CN107268061B - A kind of additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof - Google Patents
A kind of additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof Download PDFInfo
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- CN107268061B CN107268061B CN201710327503.3A CN201710327503A CN107268061B CN 107268061 B CN107268061 B CN 107268061B CN 201710327503 A CN201710327503 A CN 201710327503A CN 107268061 B CN107268061 B CN 107268061B
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
Abstract
The invention discloses a kind of additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof.The present invention is that additive Mn film of Nano tube array of titanium dioxide is prepared in situ with anodizing, combines anodic oxidation to be removed by heat treatment, and be transferred on ceramic tube and be fabricated to gas sensor.Preparation process of the present invention is simple, cost is relatively low, technological parameter is convenient for controlling, the additive Mn film of Nano tube array of titanium dioxide compound with regular structure of preparation, and nanotube size uniformity, optical band gap reduces, and air-sensitive performance is obviously improved.
Description
Technical field
The invention belongs to Semiconductor gas sensors materials and device preparation field, and in particular to a kind of additive Mn nano titania
Pipe array films and gas sensor with and preparation method thereof.
Background technique
Gas sensor is a kind of senser element for detecting specific gas in environment, by the way that gaseous species and concentration etc. to have
Close information be converted to electric signal, obtained according to these electric signals under test gas in the environment there are situations, be widely used in
The fields such as biology, industry and environmental monitoring.It is small that heater-type gas sensor overcomes directly-heated type gas sensor thermal capacity, vulnerable to
Ambient windstream influences, and the disadvantages of poor contact easily occurs, possesses preferable stability, becomes the gas sensing being currently mainly used
Device.
Gas sensor mainly includes that semiconductor gas sensor, Electro-chemical Gas Sensor and catalytic combustion type air-sensitive pass
Sensor etc., wherein semiconductor transducer is because having high sensitivity, and response and recovery time are fast, long service life and cheap
The advantages that, it is to use most wide one of sensor in the world at present.Titanium dioxide is nontoxic, inexpensive, stability is good, is a kind of excellent
Semiconductor gas sensors material.The titanium dioxide but prepared at present using conventional method is since specific surface area is smaller, optical band gap
The reasons such as larger, air-sensitive performance are still relatively low.
Titanium dioxide nano material is a kind of material being made of the unit with nano-scale, and biggish surface area can
The active site of material surface is significantly increased, gas-sensitive activity (the ACS Appl.Mater.Interfaces of titanium dioxide is promoted
2013,5:8516,J.Phys.Chem.C 2010,114:9970).Preparing titanium dioxide gas sensor generally uses powder at present
Body cladding process (ACS Appl.Mater.Interfaces 2013,5:12310) leads to unordered accumulation and influences material nano effect
The performance answered.Film of Nano tube array of titanium dioxide is a kind of nano material of unique structure, the nano tube structure aligned
Biggish specific surface area can be provided, and unidirectional tubular structure possesses preferable transmission channel and adsorption capacity
(Sens.Actuators B 2011,156:505, Sensors 2012,12:3302) so that electronics can directly along caliber to turn
Move to the surface of gas sensor.In addition, by doping (Sensors can be regulated and controled to the optical band gap of titanium dioxide
2013,13:14764), and then improve its response to gas.Manganese element ionic radius and titanium are close, can be in dioxy by doping
Change and introduce impurity energy level in the optical band gap of titanium, energy needed for reducing electron transition effectively promotes the gas sensing property of titanium dioxide
Energy.
Summary of the invention
The main purpose of the present invention is to provide a kind of preparation process, and simple, technological parameter is excellent convenient for control, air-sensitive performance
Good additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is that, a kind of additive Mn Nano tube array of titanium dioxide
Film, it is characterised in that obtained by following steps:
1) using clean commodity titanium sheet as anode, graphite flake is cathode, with ethylene glycol-ammonium fluoride (NH4F)-manganese acetate (Mn
(CH3COO)2) system makees electrolyte, 0.5~3h of anodic oxidation is carried out under 20~40V voltage；It is combined by dioxygen water process super
Sonication removes the oxide layer of titanium plate surface, place into above-mentioned identical electrolyte carry out two-step anodization reaction 1~
6h；Reacted titanium sheet is cleaned up and dried, the additive Mn film of Nano tube array of titanium dioxide being grown in titanium sheet is obtained
(titanium sheet after drying)；
2) titanium sheet after drying is subjected at 350~550 DEG C 2~5h of heat treatment, obtains the rutile titania being grown in titanium sheet
Mine phase additive Mn film of Nano tube array of titanium dioxide (titanium sheet after being heat-treated)；Titanium sheet after heat treatment is put into above-mentioned steps
1) in identical electrolyte, 10~15h of anodic oxidation reactions three times is carried out at 20~40V, by additive Mn titania nanotube
Array films are stripped down from titanium sheet；(i.e. array films can be used the titanium sheet on convex surface, it can also be used membrane material that collection falls off
Its planform, such as plane), it is cleaned up, is dried with ethyl alcohol, obtain the additive Mn nano titania not comprising titanium sheet
Pipe array films (or film of Nano tube array).
