CN106925254B - A kind of spherical titanium oxide/stannic oxide optoelectronic pole and its preparation method and application - Google Patents
A kind of spherical titanium oxide/stannic oxide optoelectronic pole and its preparation method and application Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 155
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 98
- 239000002243 precursor Substances 0.000 claims abstract description 72
- 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 30
- 239000002356 single layer Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 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
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 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 20
- 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 14
- 239000013078 crystal Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000000428 dust Substances 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
- 238000005215 recombination Methods 0.000 claims description 8
- 230000006798 recombination Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 238000007306 functionalization reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 229910010252 TiO3 Inorganic materials 0.000 claims 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000005352 clarification Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 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
- 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
- 230000000694 effects Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 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
- 238000001179 sorption measurement Methods 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
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 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
- 230000009972 noncorrosive effect Effects 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
- 230000005622 photoelectricity Effects 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
- 230000009466 transformation Effects 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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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Abstract
The present invention provides a kind of spherical titanium oxide/stannic oxide 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, utilizes 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, finally in 500 DEG C of heat preservation crystallization to get arrive spherical titanium oxide/stannic oxide optoelectronic pole.Present invention process process is simple and easy to control, and experiment condition requires lower, the TiO of preparation2/SnO2Optoelectronic pole is high to the utilization rate of light, and current density is big, is suitably applied the organic pollutant in photocatalytic degradation water or in air, has 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/stannic oxide optoelectronic pole and its preparation method and application.
Background technique
With the further expansion of industrial application and life requirement, the type and quantity sharp increase of global chemicals.By
In the use, discharge and leakage etc. of chemicals, chemical pollutant is increasing in kind and quantity, so that chemical contamination has accounted for
According to the 80%~90% of total environment pollution.Thus, efficiently controlling and administer various chemical contaminations is in comprehensive environmental improvement
Emphasis, exploitation can be the key that environmental protection the innoxious practical technique of various chemical pollutants.Photocatalysis technology is one
For administering the emerging environmental protection technology of chemical contamination, more traditional method has the advantages such as at low cost, high-efficient, without 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
Oxygenolysis organic matter, reducing heavy metal ion kill bacterium and eliminate peculiar smell.Since photocatalysis technology can be existed using solar energy
It reacts at room temperature, both economical, photochemical catalyst itself is nontoxic, harmless, non-corrosive, can Reusability；It can be by organic dirt
Object permineralization is contaminated into H2O and inorganic ions, it is without 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 many advantages, such as that inexpensive, nontoxic, oxidability is strong, stability is good, forbidden bandwidth 3.2eV is
Most study and most widely used metal-oxide semiconductor (MOS) photochemical catalyst at present.TiO2It is a kind of multifunctional material, is urged in light
Change, light degradation and novel solar battery etc. have a wide range of applications.Meanwhile TiO2It is mainly leaned on as n-type semiconductor
Photo-generated carrier (mainly light induced electron) is conductive.
SnO2It is a kind of metal semiconductor oxide of rutile (rutile) structure, spatial symmetry P4/mnm.It is brilliant
Lattice constant a is 0.4731nm, c 0.31861nm.SnO2It is typical n-type semiconductor, band gap 3.5-3.6eV.By SnO2With
TiO2It carries out compound, the separating effect in its light induced electron and hole not only can be improved, but also recombination probability can be reduced, thus greatly
It is big to improve photocatalytic activity.
Currently, TiO2/SnO2The preparation of optoelectronic pole is mainly the following method: the sun of sol-gel method, metal titanium sheet
Pole oxidizing process, the directly thermal oxidation method of metal titanium sheet, template auxiliary synthetic method etc..These methods in terms of preparing film there is
It is certain insufficient.If membrane structure is unfavorable for photocatalytic degradation, repeatability is not high, and environmental pollution is big, loosely with substrate combination degree
Gu the disadvantages of, it is more or less that there is cannot be considered in terms of " cleaning, efficiently prepares photocatalysis film at energy conservation " this theory.
