CN106119922B - A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof - Google Patents
A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof Download PDFInfo
- Publication number
- CN106119922B CN106119922B CN201610475885.XA CN201610475885A CN106119922B CN 106119922 B CN106119922 B CN 106119922B CN 201610475885 A CN201610475885 A CN 201610475885A CN 106119922 B CN106119922 B CN 106119922B
- Authority
- CN
- China
- Prior art keywords
- chip arrays
- composite material
- deionized water
- arrays film
- tiox nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Abstract
The present invention relates to the preparation methods that cuprous oxide is electrodeposited in the composite material on TiOx nano chip arrays film.This method includes：Copper acetate, deionized water are placed in reaction vessel and stirred, then sodium acetate is added in into reaction vessel, and reaction vessel is moved in water-bath and continues to stir to get electrolyte solution；Using TiOx nano chip arrays film as the working electrode in electrodeposition process, progress electrodeposition process obtains Cu in gained electrolyte solution2O/TiO2Nano-chip arrays film composite material.Cu is obtained on the surface of TiOx nano chip arrays film by successful deposition by the method for the present invention cuprous oxide2O/TiO2Nano-chip arrays film composite material, photoelectric current is 7.1 times of the cuprous sample of non-deposited oxide to the material after tested, has very high optical electro-chemistry enhancement effect, and in solar cell, environmental catalysis purification, optical electro-chemistry can store up aspect has potential using value.
Description
Technical field
The invention belongs to photocatalytic titanium oxide electrochemical technology fields, are specifically related to a kind of cuprous oxide and are electrodeposited in titanium oxide
Composite material on nano-chip arrays film and preparation method thereof.
Background technology
Titanium dioxide is a kind of stable chemical performance, semi-conducting material environmental-friendly, cheap and easy to get, in photocatalysis, light
Degradation and opto-electronic conversion field are widely used.People modify titanium dioxide using many methods：Such as noble metal
The doping of doping, metalloid anion and transition-metal cation so that the photo-electrochemical effect of titanium dioxide nanoplate obtains
To enhancing.The photo-electrochemical effect of titanium dioxide nanosheet film needs technical staff's progress further in the prior art
Exploitation and raising.
Invention content
It is thin that TiOx nano chip arrays are electrodeposited in order to solve the above technical problem, the present invention provides a kind of cuprous oxide
Composite material on film and preparation method thereof.The composite material photo-electrochemical effect that this method obtains is enhanced, photoelectric efficiency
It is improved.
In order to achieve the object of the present invention, present invention employs following technical schemes：
A kind of cuprous oxide is electrodeposited in the composite material on TiOx nano chip arrays film, including TiOx nano piece
Array film, { 101 } crystal face of the TiOx nano piece form TiOx nano chip arrays film surface, and the composite material is also
Cuprous oxide layer including being electrodeposited in the TiOx nano chip arrays film surface.
