CN106925254A - A kind of spherical titanium oxide/tin ash optoelectronic pole and its preparation method and application - Google Patents
A kind of spherical titanium oxide/tin ash optoelectronic pole and its preparation method and application Download PDFInfo
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- CN106925254A CN106925254A CN201710203263.6A CN201710203263A CN106925254A CN 106925254 A CN106925254 A CN 106925254A CN 201710203263 A CN201710203263 A CN 201710203263A CN 106925254 A CN106925254 A CN 106925254A
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- titanium oxide
- tin ash
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 98
- 239000002243 precursor Substances 0.000 claims abstract description 72
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000010936 titanium Substances 0.000 claims abstract description 46
- 238000001338 self-assembly Methods 0.000 claims abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000002356 single layer Substances 0.000 claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 44
- 239000010410 layer Substances 0.000 claims description 37
- 239000012528 membrane Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 8
- 230000006911 nucleation Effects 0.000 claims description 8
- 230000006798 recombination Effects 0.000 claims description 8
- 238000005215 recombination Methods 0.000 claims description 8
- 230000033228 biological regulation Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 238000007306 functionalization reaction Methods 0.000 claims description 7
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 229910019985 (NH4)2TiF6 Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910010252 TiO3 Inorganic materials 0.000 claims 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 238000005352 clarification Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 150000003384 small molecules Chemical class 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000013545 self-assembled monolayer Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
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- B01D2255/802—Photocatalytic
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The present invention provides a kind of spherical titanium oxide/tin ash optoelectronic pole and its preparation method and application, first configures TiO2Precursor liquid, then by SnO2/ glass substrate irradiates under ultraviolet light, makes SnO2/ glass baseplate surface forms hydroxyl monolayer, using hydroxyl monolayer and TiO2[Ti (OH) in precursor liquid6]2‑Between reverse polymerization reaction, LBL self-assembly reversely induces small molecule [Ti (OH)6]2‑, prepare amorphous glass/SnO2‑O‑TiO2Laminated film, is most incubated crystallization after 500 DEG C, that is, obtain spherical titanium oxide/tin ash optoelectronic pole.Present invention process process is simple and easy to control, relatively low, the TiO of preparation of experiment condition requirement2/SnO2Optoelectronic pole is high to the utilization rate of light, and current density is big, is suitably applied the organic pollution in photocatalytic degradation water or in air, is had broad application prospects in photocatalysis field.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of layer-by-layer of molecular recognition absorption prepares ball
Shape titanium oxide/tin ash optoelectronic pole and its preparation method and application.
Background technology
With the further expansion of commercial Application and life requirement, the type and quantity sharp increase of global chemicals.By
Use, discharge and leakage in chemicals etc., chemical pollutant is increasing in kind and quantity so that chemical contamination has been accounted for
80%~90% polluted according to total environment.Thus, in efficiently controlling and administer various chemical contaminations and being comprehensive environmental improvement
Emphasis, exploitation can be the key of environmental protection the innoxious practical technique of various chemical pollutants.Photocatalysis technology is one
Emerging green technology for administering chemical contamination, more traditional method has the advantages such as low cost, efficiency high, non-secondary pollution.
Photocatalysis technology is that surface can be by the characteristic of activation under light illumination by semiconductor oxide materials, can be effectively using luminous energy
Oxidation Decomposition organic matter, reducing heavy metal ion, killing bacterium and elimination peculiar smell.Because photocatalysis technology can be existed using solar energy
React at room temperature, both economical, photochemical catalyst itself is nontoxic, harmless, non-corrosiveness, can Reusability；Can be by organic dirt
Contaminate thing permineralization into H2O and inorganic ions, non-secondary pollution, so there is incomparable excellent of traditional environment Treatment process
Point, is a kind of green environment Treatment process with broad prospect of application.
TiO2Due to having the advantages that inexpensive, nontoxic, oxidability is strong, good stability, its energy gap is 3.2eV, is
Current most study and most widely used metal-oxide semiconductor (MOS) photochemical catalyst.TiO2It is a kind of multifunctional material, is urged in light
The aspects such as change, light degradation and novel solar battery have a wide range of applications.Meanwhile, TiO2It is mainly as n-type semiconductor and leans on
Photo-generated carrier (mainly light induced electron) is conductive.
