CN106119922A - A kind of Red copper oxide is electrodeposited in composite on TiOx nano chip arrays thin film and preparation method thereof - Google Patents
A kind of Red copper oxide is electrodeposited in composite on TiOx nano chip arrays thin film and preparation method thereof Download PDFInfo
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- CN106119922A CN106119922A CN201610475885.XA CN201610475885A CN106119922A CN 106119922 A CN106119922 A CN 106119922A CN 201610475885 A CN201610475885 A CN 201610475885A CN 106119922 A CN106119922 A CN 106119922A
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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
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- 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
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- 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
Abstract
The present invention relates to Red copper oxide and be electrodeposited in the preparation method of the composite on TiOx nano chip arrays thin film.The method includes: copper acetate, deionized water are placed in reaction vessel stirring, then add sodium acetate in reaction vessel, and reaction vessel moves to continue stirring in water-bath obtains electrolyte solution；Using TiOx nano chip arrays thin film as the working electrode in electrodeposition process, gained electrolyte solution carries out electrodeposition process and obtains Cu2O/TiO2Nano-chip arrays film composite material.By the inventive method Red copper oxide by successful deposition on the surface of TiOx nano chip arrays thin film, obtain Cu2O/TiO2Nano-chip arrays film composite material, this material photoelectric current after tested is 7.1 times of the cuprous sample of non-deposited oxide, has the highest Optical Electro-Chemistry enhancement effect, and at solaode, environmental catalysis purifies, Optical Electro-Chemistry can be stored up aspect and be had potential using value.
Description
Technical field
The invention belongs to photocatalytic titanium oxide technical field of electrochemistry, be specifically related to a kind of Red copper oxide and be electrodeposited in titanium oxide
Composite on nano-chip arrays thin film and preparation method thereof.
Background technology
Titanium dioxide is a kind of stable chemical performance, environmental friendliness, semi-conducting material cheap and easy to get, at photocatalysis, light
Degraded and opto-electronic conversion field are widely used.People use a lot of method to modify titanium dioxide: such as noble metal
Doping, metalloid anion and the doping of transition-metal cation so that the photo-electrochemical effect of titanium dioxide nanoplate obtains
To strengthening.In prior art, the photo-electrochemical effect of the titanium dioxide nanosheet film technical staff that needs is carried out further
Exploitation and raising.
Summary of the invention
In order to solve above-mentioned technical problem, it is thin that the present invention provides a kind of Red copper oxide to be electrodeposited in TiOx nano chip arrays
Composite on film and preparation method thereof.The composite photo-electrochemical effect that the method obtains is strengthened, photoelectric efficiency
It is improved.
In order to realize the purpose of the present invention, present invention employs techniques below scheme:
A kind of Red copper oxide is electrodeposited in the composite on TiOx nano chip arrays thin film, including TiOx nano sheet
Array film, described TiOx nano sheet 101} crystal face constitute TiOx nano chip arrays film surface, this composite is also
Including the Red copper oxide layer being electrodeposited in described TiOx nano chip arrays film surface.