Summary of the invention
The purpose of the present invention is to provide a kind of spherical titanium oxide/stannic oxide optoelectronic pole and its preparation method and application,
Titanium oxide/stannic oxide optoelectronic pole is made using layer-by-layer in this method, and experiment condition requires lower, oxidation obtained
Titanium/stannic oxide 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 are as follows:
A kind of preparation method of spherical titanium oxide/stannic oxide optoelectronic pole, comprising the following steps:
1)TiO2The configuration of precursor liquid:
At room temperature, (NH is added into deionized water4)2TiF6, it stirs to clarify, boric acid is then added, stir to clarify,
It is eventually adding dust technology, adjusting pH value to 1~4, and is stirred to clarify, TiO is obtained2Precursor liquid；(the NH being wherein added4)2TiF6With
The molar ratio of boric acid is (1~3): (1~2)；
2)SnO2The functionalization of/glass substrate:
By SnO2/ glass substrate washes clean is placed on 20~40min of irradiation under the ultraviolet light of 184.9nm, makes SnO2/ glass
Glass substrate surface forms hydroxyl monolayer；
3) self assembly of film:
By SnO2The hydroxyl monolayer of/glass substrate is suspended in TiO on one side2Precursor liquid surface carries out self assembly absorption, benefit
With the hydroxyl layer and TiO of substrate surface2Precursor liquid small molecular [Ti (OH)6]2-In OH carry out polymerization reaction, 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 is then suspended in 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
It dries at room temperature；Multiple LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness repeatedly2-O-TiO2It is multiple
Close film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace, is raised to 250~550 DEG C from room temperature, heat preservation
60~180min, then cooled to room temperature to get arrive spherical titanium oxide/stannic oxide optoelectronic pole.
(NH is added in the step 1)4)2TiF6Afterwards stirring 10~20min to clarify, be added boric acid after stirring 20~
40min is to clarifying, and 10~20min of stirring is extremely clarified after dust technology is added.
TiO in the step 1)2The concentration of Ti element is 0.010~0.030mol/L in precursor liquid.
TiO in the step 3) and step 4)2The temperature of precursor liquid be 60~65 DEG C, self assembly polymerization time be 10~
13h。
Drying time in the step 3) and step 4) is 6~8h.
Heating rate in the step 9) is 10~30 DEG C/min.
Spherical titanium oxide/stannic oxide light made from spherical titanium oxide/stannic oxide optoelectronic pole preparation method
Electrode, TiO in the spherical titanium oxide/stannic oxide optoelectronic pole2Crystal form be zincite type, have I41/amdSpatial symmetry,
SnO2Crystal form be rutile-type, spatial symmetry P4/mnm；TiO2Pattern be globular nanostructures, spherical diameter be 48
~73nm.
Under simulated solar irradiation irradiation, the spherical titanium oxide/stannic oxide optoelectronic pole generates under the conditions of 1.50V
0.11mA/cm2Current density.
Spherical titanium oxide/stannic oxide 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/stannic oxide optoelectronic pole
Recombination probability during the surface recombination that interface occurs is 31.5%.
Spherical titanium oxide/stannic oxide the optoelectronic pole answering in terms of photocatalysis degradation organic contaminant under visible light
With.
Compared with the existing technology, the invention has the following advantages:
The preparation method of spherical titanium oxide/stannic oxide optoelectronic pole provided by the invention, first configures TiO2Precursor liquid, then
By SnO2/ glass substrate irradiates under ultraviolet light, makes SnO2/ glass baseplate surface forms hydroxyl monolayer, utilizes 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, finally in 500 DEG C of heat preservation crystallization to get arrive spherical oxygen
Change titanium/stannic oxide optoelectronic pole.Present invention process process is simple and easy to control, and experiment condition requirement is lower, passes through reverse adsorption liquid phase
LBL self-assembly method obtains the spherical TiO for having visible light-responded2/SnO2Optoelectronic pole.Self-assembled monolayer (self-assembled
Monolayers, SAMs) technology is one and is referred from bionic novel film technique, it is irradiated by short wave ultraviolet light in substrate
The orderly unimolecule hydroxyl adsorption layer spontaneously formed on interface, the hydroxyl adsorption layer of formation is spontaneous in air to pass through chemical bond
It is firmly adsorbed on substrate and is formed by ultra-thin hydroxyl film, there is original position to spontaneously form, the arrangement of bonding high-sequential, defect
Less, the features such as binding force is strong, in " crystalline state ", prepares inorganic material film suitable for heterogeneous nucleation induction, has preparation method
Simply, the advantages that film-formation result is good, stability is strong, thicknesses of layers is ultra-thin.
