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 182
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- 238000010168 coupling process Methods 0.000 title claims abstract description 29
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 29
- 239000004065 semiconductor Substances 0.000 title claims abstract description 29
- 230000008878 coupling Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002657 fibrous material Substances 0.000 title abstract 2
- 150000002500 ions Chemical class 0.000 title description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title description 6
- 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 199
- 239000000463 material Substances 0.000 claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920000742 Cotton Polymers 0.000 claims abstract description 43
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000007146 photocatalysis Methods 0.000 claims abstract description 17
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 10
- 239000002121 nanofiber Substances 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000005238 degreasing Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 93
- 239000000243 solution Substances 0.000 description 29
- 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
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000012510 hollow fiber Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- -1 Methylene Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 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
- 238000004519 manufacturing process Methods 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
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- 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
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
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- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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 invention relates to preparation of an ion-doped fiber structure photocatalytic nano material, in particular to SnO2、TiO2A preparation method of semiconductor coupling and ion counter doping photocatalysis nano fiber material belongs to the photocatalysis technical field.
Background
SnO2And TiO2Due to the advantages of good chemical stability, high catalytic activity, strong oxidation resistance and the like, the application of the photocatalyst is prominent in the aspect of photocatalysis. But since they are wide band gap semiconductors (SnO)2：Eg = 3.5 eV，TiO2：Eg = 3.2 eV), only excited by uv light, whereas the uv light of the sun is only around 5%, plus its photo-generated chargee --h +The recombination rate is high, thereby limiting the large-scale application of the composite material. Doping of metal ions and semiconductor coupling are two common modification methods at present. Researchers have ignored the presence of an important phenomenon, ion counter-doping, when studying semiconductor coupling. For example, numerous studies have demonstrated that in the preparation of TiO2If another metal ion (e.g. Fe) is present in the process3+），Fe3+Ions will enter into TiO automatically2In the crystal lattice of (1), thereby realizing TiO2Medium metal ion Fe3+Doping of (3). Of course, different preparation methods can be adopted to realize the metal ion Fe3+In TiO2Different distributions of (a). For example, in semiconductor TiO2And Fe2O3Coupling material TiO2-Fe2O3In the preparation of (1), if at TiO2With Fe when phase forms3+Is present, or Fe2O3With Ti as phase forms4+In the presence of the coupling material TiO thus obtained2-Fe2O3Must have a counter-doping phenomenon of ions, i.e. Fe3+Ion introduction into TiO2Phase of Ti4+Ion introduction into Fe2O3Phase (c). The counter doping of metal ions and the coupling of semiconductors can not only change the energy band structure of the metal ions, but also introduce different structural defects into the crystal lattice of a sample, thereby being beneficial to widening the absorption range of light and the photogeneratione --h +The separation of the pairs improves the photocatalytic performance of the photocatalyst.
Disclosure of Invention
The invention provides SnO2、TiO2The preparation method of the semiconductor coupling photocatalysis nanofiber material proves that the semiconductor coupling SnO2-TiO2The existence of ion counter-doping phenomenon in the material.
Preparation of photocatalytic nanofiber material
SnO according to the invention2、TiO2The preparation method of semiconductor coupling and ion counter-doping photocatalysis nano-fiber material is characterized by that the absorbent Cotton Fiber (CF) is placed in SnCl4·5H2O and Ti (OC)4H9)4Soaking the Sn in the ethanol solution for 25 to 35 min to ensure that the Sn is dissolved in the Sn4+、Ti4+Adsorbing on the surface of cotton fiber, and naturally drying to obtain precursor material (Sn)4++Ti4+) (ii)/CF; then calcining the precursor material at 590-610 ℃ for 110-130 min to remove the template, thus obtaining SnO2、TiO2Semiconductor device and method for manufacturing the sameCoupling and ion counter-doping the photocatalytic nanofiber material.
