CN108311131A - A kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material and preparation method - Google Patents
A kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material and preparation method Download PDFInfo
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- CN108311131A CN108311131A CN201711390130.0A CN201711390130A CN108311131A CN 108311131 A CN108311131 A CN 108311131A CN 201711390130 A CN201711390130 A CN 201711390130A CN 108311131 A CN108311131 A CN 108311131A
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- nanorod array
- titanic oxide
- oxide nanorod
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000002073 nanorod Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000002161 passivation Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 title claims abstract description 17
- 229910052593 corundum Inorganic materials 0.000 title claims 6
- 229910001845 yogo sapphire Inorganic materials 0.000 title claims 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000011521 glass Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003087 TiOx Inorganic materials 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 24
- 230000007547 defect Effects 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000005669 field effect Effects 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000024241 parasitism Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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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
-
- 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
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
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Abstract
The invention belongs to field of photocatalytic material, it is passivated titanic oxide nanorod array composite material more particularly to a kind of alundum (Al2O3) ultrathin membrane, which uniformly coats a diameter of 50 80nm by the aluminum oxide film that thickness is 5 30nm, the titanic oxide nanorod array that length is 500 800nm assembles.The beneficial effects of the invention are as follows：1, the present invention is using the method for atomic layer deposition in titanic oxide nanorod array coated with uniform aluminum oxide film, and preparation route is simple, and preparation process controllable precise.2, aluminum oxide film is used to be passivated titanic oxide nanorod array in the present invention, the fixed charge born in aluminum oxide film can carry out field-effect passivation to titanic oxide nanorod array surface, titanium dioxide surface defect concentration is reduced, electronics is reduced and transmits the compound probability of generation electron hole pair in titanic oxide nanorod array.
Description
Technical field
The invention belongs to field of photocatalytic material, and in particular to a kind of alundum (Al2O3) ultrathin membrane passivation titanium dioxide is received
Rice stick array composite material and preparation method thereof.
Background technology
In recent years, titanium dioxide nano-rod (titanium dioxide nanorod, TNR) array is because of its unique structure, excellent
Photoelectrochemical property has important application in solar cell, the depollution of environment, electrochemical energy storage etc., becomes this
Century great application prospect and can solve the problems, such as environment and global energy supply research hotspot.Experiment and theoretical study results
Show that the unique structure of titanic oxide nanorod array can be that efficiently separating for electron-hole provides channel, can improve
Luminous energy capture efficiency promotes photo-generated carrier separation and transmits, and has excellent photoelectrochemical behaviour so that it is in solar energy
Aspect has a wide range of applications.It is well known that solar conversion efficiency is mainly determined by efficient light absorption and charge transmission
It is fixed, however, titanic oxide nanorod array surface defect " capture/de- prisoner " phenomenon and disordered structure caused by electronics cause
The problems such as electron-transport tortuous path is complicated increases the recombination probability that electron-hole pair occurs in transmission process for electronics.
In addition, fixed charge density positive in titanic oxide nanorod array is larger, parasitic capacitance effect can be caused, reduce solar energy
Cell photoelectric transfer efficiency.In order to solve, titanium dioxide absorptivity is low and photo-generate electron-hole is high to recombination probability asks
Topic, various doping methods include that noble metal, transition metal, semiconductor doping etc. have all obtained certain progress, these elements
Doping can expand light absorption and inhibit photo-generate electron-hole to compound, but cannot reduce titanic oxide nanorod array
Surface defect and eliminate due in titanic oxide nanorod array positive fixed charge density it is excessively high caused by parasitic capacitance effect
It answers.Therefore how titanic oxide nanorod array is modified, reduces its surface defect, balance titanium dioxide nano-rod battle array
The positive fixed charge of overpopulation in row, raising titanic oxide nanorod array photo-generated carrier recombination rate, which is still, promotes it
The key technology of development.
Invention content
To solve the above-mentioned problems, the object of the present invention is to provide a kind of alundum (Al2O3) ultrathin membranes to be passivated titanium dioxide
Nanometer stick array composite material, the composite material coat a diameter of 500- by the aluminum oxide film that thickness is 5-30nm
The titanic oxide nanorod array of 800nm assembles, and titanium dioxide nano-rod battle array is passivated by alundum (Al2O3) ultrathin membrane
Row reduce titanic oxide nanorod array surface defect, balance the excessively high positive fixed electricity of density in titanic oxide nanorod array
Lotus improves titanic oxide nanorod array photo-generated carrier recombination rate.
