CN105642367B - A kind of level composite material and application using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier - Google Patents
A kind of level composite material and application using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier Download PDFInfo
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- CN105642367B CN105642367B CN201511002799.9A CN201511002799A CN105642367B CN 105642367 B CN105642367 B CN 105642367B CN 201511002799 A CN201511002799 A CN 201511002799A CN 105642367 B CN105642367 B CN 105642367B
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 239000002073 nanorod Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- 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 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 10
- 239000003643 water by type Substances 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- 229910017906 NH3H2O Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 210000001507 arthropod compound eye Anatomy 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 239000011664 nicotinic acid Substances 0.000 claims description 2
- 238000002310 reflectometry Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 32
- 125000005842 heteroatom Chemical group 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 7
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000001579 optical reflectometry Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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Abstract
The present invention relates to a kind of using monocrystalline silicon as the level composite material of the reflection bilayer P/N hetero-junctions that disappears of carrier, prepared according to following methods：(1) hydrophilic treated is carried out to silicon chip first, grows titanium dioxide crystal seed on its surface, be placed in calcining in Muffle furnace；(2) and then by silicon chip of the obtained surface in step (1) with titanium dioxide crystal seed it is placed in reaction kettle, using the method for hydrothermal synthesis in silicon chip surface induced growth titanium dioxide nano-rod；(3) polypyrrole nano-particle is deposited on the titanium dioxide nano-rod finally obtained in step (2), obtains the reflection bilayer P/N hetero junction layer level composite materials that disappear using monocrystalline silicon as carrier.The reflection bilayer P/N hetero junction layers level composite material that disappears according to the present invention using monocrystalline silicon as carrier has excellent reduction material surface light reflection and efficiently separates the ability of photogenerated charge, can be applied to the fields such as photocatalysis, photoelectric conversion device and solar cell.
Description
Technical field
The present invention relates to it is a kind of using monocrystalline silicon as carrier disappear reflection bilayer P/N hetero-junctions level composite material i.e. silicon-
Titanium dioxide-Pt/Polypyrrole composite material, while such compound can be used for photoelectric conversion and catalysis material, belong to photoelectricity material
Expect technical field.
Background technology
At present, inorganic semiconductor photochemical catalyst such as TiO2、ZnO、MnO2、V2O5、Fe3O4,、Ag2O etc. is widely used to can
The renewable sources of energy and environmental treatment field.Wherein titanium dioxide nano material is due to catalytic activity is high, stability is good, degradation
The advantages that speed is fast, degradation condition is mild, small investment, low energy consumption, high hydroxyl radical free radical yield, illumination are not corroded applies in anti-corrosion
Material, sewage purification, antibiotic and sterilizing etc. show especially prominent application prospect.But titanium dioxide is a kind of broad stopband half
Conductor can only absorb in the sunlight 5% shorter ultraviolet light of wavelength, lead to photo-catalysis capability of the titanium dioxide under sunlight
It is weaker.Therefore, improving photocatalytic activity of the titanium dioxide under sunlight has become the hot spot of the area research.
Conductive polymer polypyrrole has good environmental stability, has very strong absorption in visible region, is strong
Electron donor and excellent hole mobile material, after surface sensitizing is carried out to titanium dioxide with polypyrrole, between the two will
Hetero-junctions is formed, the separative efficiency of photogenerated charge can not only be improved so as to improve photocatalysis efficiency, and can be by composite material
Spectral response range widens visible region so as to improve the utilization rate of sunlight.Patent CN101955665A discloses a kind of poly-
The composite material and preparation method thereof of pyrroles's particle/titanium dioxide nanotube array；Patent CN102350317A discloses a kind of poly- pyrrole
Cough up/titanium dioxide compound adsorbent and its preparation, application and regeneration method；Patent CN102600907A discloses a kind of polypyrrole
Hollow form titanium dioxide nano photocatalysis agent of sensitization and preparation method thereof；It is wide to solve titanium dioxide forbidden band to a certain degree above
Degree is big, spectral response range is small, photo-generate electron-hole to it is easily compound the problems such as.However, polypyrrole/titanium dioxide compound is still
So there is order it is poor, it is easy reunite, recovery utilization rate it is relatively low, the problems such as absorptivity is not high, limit polypyrrole/dioxy
Change the popularization and application of titanium compound.