In SnCl4·5H2O and Ti (OC)4H9)4In an ethanol solution of (3), Sn4+When the content of the substances is 0.02-0.04%, SnO does not exist2Formation of a phase to obtain Sn4+Doped TiO2Hollow nano fiber structure photocatalysis material Sn4+/TiO2。
In SnCl4·5H2O and Ti (OC)4H9)4In an ethanol solution of (2), Ti4+When the amount of the substance(s) is 0.02-0.04%, no TiO is present2Phase formation to obtain Ti4+Doped SnO2Photocatalytic material Ti with hollow nanofiber structure4+/SnO2。
In SnCl4·5H2O and Ti (OC)4H9)4In an ethanol solution of (3), Sn4+When the amount of the substances is 14.50-15.50%, the SnO is ensured2Formation of a phase to give a crystalline TiO2Mainly SnO2And TiO2Coupling and ion counter-doping hollow nanofiber structure photocatalytic material Ti4+/SnO2@Sn4+/TiO2。
In SnCl4·5H2O and Ti (OC)4H9)4In an ethanol solution of (2), Ti4+When the content of the substance is 24.50-25.50%, the TiO is ensured2Formation of phases to obtain SnO2Mainly SnO2And TiO2Coupling and ion counter-doping hollow nanofiber structure photocatalytic material Sn4+/TiO2@Ti4+/SnO2。
Structural characterization of photocatalytic nanofiber material
FIG. 1 shows sample TiO2、Sn4+/TiO20.03% and Ti4+/SnO2@Sn4+/TiO215.00% XRD results. As can be seen from FIG. 1a, three typesAnatase type TiO is appeared in XRD of the sample2(A-TiO2) (which is completely coincident with JCPDSNo. 21-1272), but the intensity of the diffraction peak is determined by TiO2、Sn4+/TiO20.03% and Ti4+/SnO2@Sn4+/TiO2Decrease in order of 15.00% (Ti)4+/SnO2@Sn4+/TiO2Especially significant 15.00%); in contrast to TiO2Sample Sn4+/TiO20.03% and Ti4+/SnO2@Sn4+/TiO215.00% of diffraction peaks toward lower diffraction angle (2)θ) The direction was displaced (respectively: 25.31 ° → 25.23 °, shifted by 0.08 °; 25.31 ° → 25.16 °, shifted by 0.15 ° (see fig. 1 b). In addition, sample Ti4+/SnO2@Sn4+/TiO2SnO is also generated in XRD of 15.00 percent2The diffraction peak of (1) indicates that TiO is simultaneously contained in the sample2And SnO2The presence of a phase.
FIG. 2 shows a sample SnO2、Ti4+/SnO20.03% and Sn4+/TiO2@Ti4+/SnO2XRD results of 25.00%. It can also be seen that SnO is present in the XRD of all three samples2The diffraction peak intensity of the compound is determined according to SnO (stannic oxide) and is completely consistent with standard card JCPDS No.41-14452、Ti4+/SnO20.03% and Sn4+/TiO2@Ti4+/SnO2Slightly weakening 25.00%; in contrast to SnO2Sample Ti4+/SnO20.03% and Sn4+/TiO2@Ti4+/SnO2Diffraction peak direction high diffraction angle (2) of 25.00%θ) The direction is significantly displaced (26.20 ° → 26.61 °, respectively, shifted by 0.41 °; 26.20 ° → 26.53 °, shifted by 0.33 ° (see fig. 2 b). Similarly, sample Sn4+/TiO2@Ti4+/SnO225.00% of XRD, A-TiO also appears2Indicating that there is SnO in the sample simultaneously2And TiO2The presence of a phase.