The present invention provides the following technical solutions：
A kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material, the composite material is by thickness
The titanium dioxide that diameter of section is 50-80nm, length is 500-800nm is uniformly coated for the aluminum oxide film of 5-30nm
Nanometer stick array assembles.
The present invention also provides the systems that a kind of alundum (Al2O3) ultrathin membrane is passivated titanic oxide nanorod array composite material
Preparation Method comprises the following steps,
The preparation of S1, titanic oxide nanorod array,
Butyl titanate 10- is added under stirring conditions in S11 in the hydrochloric acid of every liter of a concentration of 5.2Mol/L
20ml is poured into after stirring evenly in reaction kettle, will be put into above-mentioned reaction for growing the carrier of titanic oxide nanorod array
In kettle, and the carrier and reaction kettle wall of inner container are at 30-40o, reaction kettle is sealed, 6-12h is reacted at 140-160 DEG C, it will
Carrier takes out from reaction kettle, and rinses its surface using deionized water, in 50-60 DEG C of freeze-day with constant temperature 10-30min, obtains table
Contain the carrier of titanic oxide nanorod array in face；
S2, aluminum oxide film is coated on titanic oxide nanorod array surface using atomic layer deposition method,
S21, the carrier that titanic oxide nanorod array is contained on the surface that S11 is obtained is put into atomic layer deposition apparatus chamber
In body, cavity temperature is set as 200 DEG C, is passed through silicon source pulse 0.02s into cavity successively, cleans pulse 8s, pulse of oxygen source
0.02s, irrigation source pulse 8s, cycle repeatedly 5-20 times to get to above-mentioned composite material.
Preferably, in the S11, carrier is FTO electro-conductive glass, above-mentioned FTO electro-conductive glass is put into reaction kettle, FTO
The conduction of electro-conductive glass is down.
Preferably, in the S11, reaction kettle is ptfe autoclave.
Preferably, in the S21, silicon source is trimethyl aluminium, purge gas N2, oxygen source H2O。
The beneficial effects of the invention are as follows：
1, the present invention aoxidizes two using the method for atomic layer deposition in titanic oxide nanorod array coated with uniform three
Aluminium film, preparation route is simple, and preparation process controllable precise.
2, aluminum oxide film is for being passivated titanic oxide nanorod array in the present invention, in aluminum oxide film
Negative fixed charge can carry out field-effect passivation to titanic oxide nanorod array surface, reduce titanium dioxide surface defect
Density reduces electronics and transmits the compound probability of generation electron-hole pair in titanic oxide nanorod array.
3, due in titanic oxide nanorod array there are the positive fixed charge that density is excessively high, the parasitism that will produce
Capacity effect, reduces the photoelectric conversion efficiency of titanic oxide nanorod array, and that is born in aluminum oxide film of the present invention consolidates
The excessively high positive fixed charge of density in titanic oxide nanorod array can effectively be balanced by determining charge, improved titanium dioxide and received
Rice stick array photo-generated carrier recombination rate is to improve its photoelectric conversion efficiency.
Description of the drawings
The structural schematic diagram of Fig. 1 composite materials of the present invention；
Fig. 2 is that prepare titanic oxide nanorod array be carrier and reaction kettle location diagram to the present invention；
Fig. 3 A are the SEM figures of composite material prepared by the embodiment of the present invention 8；
Fig. 3 B are the HRTEM figures of composite material prepared by the embodiment of the present invention 8；
Fig. 4 A are the ultraviolet visible absorption spectra figures that 4-8 of the embodiment of the present invention prepares product；
Fig. 4 B are the optical band gap figures that 4-8 of the embodiment of the present invention prepares product；
Fig. 5 is the luminescence generated by light spectrogram that 4-8 of the embodiment of the present invention prepares product；
Fig. 6 is the linear sweep voltammetry curve that 4-8 of the embodiment of the present invention prepares product.