SnO2It is a kind of metal semiconductor oxide of rutile (rutile) structure, spatial symmetry is P4/mnm.It is brilliant
Lattice constant a is 0.4731nm, and c is 0.31861nm.SnO2It is typical n-type semiconductor, band gap is 3.5-3.6eV.By SnO2With
TiO2It is combined, can be not only improved the separating effect in its light induced electron and hole, and recombination probability can be reduced, so that greatly
It is big to improve photocatalytic activity.
At present, TiO2/SnO2The preparation of optoelectronic pole mainly has following several method：The sun of sol-gel process, metal titanium sheet
Pole oxidizing process, the directly thermal oxidation method of metal titanium sheet, template auxiliary synthetic method etc..These methods are existed in terms of film is prepared
It is certain not enough.As membrane structure is unfavorable for photocatalytic degradation, repeatability is not high, and environmental pollution is big, with substrate combination degree loosely
Gu the shortcomings of, more or less existing cannot take into account " cleaning, energy-conservation, efficiently prepare photocatalysis film " this theory.
The content of the invention
It is an object of the invention to provide a kind of spherical titanium oxide/tin ash optoelectronic pole and its preparation method and application,
The method is obtained titanium oxide/tin ash optoelectronic pole, experiment condition relatively low, the obtained oxidation of requirement using layer-by-layer
Titanium/tin ash optoelectronic pole has response characteristics to light, can be used in photocatalysis degradation organic contaminant.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of spherical titanium oxide/tin ash optoelectronic pole, comprises the following steps：
1)TiO2The configuration of precursor liquid：
At room temperature, to addition (NH in deionized water4)2TiF6, stir to clarify, boric acid is subsequently adding, stir to clarify,
Dust technology is eventually adding, regulation pH value is stirred to clarify to 1~4, obtains TiO2Precursor liquid；(the NH for wherein adding4)2TiF6With
The mol ratio of boric acid is (1~3):(1~2)；
2)SnO2The functionalization of/glass substrate：
By SnO220~40min of irradiation under the ultraviolet light of 184.9nm is placed in after/glass substrate washes clean, makes SnO2/ glass
Glass substrate surface forms hydroxyl monolayer；
3) self assembly of film：
By SnO2The hydroxyl monolayer one side of/glass substrate is suspended in TiO2Precursor liquid surface carries out self assembly absorption, profit
With the hydroxyl layer and TiO of substrate surface2Precursor liquid small molecular [Ti (OH)6]2-In OH carry out polymerisation, heterogeneous nucleation from
Assembling forms amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film, then be dried at room temperature for, obtain glass/SnO2-O-
[TiO3H)]-Noncrystal membrane；
4) LBL self-assembly of film：
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates 20~40min under the ultraviolet light of 184.9nm, makes its table
Face forms hydroxyl monolayer, and the hydroxyl monolayer then is suspended in into TiO2Precursor liquid surface, to TiO2In precursor liquid
[Ti(OH)6]2-Self assembly polymerization absorption is carried out, glass/SnO is formed2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then
Dry at room temperature；Such repeated multiple times LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness2-O-TiO2It is multiple
Close film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace, and 250~550 DEG C, insulation are raised to from room temperature
60~180min, then naturally cool to room temperature, that is, obtain spherical titanium oxide/tin ash optoelectronic pole.
The step 1) middle addition (NH4)2TiF6Afterwards stirring 10~20min to clarify, add boric acid after stirring 20~
To clarifying, 10~20min of stirring is extremely clarified 40min after adding dust technology.
The step 1) in TiO2The concentration of Ti elements is 0.010~0.030mol/L in precursor liquid.
The step 3) and step 4) in TiO2The temperature of precursor liquid is 60~65 DEG C, time of self assembly polymerization for 10~
13h。
The step 3) and step 4) in drying time be 6~8h.
The step 9) in programming rate be 10~30 DEG C/min.