Spherical titanium oxide/stannic oxide 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, to improve the photocatalysis effect of optoelectronic pole.And prepared by the present invention
TiO2/SnO2Optoelectronic pole current density with higher, photoelectric respone ability is good, high to the utilization rate of light, current density
Greatly, it is suitably applied the organic pollutant in photocatalytic degradation water or in air, before there is wide application in photocatalysis field
Scape.
Detailed description of the invention
Fig. 1 is spherical TiO prepared by the present invention2/SnO2The XRD diagram of optoelectronic pole；
Fig. 2 is spherical TiO prepared by the present invention2/SnO2The SEM of optoelectronic pole schemes；
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 with reference to the accompanying drawing, raw material is analysis
It is pure.
Embodiment 1
1) configuration of precursor liquid:
(NH is added into deionized water4)2TiF6, 10min is stirred to clarifying, and boric acid is then added, stirs at room temperature
30min is eventually adding dust technology, adjusting pH value to 2.9 to clarifying, and stirs 10min to clarifying, and obtains TiO2Precursor liquid；Wherein
(the NH being added4)2TiF6Molar ratio with boric acid is 1:1；TiO2The concentration of Ti element is 0.010mol/L in precursor liquid；
2) functionalization of substrate:
By SnO2/ glass substrate is sequentially placed into water, acetone, supersound washing 10min in dehydrated alcohol.After washes clean
SnO2/ glass substrate, which is placed under the ultraviolet light of 184.9nm, irradiates 30min, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer to get arrive 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 the effect of gravity, macromolecular [TiF6-n(OH)n]2-It moves down, is not easy and glass/SnO2-OH-Hydroxyl layer
Polymerization reaction, and small molecule [Ti (OH)6]2-It moves up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
It closes reaction heterogeneous nucleation and is self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film exists the precursor thin film
It dries 6 hours at room temperature, glass/SnO is made2-O-[TiO3H)]-Noncrystal membrane；
4) the LBL self-assembly preparation of film:
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates under the ultraviolet light of 184.9nm after being dried at room temperature for
20min forms the FTO-TiO for making precursor thin film head end have 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-Into
The self assembly of row 12h is adsorbed, and glass/SnO is formed2-O-[TiO3H)]--O-[TiO3H)]-Then noncrystal membrane is done at room temperature
Dry 6h, multiple LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness repeatedly2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace after drying at room temperature, with 10 DEG C/min's
Heating rate is raised to 500 DEG C from room temperature, keeps the temperature 120min, then cooled to room temperature to get spherical titanium oxide/stannic oxide is arrived
Optoelectronic pole.
Embodiment 2
1) configuration of precursor liquid:
(NH is added into deionized water4)2TiF6, 15min is stirred to clarifying, and boric acid is then added, stirs at room temperature
20min is eventually adding dust technology, adjusting pH value to 1 to clarifying, and stirs 15min to clarifying, and obtains TiO2Precursor liquid；Wherein plus
(the NH entered4)2TiF6Molar ratio with boric acid is 3:2；TiO2The concentration of Ti element is 0.020mol/L in precursor liquid；
2) functionalization of substrate:
By SnO2/ glass substrate is sequentially placed into water, acetone, supersound washing 10min in dehydrated alcohol.After washes clean
SnO2/ glass substrate, which is placed under the ultraviolet light of 184.9nm, irradiates 20min, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer to get arrive 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 the effect of gravity, macromolecular [TiF6-n(OH)n]2-It moves down, is not easy and glass/SnO2-OH-Hydroxyl layer
Polymerization reaction, and small molecule [Ti (OH)6]2-It moves up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
It closes reaction heterogeneous nucleation and is self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film exists the precursor thin film
It dries 8 hours at room temperature, glass/SnO is made2-O-[TiO3H)]-Noncrystal membrane；
4) the LBL self-assembly preparation of film:
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates under the ultraviolet light of 184.9nm after being dried at room temperature for
30min forms the FTO-TiO for making precursor thin film head end have 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-Into
The self assembly of row 13h is adsorbed, and glass/SnO is formed2-O-[TiO3H)]--O-[TiO3H)]-Then noncrystal membrane is done at room temperature
Dry 8h, multiple LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness repeatedly2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace after drying at room temperature, with 20 DEG C/min's
Heating rate is raised to 250 DEG C from room temperature, keeps the temperature 180min, then cooled to room temperature to get spherical titanium oxide/stannic oxide is arrived
Optoelectronic pole.