Specific implementation mode
The present invention is illustrated with reference to specific embodiment.
Embodiment 1
The preparation of titanic oxide nanorod array,
Under conditions of magnetic agitation, butyl titanate 10ml is added in the hydrochloric acid of every liter of a concentration of 5.2Mol/L, stirs
It is poured into reaction kettle, the conduction of FTO electro-conductive glass is put into aforesaid reaction vessel down, and the FTO is led after mixing uniformly
Electric glass is with reaction kettle wall of inner container at 30o, reaction kettle is sealed, reacts 12h at 140 DEG C, carrier is taken from reaction kettle
Go out, and its surface is rinsed using deionized water, in 50 DEG C of freeze-day with constant temperature 10min, obtains surface and contain titanium dioxide nano-rod battle array
The carrier of row.
The titanic oxide nanorod array diameter of section prepared through this embodiment is 50-80nm.
Embodiment 2
The preparation of titanic oxide nanorod array,
Under conditions of magnetic agitation, butyl titanate 15ml is added in the hydrochloric acid of every liter of a concentration of 5.2Mol/L, stirs
It is poured into reaction kettle, the conduction of FTO electro-conductive glass is put into aforesaid reaction vessel down, and the FTO is led after mixing uniformly
Electric glass is with reaction kettle wall of inner container at 35o, reaction kettle is sealed, reacts 9h at 150 DEG C, carrier is taken out from reaction kettle,
And its surface is rinsed using deionized water, in 55 DEG C of freeze-day with constant temperature 20min, obtains surface and contain titanic oxide nanorod array
Carrier.
The titanic oxide nanorod array diameter of section prepared through this embodiment is 50-80nm.
Embodiment 3
The preparation of titanic oxide nanorod array,
Under conditions of magnetic agitation, butyl titanate 20ml is added in the hydrochloric acid of every liter of a concentration of 5.2Mol/L, stirs
It is poured into reaction kettle, the conduction of FTO electro-conductive glass is put into aforesaid reaction vessel down, and the FTO is led after mixing uniformly
Electric glass is with reaction kettle wall of inner container at 40o, reaction kettle is sealed, reacts 6h at 160 DEG C, carrier is taken out from reaction kettle,
And its surface is rinsed using deionized water, in 60 DEG C of freeze-day with constant temperature 30min, obtains surface and contain titanic oxide nanorod array
Carrier.
The titanic oxide nanorod array diameter of section prepared through this embodiment is 50-80nm.
Embodiment 4
The preparation of titanic oxide nanorod array,
Under conditions of magnetic agitation, butyl titanate 16ml is added in the hydrochloric acid of every liter of a concentration of 5.2Mol/L, stirs
It is poured into reaction kettle, the conduction of FTO electro-conductive glass is put into aforesaid reaction vessel down, and the FTO is led after mixing uniformly
Electric glass is with reaction kettle wall of inner container at 35o, reaction kettle is sealed, reacts 10h at 150 DEG C, carrier is taken from reaction kettle
Go out, and its surface is rinsed using deionized water, in 50 DEG C of freeze-day with constant temperature 30min, obtains surface and contain titanium dioxide nano-rod battle array
The carrier of row.
The titanic oxide nanorod array diameter of section prepared through this embodiment is 50-80nm.
Embodiment 5
A kind of preparation method of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material, including such as
Lower step,
The preparation of S1, titanic oxide nanorod array,
Butyl titanate is added in the hydrochloric acid of every liter of a concentration of 5.2Mol/L under conditions of magnetic agitation in S11
16ml is poured into after stirring evenly in reaction kettle, and the conduction of FTO electro-conductive glass is put into aforesaid reaction vessel down, and
The FTO electro-conductive glass is with reaction kettle wall of inner container at 35o, reaction kettle is sealed, reacts 10h at 150 DEG C, by carrier from reaction
It is taken out in kettle, and its surface is rinsed using deionized water, in 50 DEG C of freeze-day with constant temperature 30min, obtain surface and contain titanium dioxide receiving
The carrier of rice stick array；
S2, aluminum oxide film is coated on titanic oxide nanorod array surface using atomic layer deposition method,
S21, the carrier that titanic oxide nanorod array is contained on the surface that S11 is obtained is put into atomic layer deposition apparatus chamber
In body, cavity temperature is set as 200 DEG C, is passed through trimethyl aluminium pulse 0.02s, N into cavity successively2Pulse 8s, H2O pulses
0.02s, N2Pulse 8s, cycle repeatedly 5 times to get to the composite material of the present embodiment.