A kind of cuprous oxide is electrodeposited in the preparation method of the composite material on TiOx nano chip arrays film, including with
Lower preparation process：
Electrolyte solution is configured：Copper acetate, deionized water are placed in reaction vessel 4~6mim of stirring, then to described anti-
It answers and sodium acetate is added in container, and reaction vessel is moved in 30~50 DEG C of water-baths and continues 0.5~1h of stirring, obtain the electrolysis
Matter solution；The copper acetate, deionized water, sodium acetate substance amount ratio be (0.03~0.05):(27~28):
(0.06~0.1)；
Electro-deposition：Using TiOx nano chip arrays film as the working electrode in electrodeposition process, in above-mentioned gained electricity
Electrodeposition process is carried out in electrolyte solution and obtains the Cu2O/TiO2Nano-chip arrays film composite material；The electrodeposition process
Middle deposition voltage is set as -0.1V~-0.6V, and sedimentation time is 6~15min, and electrodeposition process keeps bath temperature 30~50
℃。
Further technical solution, the preparation process of the TiOx nano chip arrays film are：
A, FTO electro-conductive glass is cleaned by ultrasonic to 0.5~1h in acetone, alcohol, deionized water successively, nitrogen drying is treated
With；
B, take concentrated hydrochloric acid, deionized water be mixed 5~15min, be subsequently added into butyl titanate, continue stirring 5~
15min, add ammonium hexa-fluorotitanate futher stir 10~30min obtain configuration solution；The concentrated hydrochloric acid, deionized water, titanium
The volume ratio of sour four butyl esters is (12~15):(15~18):(0.3~0.8), the deionized water, the quality of ammonium hexa-fluorotitanate
Than for (15~18):(0.15~0.4)；
C, the FTO electro-conductive glass conduction cleaned up is put into polytetrafluoroethyllining lining upwardly, the configuration is molten
Liquid is poured into the liner, then the liner is packed into reaction kettle；
D, aforesaid reaction vessel being put into air dry oven, temperature setting is 150~180 DEG C in the air dry oven,
Baking oven switch is closed after 12~18h, takes out reaction kettle, after reaction kettle is naturally cooling to room temperature, taking-up is grown in FTO conduction glass
The TiOx nano chip arrays film sample on glass surface, and sample is cleaned repeatedly in deionized water, until cleaning up；
E, the sample is put into annealing furnace, set 2~4 DEG C/min of heating rate, to 400~550 DEG C after keep 2~
3h is naturally cooling to thereafter room temperature.
Further technical solution, the copper acetate, deionized water, which are placed in reaction vessel, stirs 5mim, continues in water-bath
Stir 1h；The copper acetate, deionized water, sodium acetate substance amount ratio be 0.025:27.8:0.07.
Further technical solution, the deposition voltage are -0.5V.
Further technical solution, platinum electrode is used as to electrode in the electrodeposition process, and Ag/AgCl is electric as reference
Pole.
Further technical solution, concentrated hydrochloric acid, deionized water, the volume ratio of butyl titanate are in the preparation process b
12:18:0.5, the deionized water, ammonium hexa-fluorotitanate mass ratio be 18:0.25.
Further technical solution, the volume of polytetrafluoroethyllining lining is 50ml in the preparation process c；It is described to prepare
Temperature setting is 170 DEG C in air dry oven in journey d, and baking oven switch is closed after 16h；Annealing furnace heats up in the preparation process e
4 DEG C/min of rate, annealing furnace is to keeping 2h after 500 DEG C.
The beneficial effects of the present invention are：
(1) for TiOx nano piece, since its { 001 } crystal face, the band edge structure of { 101 } crystal face and position are different, and
Cu of the present invention2O/TiO2Cu in nano-chip arrays film composite material2The conduction band of { 101 } crystal face of O and TiOx nano piece
Between there is the energy deviation value of bigger, therefore be capable of providing the driving force of bigger so that light induced electron is transferred to from cuprous oxide
On { 101 } crystal face of titanium oxide, so as to improve photoelectric efficiency.Further, since light induced electron is the conduction band orientation from { 001 } crystal face
Flow on the conduction band of { 101 } crystal face, work as Cu2After O is deposited on { 101 } crystal face, it will shorten electron transfer distance, and then
Photo-generate electron-hole is reduced to compound, raising material photoelectric properties.Structure novel of the present invention, photo-electrochemical effect are good.
(2) by cuprous oxide described in the method for the present invention by successful deposition in { 101 } of TiOx nano chip arrays film
On crystal face, Cu is obtained2O/TiO2Nano-chip arrays film composite material, after tested, photoelectric current is non-deposited oxide to the composite material
7.1 times of cuprous sample have very high optical electro-chemistry enhancement effect, in solar cell, environmental catalysis purification, optical electro-chemistry
There can be potential application value in terms of storage.