Spherical titanium oxide/tin ash light obtained in the preparation method of described spherical titanium oxide/tin ash optoelectronic pole
Electrode, TiO in the spherical titanium oxide/tin ash optoelectronic pole2Crystal formation be zincite type, with I41/amdSpatial symmetry,
SnO2Crystal formation be rutile-type, spatial symmetry is P4/mnm；TiO2Pattern be globular nanostructures, its spherical a diameter of 48
~73nm.
Under simulated solar light irradiation, the spherical titanium oxide/tin ash optoelectronic pole is produced under the conditions of 1.50V
0.11mA/cm2Current density.
Spherical titanium oxide/tin ash the optoelectronic pole after illumination starts density of photocurrent by 0.073mA/cm2Quickly
Decay to 0.050mA/cm2, photo-generate electron-hole is in optoelectronic pole/solution in the spherical titanium oxide/tin ash optoelectronic pole
Recombination probability during the surface recombination that interface occurs is 31.5%.
Described spherical titanium oxide/tin ash optoelectronic pole under visible light in terms of photocatalysis degradation organic contaminant should
With.
Relative to prior art, the invention has the advantages that：
The preparation method of spherical titanium oxide/tin ash optoelectronic pole that the present invention is provided, first configures TiO2Precursor liquid, then
By SnO2/ glass substrate irradiates under ultraviolet light, makes SnO2/ glass baseplate surface forms hydroxyl monolayer, using single point of hydroxyl
Sublayer and TiO2[Ti (OH) in precursor liquid6]2-Between reverse polymerization reaction, LBL self-assembly reversely induces small molecule [Ti
(OH)6]2-, prepare amorphous glass/SnO2-O-TiO2Laminated film, is most incubated crystallization after 500 DEG C, that is, obtain spherical oxygen
Change titanium/tin ash optoelectronic pole.Present invention process process is simple and easy to control, and experiment condition requirement is relatively low, by reverse adsorption liquid phase
LBL self-assembly method obtains the visible light-responded spherical TiO of tool2/SnO2Optoelectronic pole.Self-assembled monolayer (self-assembled
Monolayers, SAMs) technology is one and is referred from bionic new film technique, irradiated in substrate by short wave ultraviolet light
The orderly unimolecule hydroxyl adsorption layer spontaneously formed on interface, the hydroxyl adsorption layer of formation is spontaneous by chemical bond in atmosphere
Be firmly adsorbed on the ultra-thin hydroxyl film formed on substrate, spontaneously formed with original position, bonding high-sequential arrangement, defect
Less, adhesion it is strong, in " crystalline state " the features such as, it is adaptable to heterogeneous nucleation induction prepares inorganic material film, with preparation method
Simply, the advantages of film-formation result is good, stability is strong, thicknesses of layers is ultra-thin.
Spherical titanium oxide/tin ash optoelectronic pole prepared by the present invention is in globular nanostructures and is attached to substrate surface,
Specific surface area and organic matter adsorption capacity are effectively improved, so as to improve the photocatalysis effect of optoelectronic pole.And prepared by the present invention
TiO2/SnO2Optoelectronic pole has current density higher, and its photoelectric respone ability is good, and the utilization rate to light is high, current density
Greatly, the organic pollution in photocatalytic degradation water or in air is suitably applied, has wide application preceding in photocatalysis field
Scape.
Brief description of the drawings
Fig. 1 is spherical TiO prepared by the present invention2/SnO2The XRD of optoelectronic pole；
Fig. 2 is spherical TiO prepared by the present invention2/SnO2The SEM figures of optoelectronic pole；
Fig. 3 is spherical TiO prepared by the present invention2/SnO2The current -voltage curve of optoelectronic pole；
Fig. 4 is spherical TiO prepared by the present invention2/SnO2The time current curve of optoelectronic pole.
Specific embodiment
The present invention is described further with currently preferred specific embodiment below in conjunction with the accompanying drawings, raw material is analysis
It is pure.
