CN106881076A - Tin ash, titanium dioxide semiconductor coupling, the preparation method of ion contra-doping photocatalytic nanometer fibrous material - Google Patents
Tin ash, titanium dioxide semiconductor coupling, the preparation method of ion contra-doping photocatalytic nanometer fibrous material Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 238000010168 coupling process Methods 0.000 title claims abstract description 33
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 230000008878 coupling Effects 0.000 title claims abstract description 29
- 239000004065 semiconductor Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002657 fibrous material Substances 0.000 title claims abstract description 17
- 150000002500 ions Chemical class 0.000 title description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title description 2
- 239000004408 titanium dioxide Substances 0.000 title description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 188
- 239000000463 material Substances 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920000742 Cotton Polymers 0.000 claims abstract description 36
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 23
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 239000002121 nanofiber Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 239000012467 final product Substances 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000000835 fiber Substances 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000005238 degreasing Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 95
- 239000000243 solution Substances 0.000 description 27
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 15
- 229960000907 methylthioninium chloride Drugs 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 235000012489 doughnuts Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 241000241602 Gossypianthus Species 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- -1 Methylene Chemical group 0.000 description 1
- 241001131927 Placea Species 0.000 description 1
- 229910006735 SnO2SnO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OCLXJTCGWSSVOE-UHFFFAOYSA-N ethanol etoh Chemical compound CCO.CCO OCLXJTCGWSSVOE-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B01J35/58—
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
The invention provides a kind of SnO2、TiO2The preparation of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material, is in SnCl by degreasing cotton fiber4·5H2O and Ti (OC4H9)4Ethanol solution in soak 25 ~ 35min, make Sn4+、Ti4+Absorption spontaneously dries to obtain precursor material on cotton fiber surface；The precursor material is calcined into 110 ~ 130 min at 590 ~ 610 DEG C and removes template, obtain final product semiconductor coupling photocatalytic nanometer fibre structure material (SnO2‑TiO2)；Importantly, the present invention is by regulating and controlling Ti (OC4H9)4And SnCl4·5H2The consumption of O, is realizing SnO2、TiO2While semi-conducting material is coupled, ion Sn is realized4+、Ti4+In phase TiO2、SnO2In contra-doping, greatly improve TiO2、SnO2Photocatalysis performance.
Description
Technical field
The present invention relates to a kind of preparation of the fibre structure photocatalysis nano material of ion doping, more particularly to one kind
SnO2、TiO2The preparation method of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material, belongs to photocatalysis technology field.
Background technology
SnO2And TiO2The advantages of due to good chemical stability, high catalytic activity, strong anti-oxidation ability, make it in light
Application in terms of catalysis is more prominent.But because they are wide band gap semiconducters（SnO2：EG=3.5 eV, TiO2：Eg = 3.2
eV）, ultraviolet excitation can only be used, and the ultraviolet light in sunshine only accounts for 5 % or so, in addition its photogenerated chargee --h +Recombination rate
Height, so as to limit the application of its scale.The doping of metal ion and semiconductor coupling are that more conventional at present two kinds change
Property method.All the time, researchers ignore an important phenomenon-ion contra-doping when semiconductor coupling is studied and show
The presence of elephant.For example, substantial amounts of research is it has been proved that preparing TiO2If during there is another metal ion（Such as Fe3+）,
Fe3+Ion will be automatically into TiO2Lattice in, so as to realize TiO2Middle metal cations Fe3+Doping.Certainly, using not
Same preparation method, it is possible to achieve metal cations Fe3+In TiO2In different distributions.For another example, in semiconductor TiO2And Fe2O3Coupling
Condensation material TiO2-Fe2O3Preparation in, if in TiO2There is Fe when mutually being formed3+In the presence of, or Fe2O3There is Ti when mutually being formed4+In the presence of that
In the coupling material TiO of gained2-Fe2O3In certainly exist the contra-doping phenomenon of ion, i.e. Fe3+Ion enters into TiO2Phase
In, Ti4+Ion enters into Fe2O3Xiang Zhong.And the coupling of this contra-doping and semiconductor of metal ion can not only change it
Band structure, and different faults of construction can be introduced in sample lattice, so as to be conducive to widening light absorption region and
Photoproductione --h +To separation, its photocatalysis performance is lifted.
The content of the invention
Invention provides a kind of SnO2、TiO2The preparation method of semiconductor coupling photocatalytic nanometer fibrous material, it is heavier
What is wanted is to demonstrate semiconductor coupling SnO2-TiO2The presence of material intermediate ion contra-doping phenomenon.
