CN109704400A - A method of preparing black titanium dioxide block in oxygen or air atmosphere - Google Patents
A method of preparing black titanium dioxide block in oxygen or air atmosphere Download PDFInfo
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Abstract
The present invention relates to a kind of method for preparing black titanium dioxide block in oxygen or air atmosphere, contain Ti in the black titanium dioxide block3+, the Ti in titanium elements3+Content >=1%, preferably 20~30%.
Description
Technical field
The invention discloses a kind of methods that black titanium dioxide is prepared in oxygen or air atmosphere, in particular to a kind of
The method that open gas suspension laser heating technique prepares black titanium dioxide block, belongs to technical field of preparation for inorganic material.
Background technique
Titanium dioxide has that chemical property stability is good, at low cost, catalytic activity is high, nontoxic etc. as a kind of photochemical catalyst
Advantage is studied and is applied extensively in environment, energy field.But (Anatase is since the forbidden bandwidth of titanium dioxide is big
3.2ev, Rutile Type 3.0ev), it is only capable of absorption and accounts for ultraviolet light of the sunshine gross energy less than 5%, optical response range is narrow, and
It is extremely low to the absorption rate of sunlight in solar spectrum based on visible light (44%) and infrared light (49%).Therefore it opens up
The band structure of wide titanium dioxide improves the absorption in visible light and infrared light district, the raising to the catalytic performance of titanium dioxide
It is of great significance.
It include at present nonmetalloid to titania modified method to improve utilization of the titanium dioxide to sunlight
Doping, transition or rare earth ion doping, noble metal loading, semiconductors coupling, dye sensitization etc..Although above method is one
Determine the spectral response for expanding titanium dioxide in degree, but be limited in scope in the presence of expanding, light absorption improves insufficient disadvantage.2011
Year, Chen Xiaobo et al. first passage is in 200 DEG C of H2Pressure be 20.0bar under conditions of to white TiO2Hydrogenation treatment obtains after 5 days
Black titanium dioxide it is characterized in that light abstraction width extends to infrared light region changes the knot of titanium dioxide significantly
Structure, chemistry, electronics and optical property cause great concern from this black titanium dioxide in photocatalysis field.System at present
The method of standby black titanium dioxide are as follows: hydrogen heat treating process, high temperature and pressure or normal pressure hydrogenation method, anodizing, plasma are auxiliary
It helps hydrogenation method and chemical reduction method includes aluminum reduction method, zinc reduction, magnesium reduction, NaBH4Reduction method, NaH reduction method etc..It is yellow
Rich and powerful seminar uses preparing black titanium dioxide by using dual-temperature area reducing, and white titania and metallic aluminium are put into airtight tube type
It is evacuated to 0.1Pa in furnace, then is separately heated to 300-500 DEG C and 800 DEG C.The black for having amorphous layer to surface is obtained after reaction 8h
Titanium dioxide.It is that titanium dioxide is containing NH that anodizing, which has been reported that,4F (0.25wt%) and H2The ethylene glycol of O (2vol%)
In, it is carried out anodic oxidation 10 hours at 60V.Second of anodic oxidation is carried out after stripping nano pipe.In ambiance
It is sintered 1 hour at 450 DEG C and removes anode TiO2After layer, the black titanium dioxide for the visible absorption for having big is obtained.Wang
Titanium dioxide is put into airtight tube type furnace by cosmos etc. with ion auxiliary hydrogenation method, in hydrogen pressure 100Pa, plasma rf
Black titanium dioxide is prepared in power 200W, 500 DEG C of heating 8h.
In conclusion existing, to prepare black titanium dioxide method mostly be to need high temperature and pressure, and in a reducing atmosphere
It realizes.Relatively high to equipment requirement in specific operating process, the preparation process period is longer, furthermore reducing atmosphere in order to obtain
The adjuvants such as metallic aluminium, hydrogen are added, subsequent processing is needed to purify, and wait insecurity factors there are inflammable and explosive.It is based on
The above fact needs to explore and develop a kind of easy, direct, comparatively safe method and prepares black titanium dioxide.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide one kind under oxygen or air atmosphere normal pressure
The method that laser heating prepares black titanium dioxide block.This method is easy to operate, in normal pressure, directly closes in oxygen or air
At black titanium dioxide.Gained titanium dioxide has widened optical response range, and the absorption to visible light and infrared light greatly improved.