(3) the scanned Electronic Speculum observation of the TiOx nano chip arrays film being prepared by the method for the present invention, oxygen
It is dense sheet-like array structure to change titanium nanometer sheet, and a few vertical growths are on FTO electro-conductive glass, i.e., TiOx nano piece with
FTO electro-conductive glass is substantially vertical.It is learnt by Wulff structures, two sides of TiOx nano piece are { 001 } crystal face, four sides
Side is { 101 } crystal face, therefore the surface almost all of the TiOx nano chip arrays film is made of { 101 } crystal face.
In addition, monocrystalline TiOx nano chip arrays Direct Hydrothermal is grown on electro-conductive glass FTO, compared to the film preparation of polycrystal powder,
The directly growth in situ of monocrystalline TiOx nano piece sample can reduce resistance and sample and substrate FTO electro-conductive glass between crystal boundary
Between resistance, be conducive to electron transfer.
(4) present invention passes through preferred preparation parameter so that obtained Cu2O/TiO2Nano-chip arrays film composite material
Photo-electrochemical effect is farthest enhanced, such as：
The electric current measured by linear sweep voltammetry (LSV) shows that, when biasing 1.2V, deposition voltage is in -0.5V systems
Standby obtained sample shows maximum photoelectric current, reaches 17.22mA/cm2, it is 64.7 times of the cuprous sample of non-deposited oxide；
It is shown by transient state photocurrent response (I-t), when turning on light and recycling for the 4th, deposition voltage is prepared into -0.5V
The sample arrived has maximum photoelectric current；
In addition, shown by X-ray diffraction (XRD) collection of illustrative plates, deposition voltage reach -0.4V and more than when, this hair
Part cuprous oxide will be reduced into copper simple substance on the bright sample being prepared, and copper simple substance is due to high conductivity, it will
Electronics is promoted to flow to the conduction band of titanium oxide { 101 } crystal face by cuprous oxide, this is also good for photoelectric properties enhancing.
Stability test finds that TiOx nano chip arrays film has good stability in itself, is tested in 6000s
When, photoelectric current is almost unchanged, and the Cu that deposition voltage is prepared in -0.5V2O/TiO2Nano-chip arrays film composite material sample
Product show that electric current first increases, then land, this is because that sample surfaces is caused to start is more coarse for photoetch, increase specific surface
Product, electric current raising, then photoetch causes photoelectric current to decline, and from the point of view of whole test result, the present invention equally also has very
Good stability.
Description of the drawings
Fig. 1 is direction of growth schematic diagram of the TiOx nano piece of the present invention on FTO electro-conductive glass.
Fig. 2 is Cu of the present invention2O/TiO2The photoelectric properties enhancing principle schematic of nano-chip arrays film composite material.
Fig. 3 does not deposit Cu for the present invention2The TiO of O2Nano-chip arrays side surface of thin film scanning electron microscope (SEM) photograph.
Fig. 4 does not deposit Cu for the present invention2The 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 measured 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.
The meaning marked in attached drawing is as follows：
10- TiOx nano chip arrays film 20- cuprous oxide layer FTO- electro-conductive glass
Specific embodiment
More specific detail is made to technical solution of the present invention with reference to embodiment and attached drawing：
Embodiment 1
The preparation of TiOx nano chip arrays film：
A, FTO electro-conductive glass is cut into 2 × 4cm fritters, be cleaned by ultrasonic in acetone, alcohol, deionized water successively
0.5h, nitrogen drying are for use；
B, it takes concentrated hydrochloric acid, deionized water that 5min is mixed, is subsequently added into butyl titanate, continue to stir 5min, then add
Enter ammonium hexa-fluorotitanate futher stir 10min obtain configuration solution；The concentrated hydrochloric acid, deionized water, the volume of butyl titanate
Than being 14:15:0.3, the deionized water, ammonium hexa-fluorotitanate mass ratio be 15:0.15；The mass concentration of the concentrated hydrochloric acid is
37%, the hydrochloric acid solution of other certain concentration can also be used according to the amount of active principle to be configured；
C, the FTO electro-conductive glass conduction cleaned up is put into polytetrafluoroethyllining lining upwardly, configuration solution is fallen
Enter in the liner, then the liner is packed into reaction kettle；
D, aforesaid reaction vessel is put into air dry oven, temperature setting is 150 DEG C in the air dry oven, after 12h
Baking oven switch is closed, takes out reaction kettle, after reaction kettle is naturally cooling to room temperature, taking-up is grown in FTO conductive glass surfaces
TiOx nano chip arrays film sample, and sample is cleaned repeatedly in deionized water, until cleaning up；
E, the sample is put into annealing furnace, 2 DEG C/min of heating rate is set, to 400 DEG C after keep 2h, it is natural thereafter
It is cooled to room temperature.