Embodiment 3
1) configuration of precursor liquid:
(NH is added into deionized water4)2TiF6, 20min is stirred to clarifying, and boric acid is then added, stirs at room temperature
40min is eventually adding dust technology, adjusting pH value to 4 to clarifying, and stirs 20min to clarifying, and obtains TiO2Precursor liquid；Wherein plus
(the NH entered4)2TiF6Molar ratio with boric acid is 1:1.5；TiO2The concentration of Ti element is 0.030mol/L in precursor liquid；
2) functionalization of substrate:
By SnO2/ glass substrate is sequentially placed into water, acetone, supersound washing 10min in dehydrated alcohol.After washes clean
SnO2/ glass substrate, which is placed under the ultraviolet light of 184.9nm, irradiates 40min, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer to get arrive 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 the effect of gravity, macromolecular [TiF6-n(OH)n]2-It moves down, is not easy and glass/SnO2-OH-Hydroxyl layer
Polymerization reaction, and small molecule [Ti (OH)6]2-It moves up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
It closes reaction heterogeneous nucleation and is self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film exists the precursor thin film
It dries 7 hours at room temperature, glass/SnO is made2-O-[TiO3H)]-Noncrystal membrane；
4) the LBL self-assembly preparation of film:
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates under the ultraviolet light of 184.9nm after being dried at room temperature for
40min forms the FTO-TiO for making precursor thin film head end have 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-Into
The self assembly of row 10h is adsorbed, and glass/SnO is formed2-O-[TiO3H)]--O-[TiO3H)]-Then noncrystal membrane is done at room temperature
Dry 7h, multiple LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness repeatedly2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace after drying at room temperature, with 30 DEG C/min's
Heating rate is raised to 550 DEG C from room temperature, keeps the temperature 60min, then cooled to room temperature to get spherical titanium oxide/stannic oxide is arrived
Optoelectronic pole.
Embodiment 4
1) configuration of precursor liquid:
(NH is added into deionized water4)2TiF6, 12min is stirred to clarifying, and boric acid is then added, stirs at room temperature
25min is eventually adding dust technology, adjusting pH value to 2 to clarifying, and stirs 12min to clarifying, and obtains TiO2Precursor liquid；Wherein plus
(the NH entered4)2TiF6Molar ratio with boric acid is 1.8:1；TiO2The concentration of Ti element is 0.015mol/L in precursor liquid；
2) functionalization of substrate:
By SnO2/ glass substrate is sequentially placed into water, acetone, supersound washing 10min in dehydrated alcohol.After washes clean
SnO2/ glass substrate, which is placed under the ultraviolet light of 184.9nm, irradiates 25min, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer to get arrive 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, utilizes 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
Polymerization reaction, wherein under the effect of gravity, macromolecular [TiF6-n(OH)n]2-It moves down, is not easy and glass/SnO2-OH-Hydroxyl
Layers of polymer reaction, and small molecule [Ti (OH)6]2-It moves up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-
Polymerization reaction 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 made2-O-[TiO3H)]-Noncrystal membrane；
4) the LBL self-assembly preparation of film:
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates under the ultraviolet light of 184.9nm after being dried at room temperature for
25min forms the FTO-TiO for making precursor thin film head end have 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-Into
The self assembly of row 12.5h is adsorbed, and glass/SnO is formed2-O-[TiO3H)]--O-[TiO3H)]-Noncrystal membrane, then at room temperature
Dry 6.5h, multiple LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness repeatedly2-O-TiO2It is compound
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace after drying at room temperature, with 15 DEG C/min's
Heating rate is raised to 450 DEG C from room temperature, keeps the temperature 80min, then cooled to room temperature to get spherical titanium oxide/stannic oxide is arrived
Optoelectronic pole.