On the one hand, the present invention provides a kind of black titanium dioxide block, contain in the black titanium dioxide block
Ti3+, the Ti in titanium elements3+Content >=1%, preferably 20~30% (wherein, the meaning of content be " Ti3+With titanium elements total amount
Atomic ratio ").
In the disclosure, contain Ti in black titanium dioxide block3+(>=1%) and Lacking oxygen (>=1%), causes forbidden bandwidth
Become smaller, to the influx and translocation of visible light and near infrared light, the photo-thermal effect in near-infrared region is obvious, and potential application is in photo-thermal
Treatment.
Preferably, the black titanium dioxide block is black titanium dioxide ball, diameter is 2~4mm.
Preferably, the forbidden bandwidth of the black titanium dioxide block is 2.61eV.
Preferably, the black titanium dioxide block is there are a large amount of Lacking oxygen content >=1%, (wherein, the meaning of content is
" atomic ratio of Lacking oxygen and O atom total amount "), preferably 20~30%.
It is significantly increased preferably, the black titanium dioxide block is absorbed in visible and near-infrared region.
Preferably, black titanium dioxide block temperature under the irradiation of near infrared light 808nm can rise to~119
℃。
On the other hand, the present invention also provides a kind of prepares above-mentioned black titanium dioxide block in oxygen or air atmosphere
The method of body, includes the following steps:
(1) by white TiO2Raw material is tabletted and is calcined；
(2) post-calcination sample is cut into the small pieces of 25~125mg, is placed in gas suspension furnace, being passed through oxygen or air keeps it outstanding
It is floating, it opens laser and is quickly cooled down after increasing power heating sample to molten condition, obtain the black titanium dioxide block；
Rate >=200 DEG C/sec of the rapid cooling.
In the disclosure, first by white TiO2Raw material is tabletted and is calcined, and the small of 25~125mg is then cut into
Block is placed in the nozzle of gas suspension furnace, and being passed through oxygen or air makes its suspension, opens laser, and be slowly increased laser function
Rate, heating makes sample melted state, while adjusting gas flow, fusing sample is made to be in suspended state, suspending stabilized to melt
Afterwards, laser is closed, is quickly cooled down, pure black titanium dioxide is obtained after sample solidification and is the black two of a monolith body
Titanium oxide block.Wherein, the material for melting being maintained at by gas (oxygen, air or nitrogen) and being quickly cooled down in whole process
Suspension is constantly in avoid contacting with chamber wall without container state, rate of temperature fall is not less than 200 DEG C/sec (200~500 DEG C/sec),
Laser heating high-temperature fusion aggravates the movement velocity of atomic ion electronics Lacking oxygen etc., the projecting ring of partial pressure of oxygen in melt
Border, the oxygen atom in the sample of molten condition can escape, and lead to Ti3+Make with the process of the appearance of Lacking oxygen, and rapid cooling
Ti3+And Lacking oxygen is fixed on the state moved in the melt originally, oxygen has little time diffusion and is formed solid-state, therefore prepares
Carry out pure black titanium dioxide and is the black titanium dioxide block of a monolith body.
Preferably, the white TiO2Raw material includes crystal phase titanium dioxide or amorphous phase titanium dioxide.
Preferably, the tabletted mode be it is dry-pressing formed, the dry-pressing formed pressure be 2~5MPa, pressure maintaining
Time is 1~2 minute.
Preferably, the temperature of the calcining is 1100~1300 DEG C, the time is 2~8 hours.
Preferably, the pressure for being passed through oxygen or air in the gas suspension furnace is 0.2~1.5MPa.
Preferably, the power of the laser is 60~90W, the time of the heating is 30~120 seconds；The laser heating
Melt temperature be higher than TiO2Fusing point (1850 DEG C)；Preferably, the wavelength of the laser is 800~1100nm.Spy of the invention
Laser parameter is determined in 800~1100nm of near infrared region, and continuous wave carbon dioxide laser, the power of laser is 60~90W.Its
In, the use of near infrared region 800~1100nm laser is small to tissue fanout free region or injury, therefore operates and more pacify
It is complete.