Embodiment 1
1) configuration of precursor liquid：
To addition (NH in deionized water4)2TiF6, 10min is stirred to clarifying, boric acid is subsequently adding, stir at room temperature
30min is eventually adding dust technology to clarifying, and regulation pH value stirs 10min to clarifying to 2.9, obtains TiO2Precursor liquid；Wherein
(the NH for adding4)2TiF6It is 1 with the mol ratio of boric acid:1；TiO2The concentration of Ti elements is 0.010mol/L in precursor liquid；
2) functionalization of substrate：
By SnO2/ glass substrate is sequentially placed into supersound washing 10min in water, acetone, absolute ethyl alcohol.After washes clean
SnO2/ glass substrate irradiates 30min under being placed in the ultraviolet light of 184.9nm, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer, that is, obtain glass/SnO2-OH-Hydroxyl layer；
3) self assembly of film：
By glass/SnO2-OH-Hydroxyl layer is suspended in 65 DEG C of TiO2Precursor liquid surface self-organization adsorb 12h, using glass/
SnO2-OH-Hydroxyl layer and TiO2Precursor liquid small molecular [Ti (OH)6]2-With macromolecular [TiF6-n(OH)n]2-In OH gathered
Reaction is closed, wherein under gravity, macromolecular [TiF6-n(OH)n]2-Move down, be difficult and glass/SnO2-OH-Hydroxyl layer
Polymerisation, and small molecule [Ti (OH)6]2-Move up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
Close reaction heterogeneous nucleation and be self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film, the precursor thin film is existed
Dry 6 hours at room temperature, glass/SnO is obtained2-O-[TiO3H)]-Noncrystal membrane；
4) prepared by the LBL self-assembly of film：
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates after being dried at room temperature under the ultraviolet light of 184.9nm
20min, formation makes precursor thin film head end have the FTO-TiO of hydroxyl monolayer2-OH-TiO2-OH-Hydroxyl monolayer, then
The hydroxyl monolayer is suspended in 65 DEG C of TiO2Precursor liquid surface, to TiO2Small molecule [Ti (OH) in precursor liquid6]2-Enter
The self assembly absorption of row 12h, forms glass/SnO2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then does at room temperature
Dry 6h, such repeated multiple times LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2During laminated film is put into Muffle furnace after drying at room temperature, with 10 DEG C/min's
Programming rate is raised to 500 DEG C from room temperature, is incubated 120min, then naturally cools to room temperature, that is, obtain spherical titanium oxide/tin ash
Optoelectronic pole.
Embodiment 2
1) configuration of precursor liquid：
To addition (NH in deionized water4)2TiF6, 15min is stirred to clarifying, boric acid is subsequently adding, stir at room temperature
20min is eventually adding dust technology to clarifying, and regulation pH value stirs 15min to clarifying to 1, obtains TiO2Precursor liquid；Wherein plus
(the NH for entering4)2TiF6It is 3 with the mol ratio of boric acid:2；TiO2The concentration of Ti elements is 0.020mol/L in precursor liquid；
2) functionalization of substrate：
By SnO2/ glass substrate is sequentially placed into supersound washing 10min in water, acetone, absolute ethyl alcohol.After washes clean
SnO2/ glass substrate irradiates 20min under being placed in the ultraviolet light of 184.9nm, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer, that is, obtain glass/SnO2-OH-Hydroxyl layer；
3) self assembly of film：
By glass/SnO2-OH-Hydroxyl layer is suspended in 60 DEG C of TiO2Precursor liquid surface self-organization adsorb 13h, using glass/
SnO2-OH-Hydroxyl layer and TiO2Precursor liquid small molecular [Ti (OH)6]2-With macromolecular [TiF6-n(OH)n]2-In OH gathered
Reaction is closed, wherein under gravity, macromolecular [TiF6-n(OH)n]2-Move down, be difficult and glass/SnO2-OH-Hydroxyl layer
Polymerisation, and small molecule [Ti (OH)6]2-Move up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
Close reaction heterogeneous nucleation and be self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film, the precursor thin film is existed
Dry 8 hours at room temperature, glass/SnO is obtained2-O-[TiO3H)]-Noncrystal membrane；
4) prepared by the LBL self-assembly of film：
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates after being dried at room temperature under the ultraviolet light of 184.9nm
30min, formation makes precursor thin film head end have the FTO-TiO of hydroxyl monolayer2-OH-TiO2-OH-Hydroxyl monolayer, then
The hydroxyl monolayer is suspended in 60 DEG C of TiO2Precursor liquid surface, to TiO2Small molecule [Ti (OH) in precursor liquid6]2-Enter
The self assembly absorption of row 13h, forms glass/SnO2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then does at room temperature
Dry 8h, such repeated multiple times LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2During laminated film is put into Muffle furnace after drying at room temperature, with 20 DEG C/min's
Programming rate is raised to 250 DEG C from room temperature, is incubated 180min, then naturally cools to room temperature, that is, obtain spherical titanium oxide/tin ash
Optoelectronic pole.