Embodiment 5
1) configuration of precursor liquid:
(NH is added into deionized water4)2TiF6, 18min is stirred to clarifying, and boric acid is then added, stirs at room temperature
35min is eventually adding dust technology, adjusting pH value to 2.5 to clarifying, and stirs 18min to clarifying, and obtains TiO2Precursor liquid；Wherein
(the NH being added4)2TiF6Molar ratio with boric acid is 2:1.8；TiO2The concentration of Ti element is 0.025mol/L in precursor liquid；
2) functionalization of substrate:
By SnO2/ glass substrate is sequentially placed into water, acetone, supersound washing 10min in dehydrated alcohol.After washes clean
SnO2/ glass substrate, which is placed under the ultraviolet light of 184.9nm, irradiates 35min, makes SnO2/ glass baseplate surface forms hydroxyl unimolecule
Layer to get arrive 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 the effect of gravity, macromolecular [TiF6-n(OH)n]2-It moves down, is not easy and glass/SnO2-OH-Hydroxyl layer
Polymerization reaction, and small molecule [Ti (OH)6]2-It moves up, glass/SnO2-OH-Hydroxyl layer and small molecule [Ti (OH)6]2-It is poly-
It closes reaction heterogeneous nucleation and is self-assembly of amorphous glass/SnO2-O-[Ti(OH)5]-Precursor thin film exists the precursor thin film
It dries 7.5 hours at room temperature, glass/SnO is made2-O-[TiO3H)]-Noncrystal membrane；
4) the LBL self-assembly preparation of film:
By glass/SnO2-O-[TiO3H)]-Noncrystal membrane irradiates under the ultraviolet light of 184.9nm after being dried at room temperature for
35min forms the FTO-TiO for making precursor thin film head end have 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-Into
The self assembly of row 11h is adsorbed, and glass/SnO is formed2-O-[TiO3H)]--O-[TiO3H)]-Then noncrystal membrane is done at room temperature
Dry 7.5h, multiple LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness repeatedly2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace after drying at room temperature, with 25 DEG C/min's
Heating rate is raised to 350 DEG C from room temperature, keeps the temperature 100min, then cooled to room temperature to get spherical titanium oxide/stannic oxide is arrived
Optoelectronic pole.
Fig. 1 is TiO produced by 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 maximums correspond to 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 of preparation is TiO2/
SnO2Optoelectronic pole.
Fig. 2 is TiO produced by the present invention2/SnO2The SEM of optoelectronic pole schemes, it can be seen that prepared photoelectricity pole surface
TiO2Pattern is globular nanostructures, and 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
Being added to during 1.5V corresponding electric current increases to 0.11mA by 0mA, i.e., with the increase of institute's biasing, the electric current of sample is close
Degree is gradually increased.This is because the separation rate of electron-hole pair increases under the DC Electric Field being gradually increased, from
And bigger anode photoelectric current is obtained, there is laminated film more sensitive visible light-responded.Illustrate prepared by the present invention
TiO2/SnO2Optoelectronic pole is suitably applied the organic pollutant 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 significantly increases after illumination, and current-responsive is rapid,
Illustrate TiO2/SnO2Optoelectronic pole has sensitive visible light-responded characteristic.The anode spike that illumination moment generates, in a period of time
Interior just to reach stable state, this may be caused by surface state capture of the partial photonic by deep energy level.Illumination start rear density of photocurrent by
0.073mA rapidly decays to 0.050mA, and reason is mainly sent out due to photo-generate electron-hole at " optoelectronic pole/solution " interface
Caused by raw surface recombination process.Therefore, the recombination probability for influencing electrode surface recombination process is 31.5%.
Above said content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent transformation taken, all are covered by the claims of the invention.
Claims (10)
1. a kind of preparation method of spherical titanium oxide/stannic oxide optoelectronic pole, which comprises the following steps:
1) TiO2The configuration of precursor liquid:
At room temperature, (NH is added into deionized water4)2TiF6, stir to clarify, boric acid be then added, stir to clarify, finally
Dust technology, adjusting pH value to 1 ~ 4 is added, and stirs to clarify, obtains TiO2Precursor liquid；(the NH being wherein added4)2TiF6And boric acid
Molar ratio be (1 ~ 3): (1 ~ 2)；
2) SnO2The functionalization of/glass substrate:
By SnO2/ glass substrate washes clean is placed on 20 ~ 40min of irradiation under the ultraviolet light of 184.9nm, makes SnO2/ glass substrate
Surface forms hydroxyl monolayer；
3) self assembly of film:
By SnO2The hydroxyl monolayer of/glass substrate is suspended in TiO on one side2Precursor liquid surface carries out self assembly absorption, utilizes base
The hydroxyl layer and TiO of plate surface2Precursor liquid small molecular [Ti (OH)6]2-In OH carry out polymerization reaction, 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, forms its surface
Then the hydroxyl monolayer is suspended in TiO by hydroxyl monolayer2Precursor 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 temperature
Lower drying；Multiple LBL self-assembly obtains amorphous glass/SnO up to reaching required thickness repeatedly2-O-TiO2THIN COMPOSITE
Film；
5) crystallization of film
By amorphous glass/SnO2-O-TiO2Laminated film is put into Muffle furnace, is raised to 250 ~ 550 DEG C from room temperature, and heat preservation 60 ~
180 min, then cooled to room temperature to get arrive spherical titanium oxide/stannic oxide optoelectronic pole.
2. the preparation method of spherical titanium oxide/stannic oxide optoelectronic pole according to claim 1, which is characterized in that described
(NH is added in step 1)4)2TiF610 ~ 20min of stirring is to clarifying afterwards, and 20 ~ 40min of stirring is added dilute to clarifying after boric acid is added
10 ~ 20min is stirred after nitric acid to clarification.
3. the preparation method of spherical titanium oxide/stannic oxide optoelectronic pole according to claim 1, which is characterized in that described
TiO in step 1)2The concentration of Ti element is 0.010 ~ 0.030 mol/L in precursor liquid.
4. the preparation method of spherical titanium oxide/stannic oxide optoelectronic pole according to claim 1, which is characterized in that described
TiO in step 3) and step 4)2The 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/stannic oxide optoelectronic pole according to claim 1, which is characterized in that described
Drying time in step 3) and step 4) is 6 ~ 8h.
6. the preparation method of spherical titanium oxide/stannic oxide optoelectronic pole according to claim 1, which is characterized in that described
Heating rate in step 5) is 10 ~ 30 DEG C/min.
7. ball made from spherical titanium oxide/stannic oxide optoelectronic pole preparation method described in any one of claim 1-6
Shape titanium oxide/stannic oxide optoelectronic pole, which is characterized in that TiO in the spherical titanium oxide/stannic oxide optoelectronic pole2Crystal form
For Detitanium-ore-type, there is I41/amdSpatial symmetry, SnO2Crystal form be rutile-type, spatial symmetry P4/mnm；TiO2Shape
Looks are globular nanostructures, and spherical diameter is 48 ~ 73nm.
8. spherical titanium oxide/stannic oxide optoelectronic pole according to claim 7, which is characterized in that in simulated solar illumination
It penetrates down, the spherical titanium oxide/stannic oxide optoelectronic pole generates 0.11 mA/cm under the conditions of 1.50V2Current density.
9. spherical titanium oxide/stannic oxide optoelectronic pole according to claim 7, which is characterized in that the spherical titanium oxide/
Stannic oxide optoelectronic pole after illumination starts density of photocurrent by 0.073 mA/cm2Rapidly decay to 0.050mA/cm2, the ball
During photo-generate electron-hole is to the surface recombination occurred in optoelectronic pole/solution interface in shape titanium oxide/stannic oxide optoelectronic pole
Recombination probability be 31.5%.
10. spherical titanium oxide/stannic oxide optoelectronic pole described in any one of claim 7-9 under visible light drop by photocatalysis
Solve the application in terms of organic pollutant.
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| JPH03285821A (en) * | 1990-03-30 | 1991-12-17 | Nippon Sheet Glass Co Ltd | Production of titanium oxide coating film |
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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 |
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