First, the preparation of photocatalytic nanometer fibrous material
SnO of the present invention2、TiO2The preparation method of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material, is by degreasing
Cotton fiber (CF) is in SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in soak 25 ~ 35 min, make Sn4+、Ti4+Absorption is in cotton
Flower fiber surface, spontaneously dries to obtain precursor material (Sn4++Ti4+)/CF；Again by the precursor material in calcining at 590 ~ 610 DEG C
110 ~ 130 min obtain final product SnO to remove template2、TiO2Semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material.
In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Sn4+Material amount content be 0.02 ~ 0.04 %
When, do not have SnO2The formation of phase, is obtained Sn4+The TiO of doping2Hollow Nano fiber in use structure catalysis material Sn4+/TiO2。
In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Ti4+Material amount content be 0.02 ~ 0.04 %
When, do not have TiO2Mutually formed, Ti is obtained4+The SnO of doping2Hollow Nano fiber in use structure catalysis material Ti4+/SnO2。
In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Sn4+Material amount content be 14.50 ~ 15.50 %
When, it is ensured that SnO2The generation of phase, obtains with TiO2It is main body, SnO2And TiO2Coupling, ion contra-doping hollow Nano fiber in use knot
Structure catalysis material Ti4+/SnO2@Sn4+/TiO2。
In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Ti4+Material amount content be 24.50 ~ 25.50 %
When, it is ensured that TiO2The generation of phase, obtains with SnO2It is main body, SnO2And TiO2Coupling, ion contra-doping hollow Nano fiber in use knot
Structure catalysis material Sn4+/TiO2@Ti4+/SnO2。
2nd, the structural characterization of photocatalytic nanometer fibrous material
Fig. 1 is sample TiO2、Sn4+/TiO2~ 0.03 % and Ti4+/SnO2@Sn4+/TiO2The XRD results of ~ 15.00 %.By Fig. 1 a
As can be seen that occurring in that Detitanium-ore-type TiO in three kinds of XRD of sample2(A-TiO2) diffraction maximum（With standard card JCPDS
No.21-1272 fits like a glove）, but its diffraction peak intensity is with TiO2、Sn4+/TiO2~ 0.03 % and Ti4+/SnO2@Sn4+/TiO2~
15.00 % weaken successively（Ti4+/SnO2@Sn4+/TiO2~ 15.00 % are especially notable）；Relative to TiO2, sample Sn4+/TiO2~
0.03 % and Ti4+/SnO2@Sn4+/TiO2The diffraction maximum of ~ 15.00 % is also to the low angle of diffraction（2θ）Direction there occurs displacement（Respectively
For：25.31 ° → 25.23 °, move 0.08 °；25.31 ° → 25.16 °, move 0.15 °）（See Fig. 1 b）.In addition, sample
Ti4+/SnO2@Sn4+/TiO2SnO is have also appeared in the XRD of ~ 15.00 %2Diffraction maximum, illustrate in the sample while there is TiO2With
SnO2The presence of phase.
Fig. 2 is sample SnO2、Ti4+/SnO2~ 0.03 % and Sn4+/TiO2@Ti4+/SnO2The XRD results of ~ 25.00 %.Together
Sample occurs in that SnO in can be seen that three kinds of XRD of sample2Diffraction maximum（It is complete with standard card JCPDS No.41-1445
It coincide）, its diffraction peak intensity is with SnO2、Ti4+/SnO2~ 0.03 % and Sn4+/TiO2@Ti4+/SnO2~ 25.00 % slightly have decrease；
Relative to SnO2, sample Ti4+/SnO2~ 0.03 % and Sn4+/TiO2@Ti4+/SnO2The diffraction maximum of ~ 25.00 % is to the angle of diffraction high
（2θ）Direction there occurs notable displacement（Respectively 26.20 ° → 26.61 °, move 0.41 °；26.20 ° → 26.53 °, move
0.33°）（See Fig. 2 b）.Similarly, sample Sn4+/TiO2@Ti4+/SnO2A-TiO is have also appeared in the XRD of ~ 25.00 %2Spread out
Peak is penetrated, is illustrated in the sample while there is SnO2And TiO2The presence of phase.
