CN105986292A - Preparation method for titanium dioxide nanotube array decorated with cobalt and nickel double-layer hydroxide and application of photoelectron-chemistry hydrolysis hydrogen production - Google Patents
Preparation method for titanium dioxide nanotube array decorated with cobalt and nickel double-layer hydroxide and application of photoelectron-chemistry hydrolysis hydrogen production Download PDFInfo
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- CN105986292A CN105986292A CN201610037434.8A CN201610037434A CN105986292A CN 105986292 A CN105986292 A CN 105986292A CN 201610037434 A CN201610037434 A CN 201610037434A CN 105986292 A CN105986292 A CN 105986292A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002071 nanotube Substances 0.000 title claims abstract description 55
- 239000010941 cobalt Substances 0.000 title claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 title claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000004070 electrodeposition Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000001291 vacuum drying Methods 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
- 150000004679 hydroxides Chemical class 0.000 claims description 25
- 229940051250 hexylene glycol Drugs 0.000 claims description 20
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 15
- 230000005518 electrochemistry Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002064 nanoplatelet Substances 0.000 claims description 4
- 238000002048 anodisation reaction Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000005034 decoration Methods 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 12
- 238000004321 preservation Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007073 chemical hydrolysis Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method for a titanium dioxide nanotube array electrode decorated with a cobalt and nickel double-layer hydroxide and application of photoelectron-chemistry hydrolysis hydrogen production. Through an electrochemical deposition method, the tube walls of titanium dioxide nanotubes are rapidly and controllably decorated with the cobalt and nickel double-layer hydroxide. The reaction process is rapid and efficient, and the covering density of CoNi-LHDs on the surfaces of the titanium dioxide nanotubes is controllable. The decoration of the CoNi-LHDs remarkably improves the ultraviolet light absorption efficiency of the titanium dioxide nanotubes and prolongs the service life of photo-generated electrons, separation between the photo-generated electrons and holes is accelerated, and the clean contact interfaces between the photo-generated electrons and the holes are also beneficial for transmission of the photo-generated electrons. By the adoption of the new method for compounding the titanium dioxide heterogeneous nanotube array electrode decorated with the cobalt and nickel double-layer hydroxide rapidly and controllably, operation is easy, industrialization is easy, and the new method has important application value.
Description
Technical field
The invention belongs to the synthesis field of inorganic semiconductor nanometer material, relate to a kind of cobalt, nickel double-layered hydroxides
(CoNi-LDHs) titanium dioxide (TiO modifying2) nanotube (TiO2@CoNi-LDHs) array electrode
Preparation method and in Optical Electro-Chemistry hydrolytic hydrogen production apply.
Background technology
From 1972, Tokyo Univ Japan Fujishima A and Honda K two professor's first report discovery
TiO2Single Crystalline Electrodes photochemical catalyzing thus produce this phenomenon of hydrogen and start, photolysis water hydrogen technology has been drawn
Play extensive concern.Directly utilize the method that solar energy prepares this clean energy resource of hydrogen as a kind of, in money
In the source age in short supply, the technology of development photocatalytic water seems ever more important.Increasing semi-conducting material all by with
It is used as the electrode material of photocatalytic water, such as ZnO, Fe2O3, TiO2, WO3Deng main research direction
It is being devoted to improve these semi-conducting materials to the absorption of visible ray and electricity conversion thereof.
TiO2It as a kind of stable and that there is superior electrochemical properties semi-conducting material, is widely used in gas
The fields such as body senses, piezoelectric, photochemical catalyst.TiO2Energy gap be 3.2eV, greater band gap, its
Light abstraction width is limited in ultraviolet region (only accounting for the 5% of solar energy gross energy), light induced electron under illumination condition
-hole-recombination is exceedingly fast, and photoelectric catalytically active is relatively low, thus directly uses TiO2As light anode material, it is difficult to high
Effect utilizes sunshine.A lot of method has been had to be used to change TiO2Specific surface and improve it to visible ray
Absorb and utilize, wherein based on nano-array surface deposit cobalt, nickel double-layered hydroxides to strengthen photoelectric conversion effect
The method of rate has obtained very big development.On the one hand cobalt, nickel double-layered hydroxides expand the absorption area to light,
On the other hand due to it, there is photoelectric catalytically active, the absorption to visible ray for the material can be promoted, in accelerated material
The separation of portion's light induced electron and transmission, be remarkably improved the Optical Electro-Chemistry activity of material.Therefore, a kind of letter of development
Easily controlled, easily operated electrochemical deposition synthesizes cobalt, the TiO of nickel double-layered hydroxides2The side of nano-array
Method has important theoretical research and is worth and actual application value.