A kind of Red copper oxide is electrodeposited in the preparation method of the composite on TiOx nano chip arrays thin film, including with
Lower preparation process:
Configuration electrolyte solution: copper acetate, deionized water are placed in reaction vessel stirring 4～6mim, then to described instead
Answer addition sodium acetate in container, and reaction vessel moves to continue in 30～50 DEG C of water-baths stirring 0.5～1h, obtain described electrolysis
Matter solution；Described copper acetate, deionized water, the ratio of amount of material of sodium acetate are (0.03～0.05): (27～28):
(0.06～0.1)；
Electro-deposition: using TiOx nano chip arrays thin film as the working electrode in electrodeposition process, at above-mentioned gained electricity
Electrolyte solution carries out electrodeposition process and obtains described Cu2O/TiO2Nano-chip arrays film composite material；Described electrodeposition process
Middle deposition voltage is set to-0.1V～-0.6V, and sedimentation time is 6～15min, and electrodeposition process keeps bath temperature 30～50
℃。
Further technical scheme, the preparation process of described TiOx nano chip arrays thin film is:
A, by FTO electro-conductive glass ultrasonic cleaning 0.5～1h in acetone, ethanol, deionized water successively, nitrogen dries up to be treated
With；
B, take concentrated hydrochloric acid, deionized water mix and blend 5～15min, be subsequently added into butyl titanate, continue stirring 5～
15min, add ammonium hexa-fluorotitanate stir further 10～30min obtain configure solution；Described concentrated hydrochloric acid, deionized water, titanium
The volume ratio of acid four butyl esters is (12～15): (15～18): (0.3～0.8), described deionized water, the quality of ammonium hexa-fluorotitanate
Than being (15～18): (0.15～0.4)；
C, the FTO electro-conductive glass conducting surface cleaned up upwards is put in polytetrafluoroethyllining lining, by molten for described configuration
Liquid is poured in described liner, then is loaded in reactor by described liner；
D, putting in air dry oven by aforesaid reaction vessel, described forced air drying the temperature inside the box is set to 150～180 DEG C,
Close baking oven switch after 12～18h, take out reactor, after question response still is naturally cooling to room temperature, takes out and be grown in FTO conduction glass
The TiOx nano chip arrays film sample on glass surface, and sample is cleaned the most repeatedly, until cleaning up；
E, described sample is put in annealing furnace, heating rate 2～4 DEG C/min is set, keep after 400～550 DEG C 2～
3h, is naturally cooling to thereafter room temperature.
Further technical scheme, described copper acetate, deionized water are placed in reaction vessel stirring 5mim, continue in water-bath
Stirring 1h；Described copper acetate, deionized water, the ratio of amount of material of sodium acetate are 0.025:27.8:0.07.
Further technical scheme, described deposition voltage is-0.5V.
Further technical scheme, in described electrodeposition process, platinum electrode is as to electrode, and Ag/AgCl is as reference electricity
Pole.
Further technical scheme, in described preparation process b, concentrated hydrochloric acid, deionized water, the volume ratio of butyl titanate are
12:18:0.5, described deionized water, the mass ratio of ammonium hexa-fluorotitanate are 18:0.25.
Further technical scheme, in described preparation process c, teflon-lined volume is 50ml；Described prepared
In journey d, forced air drying the temperature inside the box is set to 170 DEG C, closes baking oven switch after 16h；In described preparation process e, annealing furnace heats up
4 DEG C/min of speed, keeps 2h after annealing furnace to 500 DEG C.
The beneficial effects of the present invention is:
(1) for TiOx nano sheet, due to its 001} crystal face, the band edge structure of 101} crystal face is different with position, and
Cu of the present invention2O/TiO2Cu in nano-chip arrays film composite material2O and the { conduction band of 101} crystal face of TiOx nano sheet
Between there is bigger energy deviation value, therefore, it is possible to provide bigger driving force light induced electron is transferred to from Red copper oxide
Titanium oxide { on 101} crystal face, thus improve photoelectric efficiency.Additionally, due to light induced electron is from { the conduction band orientation of 001} crystal face
Flow to { on the conduction band of 101} crystal face, work as Cu2O deposit to after on 101} crystal face, it will and shorten electron transfer distance, and then
Minimizing photo-generate electron-hole, to compound, improves material photoelectric properties.Present configuration is novel, and photo-electrochemical effect is good.
(2) by Red copper oxide described in the inventive method by successful deposition at the { 101} of TiOx nano chip arrays thin film
On crystal face, obtain Cu2O/TiO2Nano-chip arrays film composite material, after tested, photoelectric current is non-deposited oxide to this composite
7.1 times of cuprous sample, have the highest Optical Electro-Chemistry enhancement effect, in solaode, environmental catalysis purification, Optical Electro-Chemistry
Aspect can be stored up there is potential using value.
(3) the described TiOx nano scanned electron microscopic observation of chip arrays thin film obtained, oxygen it are prepared by the method for the present invention
Changing titanium nanometer sheet is dense sheet-like array structure, and a few vertical growth is on FTO electro-conductive glass, i.e. TiOx nano sheet with
FTO electro-conductive glass is substantially vertical.Being learnt by Wulff structure, two sides of TiOx nano sheet are { 001} crystal face, four sides
Limit is that { 101} crystal face, { 101} crystal face is constituted the surface almost all of the most described TiOx nano chip arrays thin film by described.