Uniformly to coat section straight by aluminum oxide film that thickness is 6nm for the composite material prepared through this embodiment
Diameter is that the titanic oxide nanorod array of 50-80nm assembles.
Embodiment 6
In the present embodiment alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material preparation method with
Preparation method in embodiment 5 is the difference is that " in S21, the present embodiment is passed through trimethyl aluminium pulse into cavity successively
0.02s, N2Pulse 8s, H2O pulses 0.02s, N2Pulse 8s, cycle 10 times repeatedly ".
Uniformly to coat section straight by aluminum oxide film that thickness is 12nm for the composite material prepared through this embodiment
Diameter is that the titanic oxide nanorod array of 50-80nm assembles.
Embodiment 7
In the present embodiment alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material preparation method with
Preparation method in embodiment 5 is the difference is that " in S21, the present embodiment is passed through trimethyl aluminium pulse into cavity successively
0.02s, N2Pulse 8s, H2O pulses 0.02s, N2Pulse 8s, cycle 15 times repeatedly ".
Uniformly to coat section straight by aluminum oxide film that thickness is 18nm for the composite material prepared through this embodiment
Diameter is that the titanic oxide nanorod array of 50-80nm assembles.
Embodiment 8
In the present embodiment alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material preparation method with
Preparation method in embodiment 5 is the difference is that " in S21, the present embodiment is passed through trimethyl aluminium pulse into cavity successively
0.02s, N2Pulse 8s, H2O pulses 0.02s, N2Pulse 8s, cycle 20 times repeatedly ".
Uniformly to coat section straight by aluminum oxide film that thickness is 24nm for the composite material prepared through this embodiment
Diameter is that the titanic oxide nanorod array of 50-80nm assembles.
Results and discussion
The product obtained in above-described embodiment is characterized.The micro- of product is observed using scanning electron microscope (SEM)
See pattern；The superfinishing micro-structure of product is observed using high-resolution-ration transmission electric-lens (HRTEM)；Using UV-Vis spectrophotometry luminosity
Count transmissivity and band gap that (UV-Vis) obtains product；Using photoluminescence spectrum (PL) to surface defect state and electronics-sky
Cave combining case is analyzed；Linear sweep voltammetry test is carried out to product using simulated solar light source and electrochemical workstation.
Fig. 3 A are the SEM figures of composite material prepared by the embodiment of the present invention 8, it can be seen that titanium dioxide is equal by size
Even nanometer stick array is assembled, and titanium dioxide nano-rod diameter of section is 50-150nm, length 500-800nm, top
Raised nutty structure is presented, Fig. 3 B are the HRTEM figures of composite material prepared by the embodiment of the present invention 8, it can be seen that titanium dioxide
Titanium nanorod surfaces have coated one layer of aluminum oxide film.
Fig. 4 is the ultraviolet visible absorption spectra and optical band gap that 4-8 of the embodiment of the present invention prepares product；0 cycle pairs in figure
Embodiment 4 is answered to prepare titanic oxide nanorod array, composite material prepared by 5cycle corresponding embodiments 5,10cycle is corresponded to
Composite material prepared by embodiment 6, composite material prepared by 15cycle corresponding embodiments 7,20cycle corresponding embodiments 8 are made
Standby composite material；Fig. 4 A are ultraviolet visible absorption spectra, by spectrogram as can be seen that using alundum (Al2O3) to titanium dioxide
Nanometer rods carry out different cycles passivation, can improve titanium dioxide nano-rod ultraviolet region absorptivity, be conducive to its
Application in terms of photoelectric device.Fig. 4 B are optical band gap figure, by figure as can be seen that passing through three using titanium dioxide nano-rod
After Al 2 O passivation, band gap increases to 3.08eV, band gap variation value very little, that is to say, that received in titanium dioxide by 3.01eV
Rice stick deposits relatively thin alundum (Al2O3) passivation layer, can ignore on band gap influence.