Content of the invention
In view of this, the present invention provides the dioxy that a kind of cobalt, nickel double-layered hydroxides (CoNi-LDHs) are modified
Change titanium (TiO2) heterogeneous nanotube (i.e. TiO2@CoNi-LDHs) preparation method of array electrode, and at photoelectricity
Chemical hydrolysis hydrogen manufacturing is applied.
The present invention adopts the following technical scheme that to achieve these goals
The TiO that a kind of cobalt, nickel double-layered hydroxides are modified2The preparation method of nanometer pipe array electrode, its feature exists
In comprising the following steps:
(1) clean titanium sheet is carried out in the hexylene glycol aqueous solution dissolved with ammonium fluoride two-step anodization reaction,
Gained sample after reaction is cleaned and is placed in vacuum drying chamber vacuum drying, obtain growth in situ in titanium sheet substrate
On TiO2Nano-tube array；
(2), after the sample obtained by step (1) being placed in Muffle furnace the high temperature anneal, crystallinity is obtained good
Good TiO2Nano-tube array；
(3) by the TiO obtained by step (2)2Nano-tube array immerses in the electrolyte solution containing cobalt, nickel
A period of time, use three-electrode system to carry out electrochemical deposition, obtain TiO2The heterogeneous nanotube of@CoNi-LDHs
Array electrode.
The TiO that described a kind of cobalt, nickel double-layered hydroxides are modified2The preparation method of nanometer pipe array electrode, it is special
Levy and be: the amount of the ammonium fluoride described in step (1) is 0.1-10.0g.
The TiO that described a kind of cobalt, nickel double-layered hydroxides are modified2The preparation method of nanometer pipe array electrode, it is special
Levy and be: the volume of the hexylene glycol in step (1) is 10-90ml, and water volume is 0-10ml, dissolved with fluorine
The cumulative volume of the hexylene glycol aqueous solution changing ammonium is 100ml.
The TiO that described a kind of cobalt, nickel double-layered hydroxides are modified2The preparation method of nanometer pipe array electrode, it is special
Levy and be: in step (1), the constant voltage of anodic oxidation reactions is 10-80V for the first time, and the reaction time is 0.5-5
h；The constant voltage of anodic oxidation reactions is 20-80V for the second time, and the reaction time is 0.5-6h.Step (1)
In described vacuum drying temperature be 10-80 DEG C, the time is 1-12h.
The TiO that described a kind of cobalt, nickel double-layered hydroxides are modified2The preparation method of nanometer pipe array electrode, it is special
Levy and be: the calcination time in Muffle furnace described in step (2) is 10-120min, and calcining heat is
100-800℃。
The TiO that described a kind of cobalt, nickel double-layered hydroxides are modified2The preparation method of nanometer pipe array electrode, it is special
Levy and be: the CoCl described in step (3)2·6H2O、Ni(NO3)2·6H2The concentration of O electrolyte solution is 1mM-50
MM, volume is 50ml, and the electrochemical deposition time is 5-600s, and constant potential is-2.0-0V.
The TiO that described cobalt, nickel double-layered hydroxides are modified2The preparation method of nano-tube array, it is characterised in that:
CoNi-LDHs nanoplatelet is mainly deposited on TiO2The tube wall of nanotube and top, sample is at ultraviolet region
There is bigger absorption to light.
The TiO that described cobalt, nickel double-layered hydroxides are modified2Nanometer pipe array electrode produces in Optical Electro-Chemistry hydrolysis
The application in hydrogen field.
The TiO that a kind of cobalt, nickel double-layered hydroxides are modified2The preparation method of nanometer pipe array electrode, including with
Lower step:
(1) clean titanium sheet is carried out in the hexylene glycol aqueous solution dissolved with ammonium fluoride two-step anodization reaction,
Sample after reaction is carried out surface treatment and is placed in vacuum drying chamber dry, obtain vertical-growth in titanium sheet substrate
On TiO2Nano-tube array presoma；
(2), after the sample obtained by step (1) being placed in Muffle furnace the high temperature anneal, crystallinity is obtained good
Good TiO2Nano-tube array；
(3) by the TiO obtained by step (2)2Nano-tube array immerses a period of time in electrolyte solution,
By the TiO that electro-deposition method prepares cobalt, nickel double-hydroxide is modified2Heterogeneous nanometer pipe array electrode.