Cuprous oxide is electrodeposited in the preparation method of the composite material on TiOx nano chip arrays film, i.e., in titanium oxide
The method of selective electrodeposition cuprous oxide on nano-chip arrays { 101 } crystal face, including：
Electrolyte solution is configured：Copper acetate, deionized water are placed in reaction vessel and stir 4mim, then is held to the reaction
Sodium acetate is added in device, and reaction vessel is moved in 30 DEG C of water-baths and continues to stir 0.5h, obtains the electrolyte solution；It is described
Copper acetate, deionized water, sodium acetate substance amount ratio be 0.03:27:0.06；
Electro-deposition：Using TiOx nano chip arrays film as the working electrode in electrodeposition process, in above-mentioned gained electricity
Electrodeposition process is carried out in electrolyte solution and obtains the Cu2O/TiO2Nano-chip arrays film composite material；The electrodeposition process
Middle platinum electrode is used as to electrode, and Ag/AgCl is as reference electrode；Deposition voltage is set as -0.1V in the electrodeposition process, sinks
The product time is 6min, and electrodeposition process keeps 30 DEG C of bath temperature.
Embodiment 2
The preparation of TiOx nano chip arrays film：
A, FTO electro-conductive glass is cut into 2 × 4cm fritters, is cleaned by ultrasonic 1h in acetone, alcohol, deionized water successively,
Nitrogen drying is for use；
B, it takes concentrated hydrochloric acid, deionized water that 15min is mixed, is subsequently added into butyl titanate, continue to stir 15min, then
Addition ammonium hexa-fluorotitanate futher stirs 30min and obtains configuration solution；The concentrated hydrochloric acid, deionized water, butyl titanate body
Product is than being 15:17:0.8, the deionized water, ammonium hexa-fluorotitanate mass ratio be 18:0.4；
C, the FTO electro-conductive glass conduction cleaned up is put into polytetrafluoroethyllining lining upwardly, configuration solution is fallen
Enter in the liner, then the liner is packed into reaction kettle；
D, aforesaid reaction vessel is put into air dry oven, temperature setting is 180 DEG C in the air dry oven, after 18h
Baking oven switch is closed, takes out reaction kettle, after reaction kettle is naturally cooling to room temperature, taking-up is grown in FTO conductive glass surfaces
TiOx nano chip arrays film sample, and sample is cleaned repeatedly in deionized water, until cleaning up；
E, the sample is put into annealing furnace, 4 DEG C/min of heating rate is set, to 550 DEG C after keep 3h, it is natural thereafter
It is cooled to room temperature.
