shown, the characteristic absorption peak intensity of methyl orange is gradually as the ultraviolet light time from 0 increases to 30min
It reduces, this illustrates methyl orange by SiO2@TiO2:Sm3+Composite material is gradually degraded.The degradation rate of various time points is respectively
16.1%, 27.3%, 39.6%, 50.6%, 60.5%, 73.3%.
Fig. 6: SiO in the embodiment of the present invention 4,5,62@TiO2:Sm3+The SEM photograph of composite material.
The prepared SiO of SEM photograph (a, b, c) display2@TiO2:Sm3+Composite material is with SiO2For core, TiO2For shell
SiO2@TiO2:Sm3+Spherical structure material, diameter are respectively 350~600nm, and 0.9~1.2 μm and 0.8~1.1 μm.
Fig. 7: SiO in the embodiment of the present invention 72@TiO2:Sm3+The XRD diagram of composite material.
As shown, prepared sample is pure anatase phase, crystallinity is poor.
Specific embodiment
Embodiment 1
(1) 5mL TEOS is added drop-wise to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, with dehydrated alcohol and deionized water alternately washing 4 times, dry 6h is obtained at 60 DEG C
SiO2Powder.
(3) by 0.25g SiO2Powder ultrasonic disperse is then stirring in 37.5mL dehydrated alcohol and 0.5mL deionized water
1.35mL TBOT and 0.08mL Sm (NO is added in the state of mixing3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.59g, about 0.8~1.1 μm of diameter.
Embodiment 2
(1) 5mL TEOS is added drop-wise to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, with dehydrated alcohol and deionized water alternately washing 4 times, dry 6h is obtained at 60 DEG C
SiO2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37mL dehydrated alcohol and 1mL deionized water, then in the state of stirring
Lower addition 1.35mL TBOT and 0.08mL Sm (NO3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.54g, about 0.8~1.1 μm of diameter.However have
A little TiO2Nanoparticle independent nucleation, and reunite together, this is because the increase of water, promotes the too fast hydrolysis institute of TBOT
It causes.Shown in its scanning electron microscopic picture such as Fig. 2 (b).
Embodiment 3
(1) 5mL TEOS is added drop-wise to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge separation product, with dehydrated alcohol and deionized water alternately washing 4 times, dry 6h is obtained at 60 DEG C
To SiO2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 36mL dehydrated alcohol and 2mL deionized water, then in the state of stirring
Lower addition 1.35mL TBOT and 0.08mL Sm (NO3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.51g, about 0.8~1.1 μm of diameter.It can see
Out, the hydrolysis rate of gradually increasing with rate of water added, TBOT is accelerated, more and more TiO2Particle independent nucleation is simultaneously reunited.Its
Shown in scanning electron microscopic picture such as Fig. 2 (c).
Embodiment 4
(1) 5mL TEOS is added drop-wise to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 2.5mL deionization
In the mixed solution of water, 10h is stirred.
(2) by centrifuge washing, with dehydrated alcohol and deionized water alternately washing 4 times, dry 6h is obtained at 60 DEG C
SiO2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.08mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shines and is catalyzed difunctional spherical structure material, product quality is 0.58g, diameter about 350~600nm.
Embodiment 5
(1) 5mL TEOS is added drop-wise to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 10mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, with dehydrated alcohol and deionized water alternately washing 4 times, dry 6h is obtained at 60 DEG C
SiO2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.08mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.59g, about 0.9~1.2 μm of diameter.
Embodiment 6
(1) 5mL TEOS is added drop-wise to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge separation product, with dehydrated alcohol and deionized water alternately washing 4 times, dry 6h is obtained at 60 DEG C
To SiO2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.08mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 100 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.61g, about 0.8~1.1 μm of diameter.
Embodiment 7
(1) 5mL TEOS is added drop-wise to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, with dehydrated alcohol and deionized water alternately washing 4 times, dry 6h is obtained at 60 DEG C
SiO2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.08mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) up to the SiO not calcined2For core, TiO2For the SiO of shell2@TiO2:Sm3+Shine and be catalyzed difunctional spherical junctions
Structure material, product quality are 0.61g, about 0.8~1.1 μm of diameter.
Embodiment 8
(1) 5mL TEOS is added to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, it is dried to obtain SiO2Powder.With alternately washing 4 times of dehydrated alcohol and deionized water, In
Dry 6h obtains SiO at 60 DEG C2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.04mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.59g, about 0.8~1.1 μm of diameter.
Embodiment 9
(1) 5mL TEOS is added to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, it is dried to obtain SiO2Powder.With alternately washing 4 times of dehydrated alcohol and deionized water, In
Dry 6h obtains SiO at 60 DEG C2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.16mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.59g, about 0.8~1.1 μm of diameter.
Embodiment 10
(1) 5mL TEOS is added to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, it is dried to obtain SiO2Powder.With alternately washing 4 times of dehydrated alcohol and deionized water, In
Dry 6h obtains SiO at 60 DEG C2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.24mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.59g, about 0.8~1.1 μm of diameter.
Embodiment 11
(1) 5mL TEOS is added to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 6mL deionized water
Mixed solution in, stir 10h.