Invention content
The invention aims to overcome traditional titanium dioxide/polypyrrole compound it is unordered, it is easy reunite, difficult recycling and light
The shortcomings such as electric transformation efficiency is low provide a kind of level composite wood using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier
Material, while there is good disappear reflecting properties and to efficiently separate photogenerated charge ability, improve the electricity conversion of material, table
Reveal excellent photo-catalysis capability.
It is described using a kind of heterogeneous using monocrystalline silicon as the reflection bilayer P/N that disappears of carrier according to technical solution provided by the invention
The level composite material of knot is with silicon (Si), titanium dioxide (TiO2) and polypyrrole (PPy) level orderly form, i.e. Si/TiO2/
PPy level composite materials, Si are P (100) type monocrystalline silicon；TiO2It is the TiO of Rutile Type2Nanometer rods, for N-type semiconductor, tetragonous
Post shapes are highly 500~4000nm, and a diameter of 40~250nm, orderly vertical-growth is in monocrystalline silicon surface；PPy is polypyrrole
Nano-particle is P-type semiconductor, and grain size is 10~60nm, and homoepitaxial is in TiO2Nanorod surfaces.Si/TiO2/ PPy levels are answered
Si and TiO in condensation material2Interface, TiO2Double P/N hetero-junctions are formed with PPy interfaces, photogenerated charge can be efficiently separated, simultaneously
With bionic insect compound eye structural, reflectivity of the incident light on surface can be effectively reduced.
A kind of preparation side of prepared level composite material using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier
Method, it is characterized in that, include the following steps：
(1) hydrophilic treated is carried out to silicon chip first, grows TiO on its surface2Crystal seed is placed in one section of calcining in Muffle furnace
Natural cooling after time；
(2) and then by obtained surface in step (1) has TiO2The silicon chip of crystal seed is placed in reaction kettle, using hydro-thermal
Synthetic method is in silicon chip surface induced growth TiO2Nanometer rods；
(3) TiO finally obtained in step (2)2PPy nano-particles are deposited in nanometer rods, obtain Si/TiO2/ PPy layers
Level composite material.
Further, the hydrophilic treated operation described in step (1) is that silicon chip is placed in NH3H2O、H2O2And H2The mixing of O is molten
In liquid, volume ratio 1:1:5, temperature is 90 DEG C, heating time 30min.
Further, the growth TiO described in step (1)2Crystal seed condition is a concentration of for the silicon chip after hydrophilic treated is dipped in
It is lifted in the aqueous isopropanol of the butyl titanate of 0.05~1mol/L, the speed of lifting is 1~10mm/s, repeats to lift
5~30 times, the speed of spin coating is 500~7000 turns/min, finally calcines above-mentioned sample about in 450~500 DEG C of Muffle furnaces
30~60min.
Further, at a temperature of the hydrothermal synthesizing condition described in step (2) is 80~200 DEG C, equipped with 10~20mL
2~19h is handled in the reaction kettle of deionized water, 6~17mL concentrated hydrochloric acids (mass fraction 37%) and 0.5~5mL butyl titanates,
Sample is then taken out to be dried up with nitrogen.
Further, described in step (3) in TiO2PPy nano-particles are deposited in nanometer rods, refer to utilize in-situ oxidation
Method is in TiO2PPy conducting polymer particles are deposited in nanometer rods, reaction condition is：By the FeCl of 0.01~0.06g3, 50~
150uL pyrroles, 5~10mL ultra-pure waters are placed in beaker, form reaction solution.The surface that area is 1.5cm × 1.0cm is grown
There is TiO2The silicon chip of nanometer rods is placed in reaction solution, is kept stirring 10~60min at room temperature, is obtained Si/TiO2/ PPy levels are compound
Material.