Embodiment 3
1) configuration of precursor liquid：
To addition (NH in deionized water4)2TiF6, 20min is stirred to clarifying, boric acid is subsequently adding, stir at room temperature
40min is eventually adding dust technology to clarifying, and regulation pH value stirs 20min to clarifying to 4, obtains TiO2Precursor liquid；Wherein plus
(the NH for entering4)2TiF6It is 1 with the mol ratio of boric acid:1.5；TiO2The concentration of Ti elements is 0.030mol/L in precursor liquid；
2) functionalization of substrate：
By SnO2/ glass substrate is sequentially placed into supersound washing 10min in water, acetone, absolute ethyl alcohol.After washes clean
SnO2/ glass substrate irradiates 40min under being placed in the ultraviolet light of 184.9nm, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer, that is, obtain glass/SnO2-OH-Hydroxyl layer；
3) self assembly of film：
By glass/SnO2-OH-Hydroxyl layer is suspended in 62 DEG C of TiO2Precursor liquid surface self-organization adsorb 10h, using glass/
SnO2-OH-Hydroxyl layer and TiO2Precursor liquid small molecular [Ti (OH)6]2-With macromolecular [TiF6-n(OH)n]2-In OH gathered
Reaction is closed, wherein under gravity, macromolecular [TiF6-n(OH)n]2-Move down, be difficult and glass/SnO2-OH-Hydroxyl layer
Polymerisation, and small molecule [Ti (OH)6]2-Move up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
Close reaction heterogeneous nucleation and be self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film, the precursor thin film is existed
Dry 7 hours at room temperature, glass/SnO is obtained2-O-[TiO3H)]-Noncrystal membrane；
4) prepared by the LBL self-assembly of film：
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates after being dried at room temperature under the ultraviolet light of 184.9nm
40min, formation makes precursor thin film head end have the FTO-TiO of hydroxyl monolayer2-OH-TiO2-OH-Hydroxyl monolayer, then
The hydroxyl monolayer is suspended in 62 DEG C of TiO2Precursor liquid surface, to TiO2Small molecule [Ti (OH) in precursor liquid6]2-Enter
The self assembly absorption of row 10h, forms glass/SnO2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then does at room temperature
Dry 7h, such repeated multiple times LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2During laminated film is put into Muffle furnace after drying at room temperature, with 30 DEG C/min's
Programming rate is raised to 550 DEG C from room temperature, is incubated 60min, then naturally cools to room temperature, that is, obtain spherical titanium oxide/tin ash
Optoelectronic pole.