Additionally, monocrystalline TiOx nano chip arrays Direct Hydrothermal is grown on electro-conductive glass FTO, compare the film preparation of polycrystal powder,
The original position direct growth of monocrystalline TiOx nano sheet sample can reduce resistance between crystal boundary, and sample and substrate FTO electro-conductive glass
Between resistance, beneficially electron transfer.
(4) present invention passes through preferred preparation parameter so that the Cu obtained2O/TiO2Nano-chip arrays film composite material
Photo-electrochemical effect is farthest strengthened, such as:
The electric current recorded by linear sweep voltammetry (LSV) is shown, when biasing 1.2V, deposition voltage is in-0.5V system
The standby sample obtained demonstrates the photoelectric current of maximum, reaches 17.22mA/cm-2, it is 64.7 times of the cuprous sample of non-deposited oxide；
Being shown by transient state photocurrent response (I-t), when turning on light and circulate for the 4th, deposition voltage is prepared at-0.5V
To sample have maximum photoelectric current；
It addition, shown by X-ray diffraction (XRD) collection of illustrative plates, deposition voltage reach-0.4V and above when, this
The bright sample upper part Red copper oxide prepared will be reduced into copper simple substance, and copper simple substance is owing to having high electrical conductivity, it will
{ conduction band of 101} crystal face, this is also good for photoelectric properties enhancing to promote to be flowed to titanium oxide by Red copper oxide by electronics.
Stability test finds, TiOx nano chip arrays thin film itself has good stability, tests at 6000s
Time, photoelectric current is almost unchanged, and the Cu that deposition voltage prepares at-0.5V2O/TiO2Nano-chip arrays film composite material sample
Product show, electric current first raises, then land, and this is that to cause sample surfaces to start more coarse due to photoetch, increases specific surface
Long-pending, electric current raises, and then photoetch causes photoelectric current to decline, and from the point of view of overall test result, the present invention the most also has very
Good stability.
Accompanying drawing explanation
Fig. 1 is the TiOx nano sheet of the present invention direction of growth schematic diagram on FTO electro-conductive glass.
Fig. 2 is Cu of the present invention2O/TiO2The photoelectric properties of nano-chip arrays film composite material strengthen principle schematic.
Fig. 3 is that the present invention does not deposits Cu2The TiO of O2Nano-chip arrays side surface of thin film scanning electron microscope (SEM) photograph.
Fig. 4 is that the present invention does not deposits Cu2The TiO of O2Nano-chip arrays film surface scanning electron microscope (SEM) photograph.
Fig. 5 is Cu of the present invention2O/TiO2The scanning electron microscope (SEM) photograph of nano-chip arrays film composite material.
Fig. 6 is Cu of the present invention2O/TiO2Nano-chip arrays film composite material is recorded by linear sweep voltammetry (LSV)
Current curve.
Fig. 7 is Cu of the present invention2O/TiO2Nano-chip arrays film composite material is shown by transient state photocurrent response (I-t)
Current curve.
Fig. 8 is Cu of the present invention2O/TiO2The stability test curve of nano-chip arrays film composite material.
In accompanying drawing, the implication of labelling is as follows:
10-TiOx nano chip arrays thin film 20-Red copper oxide layer FTO-electro-conductive glass
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing technical solution of the present invention made more specific detail:
Embodiment 1
The preparation of TiOx nano chip arrays thin film:
A, FTO electro-conductive glass is cut into 2 × 4cm fritter, successively ultrasonic cleaning in acetone, ethanol, deionized water
0.5h, nitrogen dries up stand-by；
B, take concentrated hydrochloric acid, deionized water mix and blend 5min, be subsequently added into butyl titanate, continue stirring 5min, then add
Enter ammonium hexa-fluorotitanate stir further 10min obtain configure solution；Described concentrated hydrochloric acid, deionized water, the volume of butyl titanate
Ratio is 14:15:0.3, and described deionized water, the mass ratio of ammonium hexa-fluorotitanate are 15:0.15；The mass concentration of described concentrated hydrochloric acid is
37%, the hydrochloric acid solution of other concentration can also configure use according to the amount of active substance certainly；
C, the FTO electro-conductive glass conducting surface cleaned up upwards is put in polytetrafluoroethyllining lining, configuration solution is fallen
Enter in described liner, more described liner is loaded in reactor；
D, putting in air dry oven by aforesaid reaction vessel, described forced air drying the temperature inside the box is set to 150 DEG C, after 12h
Closedown baking oven switchs, and takes out reactor, after question response still is naturally cooling to room temperature, takes out and is grown in FTO conductive glass surface
TiOx nano chip arrays film sample, and sample is cleaned the most repeatedly, until cleaning up；
E, described sample is put in annealing furnace, 2 DEG C/min of heating rate is set, after 400 DEG C, keep 2h, natural thereafter
It is cooled to room temperature.