Further, Si/TiO2/ PPy levels composite material is used as the application of photocatalysis degradation organic contaminant, will
The Si/TiO of 1.5cm × 1.0cm areas2/ PPy level composite materials are positioned over the methylene blue solution of 5mL, a concentration of 1.0 ×
10-5Then mol/L places it in dark place 1h and it is allowed to reach absorption-desorption balance, carries out illumination to solution with light source later, right
Methylene blue is degraded.Meanwhile this kind of composite material is not limited to apply in photocatalysis degradation organic contaminant, also is adapted for
In the fields such as other photocatalysis fields and photoelectric conversion device, solar cell.
The present invention has following superiority：
(1) monocrystalline silicon surface level load TiO2Nanometer rods, PPy nano-particles, form bionical composite construction, have excellent
The reflecting properties that disappear.
(2) in the monocrystalline silicon of p-type and N-type TiO2Contact interface, the N-type TiO of nanometer rods2Nanometer rods and p-type PPy nanoparticles
The contact interface of son forms double P/N heterojunction structures, efficiently separates photo-generated carrier, reduces the compound of electron-hole pair, has
There is excellent electricity conversion.
(3) this kind of Si/TiO2Using monocrystalline silicon as carrier, nano-complex is not susceptible to reunite/PPy levels composite material,
With high specific surface area, effective catalytic activity point is increased, recycling is easy, conducive to Reusability, is polluted in photocatalytic degradation
Object space face has certain use value.
(4) this kind of Si/TiO2/ PPy levels composite material and preparation method thereof is easy, and mild condition is easily-controllable, will to consersion unit
It asks low, meets the requirement of large-scale production.
Description of the drawings
Fig. 1 is to prepare a kind of technique of the level composite material using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier
Schematic diagram；
Fig. 2 is that monocrystalline silicon surface loads TiO in embodiment 32The scanning electron microscopic picture of nanometer rods；
Fig. 3 is that monocrystalline silicon surface level loads TiO in embodiment 32The scanning electron microscopic picture of nanometer rods, PPy nano-particles.
Specific embodiment
Embodiment 1：
Step 1：Monocrystalline silicon surface grows TiO2Crystal seed
Silicon chip is placed in NH3H2O、H2O2And H2In the mixed solution of O, volume ratio 1:1:5, temperature is 80 DEG C, during heating
Between 30min.Then, it is dipped in the aqueous isopropanol of the butyl titanate of a concentration of 0.075mol/L and is lifted, the speed of lifting
Degree is 2mm/s, repeats lifting 20 times, above-mentioned sample is finally calcined about 30min in 450 DEG C of Muffle furnaces.
Step 2：TiO2Crystal seed induces TiO2The preparation of nanometer rods
The surface obtained in step 2 had into TiO2The silicon chip of crystal seed, which is placed under hydrothermal condition, carries out growth TiO2Nanometer
Stick.Hydrothermal synthesizing condition be 130 DEG C at a temperature of, equipped with 10mL deionized waters, 10mL concentrated hydrochloric acids (mass fraction 37%) and
8h is handled in the reaction kettle of 0.5mL butyl titanates, sample is then taken out and is dried up with nitrogen.
Step 3：TiO2PPy nano-particles are prepared in situ in nanorod surfaces
Using oxidation in situ in step 2 obtained TiO2PPy nano-particles are deposited in nanometer rods.Reaction condition
For：By the FeCl of 0.03g3, 112.8uL pyrroles, 6mL ultra-pure waters be placed in beaker, form reaction solution；It is 1.5cm by area
The growth of × 1.0cm surfaces has TiO2The silicon chip of nanometer rods is placed in reaction solution, and 25min is stirred in holding at room temperature, after reaction,
It is rinsed after sample is taken out with a large amount of water, obtains Si/TiO2/ PPy level composite materials.
Si/TiO obtained above2In/PPy level composite materials, the average grain diameter of PPy nano-particles is 35nm, TiO2It receives
The average diameter of rice stick is 83nm, average height 818nm.It is tested by uv drs it is found that Si/TiO2/ PPy levels are answered
Condensation material shows the outstanding reflecting properties that disappear, light reflectivity 11%；Pass through photoelectricity current test, Si/TiO2/ PPy levels are answered
The photoelectric current of condensation material is about respectively pure TiO210 times and 8 times of nanometer rods and pure PPy nano-particles；Pass through the simulated solar ring of light
Border, Si/TiO2It is dense to investigate methylene blue with reference to ultraviolet specrophotometer for/PPy level composite material photocatalytic degradation methylene blues
Degree changes with time, in 7h that dyestuff methylene blue is degradable, and degradation efficiency is higher than pure TiO2Nanometer rods and pure PPy
Nano-particle.