Embodiment 4
1) configuration of precursor liquid：
To addition (NH in deionized water4)2TiF6, 12min is stirred to clarifying, boric acid is subsequently adding, stir at room temperature
25min is eventually adding dust technology to clarifying, and regulation pH value stirs 12min to clarifying to 2, obtains TiO2Precursor liquid；Wherein plus
(the NH for entering4)2TiF6It is 1.8 with the mol ratio of boric acid:1；TiO2The concentration of Ti elements is 0.015mol/L in precursor liquid；
2) functionalization of substrate：
By SnO2/ glass substrate is sequentially placed into supersound washing 10min in water, acetone, absolute ethyl alcohol.After washes clean
SnO2/ glass substrate irradiates 25min under being placed in the ultraviolet light of 184.9nm, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer, that is, obtain glass/SnO2-OH-Hydroxyl layer；
3) self assembly of film：
By glass/SnO2-OH-Hydroxyl layer is suspended in 63 DEG C of TiO2Precursor liquid surface self-organization adsorbs 12.5h, using glass
Glass/SnO2-OH-Hydroxyl layer and TiO2Precursor liquid small molecular [Ti (OH)6]2-With macromolecular [TiF6-n(OH)n]2-In OH carry out
Polymerisation, wherein under gravity, macromolecular [TiF6-n(OH)n]2-Move down, be difficult and glass/SnO2-OH-Hydroxyl
Layers of polymer reacts, and small molecule [Ti (OH)6]2-Move up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-
Polymerisation heterogeneous nucleation is self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film, by the precursor thin film
It is dried at room temperature for 6.5 hours, glass/SnO is obtained2-O-[TiO3H)]-Noncrystal membrane；
4) prepared by the LBL self-assembly of film：
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates after being dried at room temperature under the ultraviolet light of 184.9nm
25min, formation makes precursor thin film head end have the FTO-TiO of hydroxyl monolayer2-OH-TiO2-OH-Hydroxyl monolayer, then
The hydroxyl monolayer is suspended in 63 DEG C of TiO2Precursor liquid surface, to TiO2Small molecule [Ti (OH) in precursor liquid6]2-Enter
The self assembly absorption of row 12.5h, forms glass/SnO2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then at room temperature
6.5h is dried, such repeated multiple times LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness2-O-TiO2It is compound
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2During laminated film is put into Muffle furnace after drying at room temperature, with 15 DEG C/min's
Programming rate is raised to 450 DEG C from room temperature, is incubated 80min, then naturally cools to room temperature, that is, obtain spherical titanium oxide/tin ash
Optoelectronic pole.
Embodiment 5
1) configuration of precursor liquid：
To addition (NH in deionized water4)2TiF6, 18min is stirred to clarifying, boric acid is subsequently adding, stir at room temperature
35min is eventually adding dust technology to clarifying, and regulation pH value stirs 18min to clarifying to 2.5, obtains TiO2Precursor liquid；Wherein
(the NH for adding4)2TiF6It is 2 with the mol ratio of boric acid:1.8；TiO2The concentration of Ti elements is 0.025mol/L in precursor liquid；
2) functionalization of substrate：
By SnO2/ glass substrate is sequentially placed into supersound washing 10min in water, acetone, absolute ethyl alcohol.After washes clean
SnO2/ glass substrate irradiates 35min under being placed in the ultraviolet light of 184.9nm, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer, that is, obtain glass/SnO2-OH-Hydroxyl layer；
3) self assembly of film：
By glass/SnO2-OH-Hydroxyl layer is suspended in 64 DEG C of TiO2Precursor liquid surface self-organization adsorb 11h, using glass/
SnO2-OH-Hydroxyl layer and TiO2Precursor liquid small molecular [Ti (OH)6]2-With macromolecular [TiF6-n(OH)n]2-In OH gathered
Reaction is closed, wherein under gravity, macromolecular [TiF6-n(OH)n]2-Move down, be difficult and glass/SnO2-OH-Hydroxyl layer
Polymerisation, and small molecule [Ti (OH)6]2-Move up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
Close reaction heterogeneous nucleation and be self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film, the precursor thin film is existed
Dry 7.5 hours at room temperature, glass/SnO is obtained2-O-[TiO3H)]-Noncrystal membrane；
4) prepared by the LBL self-assembly of film：
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates after being dried at room temperature under the ultraviolet light of 184.9nm
35min, formation makes precursor thin film head end have the FTO-TiO of hydroxyl monolayer2-OH-TiO2-OH-Hydroxyl monolayer, then
The hydroxyl monolayer is suspended in 64 DEG C of TiO2Precursor liquid surface, to TiO2Small molecule [Ti (OH) in precursor liquid6]2-Enter
The self assembly absorption of row 11h, forms glass/SnO2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then does at room temperature
Dry 7.5h, such repeated multiple times LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2During laminated film is put into Muffle furnace after drying at room temperature, with 25 DEG C/min's
Programming rate is raised to 350 DEG C from room temperature, is incubated 100min, then naturally cools to room temperature, that is, obtain spherical titanium oxide/tin ash
Optoelectronic pole.