Red copper oxide is electrodeposited in the preparation method of the composite on TiOx nano chip arrays thin film, i.e. at titanium oxide
Nano-chip arrays the method for selective electrodeposition Red copper oxide on 101} crystal face, including:
Configuration electrolyte solution: copper acetate, deionized water are placed in reaction vessel stirring 4mim, then hold to described reaction
Device adds sodium acetate, and moves to reaction vessel 30 DEG C of water-baths continue stirring 0.5h, obtain described electrolyte solution；Described
Copper acetate, deionized water, the ratio of amount of material of sodium acetate are 0.03:27:0.06；
Electro-deposition: using TiOx nano chip arrays thin film as the working electrode in electrodeposition process, at above-mentioned gained electricity
Electrolyte solution carries out electrodeposition process and obtains described Cu2O/TiO2Nano-chip arrays film composite material；Described electrodeposition process
Middle platinum electrode is as to electrode, and Ag/AgCl is as reference electrode；In described electrodeposition process, deposition voltage is set to-0.1V, heavy
The long-pending time is 6min, and electrodeposition process keeps bath temperature 30 DEG C.
Embodiment 2
The preparation of TiOx nano chip arrays thin film:
A, FTO electro-conductive glass is cut into 2 × 4cm fritter, ultrasonic cleaning 1h in acetone, ethanol, deionized water successively,
Nitrogen dries up stand-by；
B, take concentrated hydrochloric acid, deionized water mix and blend 15min, be subsequently added into butyl titanate, continue stirring 15min, then
Addition ammonium hexa-fluorotitanate stirs 30min further and obtains configuring solution；Described concentrated hydrochloric acid, deionized water, the body of butyl titanate
Long-pending ratio is 15:17:0.8, and described deionized water, the mass ratio of ammonium hexa-fluorotitanate are 18:0.4；
C, the FTO electro-conductive glass conducting surface cleaned up upwards is put in polytetrafluoroethyllining lining, configuration solution is fallen
Enter in described liner, more described liner is loaded in reactor；
D, putting in air dry oven by aforesaid reaction vessel, described forced air drying the temperature inside the box is set to 180 DEG C, after 18h
Closedown baking oven switchs, and takes out reactor, after question response still is naturally cooling to room temperature, takes out and is grown in FTO conductive glass surface
TiOx nano chip arrays film sample, and sample is cleaned the most repeatedly, until cleaning up；
E, described sample is put in annealing furnace, 4 DEG C/min of heating rate is set, after 550 DEG C, keep 3h, natural thereafter
It is cooled to room temperature.
Red copper oxide is electrodeposited in the preparation method of the composite on TiOx nano chip arrays thin film:
Configuration electrolyte solution: copper acetate, deionized water are placed in reaction vessel stirring 6mim, then hold to described reaction
Device adds sodium acetate, and moves to reaction vessel 50 DEG C of water-baths continue stirring 1h, obtain described electrolyte solution；Described second
Acid copper, deionized water, the ratio of amount of material of sodium acetate are 0.05:28:0.1；
Electro-deposition: using TiOx nano chip arrays thin film as the working electrode in electrodeposition process, at above-mentioned gained electricity
Electrolyte solution carries out electrodeposition process and obtains described Cu2O/TiO2Nano-chip arrays film composite material；Described electrodeposition process
Middle platinum electrode is as to electrode, and Ag/AgCl is as reference electrode；In described electrodeposition process, deposition voltage is set to-0.6V, heavy
The long-pending time is 15min, and electrodeposition process keeps bath temperature 50 DEG C.