The amount of the ammonium fluoride described in step (1) is 0.1-10.0g.
The volume of the hexylene glycol in step (1) is 10-90ml, and water volume is 0-10ml, solution overall
Amass as 100ml.
The constant voltage of step (1) Anodic Oxidation reaction is 10-80V, and the reaction time is 0.5-5h.
Vacuum drying temperature described in step (1) is 20-80 DEG C, and the time is 1-12h.
Calcination time in Muffle furnace described in step (2) is 30-120min, and calcining heat is
400-800℃。
CoCl described in step (3)2·6H2O、Ni(NO3)2·6H2The concentration of O electrolyte solution is 1mM-50mM,
Volume is 50ml.
The electrochemical deposition time described in step (3) is 5-600s, and constant potential is-2.0-0V.
The TiO that cobalt prepared by the present invention, nickel double-layered hydroxides are modified2The maximum suction of nanometer pipe array electrode
Receive peak at ultraviolet region.
The TiO that cobalt provided by the present invention, nickel double-layered hydroxides are modified2Nanometer pipe array electrode is relative to just
The TiO beginning2Nanometer pipe array electrode all dramatically increases at the aspect such as stability and photoelectric transformation efficiency.
The present invention utilizes electrochemical deposition method to develop a kind of quick, controlledly synthesis cobalt, nickel double-layered hydroxides
The TiO modifying2The method of nanometer pipe array electrode.CoNi-LDHs nanoplatelet is deposited directly to TiO2
Nanotube tube wall and top.LDHs and TiO2Cleaning contact interface be conducive to light induced electron quick separating and
Transfer, is favorably improved the Optical Electro-Chemistry activity of combination electrode.
Compared with prior art, the invention provides a kind of quick, controlledly synthesis cobalt, nickel double-hydroxide modification
TiO2The new method of nanometer pipe array electrode.The deposition process of electrochemistry not only rapidly and efficiently, and
CoNi-LDHs nanoplatelet is at TiO2Nanotube surface coverage density is controlled, simultaneously good between the two
Contact be more beneficial for the transmission of light induced electron, be remarkably improved the Optical Electro-Chemistry activity of material.At clean energy resource
Preparation aspect there is important application prospect.This quick, the modification of controlledly synthesis cobalt, nickel double-hydroxide
TiO2The new method simple operation of heterogeneous nanometer pipe array electrode, it is easy to industrialization, has important using value.
Brief description
Fig. 1 is TiO2The SEM picture of nano-tube array.
Fig. 2 is TiO2The SEM picture of the heterogeneous nano-tube array of@CoNi-LDHs.
Fig. 3 is TiO2The SEM picture in nano-tube array cross section.
Fig. 4 is TiO2The SEM picture in@CoNi-LDHs heterogeneous nano-tube array cross section.
Fig. 5 is TiO2Nano-tube array and TiO2The Raman spectrogram of the heterogeneous nano-tube array of@CoNi-LDHs.
Fig. 6 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs is at light
Linear sweep voltammetry curve under the conditions of according to.
Fig. 7 is TiO2Nanometer pipe array electrode and TiO2The light of the heterogeneous nanometer pipe array electrode of@CoNi-LDHs
Solve water efficiency spectrogram.
Fig. 8 is TiO2Nanometer pipe array electrode and TiO2The electricity of the heterogeneous nanometer pipe array electrode of@CoNi-LDHs
Sub-life-span spectrogram.
Fig. 9 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs
IPCE spectrogram.
Figure 10 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs steady
Qualitative spectrogram.
Figure 11 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs is not
With the current-vs-time spectrogram under light intensity.
Figure 12 is TiO2Nanometer pipe array electrode and TiO2Consolidating of the heterogeneous nanometer pipe array electrode of@CoNi-LDHs
Body ultraviolet-visible spectrogram.
Figure 13 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs glimmering
Light spectrogram.
Figure 14 is TiO2Nanometer pipe array electrode and TiO2The light of the heterogeneous nanometer pipe array electrode of@CoNi-LDHs
Capture rate spectrogram.
Figure 15 is single nanotube enlarged diagram and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs
Mechanism schematic diagram.
Detailed description of the invention
Below in conjunction with specific embodiment, of the present invention related content is expanded on further.It is pointed out that these are real
Execute example be merely to illustrate the present invention rather than limit the scope of the present invention, and, in having read the present invention
After appearance, the present invention can be made various change or modification, these equivalent form of values by relevant technical staff in the field
Fall into the application appended claims limited range equally.