Fig. 1 is the obtained TiO of the present invention2/SnO2The XRD spectrum of optoelectronic pole, as can be seen from Figure 12 θ be 26.8 °,
38.9 °, 52.0 °, corresponding (101) crystal face of 61.7 ° of diffraction maximums, (200) crystal face, (211) crystal face, (105) crystal face standard spectrogram
In Detitanium-ore-type TiO2Film (JCPDS PDF#21-1272, space group I41/amd) diffraction maximum fit like a glove；2 θ are
26.2 °, 37.9 °, 52.2 °, 63.5 ° of diffraction maximum correspondence rutile-type SnO2(JCPDS PDF#46-1088, space group P4/mnm)
(110) crystal face, (200) crystal face, (211) crystal face, (301) crystallographic plane diffraction peak fit like a glove, and illustrate that the film for preparing is TiO2/
SnO2Optoelectronic pole.
Fig. 2 is the obtained TiO of the present invention2/SnO2The SEM figures of optoelectronic pole, it can be seen that prepared optoelectronic pole surface
TiO2Pattern is globular nanostructures, and its spherical diameter is about 48~73nm, and membrane structure is comparatively dense.
Fig. 3 is TiO prepared by the present invention2/SnO2The current -voltage curve of optoelectronic pole, it can be seen that its voltage is increased by 0V
Corresponding electric current increases to 0.11mA by 0mA during being added to 1.5V, i.e., with the increase of institute's biasing, the electric current of sample is close
Degree gradually increases.This is that due under the DC Electric Field for gradually increasing, the separation rate of electron-hole pair increases, from
And bigger anode photoelectric current is obtained, there is laminated film more sensitive visible light-responded.Illustrate present invention preparation
TiO2/SnO2Optoelectronic pole is suitably applied the organic pollution in photocatalytic degradation water or in air.
Fig. 4 is TiO prepared by the present invention2/SnO2The time current curve of optoelectronic pole, as can be seen from Figure 4 TiO2/
SnO2Optoelectronic pole only has very weak anode photoelectric current before illumination, and anode current is significantly increased after illumination, and current-responsive is rapid,
Illustrate TiO2/SnO2Optoelectronic pole has sensitive visible light-responded characteristic.The anode spike that illumination moment produces, in a period of time
Interior just to reach stable state, this is probably partial photonic caused by the surface state capture of deep energy level.Illumination start rear density of photocurrent by
0.073mA rapidly decays to 0.050mA, and its reason is mainly due to photo-generate electron-hole in " optoelectronic pole/solution " interface hair
Caused by raw surface recombination process.Therefore, the recombination probability of influence electrode surface recombination process is 31.5%.
Above said content is to combine specific preferred embodiment further description made for the present invention, is not
All or unique implementation method, those of ordinary skill in the art by read description of the invention and to technical solution of the present invention
Any equivalent conversion taken, is claim of the invention and is covered.
Claims (10)
1. a kind of preparation method of spherical titanium oxide/tin ash optoelectronic pole, it is characterised in that comprise the following steps：
1)TiO2The configuration of precursor liquid：
At room temperature, to addition (NH in deionized water4)2TiF6, stir to clarify, boric acid is subsequently adding, stir to clarify, finally
Dust technology is added, regulation pH value is stirred to clarify to 1~4, obtains TiO2Precursor liquid；(the NH for wherein adding4)2TiF6And boric acid
Mol ratio be (1~3):(1~2)；
2)SnO2The functionalization of/glass substrate：
By SnO220~40min of irradiation under the ultraviolet light of 184.9nm is placed in after/glass substrate washes clean, makes SnO2/ glass base
Plate surface forms hydroxyl monolayer；
3) self assembly of film：
By SnO2The hydroxyl monolayer one side of/glass substrate is suspended in TiO2Precursor liquid surface carries out self assembly absorption, using base
The hydroxyl layer and TiO of plate surface2Precursor liquid small molecular [Ti (OH)6]2-In OH carry out polymerisation, heterogeneous nucleation self assembly
Form amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film, then be dried at room temperature for, obtain glass/SnO2-O-
[TiO3H)]-Noncrystal membrane；
4) LBL self-assembly of film：
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates 20~40min under the ultraviolet light of 184.9nm, makes its surface shape
Into hydroxyl monolayer, the hydroxyl monolayer is then suspended in TiO2Precursor liquid surface, to TiO2[Ti in precursor liquid
(OH)6]2-Self assembly polymerization absorption is carried out, glass/SnO is formed2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then in room
The lower drying of temperature；Such repeated multiple times LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness2-O-TiO2It is compound
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace, and 250~550 DEG C are raised to from room temperature, and insulation 60~
180min, then naturally cool to room temperature, that is, obtain spherical titanium oxide/tin ash optoelectronic pole.