Where the diffraction peak intensity is dominantThe crystal property and the lattice defect of the sample are related. Sn (tin)4+(0.0690 nm) and Ti4 +(0.0605 nm) have relatively similar ionic radii. From sample Sn4+/TiO20.03% (see FIG. 1) and Ti4+/SnO2XRD results of-0.03% (see FIG. 2) show that Sn4+Into TiO2And replaces a portion of the smaller radius Ti4+Result in TiO2The deformation of the unit cell is increased to shift the diffraction peak to the low diffraction angle direction and simultaneously make TiO2The crystallization property of (2) is lowered; and Ti4+Into SnO2By replacing a part of Sn with a larger radius4+Result in SnO2The deformation of the unit cell is reduced, so that the diffraction peak is shifted to the direction of high diffraction angle, and SnO is enabled2The crystallization property of (a) is slightly lowered. It is further worth pointing out that: sample Ti4+/SnO2@Sn4+/TiO215.00% of medium TiO2The diffraction peak of (B) is also shifted toward the direction of low diffraction angle, and the sample Sn4+/TiO2@Ti4+/SnO225.00% of medium SnO2The diffraction peak of (a) is shifted toward a high diffraction angle direction. The results show that: in sample Ti4+/SnO2@Sn4+/TiO215.00% of medium Sn4+In the formation of a guest phase SnO2At the same time, there is a part of Sn4+Ion into bulk phase TiO2In (1), i.e. sample Ti4+/SnO2@Sn4+/TiO2TiO of main body phase of 15.00 percent2Metal ion Sn which is actually in guest phase4+And (4) doping. Likewise, sample Sn4+/TiO2@Ti4+/SnO225.00% of medium-bulk phase SnO2Metal ions Ti being substantially in the guest phase4+And (4) doping. It is conceivable that the metal ion of the host phase enters the guest phase naturally.
FIG. 3 shows 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+/SnO2SEM image of 25.00% (f). As can be seen from the SEM images, the samples produced all replicated the morphology of the cotton fibers, with a hollow fiber structure (caused by the removal of the template); sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO215.00% of the fiber walls are relatively compact and have slight cracks; while the sample SnO2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO225.00 percent of fiber walls present a porous structure and are obviously cracked (sample SnO)2And Ti4+/SnO2Especially significant 0.03%). The results show that: metallic ion Sn4+And Ti4+Different adsorption properties on the surface of cotton fibers, Ti4+Is relatively Sn4+The fiber is easier to be adsorbed on the surface of the cotton fiber to form a denser adsorption layer, so that the fiber wall forming the target material is denser.
Third, the photocatalysis performance of the photocatalysis nanofiber material
The photocatalytic performance of the series of materials developed by the invention is characterized by utilizing the photocatalytic degradation and decoloration of Methylene Blue (MB) solution.
Photocatalytic degradation experiment: dispersing 40 mg sample in 40 mL of 10 mg.L-1Methylene Blue (MB) solution of (a); stirring for 30min in a dark state, performing a photocatalytic degradation decolorization experiment under the irradiation condition of a 300W Mercury Lamp (ML) after reaching absorption-desorption equilibrium; 5 mL of the supernatant was sampled at regular intervals, immediately centrifuged to remove solid samples, and the absorbance of the supernatant at 664 nm (the maximum absorption wavelength of MB) was measured with a spectrophotometerA tDecolorization rate of MB solution on sampleD t% and ln: (C 0/C t) Over timetThe photocatalytic performance of the sample and the degradation kinetic behavior of the MB molecules on the sample surface were studied.
Decoloring rate:D t(%) = [(A 0-A t)/A 0]× (100%), first order kinetic equation ln: (100%)C 0/C t)(≈ln(A 0/A t) =k 1 t. Wherein,A 0andA t、C 0andC trespectively, the initial and light time of the MB solution istAbsorbance and concentration values.
FIG. 4 shows sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO215.00% of MB solution photocatalytic degradationD t% ~tAnd ln (C 0 /C t) ~tThe result of (1). As can be seen from fig. 4, under the irradiation of 300W Hg (dominant wavelength is 365 nm) ultraviolet light, all samples have significant photocatalytic effect on degradation and decoloration of MB solution; modified material Sn4+/TiO20.03% and Ti4+/SnO2@Sn4+/TiO215.00% of photocatalytic activity higher than that of pure TiO2And ion-doping the material Sn4 +/TiO20.03% of photocatalytic activity higher than that of semiconductor coupling and ion counter doping material Ti4+/SnO2@Sn4+/TiO215.00 percent. As can be seen from fig. 4 b: MB solution in sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO2To 15.00% of ln: (C 0 /C t) Andtthe substantially linear relationship, that is, photocatalytic degradation follows first order kinetic behavior; first order kinetic rate constant obtained from slope of straight linek 1Values (listed in Table 1) and are obtained fromk 1The value is known as: sn (tin)4+/TiO2About 0.03% photocatalytic activity of about pure TiO22.8 times of that of Ti4+/SnO2@Sn4+/TiO2About 15.00% of about pure TiO21.8 times of the total weight of the powder.
TABLE 1
| Sample (I) | |||
| 0.104 | 0.292 | 0.188 | |
| Sample (I) | |||
| 0.025 | 0.036 | 0.092 |
FIG. 5 is SnO2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO225.00% of MB solution photocatalytic degradationD t% ~tAnd ln (C 0 /C t) ~tThe result of (1). It can also be seen that Ti4+/SnO20.03% and Sn4+/TiO2@Ti4+/SnO225.00% of photocatalysisThe activity is higher than that of pure SnO2；Ti4+/SnO20.03% and Sn4+/TiO2@Ti4+/SnO2To 25.00 percent of catalytic activity is increased in sequence, and the sample Sn4+/TiO2@Ti4+/SnO2And the catalytic activity is obviously improved by 25.00 percent. Similarly, MB solution in sample SnO2、Ti4+/ SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO2Photocatalytic degradation of 25.00% obeys first order kinetic behavior, and Ti4+/SnO2About pure SnO with a rate constant of 0.03%21.4 times of; sn (tin)4+/TiO2@Ti4+/SnO225.00% of pure SnO2Approximately 3.7 times higher.
The difference of the photocatalytic degradation performance of the MB solution of the samples is related to factors such as an energy band structure, lattice defects, crystallization performance, composition, content and the like of the material, and also related to the photocatalytic performance of each component.
In summary, the present invention has the following advantages over the prior art:
1. the invention uses SnCl4·5H2O、Ti(OC4H9)4The SnO is prepared by taking absorbent cotton fiber CF as a template and ethanol EtOH as a solvent through a template-assisted two-step dipping-calcining method2、TiO2Semiconductor coupling and ion counter doping photocatalysis nanofiber material Ti4+/SnO2-Sn4+/TiO2(ii) a The XRD result fully proves that under proper conditions, the counter doping of ions can be realized while the coupling of the semiconductor material is realized, an experimental basis is provided for further comprehensively describing the catalytic process of the semiconductor coupling photocatalytic material, and a reliable experimental basis is provided for the establishment of the counter doping concept and theory of ions;
2. the invention regulates and controls Ti (OC)4H9)4And SnCl4·5H2O amount, prepared SnO2、TiO2Semiconductor coupling, ion counter dopingHetero-photocatalysis nanofiber material Sn4+/TiO2-Ti4+/SnO2The photocatalytic activity of the composite is higher than that of pure SnO2And TiO2；
3. The invention has simple preparation process, no other additives, low cost and environmental protection.
Drawings
FIG. 1 shows sample TiO2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO215.00% XRD pattern.
FIG. 2 shows a sample SnO2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO225.00% XRD pattern.
FIG. 3 shows 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+/SnO2SEM image of 25.00% (f).
FIG. 4 shows the MB solution in TiO sample2、Sn4+/TiO2~0.03 %、Ti4+/SnO2@Sn4+/TiO215.00% of photocatalytic degradationD t% ~t、ln(C 0 /C t) ~t。
FIG. 5 shows the SnO concentration of MB solution in a sample2、Ti4+/SnO2~0.03 %、Sn4+/TiO2@Ti4+/SnO225.00% of photocatalytic degradation by lightD t% ~t、ln(C 0 /C t) ~t。
Detailed Description
The preparation of the series of samples according to the invention is further illustrated by the following specific examples.
Example 1, Sn4+/TiO20.03% preparation
Under magnetic stirring, 1.5000 g of Ti (OC) was added to 75.00 mL of EtOH4H9)4Obtaining solution A Ti (OC)4H9)4EtOH; in solution A according to Sn4+SnCl is added into the mixture with the mass content of 0.03 percent4·5H2And O, obtaining a mixed solution: (SnCl)4+Ti(OC4H9)4) EtOH; soaking 1.2000 g CF in the mixed solution for 30min to make Sn4+、Ti4+Adsorbing on the CF surface; taking out of the air and naturally drying to obtain the precursor material (Sn)4++Ti4+) (ii)/CF; precursor material (Sn)4++Ti4+) calcining/CF at 600 deg.C for 120 min, naturally cooling to room temperature to obtain Sn4+Ionically doped TiO2Hollow fiber structure material Sn4+/TiO2~0.03 %。
Comparative example: pure TiO2The preparation of (1): under magnetic stirring, 1.5000 g of Ti (OC) was added to 75.00 mL of EtOH4H9)4Obtaining solution A Ti (OC)4H9)4EtOH; soaking 1.2000 g CF in solution A for 30min to obtain Ti4+Ions are adsorbed on the CF surface; taking out of the air and naturally drying to obtain the precursor material Ti4+(ii)/CF; adding a precursor material Ti4+Calcining CF at 600 deg.C for 120 min, and naturally cooling to room temperature to obtain pure TiO2A hollow fiber structural material.
With pure TiO2Comparative sample Sn4+/TiO2Has a 0.08 ° shift of the main diffraction peak to the low diffraction angle direction (see fig. 1 b); sn (tin)4+/TiO20.03% of catalytic activity of pure TiO22.8 times (see table 1).
Example 2 Ti4+/SnO20.03% preparation
1.5000 g of SnCl was added to 75.00 mL of EtOH with magnetic stirring4·5H2O to obtain B solution SnCl4EtOH; in solution B according to Ti4+The amount of the substance(s) is 0.03% by adding Ti (OC)4H9)4Obtaining a mixed solution (Ti (OC)4H9)4+SnCl4) EtOH; soaking 1.2000 g CF in the mixed solution for 30min to make Sn4+、Ti4+Adsorbing ions on the CF surface, taking out the CF surface and naturally drying the CF surface in the air to obtain the precursor material (Sn)4++Ti4+) (ii)/CF; precursor material (Sn)4++Ti4+) calcining/CF at 600 deg.C for 120 min, and naturally cooling to room temperature to obtain Ti4+Ion-doped SnO2Hollow fiber structure material Ti4+/SnO2~0.03 %。
Comparative example: pure SnO2The preparation of (1): 1.5000 g of SnCl was added to 75.00 mL of EtOH with magnetic stirring4·5H2O to obtain B solution SnCl4EtOH; soaking 1.2000 g CF in the solution B for 30min to make Sn4+Adsorbing ions on the surface of CF, taking out the CF and naturally drying the CF in the air to obtain the precursor Sn4+(ii)/CF; precursor material Sn4+calcining/CF at 600 deg.C for 120 min, and naturally cooling to room temperature to obtain pure SnO2A hollow fiber structural material.
With pure SnO2Comparative sample Ti4+/SnO20.03% of XRD, the main diffraction peak is shifted to 0.41 degrees in the direction of high diffraction angle (see figure 2 b); ti4+/SnO20.03% of pure SnO21.4 times (see table 1).
Example 3 ion counter-doped, semiconducting coupling material Ti4+/SnO2@Sn4+/TiO2Preparation of
Under magnetic stirring, 1.5000 g of Ti (OC) was added to 75.00 mL of EtOH4H9)4Obtaining solution A Ti (OC)4H9)4EtOH; according to SnO in solution A2The amount of the substance(s) is 15.00 percent, SnCl is added4·5H2And O, obtaining a mixed solution: (SnCl)4+Ti(OC4H9)4) EtOH; soaking 1.2000 g CF in the mixed solution for 30min to make Sn4+、Ti4+Adsorbing on the CF surface; taking out of the air and naturally drying to obtain the precursor material (Sn)4++Ti4+) (ii)/CF; precursor material (Sn)4++Ti4+) calcining/CF at 600 deg.C for 120 min, and naturally cooling to room temperature to obtain TiO2Counter-doping of ions, TiO, as host phase2And SnO2Coupled hollow fiber structure material Ti4+/SnO2@Sn4+/TiO2~15.00 %。
With pure TiO2In contrast, in sample Ti4+/SnO2@Sn4+/TiO2Major phase TiO in XRD of 15.00%2The main diffraction peak of (A) is shifted by 0.15 DEG in the direction of low diffraction angle (see FIG. 1 b), indicating that the metal ion Sn in the guest phase is4+Into the TiO2In the crystal lattice of (a); ti4+/SnO2@Sn4+/TiO215.00% of pure TiO in catalytic activity21.8 times (see table 1).
Example 4 ion counter-doping, semiconductor coupling Material Sn4+/TiO2@Ti4+/SnO2Preparation of
1.5000 g of SnCl was added to 75.00 mL of EtOH with magnetic stirring4·5H2O to obtain B solution SnCl4EtOH; according to TiO in solution B2In an amount of 25.00% by weight of Ti (OC) is added4H9)4Obtaining a mixed solution (Ti (OC)4H9)4+SnCl4) EtOH; soaking 1.2000 g CF in the mixed solution for 30min to make Sn4+、Ti4+Adsorbing ions on the CF surface, taking out the CF surface and naturally drying the CF surface in the air to obtain the precursor material (Sn)4++Ti4+) (ii)/CF; precursor material (Sn)4++Ti4+) calcining/CF at 600 deg.C for 120 min, and naturally cooling to room temperature to obtain SnO2Ionic counter-doped, TiO as host phase2And SnO2Coupled hollow fiber structure material Sn4+/TiO2@Ti4+/SnO2~25.00 %。
With pure SnO2In contrast, in sample Sn4+/TiO2@Ti4+/SnO225.00% of SnO in bulk phase in XRD2The main diffraction peak of (A) is shifted by 0.33 DEG in the high diffraction angle direction (see FIG. 2 b), indicating that the metal ion Ti in the guest phase is present4+Enter SnO2In the crystal lattice of (a); sn (tin)4+/TiO2@Ti4+/SnO225.00% of pure SnO23.7 times (see table 1).
Claims (5)
1.SnO2、TiO2The preparation method of semiconductor coupling and ion counter-doping photocatalysis nano-fiber material is characterized by that the absorbent cotton fiber is placed in SnCl4·5H2O and Ti (OC)4H9)4Soaking the Sn in the ethanol solution for 25 to 35 min to ensure that the Sn is dissolved in the Sn4+、Ti4+Uniformly adsorbed on the CF surface, and naturally dried to obtain the precursor material (Sn)4++Ti4+) (ii)/CF; calcining the precursor material at 590-610 ℃ for 110-130 min to remove the cotton fiber template, thus obtaining SnO2、TiO2Semiconductor coupled, ion counter-doped lightA catalytic nanofiber material.
2. The SnO of claim 12、TiO2The preparation method of the semiconductor coupling and ion counter-doping photocatalysis nanofiber material is characterized by comprising the following steps of: in SnCl4·5H2O and Ti (OC)4H9)4In an ethanol solution of (3), Sn4+When the amount of the substance(s) is 0.02-0.04%, SnO is not present2Formation of a phase to obtain Sn4+Doped TiO2Hollow nanofiber structure material Sn4+/TiO2。
3. The SnO of claim 12、TiO2The preparation method of the semiconductor coupling and ion counter-doping photocatalysis nanofiber material is characterized by comprising the following steps of: in SnCl4·5H2O and Ti (OC)4H9)4In an ethanol solution of (2), Ti4+When the amount of the substance(s) is 0.02-0.04%, TiO is not present2Formation of a phase to obtain Ti4+Doped SnO2Hollow nanofiber structure material Ti4+/SnO2。
4. The SnO of claim 12、TiO2The preparation method of the semiconductor coupling and ion counter-doping photocatalysis nanofiber material is characterized by comprising the following steps of: in SnCl4·5H2O and Ti (OC)4H9)4In an ethanol solution of (3), Sn4+When the amount of the substance(s) is 14.50-15.50%, SnO is contained2Phase formation to obtain the product of TiO2Semiconductor coupling and ion counter doping hollow nano fiber structure material Ti as main body4+/SnO2@Sn4+/TiO2。
5. The SnO of claim 12、TiO2The preparation method of the semiconductor coupling and ion counter-doping photocatalysis nanofiber material is characterized by comprising the following steps of: in SnCl4·5H2O andTi(OC4H9)4in an ethanol solution of (2), Ti4+When the amount of the substance(s) is 24.50-25.50%, TiO is present2Phase formation to obtain SnO2Semiconductor coupling and ion counter doping hollow nano fiber structure material Sn as main body4+/TiO2@Ti4+/SnO2。
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