Embodiment 2：
Step 1：Monocrystalline silicon surface grows TiO2Crystal seed
Silicon chip is placed in NH3H2O、H2O2And H2In the mixed solution of O, volume ratio 1:1:5, temperature is 80 DEG C, during heating
Between 40min.Then, it is dipped in the aqueous isopropanol of the butyl titanate of a concentration of 0.05mol/L and is lifted, the speed of lifting
It is 2mm/s, repeats lifting 15 times, above-mentioned sample is finally calcined into about 1h in 450 DEG C of Muffle furnaces.
Step 2：TiO2Crystal seed induces TiO2The preparation of nanometer rods
The surface obtained in step 1 had into TiO2The silicon chip of crystal seed, which is placed under hydrothermal condition, carries out growth TiO2Nanometer
Stick.Hydrothermal synthesizing condition be 130 DEG C at a temperature of, equipped with 10mL deionized waters, 10mL concentrated hydrochloric acids (mass fraction 37%) and
8h is handled in the reaction kettle of 0.5mL butyl titanates, sample is then taken out and is dried up with nitrogen.
Step 3：TiO2PPy nano-particles are prepared in situ in nanorod surfaces
Using oxidation in situ in step 2 obtained TiO2PPy nano-particles are deposited in nanometer rods.Reaction condition
For：By the FeCl of 0.03g3, 112.8uL pyrroles, 6mL ultra-pure waters be placed in beaker, form reaction solution；It is 1.5cm by area
The growth of × 1.0cm surfaces has TiO2The silicon chip of nanometer rods is placed in reaction solution, and 15min is stirred in holding at room temperature, after reaction,
It is rinsed after sample is taken out with a large amount of water, obtains Si/TiO2/ PPy level composite materials.
Si/TiO obtained above2In/PPy level composite materials, the average grain diameter of PPy nano-particles is 19nm, TiO2It receives
The average diameter of rice stick is 83nm, average height 818nm.It is tested by uv drs it is found that Si/TiO2/ PPy levels are answered
Condensation material shows the outstanding reflecting properties that disappear, light reflectivity 9%；Pass through photoelectricity current test, Si/TiO2/ PPy levels are compound
The photoelectric current of material is about respectively pure TiO212 times and 10 times of nanometer rods and pure PPy nano-particles；Pass through the simulated solar ring of light
Border, Si/TiO2It is dense to investigate methylene blue with reference to ultraviolet specrophotometer for/PPy level composite material photocatalytic degradation methylene blues
Degree changes with time, in 6.5h that dyestuff methylene blue is degradable, and degradation efficiency is higher than pure TiO2Nanometer rods and pure
PPy nano-particles.
Embodiment 3：
Step 1：Monocrystalline silicon surface grows TiO2Crystal seed
Silicon chip is placed in NH3H2O、H2O2And H2In the mixed solution of O, volume ratio 1:1:5, temperature is 90 DEG C, during heating
Between 30min.Then, it is dipped in the aqueous isopropanol of the butyl titanate of a concentration of 0.1mol/L and is lifted, the speed of lifting
It is 2mm/s, repeats lifting 10 times, above-mentioned sample is finally calcined into about 30min in 500 DEG C of Muffle furnaces.
Step 2：TiO2Crystal seed induces TiO2The preparation of nanometer rods
The surface obtained in step 1 had into TiO2The silicon chip of crystal seed, which is placed under hydrothermal condition, carries out growth TiO2Nanometer
Stick.Hydrothermal synthesizing condition be 120 DEG C at a temperature of, equipped with 10mL deionized waters, 10mL concentrated hydrochloric acids (mass fraction 37%) and
8h is handled in the reaction kettle of 0.5mL butyl titanates, sample is then taken out and is dried up with nitrogen.
Step 3：TiO2PPy nano-particles are prepared in situ in nanorod surfaces
Using oxidation in situ in step 2 obtained TiO2PPy nano-particles are deposited in nanometer rods.Reaction condition
For：By the FeCl of 0.03g3, 112.8uL pyrroles, 6mL ultra-pure waters be placed in beaker, form reaction solution；It is 1.5cm by area
The growth of × 1.0cm surfaces has TiO2The silicon chip of nanometer rods is placed in reaction solution, and 10min is stirred in holding at room temperature, after reaction,
It is rinsed after sample is taken out with a large amount of water, obtains Si/TiO2/ PPy level composite materials.
Si/TiO obtained above2In/PPy level composite materials, the average grain diameter of PPy nano-particles is 12nm, TiO2It receives
The average diameter of rice stick is 83nm, average height 818nm.It is tested by uv drs it is found that Si/TiO2/ PPy levels are answered
Condensation material shows the outstanding reflecting properties that disappear, light reflectivity 7%；Pass through photoelectricity current test, Si/TiO2/ PPy levels are compound
The photoelectric current of material is about respectively pure TiO215 times and 12 times of nanometer rods and PPy nano-particles；By simulated solar luminous environment,
Si/TiO2/ PPy level composite material photocatalytic degradation methylene blues investigate methylene blue concentration with reference to ultraviolet specrophotometer
It changes with time, it is in 6h that dyestuff methylene blue is degradable, and degradation efficiency is higher than pure TiO2Nanometer rods and pure PPy receive
Rice corpuscles.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, it is impossible to assert
The specific implementation of the present invention is confined to these explanations.For the personnel of the technical field of the invention, this is not being departed from
Under the premise of inventive concept, many simple deduction or replace can be also made, should all be considered as belonging to protection scope of the present invention.
Claims (9)
1. it is a kind of using monocrystalline silicon as the level composite material of the reflection bilayer P/N hetero-junctions that disappears of carrier, it is with silicon (Si), titanium dioxide
Titanium (TiO2) and polypyrrole (PPy) level orderly form, i.e. Si/TiO2/ PPy level composite materials, Si are P (100) type monocrystalline
Silicon；TiO2It is the TiO of Rutile Type2Nanometer rods are N-type semiconductor, and quadrangular shape is highly 500~4000nm, a diameter of
40~250nm, orderly vertical-growth is in monocrystalline silicon surface；PPy is polypyrrole nano-particle, is P-type semiconductor, grain size for 10~
60nm, homoepitaxial is in TiO2Nanorod surfaces；Si/TiO2Si and TiO in/PPy level composite materials2Interface, TiO2With
PPy interfaces form double P/N hetero-junctions, can efficiently separate photogenerated charge, while have bionic insect compound eye structural, can be effective
Reduce reflectivity of the incident light on surface.
2. a kind of prepare the reflection bilayer P/N hetero-junctions level composite woods that disappear using monocrystalline silicon as carrier as described in claim 1
The preparation method of material, it is characterized in that, include the following steps：
(1) hydrophilic treated is carried out to silicon chip first, grows TiO on its surface2Crystal seed is placed in calcining a period of time in Muffle furnace
Natural cooling afterwards；
(2) and then by obtained surface in step (1) has TiO2The silicon chip of crystal seed is placed in reaction kettle, using hydrothermal synthesis
Method silicon chip surface grow TiO2Nanometer rods；
(3) TiO finally obtained in step (2)2PPy nano-particles are deposited in nanometer rods, obtain Si/TiO2/ PPy levels are answered
Condensation material.
3. preparation method according to claim 2, it is characterised in that：Hydrophilic treated operation described in step (1) is by silicon
Piece is placed in NH3H2O、H2O2And H2In the mixed solution of O, volume ratio 1:1:5, temperature is 90 DEG C, heating time 30min.
4. preparation method according to claim 2, it is characterised in that：Growth TiO described in step (1)2Crystal seed condition is will
Silicon chip after hydrophilic treated is dipped in the aqueous isopropanol of the butyl titanate of a concentration of 0.05~1mol/L and is lifted or revolved
It applies, the speed of lifting is 1~10mm/s, repeats lifting 5~30 times, the speed of spin coating is 500~7000 turns/min, finally by table
Has TiO in face2The silicon chip of particle calcines 30~60min in 450~500 DEG C of Muffle furnaces.