Cuprous oxide is electrodeposited in the preparation method of the composite material on TiOx nano chip arrays film：
Electrolyte solution is configured：Copper acetate, deionized water are placed in reaction vessel and stir 6mim, then is held to the reaction
Sodium acetate is added in device, and reaction vessel is moved in 50 DEG C of water-baths and continues to stir 1h, obtains the electrolyte solution；The second
Sour copper, deionized water, sodium acetate substance amount ratio be 0.05:28:0.1；
Electro-deposition：Using TiOx nano chip arrays film as the working electrode in electrodeposition process, in above-mentioned gained electricity
Electrodeposition process is carried out in electrolyte solution and obtains the Cu2O/TiO2Nano-chip arrays film composite material；The electrodeposition process
Middle platinum electrode is used as to electrode, and Ag/AgCl is as reference electrode；Deposition voltage is set as -0.6V in the electrodeposition process, sinks
The product time is 15min, and electrodeposition process keeps 50 DEG C of bath temperature.
Embodiment 3
The preparation of TiOx nano chip arrays film：
A, FTO electro-conductive glass is cut into 2 × 4cm fritters, be cleaned by ultrasonic in acetone, alcohol, deionized water successively
0.6h, nitrogen drying are for use；
B, it takes concentrated hydrochloric acid, deionized water that 10min is mixed, is subsequently added into butyl titanate, continue to stir 10min, then
Addition ammonium hexa-fluorotitanate futher stirs 20min and obtains configuration solution；The concentrated hydrochloric acid, deionized water, butyl titanate body
Product is than being 12:18:0.5, the deionized water, ammonium hexa-fluorotitanate mass ratio be 18:0.25；
C, the FTO electro-conductive glass conduction cleaned up is put into polytetrafluoroethyllining lining upwardly, configuration solution is fallen
Enter in the liner, then the liner is packed into reaction kettle；
D, aforesaid reaction vessel is put into air dry oven, temperature setting is 170 DEG C in the air dry oven, after 16h
Baking oven switch is closed, takes out reaction kettle, after reaction kettle is naturally cooling to room temperature, taking-up is grown in FTO conductive glass surfaces
TiOx nano chip arrays film sample, and sample is cleaned repeatedly in deionized water, until cleaning up；
E, the sample is put into annealing furnace, set 3 DEG C/min of heating rate, to 500 DEG C after keep 2.5h, thereafter from
So it is cooled to room temperature.
Cuprous oxide is electrodeposited in the preparation method of the composite material on TiOx nano chip arrays film：
Electrolyte solution is configured：Copper acetate, deionized water are placed in reaction vessel and stir 5mim, then is held to the reaction
Sodium acetate is added in device, and reaction vessel is moved in 40 DEG C of water-baths and continues to stir 0.6h, obtains the electrolyte solution；It is described
Copper acetate, deionized water, sodium acetate substance amount ratio be 0.025:27.8:0.07；
Electro-deposition：Using TiOx nano chip arrays film as the working electrode in electrodeposition process, in above-mentioned gained electricity
Electrodeposition process is carried out in electrolyte solution and obtains the Cu2O/TiO2Nano-chip arrays film composite material；The electrodeposition process
Middle platinum electrode is used as to electrode, and Ag/AgCl is as reference electrode；Deposition voltage is set as -0.5V in the electrodeposition process, sinks
The product time is 8min, and electrodeposition process keeps 40 DEG C of bath temperature.
The Cu being prepared under Parameter Conditions described in above-described embodiment2O/TiO2Nano-chip arrays film composite material with
Cu is not deposited2The TiOx nano chip arrays film of O is compared, and composite material photo-electrochemical effect of the present invention obtains significantly after tested
Enhancing, photoelectric efficiency are significantly improved.