Embodiment 3
The preparation of TiOx nano chip arrays thin film:
A, FTO electro-conductive glass is cut into 2 × 4cm fritter, successively ultrasonic cleaning in acetone, ethanol, deionized water
0.6h, nitrogen dries up stand-by；
B, take concentrated hydrochloric acid, deionized water mix and blend 10min, be subsequently added into butyl titanate, continue stirring 10min, then
Addition ammonium hexa-fluorotitanate stirs 20min further and obtains configuring solution；Described concentrated hydrochloric acid, deionized water, the body of butyl titanate
Long-pending ratio is 12:18:0.5, and described deionized water, the mass ratio of ammonium hexa-fluorotitanate are 18:0.25；
C, the FTO electro-conductive glass conducting surface cleaned up upwards is put in polytetrafluoroethyllining lining, configuration solution is fallen
Enter in described liner, more described liner is loaded in reactor；
D, putting in air dry oven by aforesaid reaction vessel, described forced air drying the temperature inside the box is set to 170 DEG C, after 16h
Closedown baking oven switchs, and takes out reactor, after question response still is naturally cooling to room temperature, takes out and is grown in FTO conductive glass surface
TiOx nano chip arrays film sample, and sample is cleaned the most repeatedly, until cleaning up；
E, described sample is put in annealing furnace, 3 DEG C/min of heating rate is set, after 500 DEG C, keep 2.5h, thereafter from
So it is cooled to room temperature.
Red copper oxide is electrodeposited in the preparation method of the composite on TiOx nano chip arrays thin film:
Configuration electrolyte solution: copper acetate, deionized water are placed in reaction vessel stirring 5mim, then hold to described reaction
Device adds sodium acetate, and moves to reaction vessel 40 DEG C of water-baths continue stirring 0.6h, obtain described electrolyte solution；Described
Copper acetate, deionized water, the ratio of amount of material of sodium acetate are 0.025:27.8:0.07；
Electro-deposition: using TiOx nano chip arrays thin film as the working electrode in electrodeposition process, at above-mentioned gained electricity
Electrolyte solution carries out electrodeposition process and obtains described Cu2O/TiO2Nano-chip arrays film composite material；Described electrodeposition process
Middle platinum electrode is as to electrode, and Ag/AgCl is as reference electrode；In described electrodeposition process, deposition voltage is set to-0.5V, heavy
The long-pending time is 8min, and electrodeposition process keeps bath temperature 40 DEG C.
The Cu prepared under Parameter Conditions described in above-described embodiment2O/TiO2Nano-chip arrays film composite material with
Do not deposit Cu2The TiOx nano chip arrays thin film of O is compared, and composite photo-electrochemical effect the most of the present invention obtains significantly
Strengthen, photoelectric efficiency is significantly improved.
Fig. 1 simulates the TiOx nano sheet direction of growth on FTO electro-conductive glass.It is prepared by the method for the present invention and obtains
TiO2The scanned electron microscopic observation of nano-chip arrays thin film, as shown in Figure 3,4, TiOx nano sheet is dense sheet-like array knot
Structure, and a few vertical growth is on FTO electro-conductive glass, i.e. TiOx nano sheet is substantially vertical with FTO electro-conductive glass；Additionally by
Scanning electron microscope Fig. 5 observes, and there is the Red copper oxide layer of other materials, i.e. electro-deposition on the surface of TiOx nano chip arrays thin film 10
20。
In conjunction with Fig. 2, from principle, analyze Cu of the present invention2O/TiO2The photoelectric properties of nano-chip arrays film composite material:
For TiOx nano sheet, due to its 001} crystal face, 101} crystal face crystal face band edge structure is different with position, 001} crystal face,
Cu2Energy deviation value between O conduction band is less, and Cu of the present invention2O/TiO2Cu in nano-chip arrays film composite material2O
And TiOx nano sheet there is between the conduction band CB of 101} crystal face bigger energy deviation value, therefore, it is possible to provide bigger
Driving force makes light induced electron { 101} crystal face, thus improve photoelectric efficiency from what titanium oxide transferred to by Red copper oxide.Additionally,
Owing to light induced electron is from { the flowing to of the conduction band CB of 001} crystal face orientation { the conduction band CB of 101} crystal face, works as Cu2O deposits to
{ after on 101} crystal face, it will shorten electron transfer distance, and then minimizing photo-generate electron-hole is to compound, improves material photo electric
Energy.Present configuration is novel, and photo-electrochemical effect is good.