(2) by centrifuge washing, it is dried to obtain SiO2Powder.With alternately washing 4 times of dehydrated alcohol and deionized water, In
Dry 6h obtains SiO at 60 DEG C2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.32mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shining and is catalyzed difunctional spherical structure material, product quality is 0.59g, about 0.8~1.1 μm of diameter.
Embodiment 12
(1) 5mL TEOS is added to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 2.5mL deionization
In the mixed solution of water, 10h is stirred.
(2) by centrifuge washing, it is dried to obtain SiO2Powder.With alternately washing 4 times of dehydrated alcohol and deionized water, In
Dry 6h obtains SiO at 60 DEG C2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.32mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 700 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shines and is catalyzed difunctional spherical structure material, product quality is 0.59g, diameter about 350~600nm.Wherein wrap
The TiO covered2The partial size of nanoparticle is 10~40nm.
Embodiment 13
(1) 5mL TEOS is added to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 2.5mL deionization
In the mixed solution of water, 10h is stirred.
(2) by centrifuge washing, it is dried to obtain SiO2Powder.With alternately washing 4 times of dehydrated alcohol and deionized water, In
Dry 6h obtains SiO at 60 DEG C2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.32mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 800 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shines and is catalyzed difunctional spherical structure material, product quality is 0.59g, diameter about 350~600nm.Wherein wrap
The TiO covered2The partial size of nanoparticle is 10~50nm.
Embodiment 14
(1) 5mL TEOS is added to 20mL isopropanol, 0.35mL ammonium hydroxide (mass fraction 25%) and 2.5mL deionization
In the mixed solution of water, 10h is stirred.
(2) by centrifuge washing, it is dried to obtain SiO2Powder.With alternately washing 4 times of dehydrated alcohol and deionized water, In
Dry 6h obtains SiO at 60 DEG C2Powder.
(3) by 0.25g SiO2Ultrasonic disperse is in 37.5mL dehydrated alcohol and 0.5mL deionized water, then in stirring
1.35mL TBOT and 0.32mL Sm (NO is added under state3)3Solution (0.5mol/L), solution continue to stir 10min.
(4) it transfers the solution into the reaction kettle of the polytetrafluoroethyllining lining of 50mL, 3h is reacted at 140 DEG C, it later will be anti-
Answer kettle cooled to room temperature.Obtained solid product dehydrated alcohol and deionized water alternating centrifugal are washed, at 60 DEG C
Dry 6h obtains final product.
(5) sample is placed in Muffle furnace, calcines 3h under the conditions of 900 DEG C to get SiO2For core, TiO2For the SiO of shell2@
TiO2:Sm3+It shines and is catalyzed difunctional spherical structure material, product quality is 0.58g, diameter about 350~600nm.Wherein wrap
The TiO covered2The partial size of nanoparticle is 20~60nm.
Claims (4)
1. a kind of SiO2@TiO2:Sm3+Luminous and the difunctional composite material of photocatalysis preparation method, it is characterised in that:
(1)SiO2The preparation of powder
3~6mL ethyl orthosilicate is added to 2~10mL deionized water, 18~23mL isopropanol, 0.1~0.5mL, quality point
In the mixed solution of 25%~28% ammonium hydroxide of number, 8~10h is stirred at room temperature, then by centrifuge washing, with dehydrated alcohol and go from
Alternately washing 3~5 times of sub- water, dry 5~8h obtains SiO at 50~80 DEG C2Powder；
(2)SiO2@TiO2:Sm3+The preparation of composite material
0.1~0.3g SiO that step (1) is obtained2Powder ultrasonic disperse to 36~38mL dehydrated alcohol and 0.5~2mL go from
In the mixed solution of sub- water, 1~1.4mL butyl titanate and 0.01~0.48mL, 0.3~0.8mol/L nitric acid are added after stirring
Above-mentioned solution is transferred in the reaction kettle of polytetrafluoroethyllining lining by samarium aqueous solution, and cooled to room temperature after reaction will obtain
Solid product dehydrated alcohol and deionized water alternating centrifugal wash 3~5 times, dry 5~8h, obtains at 50~80 DEG C
SiO2@TiO2:Sm3+Powder；
(3) product postprocessing
By above-mentioned SiO2@TiO2:Sm3+SiO is obtained after powder calcination2@TiO2:Sm3+It shines and the difunctional composite material of photocatalysis.
2. a kind of SiO as described in claim 12@TiO2:Sm3+Luminous and the difunctional composite material of photocatalysis preparation method,
It is characterized by: the temperature reacted in reaction kettle is 100~150 DEG C, the time of reaction is 1~4h.
3. a kind of SiO as described in claim 12@TiO2:Sm3+Luminous and the difunctional composite material of photocatalysis preparation method,
It is characterized by: the temperature of calcining is 700 DEG C~900 DEG C, the time of calcining is 2~4h.
4. a kind of SiO2@TiO2:Sm3+The luminous and difunctional composite material of photocatalysis, it is characterised in that: be by claims 1 to 3
Method described in any one is prepared.
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| Design of europium doped SiO2–TiO2 hybrids as novel luminescent photocatalyst;Yuhui Zheng等;《Journal of Luminescence》;20120205;第132卷;第1639-1641页 * |
| 应用于热控的壳厚可控核壳结构Si02@Ti02颗粒制备;王光海等;《无机化学学报》;20120131;第28卷(第1期);第171-175页 * |
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