The preparation method of above-mentioned a kind of additive Mn film of Nano tube array of titanium dioxide, it is characterised in that comprise the steps of:
1) using clean commodity titanium sheet as anode, graphite flake is cathode, with ethylene glycol-ammonium fluoride (NH4F)-manganese acetate (Mn
(CH3COO)2) system makees electrolyte, 0.5~3h of anodic oxidation is carried out under 20~40V voltage；It is combined by dioxygen water process super
Sonication removes the oxide layer of titanium plate surface, place into above-mentioned identical electrolyte carry out two-step anodization reaction 1~
6h；Reacted titanium sheet is cleaned up and dried, the additive Mn film of Nano tube array of titanium dioxide being grown in titanium sheet is obtained
(titanium sheet after drying)；
2) titanium sheet after drying is subjected at 350~550 DEG C 2~5h of heat treatment, obtains the rutile titania being grown in titanium sheet
Mine phase additive Mn film of Nano tube array of titanium dioxide (titanium sheet after being heat-treated)；Titanium sheet after heat treatment is put into above-mentioned steps
1) in identical electrolyte, 10~15h of anodic oxidation reactions three times is carried out at 20~40V, by additive Mn titania nanotube
Array films are stripped down from titanium sheet；(i.e. array films can be used the titanium sheet on convex surface, it can also be used membrane material that collection falls off
Its planform, such as plane), it is cleaned up, is dried with ethyl alcohol, obtain the additive Mn nano titania not comprising titanium sheet
Pipe array films (or film of Nano tube array).
It is described to strip down additive Mn film of Nano tube array of titanium dioxide from titanium sheet are as follows: anode is combined by heat treatment
Oxidation technology carries out.
The titanium sheet is bending, when carrying out anodic oxidation reactions, the convex surface face cathode of titanium sheet.
The electrolyte includes the ammonium fluoride (NH of the deionized water of 0.9~7.2wt%, 0.2~1wt%4) and 0.05 F~
Manganese acetate (Mn (the CH of 1g/L3COO)2), ethylene glycol is surplus.
In the TiO 2 sol component, butyl titanate: dehydrated alcohol: acetylacetone,2,4-pentanedione: water=20mL:110mL:
5mL:3mL。
A kind of additive Mn film of Nano tube array of titanium dioxide gas sensor, it is characterised in that obtained by following steps: by manganese
Doped titanium dioxide nanotube array film (or film of Nano tube array) is put into the TiO 2 sol of preparation, then by gas sensitive element
Part ceramic tube is put into TiO 2 sol, is wrapped in film of Nano tube array on gas sensor ceramic tube；Nanotube will be wrapped up
The ceramic tube of array films is put into 80~120 DEG C of baking oven drying, places into and is heat-treated 2~5h in Muffle furnace at 350~550 DEG C,
Obtain additive Mn film of Nano tube array of titanium dioxide gas sensor.
A kind of production method of above-mentioned additive Mn film of Nano tube array of titanium dioxide gas sensor, it is characterised in that comprising with
Lower step: additive Mn film of Nano tube array of titanium dioxide (or film of Nano tube array) is put into the TiO 2 sol of preparation
In, then gas sensor ceramic tube is put into TiO 2 sol, it is wrapped in film of Nano tube array on gas sensor ceramic tube；
The ceramic tube for wrapping up film of Nano tube array is put into 80~120 DEG C of baking oven drying, is placed into Muffle furnace at 350~550 DEG C
It is heat-treated 2~5h, obtains additive Mn film of Nano tube array of titanium dioxide gas sensor.
Beneficial effects of the present invention:
1, a kind of ethylene glycol electrolyte system is researched and developed, and manganese source is added wherein, manganese element is realized using anodizing
Original position doping to titanium dioxide, the complete additive Mn film of Nano tube array of titanium dioxide of preparation structure, reduces in titanium sheet
The optical band gap of titanium dioxide, improves air-sensitive performance；Anode oxidation process is combined using heat treatment, by the nanotube battle array of preparation
Column film is completely removed from titanium sheet.This method help to obtain large scale additive Mn film of Nano tube array of titanium dioxide, is convenient for
Industrialization.
2, present invention is alternatively directed to the design feature of heater-type gas sensor columnar ceramic tube elements, design when preparing sample
Titanium sheet is bending, obtains bending additive Mn film of Nano tube array of titanium dioxide, and using TiO 2 sol as bonding
Agent is perfectly adhered to the film of Nano tube array on columnar ceramic pipe, good with ceramic tube shape compatible degree.It is applied with conventional powder
The method of covering is compared, and the gas sensor that the present invention makes has the one-way pipeline shape structure of proper alignment, possesses excellent longitudinal transmission
Channel and adsorption capacity improve the air-sensitive performance of element.
3, process of the invention is simple, cost is relatively low, technological parameter is convenient for control, is advantageously implemented scale.The nanometer
Structure can provide biggish specific surface area, and the integrality of array membrane material can effectively play the advantage of nano material, and unidirectional
Tubular structure possesses preferable transmission channel and adsorption capacity；Additive Mn can introduce impurity energy in the optical band gap of titanium dioxide
Grade effectively promotes the air-sensitive performance of titanium dioxide.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of additive Mn film of Nano tube array of titanium dioxide gas sensor.1 is additive Mn dioxy in figure
Change titanium nanotube, 2 be Pt electrode, and 3 be ceramic tube, and 4 be nichrome resistance, and 5 be gas molecule.
Fig. 2 is the pictorial diagram of additive Mn film of Nano tube array of titanium dioxide gas sensor.
Fig. 3 is the XRD spectrum of additive Mn film of Nano tube array of titanium dioxide (Mn-TNTAs) prepared by embodiment 1.
Fig. 4 is the FE-SEM image (top view) of additive Mn film of Nano tube array of titanium dioxide prepared by embodiment 1.
Fig. 5 is the FE-SEM image (side view) of additive Mn film of Nano tube array of titanium dioxide prepared by embodiment 1.
Fig. 6 is the XPS Mn2p map of additive Mn film of Nano tube array of titanium dioxide prepared by embodiment 1.
Fig. 7 is the film of Nano tube array of titanium dioxide (b-TNTAs) and embodiment of commodity P25 (a-P25), undoped manganese
(the α hv) of the additive Mn film of Nano tube array of titanium dioxide (c-Mn-TNTAs) of 1 preparation2~hv curve graph.
Fig. 8 is commodity P25 (a-P25) gas sensor, the film of Nano tube array of titanium dioxide (b-TNTAs) undoped with manganese
Additive Mn film of Nano tube array of titanium dioxide (c-Mn-TNTAs) gas sensor prepared by gas sensor and embodiment 1 is in 4.5V
To the sensitivity curve of ethyl alcohol under voltage.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described, but protection model of the invention should not be limited with this
It encloses.
Embodiment 1:
Using the titanium sheet of surface polishing as anode, titanium sheet is rolled into arc, the convex surface face graphite flake cathode of titanium sheet, with second two
Alcohol-NH4F-Mn(CH3COO)2System makees electrolyte, the NH of deionized water, 0.3wt% in electrolyte comprising 1.8wt%4F and
Mn (the CH of 0.1g/L3COO)2, ethylene glycol is surplus (following embodiment is identical), and anodic oxidation 1h is carried out under 30V voltage.It will
Titanium sheet after oxidation immerses 10min in 30% hydrogen peroxide, takes out and immerses ultrasound 10min in deionized water, and removal titanium plate surface is raw
At oxidation film, place into above-mentioned identical electrolyte carry out two-step anodization reaction 3h.By reacted titanium sheet second
Alcohol cleans up, and is put into 80 DEG C of baking ovens and dries, is subsequently placed into Muffle furnace and is heat-treated 3h at 450 DEG C.By what is be heat-treated
Titanium sheet is put into above-mentioned identical electrolyte, and anodic oxidation reactions 10h three times is carried out at 30V, can be by the additive Mn two in titanium sheet
Titania nanotube array film is more fully removed；The membrane material that convex surface falls off is collected, is cleaned up with ethyl alcohol, dries, obtains
Additive Mn film of Nano tube array of titanium dioxide (or film of Nano tube array), for use.
The additive Mn film of Nano tube array of titanium dioxide of collection is put into the TiO 2 sol of preparation, then by gas sensitive element
Part ceramic tube is put into TiO 2 sol, is wrapped in film of Nano tube array on gas sensor ceramic tube.Nanotube will be wrapped up
The ceramic tube of array films is put into 80 DEG C of baking oven drying, places into Muffle furnace and is heat-treated 3h at 450 DEG C, obtains additive Mn dioxy
Change titanium film of Nano tube array gas sensor.
Embodiment 2:
Referring to embodiment 1, the difference is that the NH of deionized water, 0.5wt% in electrolyte comprising 5.4wt%4F and
Mn (the CH of 0.5g/L3COO)2.In 20V voltage anodic oxygen 1.5h, two-step anodization reaction 6h (20V) prepares material.Clearly
After wash clean, be put into 110 DEG C of baking ovens and dry, then in be heat-treated 4h at 350 DEG C.Anodic oxidation reactions 12h three times
(20V).Film of Nano tube array ceramics tube elements are made according to the method for embodiment 1,110 DEG C dry, after 350 DEG C of heat treatment 4h,
Obtain additive Mn film of Nano tube array of titanium dioxide gas sensor.
Embodiment 3:
Referring to embodiment 1, the difference is that the NH of deionized water, 0.2wt% in electrolyte comprising 3.6wt%4F and
Mn (the CH of 0.2g/L3COO)2.In 40V voltage anodic oxygen 0.5h, two-step anodization reaction 1h (40V) prepares material.Clearly
After wash clean, be put into 90 DEG C of baking ovens and dry, then in be heat-treated 4h at 550 DEG C.Anodic oxidation reactions 15h (40V) three times.
Film of Nano tube array ceramics tube elements are made according to the method for embodiment 1, and 90 DEG C dry, and after being heat-treated 4h at 550 DEG C, obtain manganese
Doped titanium dioxide nanotube array film gas sensor.
Embodiment 4:
Referring to embodiment 1, the difference is that the NH of deionized water, 0.8wt% in electrolyte comprising 0.9wt%4F and
Mn (the CH of 0.05g/L3COO)2.In 35V voltage anodic oxygen 2h, two-step anodization reaction 2h (35V) prepares material.Clearly
After wash clean, be put into 100 DEG C of baking ovens and dry, then in be heat-treated 5h at 400 DEG C.Anodic oxidation reactions 11h three times
(35V).Film of Nano tube array ceramics tube elements are made according to the method for embodiment 1,100 DEG C dry, after 400 DEG C of heat treatment 5h,
Obtain additive Mn film of Nano tube array of titanium dioxide gas sensor.
Embodiment 5:
Referring to embodiment 1, the difference is that the NH of deionized water, 1wt% in electrolyte comprising 7.2wt%4F and 1g/
Mn (the CH of L3COO)2.In 25V voltage anodic oxygen 3h, two-step anodization reaction 4h (25V) prepares material.It cleans up
Afterwards, it is put into 120 DEG C of baking ovens and dries, be then heat-treated 2h at 500 DEG C.Anodic oxidation reactions 13h (25V) three times.According to reality
The method production film of Nano tube array ceramics tube elements of example 1 are applied, 120 DEG C dry, and after 500 DEG C of heat treatment 2h, obtain additive Mn two
Titania nanotube array film gas sensor.
Fig. 1 and Fig. 2 is the structural schematic diagram of additive Mn film of Nano tube array of titanium dioxide gas sensor of the invention respectively
And pictorial diagram.
Fig. 3 is the XRD spectrum of the additive Mn film of Nano tube array of titanium dioxide (Mn-TNTAs) prepared in embodiment 1.Manganese
Doped titanium dioxide nanotube array material is Anatase, without other miscellaneous phases in material.