5. preparation method according to claim 2, it is characterised in that：Hydrothermal synthesizing condition described in step (2) for 80~
At a temperature of 200 DEG C, equipped with 10~20mL deionized waters, the concentrated hydrochloric acid and 0.5~5mL that 6~17mL mass fractions are 37%
2~19h is handled in the reaction kettle of butyl titanate, sample is then taken out and is dried up with nitrogen.
6. preparation method according to claim 2, it is characterised in that：Described in step (3) in TiO2It is deposited in nanometer rods
PPy nano-particles refer to using oxidation in situ in TiO2PPy conducting polymer particles are deposited in nanometer rods, reaction condition is：
By the FeCl of 0.01~0.06g3, 50~150uL pyrroles, 5~10mL ultra-pure waters be placed in beaker, reaction solution is formed, by face
Product has TiO for the surface growth of 1.5cm × 1.0cm2The silicon chip of nanometer rods is placed in reaction solution, keep at room temperature stirring 10~
60min obtains Si/TiO2/ PPy level composite materials.
It is 7. a kind of using monocrystalline silicon as the level composite material of the reflection bilayer P/N hetero-junctions that disappears of carrier as described in claim 1
Using the level composite material is used as the application of photocatalysis degradation organic contaminant, by the Si/ of 1.5cm × 1.0cm areas
TiO2/ PPy level composite materials are positioned over the methylene blue solution of 5mL, and a concentration of 1.0 × 10-5Then mol/L is placed it in
Dark place 1h allows it to reach absorption-desorption balance, carries out illumination to solution with light source later, degrades to methylene blue.
8. a kind of level composite material using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier exists as described in claim 1
Application in photoelectric conversion device.
9. a kind of level composite material using monocrystalline silicon as the reflection bilayer P/N hetero-junctions that disappears of carrier exists as described in claim 1
Application in area of solar cell.
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| CN101555629A (en) * | 2009-04-22 | 2009-10-14 | 上海第二工业大学 | Preparation method of self-assembled sulfonic acid group silane-titanium dioxide composite film on monocrystalline silicon substrate surface |
| CN101955665A (en) * | 2010-08-18 | 2011-01-26 | 重庆大学 | Method for preparing composite material of polypyrrole granules and titanium dioxide nanotube array |
| CN102350317A (en) * | 2011-07-04 | 2012-02-15 | 西安交通大学苏州研究院 | Polypyrrole/titanium dioxide composite adsorbent, its preparation, application and regeneration methods |
| CN102600907A (en) * | 2012-03-20 | 2012-07-25 | 南京大学 | Polypyrrole-sensitized hollow titanium dioxide nanometer photocatalyst and preparation method thereof |
| CN104677767A (en) * | 2015-03-04 | 2015-06-03 | 浙江大学 | QCM (quartz crystal microbalance) based polypyrrole/ titanium dioxide frequency type film gas sensitive sensor and preparation method thereof |
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| CN101555629A (en) * | 2009-04-22 | 2009-10-14 | 上海第二工业大学 | Preparation method of self-assembled sulfonic acid group silane-titanium dioxide composite film on monocrystalline silicon substrate surface |
| CN101955665A (en) * | 2010-08-18 | 2011-01-26 | 重庆大学 | Method for preparing composite material of polypyrrole granules and titanium dioxide nanotube array |
| CN102350317A (en) * | 2011-07-04 | 2012-02-15 | 西安交通大学苏州研究院 | Polypyrrole/titanium dioxide composite adsorbent, its preparation, application and regeneration methods |
| CN102600907A (en) * | 2012-03-20 | 2012-07-25 | 南京大学 | Polypyrrole-sensitized hollow titanium dioxide nanometer photocatalyst and preparation method thereof |
| CN104677767A (en) * | 2015-03-04 | 2015-06-03 | 浙江大学 | QCM (quartz crystal microbalance) based polypyrrole/ titanium dioxide frequency type film gas sensitive sensor and preparation method thereof |
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