The crystal property main with sample of diffraction peak intensity, lattice defect are relevant herein.Sn4+（0.0690 nm）And Ti4 +（0.0605 nm）With relatively more close ionic radius.From sample Sn4+/TiO2~0.03 %（See Fig. 1）And Ti4+/SnO2~
0.03 %（See Fig. 2）XRD results can be seen that Sn4+Into TiO2Lattice and instead of the Ti of part small radii4+, lead
Cause TiO2Deformation ~ the increase of structure cell, so that diffraction maximum is subjected to displacement to low diffraction angular direction, while making TiO2Crystal property
Reduce；And Ti4+Enter into SnO2Lattice and instead of the larger Sn of partial radius4+, cause SnO2Deformation ~ the reduction of structure cell,
So that diffraction maximum is subjected to displacement to diffraction angular direction high, while making SnO2Crystal property slightly have reduction.It is more worth to point out
It is：Sample Ti4+/SnO2@Sn4+/TiO2TiO in ~ 15.00 %2Diffraction maximum be also subjected to displacement to low diffraction angular direction, and sample
Sn4+/TiO2@Ti4+/SnO2SnO in ~ 25.00 %2Diffraction maximum be subjected to displacement to diffraction angular direction high.The result explanation：In sample
Product Ti4+/SnO2@Sn4+/TiO2In ~ 15.00 %, Sn4+Forming object phase SnO2While, also there is part Sn4+Ion is entered into
Main body phase TiO2In, i.e. sample Ti4+/SnO2@Sn4+/TiO2Main body phase TiO in ~ 15.00 %2The actually metal of object phase
Ion Sn4+Doping.Equally, sample Sn4+/TiO2@Ti4+/SnO2Main body phase SnO in ~ 25.00 %2Actually object phase
Metal ion Ti4+Doping.Well imagine, it is mutually natural thing that the metal ion of main body phase enters into object.
Fig. 3 is sample TiO2(a)、Sn4+/TiO2~0.03 %(b)、Ti4+/SnO2@Sn4+/TiO2~15.00 %(c)、SnO2
(d)、Ti4+/SnO2~0.03 %(e)、Sn4+/TiO2@Ti4+/SnO2The SEM figures of ~ 25.00 % (f).From SEM figures as can be seen that institute
Obtained sample replicates the pattern of cotton fiber, with doughnut structure（Caused by the removal of template）；Sample
TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO2The fibre wall of ~ 15.00 % is relatively compact, there is slight rupture；And
Sample SnO2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO2The fibre wall of ~ 25.00 % is then presented many hollow structures, and broken
Split substantially（Sample SnO2And Ti4+/SnO2~ 0.03 % is especially notable）.The result shows：Metal ion Sn4+And Ti4+It is fine in cotton
The absorption property in dimension table face is different, Ti4+Compared with Sn4+Absorption is easier on the surface of cotton fiber, comparatively dense absorption is formed
Layer, so, the fibre wall for forming target material is dense.
3rd, the photocatalysis performance of photocatalytic nanometer fibrous material
The photocatalysis performance of the series material for decolourizing to develop the present invention using the photocatalytic degradation of methylene blue (MB) solution enters
Row is characterized.
Photocatalytic degradation is tested：By 40 mg sample dispersions in 40 mL concentration be 10 mgL-1Methylene blue (MB) it is molten
In liquid；30 min are stirred in the dark state, up to after suction-de- balance, in 300 W mercury lamps（ML）Photocatalytic degradation is carried out under the conditions of irradiation
Decolorization experiment；5 mL are sampled at regular intervals, and the removal solid sample of centrifugation immediately is clear with spectrophotometric determination upper strata
Liquid is in 664 nm（The maximum absorption wavelength of MB）The absorbance at placeA t, with percent of decolourization of the MB solution on sampleD t% and ln (C 0
/C t) with the timetChange and (one-level) Kinetics Rate Constants By Using study sample photocatalysis performance and MB molecules in sample
The degradation kinetics behavior on product surface.
Percent of decolourization：D t (%) = [(A 0-A t)/A 0The % of] × (100), first _ order kinetics equation：ln(C 0 /C t)(≈ln
(A 0/A t) = k 1 t.Wherein,A 0WithA t、C 0WithC tThe initial and light application time of respectively MB solution istWhen absorbance and dense
Angle value.