Fig. 5 is the luminescence generated by light spectrogram (PL) that 4-8 of the embodiment of the present invention prepares product；0cycle corresponding embodiments 4 in figure
Titanic oxide nanorod array, composite material prepared by 5cycle corresponding embodiments 5 are prepared, 10cycle corresponding embodiments 6 are made
Standby composite material, composite material prepared by 15cycle corresponding embodiments 7, composite wood prepared by 20cycle corresponding embodiments 8
Material；It can be seen from the figure that the PL spectral intensities of the titanium dioxide nano-rod after alundum (Al2O3) is passivated are substantially reduced, say
The defect state on the titanium dioxide nano-rod surface after bright alundum (Al2O3) passivation is reduced, and inhibits photo-generate electron-hole pair
It is compound.
Fig. 6 is the linear sweep voltammetry curve that 4-8 of the embodiment of the present invention prepares product；0cycle corresponding embodiments 4 in figure
Titanic oxide nanorod array, composite material prepared by 5cycle corresponding embodiments 5 are prepared, 10cycle corresponding embodiments 6 are made
Standby composite material, composite material prepared by 15cycle corresponding embodiments 7, composite wood prepared by 20cycle corresponding embodiments 8
Material；It can be seen from the figure that under the conditions of same light source, titanium dioxide nano-rod photoelectric current after alundum (Al2O3) is passivated
It is worth to apparent increase, especially under 0 bias, the photoelectric current of the corresponding composite materials of 20cycle is up to 0cycle pairs
10 times or so of the titanic oxide nanorod array answered, illustrate titanium dioxide nano-rod after being passivated by alundum (Al2O3)
More luminous energy can be absorbed, and there is better photo-generated carrier separative efficiency.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features.All essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (5)
1. a kind of alundum (Al2O3) ultrathin membrane is passivated titanic oxide nanorod array composite material, which is characterized in that the composite wood
Material be 5-30nm by thickness aluminum oxide film uniformly coat diameter of section be 50-80nm, two that length is 500-800nm
TiOx nano stick array assembles.
2. a kind of system of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material as described in claim 1
Preparation Method, which is characterized in that it comprises the following steps,
The preparation of S1, titanic oxide nanorod array,
Butyl titanate 10-20ml, stirring is added under stirring conditions in S11 in the hydrochloric acid of every liter of a concentration of 5.2Mol/L
It is poured into reaction kettle after uniformly, the carrier for growing titanic oxide nanorod array is put into aforesaid reaction vessel, and
Reaction kettle is sealed at 30-40 °, reacts 6-12h at 140-160 DEG C by the carrier and reaction kettle wall of inner container, by carrier from reaction
It is taken out in kettle, and its surface is rinsed using deionized water, in 50-60 DEG C of freeze-day with constant temperature 10-30min, obtained surface and contain dioxy
Change the carrier of titanium nanometer stick array；
S2, aluminum oxide film is coated on titanic oxide nanorod array surface using atomic layer deposition method,
S21, the carrier that titanic oxide nanorod array is contained on the surface that S11 is obtained is put into atomic layer deposition apparatus cavity,
Cavity temperature is set as 200 DEG C, is passed through silicon source pulse 0.02s into cavity successively, cleans pulse 8s, pulse of oxygen source 0.02s, clearly
Wash pulse 8s, cycle repeatedly 5-20 times to get to above-mentioned composite material.
3. a kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material according to claim 2
Preparation method, which is characterized in that in the S11, carrier is FTO electro-conductive glass, and above-mentioned FTO electro-conductive glass is put into reaction kettle
In, the conduction of FTO electro-conductive glass is down.
4. a kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material according to claim 2
Preparation method, which is characterized in that in the S11, reaction kettle is ptfe autoclave.
5. a kind of alundum (Al2O3) ultrathin membrane passivation titanic oxide nanorod array composite material according to claim 2
Preparation method, which is characterized in that in the S21, silicon source is trimethyl aluminium, purge gas N2, oxygen source H2O。
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Application publication date: 20180724 |