Fig. 1 simulates the direction of growth of the TiOx nano piece on FTO electro-conductive glass.It is prepared by the method for the present invention to obtain
TiO2The scanned Electronic Speculum observation of nano-chip arrays film, as shown in Figure 3,4, TiOx nano piece is dense sheet-like array knot
Structure, and a few vertical growths on FTO electro-conductive glass, i.e. TiOx nano piece and FTO electro-conductive glass is substantially vertical；Additionally by
Scanning electron microscope Fig. 5 is observed, and there is the cuprous oxide layer of other substances, i.e. electro-deposition on the surface of TiOx nano chip arrays film 10
20。
With reference to Fig. 2, Cu of the present invention is analyzed from principle2O/TiO2The photoelectric properties of nano-chip arrays film composite material：
For TiOx nano piece, since its { 001 } crystal face, { 101 } crystal face crystal face band edge structure and position are different, { 001 } crystal face,
Cu2Energy deviation value between O conduction bands is smaller, and Cu of the present invention2O/TiO2Cu in nano-chip arrays film composite material2O
Between the conduction band CB of { 101 } crystal face of TiOx nano piece there is the energy deviation value of bigger, therefore be capable of providing bigger
Driving force causes light induced electron to be transferred on { 101 } crystal face of titanium oxide from cuprous oxide, so as to improve photoelectric efficiency.In addition,
Since light induced electron is flowing on the conduction band CB of { 101 } crystal face from the conduction band CB orientations of { 001 } crystal face, work as Cu2O is deposited to
{ 101 } after on crystal face, it will shorten electron transfer distance, and then reduce photo-generate electron-hole to compound, raising material photo electric
Energy.Structure novel of the present invention, photo-electrochemical effect are good.
By cuprous oxide described in preparation method of the present invention by successful deposition in { 101 } of TiOx nano chip arrays film
On crystal face, Cu is obtained2O/TiO2Nano-chip arrays film composite material, after tested, photoelectric current is non-deposited oxide to the composite material
7.1 times of cuprous TiOx nano chip arrays film sample have very high optical electro-chemistry enhancement effect, in solar-electricity
Pond, environmental catalysis purification, optical electro-chemistry can store up aspect with potential application value.
From the test result of Fig. 6 it is found that when biasing 1.2V, deposition voltage is shown in -0.5V the samples being prepared
Maximum photoelectric current, reaches 17.22mA/cm2, it is the cuprous TiOx nano chip arrays film sample TNS of non-deposited oxide
64.7 times.
It was found from the test result of Fig. 7：The 4th turn on light cycle when, sample that deposition voltage is prepared in -0.5V
With maximum photoelectric current；
It was found from the test result of Fig. 8：The cuprous TiOx nano chip arrays film sample TNS of non-deposited oxide has in itself
There is good stability, when 6000s is tested, photoelectric current is almost unchanged, and the Cu that deposition voltage is prepared in -0.5V2O/
TiO2Nano-chip arrays film composite material sample shows that electric current first increases, then land, this is because photoetch causes sample table
Face starts more coarse, increases specific surface area, electric current raising, then photoetch causes photoelectric current to decline, from whole test
As a result from the point of view of, the present invention equally also has good stability.
Claims (7)
1. a kind of cuprous oxide is electrodeposited in the preparation method of the composite material on TiOx nano chip arrays film, including following
Preparation process：
Electrolyte solution is configured：Copper acetate, deionized water are placed in 4~6min of stirring in reaction vessel, then hold to the reaction
Sodium acetate is added in device, and reaction vessel is moved in 30~50 DEG C of water-baths and continues 0.5~1h of stirring, it is molten to obtain the electrolyte
Liquid；The copper acetate, deionized water, sodium acetate substance amount ratio be (0.03~0.05):(27~28):(0.06~
0.1)；
Electro-deposition：Using TiOx nano chip arrays film as the working electrode in electrodeposition process, in above-mentioned gained electrolyte
Electrodeposition process is carried out in solution and obtains Cu2O/TiO2Nano-chip arrays film composite material；Electricity is deposited in the electrodeposition process
Pressure is set as -0.1V~-0.6V, and sedimentation time is 6~15min, and electrodeposition process keeps 30~50 DEG C of bath temperature.