Preferably, the rate of the rapid cooling is 200~500 DEG C/sec, preferably 300~500 DEG C/s.Wherein, high
Cooling rate is conducive to the formation of titanous and Lacking oxygen in black titanium dioxide.
The beneficial effects of the present invention are:
(1) preparation of the normal pressure atmosphere (oxidation environment) existing for oxygen of the invention, does not need the reducing atmospheres such as hydrogen, reduces reality
Risk is tested, preparation is simple.Black titanium dioxide during the preparation process, passes through the laser heating melting in gas suspension and fast quickly cooling
But process makes titanium ion appraise at the current rate and introduces Lacking oxygen, causes the variation of forbidden bandwidth, has greatly increased visible light and infrared
The absorption in light area；
(2) present invention adds the methods of hydrogen, thermit reduction phase with original hydrogenization method for preparing black titanium dioxide, plasma asistance
Than this is easy to operate, and the reaction time is short, it is only necessary to can prepare black titanium dioxide within 30~120 seconds, yield is considerable；
(3) black titanium dioxide prepared by the present invention avoids introducing extraneous (auxiliary) additive, is not necessarily to purification step, and sintered
Journey makes to suspend by gas to be avoided contacting with chamber wall, free from admixture pollution, to prepare pure black titanium dioxide
Block；
(4) black titanium dioxide prepared by the present invention is prepared in open gas suspension furnace, and preparation process whole process is in normal pressure item
Part is not necessarily to special pressurized equipment and air extractor, low for equipment requirements；
(5) present invention using no container technology of preparing preparation black titanium dioxide block, greatly improved its visible light with
The absorption of infrared light district, changes band structure, has in dye-sensitized solar cells, visible light hydrogen manufacturing and environmental improvement etc.
Potential using value in field；
(6) present invention, which only needs to be improved cooler environment i.e., can reach extremely fast cooling velocity, even if not taking any measure
It can reach the rate of temperature fall higher than 300 DEG C/s, therefore the block materials that conventional method cannot be prepared can be prepared.For example, adopting
With the cooling of circulating cooling water tank (circulating water ambient gas, the black titanium dioxide block that gas cooling suspends), cooling speed
Degree is up to~500 DEG C/s fastly；
(7) it is prepared using gas suspension method, such as can be in air environment, it is only necessary to change different levitation gas oxygen, sky
The black titanium dioxide with different titanouses and Lacking oxygen content can be obtained in gas or nitrogen；
(8) it is exactly sample heating melting under suspended state using the characteristics of gas suspension method preparation in the present invention, ensure that sample
The purity of product, and due to being quickly cooled down remains the locating metastable state in the melt such as atom as much as possible, can not return
To due equilibrium state；Due to being heated using laser, feature is just to turn off laser, and sample temperature moment can be by high temperature drop
To room temperature, according to the difference of external condition, rate of temperature fall can reach 200 DEG C -500 DEG C/sec, even higher.
Detailed description of the invention
(a) is that black titanium dioxide prepared by embodiment 1 passes through the front and back state change of gas suspension laser heating in Fig. 1,
(b) the black titanium dioxide ball prepared for embodiment 1；
Fig. 2 is the powder of white titania raw material powder (left side) and 1 ground 200 mesh of black titanium dioxide ball (right side) of embodiment
Comparison diagram；
Fig. 3 is black titanium dioxide powder and original white titania (TiO prepared by embodiment 12) X-ray diffraction spectrum
Figure；
Fig. 4 is black titanium dioxide powder and white titania raw material powder (TiO prepared by embodiment 12) ultraviolet-visible-
Near-infrared diffusing reflection spectrum；
Fig. 5 is black titanium dioxide powder and white titania raw material powder (TiO prepared by embodiment 12) forbidden bandwidth spectrum
Figure；
Fig. 6 is the x-ray photoelectron spectroscopy figure of the Ti element of black titanium dioxide prepared by embodiment 1；
Fig. 7 is the x-ray photoelectron spectroscopy figure of the O element of black titanium dioxide prepared by embodiment 1；
Fig. 8 is black titanium dioxide powder (B-TiO prepared by embodiment 12) and white titania raw material powder (TiO2) warp
Temperature variation after 808nm laser irradiation.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The energy band and optical response range of titanic oxide material, the black TiO of acquisition are changed in the present invention2Visible light,
The absorption of infrared light district greatly improves.
In one embodiment of the invention, black titanium dioxide bulb diameter can be 2~4mm, forbidden bandwidth~2.61ev, and
Visible light and infrared light district absorption substantially enhance.
In the present invention, the crystallite dimension of black titanium dioxide according to thank strangle formula (formula 1) calculate crystallite dimension 45
Between~55nm:
In the present invention, the preparation step of black titanium dioxide block is simple, is not necessarily to auxiliary additive, can make under normal pressure
Standby, expense of raw materials is low.Illustrate to following exemplary the preparation method of black titanium dioxide block.
By white TiO2Raw material is tabletted, is put into calcining (pre-burning) in Muffle furnace or resistance wire furnace.White TiO2Raw material
For the titanium dioxide of simple any form, including crystal phase or amorphous phase.Wherein, tabletted mode can for dry-pressing at
Type, dry-pressing formed pressure can be 2~5MPa, and the dwell time can be 1~2 minute.The temperature of calcining can be 1100~1300 DEG C,
Time can be 2~8 hours.
Sample after pre-burning is placed in open air suspension device, being passed through oxygen or air (makes sample suspend, so as to nothing
Container laser is fired), it is heated to molten condition by laser, then be quickly cooled down to obtain black titanium dioxide block.Wherein, laser
Heating power can be 60~90W, and the time of heating can be 30~120 seconds.Laser melt heating temperature can reach~2500
DEG C, preferably optical maser wavelength is 800~1100nm.The rate of rapid cooling can be 200~500 DEG C/sec.
Black titanium dioxide prepared by the present invention purity is high is block materials, and also reduces black titanium dioxide and formed pair
The dependence of atmosphere, the creative shape for being conducive to titanous and Lacking oxygen in black titanium dioxide using high cooling rate
At.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.If without specified otherwise, original used in following embodiments
Material includes: white TiO2Raw material (for example producer is that Co., Ltd.'s high-purity chemical studies the white two that purity produced is 4N
Titanium oxide).
Embodiment 1
Oxygen atmosphere of the invention prepares black titanium dioxide, and specific step is as follows:
(1) 2g white TiO is taken2Raw material is tabletted, is put into Muffle furnace and calcines, and obtains potsherd；White TiO2Raw material is gold
Red stone phase；Tabletted mode is that dry-pressing formed, dry-pressing formed pressure is 2~5MPa, and the dwell time is 1~2 minute；It forges
The temperature of burning is 1100~1300 DEG C, and the time is 2~8 hours；
(2) post-calcination sample is cut into the small pieces of 25~125mg, is placed in gas suspension furnace, is passed through oxygen (0.6MPa), is opened
Laser is simultaneously quickly cooled down after increasing power heating sample to molten condition, and laser heating power is 70W, and time of heating is 100
Second, laser melt heating temperature reaches~2500 DEG C；Optical maser wavelength is 1064nm；Obtain the black titanium dioxide ball, diameter
For 2~4mm.Wherein, using the cooling of circulating cooling water tank (circulating water ambient gas, the black dioxy that gas cooling suspends
Change titanium block), the rate being allowed to cool is 300 DEG C/sec.Contain Ti in gained black titanium dioxide block3+And Lacking oxygen, content
For 21.5% (see attached drawing 6) of Ti ion, the content of Lacking oxygen is 26.95% (see attached drawing 7).