Fig. 4 is sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO2The photocatalytic degradation of ~ 15.00 %
MB solutionD t % ~ tAnd ln (C 0 /C t) ~ tResult.As shown in Figure 4, it is ultraviolet in 300 W Hg (dominant wavelength is 365 nm)
Under light irradiation, all samples are respectively provided with significant photocatalysis to the degradation and decolorization of MB solution；Modified material Sn4+/
TiO2~ 0.03 % and Ti4+/SnO2@Sn4+/TiO2The photocatalytic activity of ~ 15.00 % is higher than pure TiO2, and ion doping material Sn4 +/TiO2The photocatalytic activity of ~ 0.03 % is higher than semiconductor coupling, ion contra-doping material Ti4+/SnO2@Sn4+/TiO2~15.00
%.Be can be seen that by Fig. 4 b：MB solution is in sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO2~15.00 %
On ln (C 0 /C t) withtSubstantially linear, i.e., photocatalytic degradation obeys first order kinetics behavior；Can be obtained by the slope of straight line
First order kinetics speed constantk 1Value（It is listed in Table 1 below）, and byk 1Value understands：Sn4+/TiO2The photocatalytic activity of ~ 0.03 % is approximately
Pure TiO22.8 times, Ti4+/SnO2@Sn4+/TiO2~ 15.00 % are approximately pure TiO21.8 times.
Table 1
| Sample | |||
| 0.104 | 0.292 | 0.188 | |
| Sample | |||
| 0.025 | 0.036 | 0.092 |
Fig. 5 is SnO2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO2The photocatalytic degradation MB solution of ~ 25.00 %D t
% ~ tAnd ln (C 0 /C t) ~ tResult.Again it can be seen that Ti4+/SnO2~ 0.03 % and Sn4+/TiO2@Ti4+/SnO2~
The photocatalytic activity of 25.00 % is higher than pure SnO2；Ti4+/SnO2~ 0.03 % and Sn4+/TiO2@Ti4+/SnO2~ 25.00 % are catalyzed
Activity is raised successively, and sample Sn4+/TiO2@Ti4+/SnO2The catalysis activity of ~ 25.00 % is elevated significantly.Similarly, MB is molten
Liquid is in sample SnO2、Ti4+/ SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO2Photocatalytic degradation on ~ 25.00 % is obeyed
First order kinetics behavior, and Ti4+/SnO2The speed constant of ~ 0.03 % is approximately pure SnO21.4 times；Sn4+/TiO2@Ti4+/SnO2
~ 25.00 % are pure SnO2Nearly 3.7 times.
Above sample to the difference of the Photocatalytic Degradation Property of MB solution except the band structure with material, lattice defect,
The factors such as crystal property, composition, content have outside the Pass, should also be relevant with the photocatalysis performance of each component.
In sum, the present invention has advantages below compared with the prior art：
1st, the present invention is with SnCl4·5H2O、Ti(OC4H9)4It is raw material, with degreasing cotton fiber CF as template, ethanol EtOH is molten
Agent, the dipping-calcining two-step method aided in using template is obtained SnO2、TiO2Semiconductor coupling, ion contra-doping photocatalytic nanometer
Fibrous material Ti4+/SnO2-Sn4+/TiO2；XRD results are fully demonstrated under proper condition, are realizing semi-conducting material coupling
While, it is possible to achieve the contra-doping of ion, is the catalysis for further more illustrating semiconductor coupling catalysis material comprehensively
Journey provides experiment basis, while for the foundation of ion contra-doping concept and theory provides reliable experimental basis；
2nd, the present invention is by regulating and controlling Ti (OC4H9)4And SnCl4·5H2The consumption of O, the SnO for preparing2、TiO2Semiconductor coupling,
Ion contra-doping photocatalytic nanometer fibrous material Sn4+/TiO2-Ti4+/SnO2Photocatalytic activity be above pure SnO2And TiO2；
3rd, preparation process is simple of the present invention, without other any additive, low cost, environmental protections.
Brief description of the drawings
Fig. 1 is sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO2The XRD of ~ 15.00 %.
Fig. 2 is sample SnO2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO2The XRD of ~ 25.00 %.
Fig. 3 is sample TiO2(a)、Sn4+/TiO2~0.03 %(b)、Ti4+/SnO2@Sn4+/TiO2~15.00 %(c)、SnO2
(d)、Ti4+/SnO2~0.03 %(e)、Sn4+/TiO2@Ti4+/SnO2The SEM figures of ~ 25.00 % (f).
Fig. 4 is MB solution in sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO2~ 15.00 % glazings
Catalytic degradationD t % ~ t、ln(C 0 /C t) ~ t。
Fig. 5 is MB solution in sample SnO2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO2~ 25.00 % glazings are urged
Change degradedD t % ~ t、ln(C 0 /C t) ~ t。
Specific embodiment
Preparation below by specific embodiment to series of samples in the present invention is described further.