Fig. 4 is the FE-SEM image (top view) of the additive Mn film of Nano tube array of titanium dioxide prepared in embodiment 1.It receives
Mitron array structure is excellent, the outer diameter of nanotube about 60nm, pipe thickness about 8nm, reflects that the nano-tube array membrane material is gathered around
There is biggish specific surface area, material can be promoted to the response of test gas.It can control dioxy by changing anodic oxidation voltage
Change the caliber and wall thickness of titanium nano-tube array.
Fig. 5 is the FE-SEM image (side view) of the additive Mn film of Nano tube array of titanium dioxide prepared in embodiment 1, pipe
About 3.8 μm of length/film thickness.Can control the film thickness of Nano tube array of titanium dioxide by changing anodizing time, film thickness can 2~
Regulate and control in 6 μm.
Fig. 6 is the XPS Mn2p map of additive Mn film of Nano tube array of titanium dioxide prepared by embodiment 1.In conjunction with XRD points
Manganese known to analysis enters in the lattice of titanium dioxide, and manganese element exists in the form of+divalent, doping 1.8wt%.Change electrolysis
In liquid in the controllable prepared material of the additional amount of manganese source manganese element doping, the doping of manganese element can adjust in 0.9~4.1wt%
Control.
Fig. 7 is the film of Nano tube array of titanium dioxide (b-TNTAs) and embodiment of commodity P25 (a-P25), undoped manganese
(the α hv) of the additive Mn film of Nano tube array of titanium dioxide (c-Mn-TNTAs) of 1 preparation2~hv curve graph.The light of commodity P25
Band gap is 3.26eV, and the optical band gap of the film of Nano tube array of titanium dioxide undoped with manganese is 3.19eV, additive Mn titanium dioxide
The optical band gap of titanium film of Nano tube array is 3.05eV.It is compared with commodity P25, the light of additive Mn film of Nano tube array of titanium dioxide
Band gap is learned to be obviously reduced.
Fig. 8 is commodity P25 gas sensor (a-P25), the film of Nano tube array of titanium dioxide (b-TNTAs) undoped with manganese
Additive Mn film of Nano tube array of titanium dioxide (c-Mn-TNTAs) gas sensor prepared by gas sensor and embodiment 1 is in 4.5V
To the sensitivity curve of ethyl alcohol under voltage.Commodity P25 gas sensor is made of powder cladding process, the sensitivity to ethyl alcohol
Lower, when concentration of alcohol is 1000ppm, its sensitivity only has 1.3.Undoped film of Nano tube array of titanium dioxide gas sensitive element
The production method of part is same as Example 1, and when concentration of alcohol is 1000ppm, its sensitivity is 7.2.Compared with both, manganese
The sensitivity of doped titanium dioxide nanotube array membrane material dramatically increases, the sensitivity when concentration of alcohol reaches 1000ppm
Reach 11.2.
And the bound of each raw material of the present invention, section value and technological parameter (such as temperature, time) up and down
Limit, section value can realize the present invention, embodiment numerous to list herein.
Claims (7)
1. a kind of additive Mn film of Nano tube array of titanium dioxide, it is characterised in that obtained by following steps:
1) using titanium sheet as anode, graphite flake is cathode, makees electrolyte with ethylene glycol-ammonium fluoride-manganese acetate system, in 20~40V
0.5~3h of anodic oxidation is carried out under voltage；After the oxidation film removal that titanium plate surface is generated, above-mentioned identical electrolyte is placed into
Middle progress two-step anodization reacts 1~6h, obtains the additive Mn film of Nano tube array of titanium dioxide being grown in titanium sheet；It will be anti-
The titanium sheet answered is cleaned up and is dried；
2) after the titanium sheet of drying being carried out 2~5h of heat treatment at 350~550 DEG C, above-mentioned steps 1 are placed into) identical electrolyte
In, 10~15h of anodic oxidation reactions three times is carried out at 20~40V, by additive Mn film of Nano tube array of titanium dioxide from titanium sheet
On strip down；The membrane material to fall off is collected, is cleaned up with ethyl alcohol, dries, obtains additive Mn Nano tube array of titanium dioxide
Film.
2. a kind of preparation method of additive Mn film of Nano tube array of titanium dioxide as described in claim 1, it is characterised in that packet
Containing following steps:
1) using titanium sheet as anode, graphite flake is cathode, makees electrolyte with ethylene glycol-ammonium fluoride-manganese acetate system, in 20~40V
0.5~3h of anodic oxidation is carried out under voltage；After the oxidation film removal that titanium plate surface is generated, above-mentioned identical electrolyte is placed into
Middle progress two-step anodization reacts 1~6h, obtains the additive Mn film of Nano tube array of titanium dioxide being grown in titanium sheet；It will be anti-
The titanium sheet answered is cleaned up and is dried；
2) after the titanium sheet of drying being carried out 2~5h of heat treatment at 350~550 DEG C, above-mentioned steps 1 are placed into) identical electrolyte
In, 10~15h of anodic oxidation reactions three times is carried out at 20~40V, by additive Mn film of Nano tube array of titanium dioxide from titanium sheet
On strip down；The membrane material to fall off is collected, is cleaned up with ethyl alcohol, dries, obtains additive Mn Nano tube array of titanium dioxide
Film.
3. a kind of preparation method of additive Mn film of Nano tube array of titanium dioxide according to claim 2, which is characterized in that
It is described to strip down additive Mn film of Nano tube array of titanium dioxide from titanium sheet are as follows: anode oxidation process is combined by heat treatment
It carries out.
4. a kind of preparation method of additive Mn film of Nano tube array of titanium dioxide according to claim 2, which is characterized in that
The titanium sheet is bending, when carrying out anodic oxidation reactions, the convex surface face cathode of titanium sheet.
5. a kind of preparation method of additive Mn film of Nano tube array of titanium dioxide according to claim 2, which is characterized in that
The electrolyte includes deionized water, the ammonium fluoride of 0.2~1wt% and the manganese acetate of 0.05~1g/L of 0.9~7.2wt%,
Ethylene glycol is surplus.
6. a kind of additive Mn film of Nano tube array of titanium dioxide gas sensor, it is characterised in that obtained by following steps: will be by power
Benefit require 4 described in the prepared additive Mn titania nanotube of additive Mn film of Nano tube array of titanium dioxide preparation method
Array films are put into the TiO 2 sol of preparation, then gas sensor ceramic tube is put into TiO 2 sol, make additive Mn
Film of Nano tube array of titanium dioxide is wrapped on gas sensor ceramic tube；The ceramic tube for wrapping up film of Nano tube array is put into 80~
120 DEG C of baking oven drying, place into and are heat-treated 2~5h in Muffle furnace at 350~550 DEG C, obtain additive Mn nano titania
Pipe array films gas sensor.
7. a kind of production method of additive Mn film of Nano tube array of titanium dioxide gas sensor as claimed in claim 6, special
Sign, which is to comprise the steps of:, is put into additive Mn film of Nano tube array of titanium dioxide in the TiO 2 sol of preparation, then will
Gas sensor ceramic tube is put into TiO 2 sol, and additive Mn film of Nano tube array of titanium dioxide is made to be wrapped in gas sensor pottery
On porcelain tube；The ceramic tube for wrapping up film of Nano tube array is put into the drying of 80~120 DEG C of baking ovens, place into Muffle furnace 350~
It is heat-treated 2~5h at 550 DEG C, obtains additive Mn film of Nano tube array of titanium dioxide gas sensor.
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| CN108439546A (en) * | 2018-03-01 | 2018-08-24 | 南京大学 | Auto-dope TiO2Nanotube electrode, preparation method and applications |
| CN111672502A (en) * | 2020-05-21 | 2020-09-18 | 哈尔滨学院 | Method for preparing lanthanum/manganese codoped titanium oxide nanotube with photocatalytic activity by anodic oxidation |
| CN112162020A (en) * | 2020-10-09 | 2021-01-01 | 浙江科技学院 | Preparation method of high-performance hydrogen sulfide gas sensor free from humidity influence |
| CN112246202A (en) * | 2020-10-23 | 2021-01-22 | 重庆理工大学 | Reactor for efficiently generating hydroxyl radicals based on photocatalysis technology and construction method |
| CN114045544B (en) * | 2021-11-19 | 2023-12-22 | 中国科学院深圳先进技术研究院 | Titanium dioxide nanotube array film, preparation method thereof and photoelectric device |
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| "TiO2薄膜制备及其气敏特性";许明等;《传感器世界》;20090225;第16页 |
| "阳极氧化法制备锰掺杂纳米二氧化钛及其性能研究";李超男;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150115;第15、23页 |
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