2. cuprous oxide as described in claim 1 is electrodeposited in the preparation of the composite material on TiOx nano chip arrays film
Method, it is characterised in that：The preparation process of the TiOx nano chip arrays film is：
A, FTO electro-conductive glass is cleaned by ultrasonic to 0.5~1h in acetone, alcohol, deionized water successively, nitrogen drying is for use；
B, it takes concentrated hydrochloric acid, deionized water that 5~15min is mixed, is subsequently added into butyl titanate, continues 5~15min of stirring,
Add ammonium hexa-fluorotitanate futher stir 10~30min obtain configuration solution；The concentrated hydrochloric acid, deionized water, four fourth of metatitanic acid
The volume ratio of ester is (12~15):(15~18):(0.3~0.8), the deionized water, ammonium hexa-fluorotitanate mass ratio be (15
~18):(0.15~0.4)；
C, the FTO electro-conductive glass conduction cleaned up is put into polytetrafluoroethyllining lining upwardly, the configuration solution is fallen
Enter in the liner, then the liner is packed into reaction kettle；
D, aforesaid reaction vessel is put into air dry oven, in the air dry oven temperature setting be 150~180 DEG C, 12~
Baking oven switch is closed after 18h, takes out reaction kettle, after reaction kettle is naturally cooling to room temperature, taking-up is grown in FTO electro-conductive glass tables
The TiOx nano chip arrays film sample in face, and sample is cleaned repeatedly in deionized water, until cleaning up；
E, the sample is put into annealing furnace, set 2~4 DEG C/min of heating rate, to 400~550 DEG C after keep 2~3h,
Thereafter it is naturally cooling to room temperature.
3. cuprous oxide as described in claim 1 is electrodeposited in the preparation of the composite material on TiOx nano chip arrays film
Method, it is characterised in that：The copper acetate, deionized water, which are placed in reaction vessel, stirs 5mim, continues to stir 1h in water-bath；Institute
State copper acetate, deionized water, sodium acetate substance amount ratio be 0.025:27.8:0.07.
4. cuprous oxide as described in claim 1 is electrodeposited in the preparation of the composite material on TiOx nano chip arrays film
Method, it is characterised in that：The deposition voltage is -0.5V.
5. cuprous oxide as described in claim 1 is electrodeposited in the preparation of the composite material on TiOx nano chip arrays film
Method, it is characterised in that：Platinum electrode is used as to electrode in the electrodeposition process, and Ag/AgCl is as reference electrode.
6. cuprous oxide as claimed in claim 2 is electrodeposited in the preparation of the composite material on TiOx nano chip arrays film
Method, it is characterised in that：Concentrated hydrochloric acid, deionized water, the volume ratio of butyl titanate are 12 in the preparation process b:18:0.5,
The deionized water, ammonium hexa-fluorotitanate mass ratio be 18:0.25.
7. cuprous oxide as claimed in claim 2 is electrodeposited in the preparation of the composite material on TiOx nano chip arrays film
Method, it is characterised in that：The volume of polytetrafluoroethyllining lining is 50ml in the preparation process c；Air blast in the preparation process d
Temperature setting is 170 DEG C in drying box, and baking oven switch is closed after 16h；4 DEG C of annealing furnace heating rate in the preparation process e/
Min, annealing furnace is to keeping 2h after 500 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610475885.XA CN106119922B (en) | 2016-06-23 | 2016-06-23 | A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610475885.XA CN106119922B (en) | 2016-06-23 | 2016-06-23 | A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106119922A CN106119922A (en) | 2016-11-16 |
| CN106119922B true CN106119922B (en) | 2018-06-26 |
Family
ID=57267145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610475885.XA Expired - Fee Related CN106119922B (en) | 2016-06-23 | 2016-06-23 | A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106119922B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108269693B (en) * | 2018-03-01 | 2020-05-05 | 萧县亿达信息科技有限公司 | Dye-sensitized solar cell based on optimized photo-anode |