Embodiment 1
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 5mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 5s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.Fig. 1 is prepared
TiO2The SEM picture of nano-tube array.Illustrate under a very little enlargement ratio, TiO2Nano-tube array
Still remain regular pattern.Fig. 2 is TiO2The SEM picture of the heterogeneous nano-tube array of@CoNi-LDHs.
Visible CoNi-LDHs nano particle homoepitaxial is at TiO2The surface of nanotube.Fig. 3 is TiO2Nanotube battle array
The SEM picture in row cross section.Can be seen that TiO2Nano-tube array pattern is very uniform and regular.Fig. 4 is
TiO2The SEM picture in@CoNi-LDHs heterogeneous nano-tube array cross section.Show CoNi-LDHs nano particle
Homoepitaxial is at TiO2The tube wall of nanotube.Fig. 5 is TiO2Nano-tube array and TiO2@CoNi-LDHs
The Raman spectrogram of nano-tube array.It is found that in CoNi-LDHs nanoparticle deposition to TiO2Nanotube
After on, TiO2Raman signatures peak intensity there occurs change.Fig. 6 is TiO2Nano-tube array with
TiO2The linear sweep voltammetry curve under illumination condition of@CoNi-LDHs nano-tube array.Illustrate in illumination
Under the conditions of, TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs has bigger photoelectric current.Fig. 7 is TiO2
Nanometer pipe array electrode and TiO2The photocatalytic water efficiency spectrogram of@CoNi-LDHs nanometer pipe array electrode.Permissible
Discovery, TiO2The photocatalytic water efficiency of@CoNi-LDHs nanometer pipe array electrode is up to 1.01%, is original TiO2
3.3 times of nanometer pipe array electrode photocatalytic water efficiency.Fig. 8 is TiO2Nanometer pipe array electrode with
TiO2The electron lifetime spectrogram of the heterogeneous nanometer pipe array electrode of@CoNi-LDHs.In CoNi-LDHs nanometer
After grain is modified, electron lifetime substantially increases.Fig. 9 is TiO2Nanometer pipe array electrode and TiO2@CoNi-LDHs
The IPCE spectrogram of heterogeneous nanometer pipe array electrode.Illustrate that the introducing of CoNi-LDHs nano particle can improve
Photoelectric transformation efficiency.Figure 10 is TiO2Nanometer pipe array electrode and TiO2@CoNi-LDHs heterogeneous nanotube battle array
The stability spectrogram of row electrode.Showing the deposition by CoNi-LDHs nano particle, the stability of material has
Obvious raising.Figure 11 is TiO2Nanometer pipe array electrode and TiO2@CoNi-LDHs heterogeneous nanotube battle array
Current-vs-time spectrogram under different light intensity for the row electrode.Illustrate that the electrode after modifying is non-for the response of light intensity
Chang Youyi.Figure 12 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs
Solid uv-vis spectra figure.Show TiO2@CoNi-LDHs nano-tube material occurs in that at ultraviolet region
Significantly strengthen and absorb.Figure 13 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanotube of@CoNi-LDHs
The fluorescence spectrum figure of array electrode.Show CoNi-LDHs modify after light induced electron and hole separating power obvious
Strengthen.Figure 14 is TiO2Nanometer pipe array electrode and TiO2The heterogeneous nanometer pipe array electrode of@CoNi-LDHs
Light capture rate spectrogram.Show that CoNi-LDHs modifies and clearly enhance TiO2Nano-tube array is to ultraviolet light
Absorb.
Embodiment 2
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 5mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 20s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 3
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 5mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 30s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 4
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 5mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 60s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 5
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, with ethanol and
Deionized water replaces washing, is placed in vacuum drying chamber 60 DEG C, is dried 5h.Put into Muffle furnace, at 600 DEG C
High-temperature process 2h.Following compound concentration is the CoCl of 5mM2·6H2O、Ni(NO3)2·6H2O mixes
Solution, takes 50mL and is placed in beaker, is placed on electro-deposition 120s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 6
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, with ethanol and
Deionized water replaces washing, is placed in vacuum drying chamber 60 DEG C, is dried 5h.Put into Muffle furnace, at 600 DEG C
High-temperature process 2h.Following compound concentration is the CoCl of 5mM2·6H2O、Ni(NO3)2·6H2O mixes
Solution, takes 50mL and is placed in beaker, is placed on electro-deposition 300s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 7
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 5mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 600s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 8
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 10mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 30s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 9
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 15mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 30s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 10
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 30mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 30s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 11
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 60mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 30s under three-electrode system constant potential-1V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
Embodiment 12
Titanium sheet (1 × the 3cm that will polish smooth2) be dried in atmosphere after surface clean.Take the ammonium fluoride of 0.5g
It is dissolved in the hexylene glycol aqueous solution of 100mL, stirs, clean titanium sheet one end is immersed in above-mentioned solution,
The electrode holder of other end potentiostat is clamped, by Control of Voltage at 50V, 2h.Take out sample, use ethanol
Replace washing with deionized water, be placed in vacuum drying chamber 60 DEG C, be dried 5h.Put into Muffle furnace, 600 DEG C
Lower high-temperature process 2h.Following compound concentration is the CoCl of 60mM2·6H2O、Ni(NO3)2·6H2O mixes
Close solution, take 50mL and be placed in beaker, be placed on electro-deposition 30s under three-electrode system constant potential-0.5V.
Take out sample with ethanol and deionized water is alternately cleaned, be placed in vacuum drying chamber preservation.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improve
Also should be regarded as protection scope of the present invention with retouching.
Claims (8)
1. a preparation method for the titanium dioxide heterogeneous nanometer pipe array electrode that cobalt, nickel double-layered hydroxides are modified,
It is characterized in that, comprise the following steps:
(1) clean titanium sheet is carried out in the hexylene glycol aqueous solution dissolved with ammonium fluoride two-step anodization reaction,
Gained sample after reaction is cleaned and is placed in vacuum drying chamber vacuum drying, obtain growth in situ in titanium sheet substrate
On TiO2Nano-tube array；
(2), after the sample obtained by step (1) being placed in Muffle furnace the high temperature anneal, crystallinity is obtained good
Good TiO2Nano-tube array；
(3) by the TiO obtained by step (2)2Nano-tube array immerses in the electrolyte solution containing cobalt, nickel
A period of time, use three-electrode system to carry out electrochemical deposition, obtain TiO2The heterogeneous nanotube of@CoNi-LDHs
Array electrode.
2. the TiO that a kind of cobalt according to claim 1, nickel double-layered hydroxides are modified2Heterogeneous nano-tube array
The preparation method of electrode, it is characterised in that: the amount of the ammonium fluoride described in step (1) is 0.1-10.0g.
3. the TiO that a kind of cobalt according to claim 1, nickel double-layered hydroxides are modified2Heterogeneous nano-tube array
The preparation method of electrode, it is characterised in that: the volume of the hexylene glycol in step (1) is 10-90ml, water body
Amassing as 0-10ml, the cumulative volume dissolved with the hexylene glycol aqueous solution of ammonium fluoride is 100ml.
4. the TiO that a kind of cobalt according to claim 1, nickel double-layered hydroxides are modified2Heterogeneous nano-tube array
The preparation method of electrode, it is characterised in that: in step (1), the constant voltage of anodic oxidation reactions is 10-80 for the first time
V, the reaction time is 0.5-5h；The constant voltage of anodic oxidation reactions is 20-80V for the second time, and the reaction time is
0.5-6h.Described vacuum drying temperature in step (1) is 10-80 DEG C, and the time is 1-12h.
5. the TiO that a kind of cobalt according to claim 1, nickel double-layered hydroxides are modified2Heterogeneous nano-tube array
The preparation method of electrode, it is characterised in that: the calcination time in Muffle furnace described in step (2) is 10-120
Min, calcining heat is 100-800 DEG C.
6. the TiO that a kind of cobalt according to claim 1, nickel double-layered hydroxides are modified2Heterogeneous nano-tube array
The preparation method of electrode, it is characterised in that: the CoCl described in step (3)2·6H2O、Ni(NO3)2·6H2O electricity
The concentration of electrolyte solution is 1mM-50mM, and volume is 50ml, and the electrochemical deposition time is 5-600s, permanent
Current potential is-2.0-0V.
7. the TiO that the cobalt that prepared by method described in claim 1-7 any one, nickel double-layered hydroxides are modified2Heterogeneous
Nanometer pipe array electrode, it is characterised in that: CoNi-LDHs nanoplatelet is mainly deposited on TiO2Nanotube
Tube wall and top, sample has bigger absorption at ultraviolet region to light.
8. the TiO that the cobalt described in claim 7, nickel double-layered hydroxides are modified2Heterogeneous nanometer pipe array electrode is applied
Produce hydrogen field in Optical Electro-Chemistry hydrolysis.
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