Embodiment 1, Sn4+/TiO2The preparation of ~ 0.03 %
Under conditions of magnetic agitation, the Ti (OC of 1.5000 g are added in 75.00 mL EtOH4H9)4, obtain solution A Ti
(OC4H9)4/EtOH；According to Sn in solution A4+The amount content of material is that 0.03 % adds SnCl4·5H2O, obtains mixed solution：
(SnCl4+Ti(OC4H9)4)/EtOH；The CF of 1.2000 g is soaked into 30 min in mixed solution, makes Sn4+、Ti4+On CF surfaces
Absorption；Take out and spontaneously dried in air, obtain final product precursor material (Sn4++Ti4+)/CF；By precursor material (Sn4++Ti4+)/CF exists
600 DEG C of 120 min of calcining, naturally cool to room temperature, and Sn is obtained4+ The TiO of ion doping2Doughnut structural material Sn4+/
TiO2~0.03 %。
Comparative example：Pure TiO2Preparation：Under conditions of magnetic agitation, 1.5000 g are added in 75.00 mL EtOH
Ti (OC4H9)4, obtain solution A Ti (OC4H9)4/EtOH；The CF of 1.2000 g is soaked into 30 min in solution A, makes Ti4+Ion
In CF adsorptions；Take out and spontaneously dried in air, obtain final product precursor material Ti4+/CF；By precursor material Ti4+/ CF is 600
DEG C calcining 120 min, naturally cool to room temperature, obtain final product pure TiO2Doughnut structural material.
With pure TiO2Compare, sample Sn4+/TiO2XRD in main diffraction maximum 0.08 ° of position is there occurs to low diffraction angular direction
Move（See Fig. 1 b）；Sn4+/TiO2The catalysis activity of ~ 0.03 % is pure TiO22.8 times（It is shown in Table 1）.
Embodiment 2, Ti4+/SnO2~ 0.03% preparation
Under conditions of magnetic agitation, the SnCl of 1.5000 g is added in 75.00 mL EtOH4·5H2O, obtains B solution
SnCl4/EtOH；Again according to Ti in B solution4+The amount content of material add Ti (OC for 0.03 %4H9)4, obtain mixed solution
(Ti(OC4H9)4+SnCl4)/EtOH；The CF of 1.2000 g is soaked into 30 min in mixed solution, makes Sn4+、Ti4+Ion is in CF
Adsorption, takes out and is spontaneously dried in air, obtains final product precursor material (Sn4++Ti4+)/CF；By precursor material (Sn4++Ti4+)/
CF calcines 120 min at 600 DEG C, naturally cools to room temperature, you can Ti is obtained4+The SnO of ion doping2Doughnut structure
Material Ti4+/SnO2~0.03 %。
Comparative example：Pure SnO2Preparation：Under conditions of magnetic agitation, 1.5000 g are added in 75.00 mL EtOH
SnCl4·5H2O, obtains B solution SnCl4/EtOH；The CF of 1.2000 g is soaked into 30 min in B solution, makes Sn4+Ion exists
CF adsorptions, take out and are spontaneously dried in air, obtain final product precursor material Sn4+/CF；By precursor material Sn4+/ CF is at 600 DEG C
120 min of lower calcining, naturally cool to room temperature, you can pure SnO is obtained2Doughnut structural material.
With pure SnO2Compare, sample Ti4+/SnO2Main diffraction maximum there occurs to diffraction angular direction high in the XRD of ~ 0.03 %
0.41 ° of displacement（See Fig. 2 b）；Ti4+/SnO2The catalysis activity of ~ 0.03 % is pure SnO21.4 times（It is shown in Table 1）.
Embodiment 3, ion contra-doping, semiconductor coupling material Ti4+/SnO2@Sn4+/TiO2Preparation
Under conditions of magnetic agitation, the Ti (OC of 1.5000 g are added in 75.00 mL EtOH4H9)4, obtain solution A Ti
(OC4H9)4/EtOH；According to SnO in solution A2Material amount content for 15.00 % add SnCl4·5H2O, must mix molten
Liquid：(SnCl4+Ti(OC4H9)4)/EtOH；The CF of 1.2000 g is soaked into 30 min in mixed solution, makes Sn4+、Ti4+In CF
Adsorption；Take out and spontaneously dried in air, obtain final product precursor material (Sn4++Ti4+)/CF；By precursor material (Sn4++Ti4+)/
CF calcines 120 min at 600 DEG C, naturally cools to room temperature, is obtained with TiO2It is ion contra-doping, the TiO of main body phase2And SnO2
Coupling doughnut structural material Ti4+/SnO2@Sn4+/TiO2~15.00 %。
With pure TiO2Compare, in sample Ti4+/SnO2@Sn4+/TiO2In the XRD of ~ 15.00 %, main body phase TiO2Main diffraction
Peak there occurs 0.15 ° of displacement to low diffraction angular direction（See Fig. 1 b）, illustrate the metal ion Sn of object phase4+Enter into TiO2's
In lattice；Ti4+/SnO2@Sn4+/TiO2The catalysis activity of ~ 15.00 % is pure TiO21.8 times（It is shown in Table 1）.
Embodiment 4, ion contra-doping, semiconductor coupling material Sn4+/TiO2@Ti4+/SnO2Preparation
Under conditions of magnetic agitation, the SnCl of 1.5000 g is added in 75.00 mL EtOH4·5H2O, obtains B solution
SnCl4/EtOH；According to TiO in B solution2The amount content of material add Ti (OC for 25.00 %4H9)4, obtain mixed solution
(Ti(OC4H9)4+SnCl4)/EtOH；The CF of 1.2000 g is soaked into 30 min in mixed solution, makes Sn4+、Ti4+Ion is in CF
Adsorption, takes out and is spontaneously dried in air, obtains final product precursor material (Sn4++Ti4+)/CF；By precursor material (Sn4++Ti4+)/
CF calcines 120 min at 600 DEG C, naturally cools to room temperature, you can be obtained with SnO2For main body phase it is ion contra-doping,
TiO2And SnO2Coupling doughnut structural material Sn4+/TiO2@Ti4+/SnO2~25.00 %。
With pure SnO2Compare, in sample Sn4+/TiO2@Ti4+/SnO2Main body phase SnO in the XRD of ~ 25.00 %2Main diffraction
Peak there occurs 0.33 ° of displacement to diffraction angular direction high（See Fig. 2 b）, illustrate the metal ion Ti of object phase4+Enter SnO2's
In lattice；Sn4+/TiO2@Ti4+/SnO2The catalysis activity of ~ 25.00 % is pure SnO23.7 times（It is shown in Table 1）.
Claims (5)
1.SnO2、TiO2The preparation method of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material, is that absorbent cotton is fine
Dimension is in SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in soak 25 ~ 35 min, make Sn4+、Ti4+Uniform adsorption is in CF tables
Face, natural drying can obtain precursor material (Sn4++Ti4+)/CF；By the precursor material in calcining 110 ~ 130 at 590 ~ 610 DEG C
Min can obtain SnO to remove cotton fiber template2、TiO2Semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material.
2. SnO as claimed in claim 12、TiO2The preparation side of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material
Method, it is characterised in that：In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Sn4+Material amount content for 0.02 ~
During 0.04 %, there is no SnO2The formation of phase, obtains Sn4+The TiO of doping2Hollow Nano fiber in use structural material Sn4+/TiO2。
3. SnO as claimed in claim 12、TiO2The preparation side of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material
Method, it is characterised in that：In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Ti4+Material amount content for 0.02 ~
During 0.04 %, there is no TiO2The formation of phase, obtains Ti4+The SnO of doping2Hollow Nano fiber in use structural material Ti4+/SnO2。
4. SnO as claimed in claim 12、TiO2The preparation side of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material
Method, it is characterised in that：In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Sn4+Material amount content for 14.50 ~
During 15.50 %, there is SnO2Mutually generate, obtain with TiO2Semiconductor coupling, ion contra-doping hollow Nano fiber in use structure for main body
Material Ti4+/SnO2@Sn4+/TiO2。
5. SnO as claimed in claim 12、TiO2The preparation side of semiconductor coupling, ion contra-doping photocatalytic nanometer fibrous material
Method, it is characterised in that：In SnCl4·5H2O and Ti (OC4H9)4Ethanol solution in, Ti4+Material amount content for 24.50 ~
During 25.50 %, there is TiO2Mutually generate, obtain with SnO2Semiconductor coupling, ion contra-doping hollow Nano fiber in use structure for main body
Material Sn4+/TiO2@Ti4+/SnO2。
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