Characterization test:
X-ray diffraction test: black titanium dioxide ball is clayed into power and crosses 200 meshes, using Rigaku Ultima IV
X-ray diffraction instrument carries out material phase analysis, major parameter: Cu target KαRay, tube voltage 40KV, tube current 40mA, 0.02 ° of step-length,
5 °/min of scanning speed；
Ultraviolet-visible-near-infrared diffuse reflectance spectroscopy: black titanium dioxide ball is clayed into power and crosses 200 meshes, using purple
Outer spectrophotometer (Cary 5000) is tested, and observes the diffusing reflection spectrum of material, scanning range are as follows: 300-1600nm；
X-ray photoelectron spectroscopy test: it is tested using ESCALAB 250X X-ray photoelectron spectroscopy X instrument, it was demonstrated that black dioxy
Change Ti in titanium3+With Lacking oxygen and its content；
Light thermal property test: by black titanium dioxide under dry state, using the near infrared light 5min of 808nm, power is close
Spend 0.4W/cm2, real-time using infrared thermal imager (Infrared imaging thermometer, A325sc, FLIR, USA)
Backing temp is monitored, data is recorded, temperature is drawn by FLIR R&D software and changes over time relational graph.Black titanium dioxide
Light thermal property can potential application in photo-thermal therapy, select 808nm to do the optical maser wavelength of photo-thermal experiment, mainly due at the wavelength
It is best to the penetrability of tissue within the scope of tissue optical window.
(a) is that black titanium dioxide prepared by embodiment 1 passes through the front and back state change of gas suspension laser heating in Fig. 1,
White tablets are the ceramic tablets being cut into before laser heats；Not melting completely by laser irradiation is intermediate state, is passed through
Become black after the position of laser irradiation is cooling, what it is without laser irradiation is still white；The black ball on the right is by laser
The black titanium dioxide being cooled into after irradiation melting completely；
(b) is black titanium dioxide ball prepared by embodiment 1 in Fig. 1, as can be seen from Figure after laser irradiation melts completely
The black titanium dioxide being cooled into is blocky in ball；
Fig. 2 is powder Reference's figure of white titania raw material powder and ground 200 mesh of 1 black titanium dioxide ball of embodiment,
As can be seen from the figure titanium dioxide raw material powder is white powder, and the black titanium dioxide block prepared by no container is worn into
It is still in black after powder；
Fig. 3 is the X-ray diffraction spectrogram of black titanium dioxide powder prepared by embodiment 1 and original white titania, from figure
In known to contain a small amount of anatase in raw material powder, the black titanium dioxide after solvent-catalyst free all becomes Rutile Type；
Fig. 4 is ultraviolet-visible-near-infrared of black titanium dioxide powder prepared by embodiment 1 and white titania raw material powder
Diffusing reflection spectrum, Fig. 5 are black titanium dioxide powder and white titania raw material powder (TiO prepared by embodiment 12) forbidden band
Width spectrogram.Absorption of the black titanium dioxide in visible light and near-infrared region as can be known from Fig. 4 significantly increases, can from Fig. 5
Know that the forbidden bandwidth of black titanium dioxide reduces (to 2.61ev)；
Fig. 6 is the x-ray photoelectron spectroscopy figure of the Ti element of black titanium dioxide prepared by embodiment 1, it can be seen that has Ti3+
The appearance of ion (457.9eV, peak 2), content 21.5%；
Fig. 7 is the x-ray photoelectron spectroscopy figure of the O element of black titanium dioxide prepared by embodiment 1, it can be seen that 531.31ev
Place is the peak (peak 1) of Lacking oxygen, and 529.94ev is the peak (peak 2) of Ti-O key, and 529.56ev is the peak (peak 3) of surface adsorbed oxygen,
It can illustrate a large amount of appearance of having vacant position, content 26.95%；
Fig. 8 is black titanium dioxide powder (B-TiO prepared by embodiment 12) and white titania raw material powder (TiO2) warp
Temperature variation after 808nm laser irradiation, it is known that black titanium dioxide powder prepared by embodiment 1 has photo-thermal effect, warp
808nm laser irradiation can be warming up to 100 DEG C or more, up to 128 DEG C in 1min；And white titania raw material powder
(TiO2) temperature change is only 2.5 DEG C, illustrate that the photo-thermal effect of black titanium dioxide is significant.
Although above in conjunction with attached drawing, invention has been described, and the invention is not limited to above-mentioned specific implementations
Mode, the above mentioned embodiment is only schematical, rather than restrictive, and those skilled in the art are at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to of the invention
Within protection.
Claims (11)
1. a kind of black titanium dioxide block, which is characterized in that contain Ti in the black titanium dioxide block3+, in titanium elements
Middle Ti3+Content >=1%, preferably 20~30%.
2. black titanium dioxide block according to claim 1, which is characterized in that the black titanium dioxide block is black
Color titanium dioxide ball, diameter are 2~4 mm.