By Red copper oxide described in preparation method of the present invention by successful deposition at the { 101} of TiOx nano chip arrays thin film
On crystal face, obtain Cu2O/TiO2Nano-chip arrays film composite material, after tested, photoelectric current is non-deposited oxide to this composite
7.1 times of cuprous TiOx nano chip arrays film sample, have the highest Optical Electro-Chemistry enhancement effect, in solar-electricity
Pond, environmental catalysis purify, Optical Electro-Chemistry can be stored up aspect and be had potential using value.
Knowable to the test result of Fig. 6, when biasing 1.2V, the sample that deposition voltage prepares at-0.5V demonstrates
Maximum photoelectric current, reaches 17.22mA/cm-2, it is the cuprous TiOx nano chip arrays film sample TNS of non-deposited oxide
64.7 times.
Knowable to the test result of Fig. 7: when turning on light and circulate for the 4th, the sample that deposition voltage prepares at-0.5V
There is the photoelectric current of maximum；
Knowable to the test result of Fig. 8: TiOx nano chip arrays film sample TNS itself tool that non-deposited oxide is cuprous
Having good stability, when 6000s tests, photoelectric current is almost unchanged, and the Cu that deposition voltage prepares at-0.5V2O/
TiO2Nano-chip arrays film composite material sample shows, electric current first raises, then lands, and this is owing to photoetch causes sample table
Face starts more coarse, increases specific surface area, and electric current raises, and then photoetch causes photoelectric current to decline, from overall test
From the point of view of result, the present invention the most also has good stability.
Claims (8)
1. a Red copper oxide is electrodeposited in the composite on TiOx nano chip arrays thin film, it is characterised in that: include oxygen
Change titanium nano-chip arrays thin film, described TiOx nano sheet 101} crystal face constitutes TiOx nano chip arrays film surface, this
Composite also includes the Red copper oxide layer being electrodeposited in described TiOx nano chip arrays film surface.
2. the composite that a Red copper oxide as claimed in claim 1 is electrodeposited on TiOx nano chip arrays thin film
Preparation method, including following preparation process:
Configuration electrolyte solution: copper acetate, deionized water are placed in reaction vessel stirring 4～6mim, then hold to described reaction
Device adds sodium acetate, and reaction vessel moves to continue in 30～50 DEG C of water-baths stirring 0.5～1h, obtain described electrolyte molten
Liquid；Described copper acetate, deionized water, the ratio of amount of material of sodium acetate are (0.03～0.05): (27～28): (0.06～
0.1)；
Electro-deposition: using TiOx nano chip arrays thin film as the working electrode in electrodeposition process, at above-mentioned gained electrolyte
Solution carries out electrodeposition process and obtains Cu2O/TiO2Nano-chip arrays film composite material；Deposition electricity in described electrodeposition process
Pressure is set to-0.1V～-0.6V, and sedimentation time is 6～15min, electrodeposition process holding bath temperature 30～50 DEG C.
3. Red copper oxide as claimed in claim 2 is electrodeposited in the preparation of the composite on TiOx nano chip arrays thin film
Method, it is characterised in that: the preparation process of described TiOx nano chip arrays thin film is:
A, by FTO electro-conductive glass ultrasonic cleaning 0.5～1h in acetone, ethanol, deionized water successively, nitrogen dries up stand-by；
B, take concentrated hydrochloric acid, deionized water mix and blend 5～15min, be subsequently added into butyl titanate, continue stirring 5～15min,
Add ammonium hexa-fluorotitanate stir further 10～30min obtain configure solution；Described concentrated hydrochloric acid, deionized water, metatitanic acid four fourth
The volume ratio of ester is (12～15): (15～18): (0.3～0.8), and described deionized water, the mass ratio of ammonium hexa-fluorotitanate are (15
～18): (0.15～0.4)；
C, the FTO electro-conductive glass conducting surface cleaned up upwards is put in polytetrafluoroethyllining lining, described configuration solution is fallen
Enter in described liner, more described liner is loaded in reactor；
D, putting in air dry oven by aforesaid reaction vessel, described forced air drying the temperature inside the box is set to 150～180 DEG C, 12～
Close baking oven switch after 18h, take out reactor, after question response still is naturally cooling to room temperature, takes out and be grown in FTO electro-conductive glass table
The TiOx nano chip arrays film sample in face, and sample is cleaned the most repeatedly, until cleaning up；
E, described sample is put in annealing furnace, heating rate 2～4 DEG C/min is set, after 400～550 DEG C, keep 2～3h,
Thereafter room temperature it is naturally cooling to.
4. Red copper oxide as claimed in claim 2 is electrodeposited in the preparation of the composite on TiOx nano chip arrays thin film
Method, it is characterised in that: described copper acetate, deionized water are placed in reaction vessel stirring 5mim, continue stirring 1h in water-bath；Institute
The ratio of the amount stating the material of copper acetate, deionized water, sodium acetate is 0.025:27.8:0.07.
5. Red copper oxide as claimed in claim 2 is electrodeposited in the preparation of the composite on TiOx nano chip arrays thin film
Method, it is characterised in that: described deposition voltage is-0.5V.
6. Red copper oxide as claimed in claim 2 is electrodeposited in the preparation of the composite on TiOx nano chip arrays thin film
Method, it is characterised in that: in described electrodeposition process, platinum electrode is as to electrode, and Ag/AgCl is as reference electrode.
7. Red copper oxide as claimed in claim 3 is electrodeposited in the preparation of the composite on TiOx nano chip arrays thin film
Method, it is characterised in that: in described preparation process b, concentrated hydrochloric acid, deionized water, the volume ratio of butyl titanate are 12:18:0.5,
Described deionized water, the mass ratio of ammonium hexa-fluorotitanate are 18:0.25.
8. Red copper oxide as claimed in claim 3 is electrodeposited in the preparation of the composite on TiOx nano chip arrays thin film
Method, it is characterised in that: in described preparation process c, teflon-lined volume is 50ml；Air blast in described preparation process d
Dry the temperature inside the box is set to 170 DEG C, closes baking oven switch after 16h；Annealing furnace heating rate 4 DEG C in described preparation process e/
Min, keeps 2h after annealing furnace to 500 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108269693A (en) * | 2018-03-01 | 2018-07-10 | 深圳森阳环保材料科技有限公司 | Dye-sensitized solar cells based on optimization light anode |
| CN108927157A (en) * | 2018-06-27 | 2018-12-04 | 重庆市畜牧科学院 | Cu2O/{001}TiO2The preparation method of composite catalyst and its application to ammonia dynamic purification |
| CN114216945A (en) * | 2021-12-14 | 2022-03-22 | 安徽大学 | Nickel-iron oxide composite material and preparation method and application thereof |
| CN115591557A (en) * | 2022-10-10 | 2023-01-13 | 东北石油大学（Cn） | Photocatalytic nano material and preparation method and application thereof |
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| CN108269693A (en) * | 2018-03-01 | 2018-07-10 | 深圳森阳环保材料科技有限公司 | Dye-sensitized solar cells based on optimization light anode |
| CN108927157A (en) * | 2018-06-27 | 2018-12-04 | 重庆市畜牧科学院 | Cu2O/{001}TiO2The preparation method of composite catalyst and its application to ammonia dynamic purification |
| CN114216945A (en) * | 2021-12-14 | 2022-03-22 | 安徽大学 | Nickel-iron oxide composite material and preparation method and application thereof |
| CN115591557A (en) * | 2022-10-10 | 2023-01-13 | 东北石油大学（Cn） | Photocatalytic nano material and preparation method and application thereof |
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