2. the preparation method of spherical titanium oxide/tin ash optoelectronic pole according to claim 1, it is characterised in that described
Step 1) middle addition (NH4)2TiF610~20min of stirring stirs 20~40min to clarifying to clarifying after adding boric acid afterwards, adds
10~20min to clarification is stirred after dust technology.
3. the preparation method of spherical titanium oxide/tin ash optoelectronic pole according to claim 1, it is characterised in that described
Step 1) in TiO2The concentration of Ti elements is 0.010~0.030mol/L in precursor liquid.
4. the preparation method of spherical titanium oxide/tin ash optoelectronic pole according to claim 1, it is characterised in that described
Step 3) and step 4) in TiO2The temperature of precursor liquid is 60~65 DEG C, and the time of self assembly polymerization is 10~13h.
5. the preparation method of spherical titanium oxide/tin ash optoelectronic pole according to claim 1, it is characterised in that described
Step 3) and step 4) in drying time be 6~8h.
6. the preparation method of spherical titanium oxide/tin ash optoelectronic pole according to claim 1, it is characterised in that described
Step 9) in programming rate be 10~30 DEG C/min.
7. ball obtained in the preparation method of the spherical titanium oxide/tin ash optoelectronic pole in claim 1-6 described in any one
Shape titanium oxide/tin ash optoelectronic pole, it is characterised in that TiO in the spherical titanium oxide/tin ash optoelectronic pole2Crystal formation
It is zincite type, with I41/amdSpatial symmetry, SnO2Crystal formation be rutile-type, spatial symmetry is P4/mnm；TiO2Shape
Looks are globular nanostructures, its spherical a diameter of 48~73nm.
8. spherical titanium oxide/tin ash optoelectronic pole according to claim 7, it is characterised in that in simulated solar illumination
Penetrate down, the spherical titanium oxide/tin ash optoelectronic pole produces 0.11mA/cm under the conditions of 1.50V2Current density.
9. spherical titanium oxide/tin ash optoelectronic pole according to claim 7, it is characterised in that the spherical titanium oxide/
Tin ash optoelectronic pole after illumination starts density of photocurrent by 0.073mA/cm2Rapidly decay to 0.050mA/cm2, the ball
Photo-generate electron-hole is to during the surface recombination that optoelectronic pole/solution interface occurs in shape titanium oxide/tin ash optoelectronic pole
Recombination probability be 31.5%.
10. the spherical titanium oxide/tin ash optoelectronic pole in claim 7-9 described in any one under visible light drop by photocatalysis
Application in terms of solution organic pollution.
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Citations (3)
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|---|---|---|---|---|
| JPH03285821A (en) * | 1990-03-30 | 1991-12-17 | Nippon Sheet Glass Co Ltd | Production of titanium oxide coating film |
| CN102354606A (en) * | 2011-09-24 | 2012-02-15 | 东莞电子科技大学电子信息工程研究院 | Preparation method of photoanode of dye-sensitized solar cell |
| CN105948530A (en) * | 2016-04-25 | 2016-09-21 | 陕西科技大学 | BiVO4 film with polyporous netted structure and preparation method thereof |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03285821A (en) * | 1990-03-30 | 1991-12-17 | Nippon Sheet Glass Co Ltd | Production of titanium oxide coating film |
| CN102354606A (en) * | 2011-09-24 | 2012-02-15 | 东莞电子科技大学电子信息工程研究院 | Preparation method of photoanode of dye-sensitized solar cell |
| CN105948530A (en) * | 2016-04-25 | 2016-09-21 | 陕西科技大学 | BiVO4 film with polyporous netted structure and preparation method thereof |
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| CHUN-HAO HUANG ET AL.: ""Self-assembly monolayer of anatase titanium oxide from solution process on indium tin oxide glass substrate for polymer photovoltaic cells"", 《THIN SOLID FILMS》 * |
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