3. black titanium dioxide block according to claim 1 or 2, which is characterized in that the black titanium dioxide block
Forbidden bandwidth be 2.61eV.
4. black titanium dioxide block according to any one of claim 1-3, which is characterized in that the black titanium dioxide
Contain Lacking oxygen, content >=1%, preferably 20~30% in titanium block.
5. a kind of side for preparing black titanium dioxide block of any of claims 1-4 in oxygen or air atmosphere
Method, which comprises the steps of:
(1) by white TiO2Raw material is tabletted and is calcined；
(2) post-calcination sample is cut into the small pieces of 25~125mg, is placed in gas suspension furnace, being passed through oxygen or air keeps it outstanding
It is floating, it opens laser and is quickly cooled down after increasing power heating sample to molten condition, obtain the black titanium dioxide block；Institute
State rate >=200 DEG C/sec of rapid cooling.
6. according to the method described in claim 5, it is characterized in that, the white TiO2Raw material include crystal phase titanium dioxide or
Amorphous phase titanium dioxide.
7. method according to claim 5 or 6, which is characterized in that the tabletted mode be it is dry-pressing formed, it is described
Dry-pressing formed pressure is 2~5 MPa, and the dwell time is 1~2 minute.
8. the method according to any one of claim 5-7, which is characterized in that the temperature of the calcining is 1100~1300
DEG C, the time is 2~8 hours.
9. the method according to any one of claim 5-8, which is characterized in that be passed through oxygen or sky in the gas suspension furnace
The pressure of gas is 0.2~1.5 MPa.
10. the method according to any one of claim 5-9, which is characterized in that the power of the laser is 60~90W,
The time of the heating is 30~120 seconds；The melt temperature of the laser heating is higher than TiO2Fusing point；Preferably, the laser
Wavelength be 800~1100 nm.
11. the method according to any one of claim 5-10, which is characterized in that the rate of the rapid cooling is 200
~500 DEG C/sec, preferably 300~500 DEG C/sec.
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| CN111056567A (en) * | 2019-12-25 | 2020-04-24 | 苏州机数芯微科技有限公司 | Preparation method of black rutile phase titanium dioxide |
| CN111847503A (en) * | 2020-06-10 | 2020-10-30 | 宁夏中科欧德科技有限公司 | Preparation method of black titanium dioxide |
| CN115159567A (en) * | 2022-08-16 | 2022-10-11 | 济南大学 | Defect-induced heteroatom-doped titanium dioxide electrode material and preparation method thereof |
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| CN104817107B (en) * | 2015-03-31 | 2016-05-04 | 吉林大学 | A kind of method of preparing black titanium dioxide B phase and anatase-phase nano particle |
| CN106756788B (en) * | 2016-11-24 | 2019-05-21 | 天津大学 | A kind of method that Gas Sensor Films Deposited by Pulsed Laser Deposition prepares black titanium dioxide powder under subnormal ambient |
| CN109336381B (en) * | 2018-10-16 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Black bioglass and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111056567A (en) * | 2019-12-25 | 2020-04-24 | 苏州机数芯微科技有限公司 | Preparation method of black rutile phase titanium dioxide |
| CN111056567B (en) * | 2019-12-25 | 2022-02-11 | 苏州机数芯微科技有限公司 | Preparation method of black rutile phase titanium dioxide |
| CN111847503A (en) * | 2020-06-10 | 2020-10-30 | 宁夏中科欧德科技有限公司 | Preparation method of black titanium dioxide |
| CN111847503B (en) * | 2020-06-10 | 2023-02-10 | 宁夏中科欧德科技有限公司 | Preparation method of black titanium dioxide |
| CN115226724A (en) * | 2022-06-21 | 2022-10-25 | 重庆德强化工有限公司 | Nano photocatalytic sterilization material and preparation method thereof |
| CN115226724B (en) * | 2022-06-21 | 2024-03-19 | 重庆德强化工有限公司 | Nanometer photocatalysis sterilization material and preparation method thereof |
| CN115159567A (en) * | 2022-08-16 | 2022-10-11 | 济南大学 | Defect-induced heteroatom-doped titanium dioxide electrode material and preparation method thereof |
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