| CN108927157B (en) * | 2018-06-27 | 2019-12-31 | 重庆市畜牧科学院 | Cu2O/{001}TiO2Preparation method of composite catalyst and application of composite catalyst to dynamic purification of ammonia gas |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101620935B (en) * | 2009-07-21 | 2012-05-30 | 华中师范大学 | TiO2-based composite film material with functions of solar energy storage and release |
| CN103088343B (en) * | 2013-01-15 | 2016-08-10 | 西安理工大学 | Cu2o/TiO2the preparation method of nano compound film |
| CN103225097A (en) * | 2013-05-15 | 2013-07-31 | 南京航空航天大学 | Preparation of Cu2O/TNTs (TiO2 nanotubes) heterojunction nano composite material and CO2 photoreduction method |
| CN103646989A (en) * | 2013-11-27 | 2014-03-19 | 华东师范大学 | Preparation method of p-n type Cu2O/TiO2 nanowire array composite film |
-
2016
- 2016-06-23 CN CN201610475885.XA patent/CN106119922B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106119922A (en) | 2016-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106119922B (en) | A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof | |
| Kmentova et al. | Photoelectrochemical and structural properties of TiO2 nanotubes and nanorods grown on FTO substrate: Comparative study between electrochemical anodization and hydrothermal method used for the nanostructures fabrication | |
| CN106381481B (en) | A kind of preparation method of metal-doped molybdenum disulfide film | |
| Kim et al. | The study of post annealing effect on Cu2O thin-films by electrochemical deposition for photoelectrochemical applications | |
| Zhou et al. | Copper selenide (Cu 3 Se 2 and Cu 2− x Se) thin films: electrochemical deposition and electrocatalytic application in quantum dot-sensitized solar cells | |
| CN104911629B (en) | A kind of synthetic method of combination electrode | |
| Yang et al. | Electrodeposited Cu2O on the {101} facets of TiO2 nanosheet arrays and their enhanced photoelectrochemical performance | |
| Zheng et al. | Morphology evolution of dendritic Fe wire array by electrodeposition, and photoelectrochemical properties of α-Fe 2 O 3 dendritic wire array | |
| CN105498773A (en) | Preparation method for doped iron oxide nanorod catalyst | |
| CN102732928A (en) | Preparation method of cuprous oxide semiconductor film material | |
| CN106450204A (en) | Preparation method of high cycle performance SnS2/TiO2 sodium ion battery anode materials | |
| CN110054224A (en) | A kind of stratiform tungsten trioxide photoelectrode material and preparation method thereof | |
| CN108465465A (en) | A kind of semiconductive thin film and preparation method thereof | |
| CN107680816B (en) | Preparation method of the porous Ti load hollow needle NiCo2S4 to electrode | |
| CN107020103B (en) | A kind of iron oxide-molybdenum sulfide-cuprous oxide photocatalysis film and its preparation method and application | |
| Xue et al. | Electrodeposition of Cu2O nanocrystalline on TiO2 nanosheet arrays by chronopotentiometry for improvement of photoelectrochemical properties | |
| Chen et al. | Morphology selective electrodeposition of Cu2O microcrystals on ZnO nanotube arrays as efficient visible-light-driven photo-electrode | |
| CN101734866A (en) | Method for preparing nano tungsten trioxide thin film | |
| CN103523818A (en) | Preparation method of height-oriented ZnO nanocone array structure material | |
| CN108545960A (en) | A kind of Y doping zinc oxide nanometers stick array preparation method | |
| Wang et al. | Optimization of photoelectrochemical performance in Pt-modified p-Cu2O/n-Cu2O nanocomposite | |
| CN108531939A (en) | Pt modifies Fe2O3Wrap up CuFeO2Photocathode and preparation method | |
| CN104947165B (en) | A kind of preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped | |
| Karn et al. | On the synthesis of nanostructured TiO2 anatase phase and the development of the photoelectrochemical solar cell | |
| Li et al. | Effects of bath pH on structural and electrochemical performance of Cu 2 O |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180626 Termination date: 20190623 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |