CN109759040A - A kind of preparation method of modifying titanium dioxide - Google Patents
A kind of preparation method of modifying titanium dioxide Download PDFInfo
- Publication number
- CN109759040A CN109759040A CN201910162140.1A CN201910162140A CN109759040A CN 109759040 A CN109759040 A CN 109759040A CN 201910162140 A CN201910162140 A CN 201910162140A CN 109759040 A CN109759040 A CN 109759040A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- modifying
- dioxide according
- coupling agent
- 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.)
- Pending
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation methods of modifying titanium dioxide, by will be in the part functional group scion grafting to titanium dioxide of dispersing agent and coupling agent, the molecule of titanium dioxide in the liquid phase is reduced to reunite, to realize the modification of titanium dioxide, and then the dispersibility of titanium dioxide is improved, drug used in the preparation method is simple, cheap, modified condition is mild, suitable for batch production and industrial applications, have many advantages, such as that method is simple, easily operated, it is low in cost.
Description
Technical field
The present invention, which discloses, is related to light-catalysed technical field more particularly to a kind of preparation method of modifying titanium dioxide.
Background technique
Photocatalysis technology originates from the 1970s, Japanese Scientists Fujishima and Honda discovery titanium dioxide tool
There is photosensitization, so as to cause light-catalysed research boom, nano-titanium dioxide is made to attract attention.Nano-titanium dioxide makes
Used time usually requires mixing in the liquid phase, but since its partial size is small, large specific surface area, is easy to assemble in the liquid phase, influences it
Therefore how dispersibility in the liquid phase, improves the dispersibility of titanium dioxide in the liquid phase to influence the use of titanium dioxide
Focus always concerned by people.
Currently, people mainly improve the dispersibility of titanium dioxide in the liquid phase by modified mode, specifically,
When preparing titanium dioxide, Doped ions are added in predecessor, preparation has the titanium dioxide of special ion, makes dioxy obtained
Change the activity of titanium in one aspect to reinforce.Wherein, the method for preparing predecessor mainly includes: gas phase hydrolysis method, vapour phase oxidation process,
Sol-gal process, Liquid-phase hydrolysis, hydrothermal synthesis method, chemical precipitation method and microemulsion method；The ion of doping be related to metal from
Son and nonmetallic ion.Although above-mentioned ion doping method can effectively provide the dispersibility of titanium dioxide, complicated for operation, at
This height.
Therefore, a kind of new titania modified method how is researched and developed, to improve the dispersibility of titanium dioxide in the liquid phase,
As people's urgent problem to be solved.
Summary of the invention
In consideration of it, the invention discloses a kind of preparation method of modifying titanium dioxide, at least to solve to be modified dioxy in the past
There are the problems such as complicated for operation, at high cost for the method for change titanium.
Technical solution provided by the invention, specifically, a kind of preparation method of modifying titanium dioxide, this method includes as follows
Step:
1) ionized water is removed, nano-titanium dioxide is added in Xiang Suoshu deionized water, it is molten that configuration obtains nano-titanium dioxide
Liquid；
2) under the conditions of temperature is 50-70 DEG C, dispersing agent and coupling agent are added anti-in the nanometer titanium dioxide titanium solution
It answers, obtains sediment；
3) by the sediment undergoes washing, burn after obtain product.
It is preferred that the dispersing agent is one of calgon, diethanol amine or sodium metasilicate.
Further preferably, the coupling agent is silane coupling agent.
Further preferably, the coupling agent is 3- (methacryloxypropyl) propyl trimethoxy silicane or γ-(2,3- rings
The third oxygen of oxygen) propyl trimethoxy silicane.
Further preferably, the mass ratio of dispersing agent, coupling agent and nano-titanium dioxide is 3:3:20 in step 2).
Further preferably, the mass percent of nanometer titanium dioxide titanium solution described in step 1) is 5%-15%.
Further preferably, it is handled when configuration nanometer titanium dioxide titanium solution using stirring and ultrasonic oscillation in step 1),
In, ultrasonic oscillation frequency is 40KHz, pH value 4-8, and configuration temperature is 15-30 DEG C.
Further preferably, nanometer titanium dioxide titanium solution is added in dispersing agent described in step 2) and coupling agent under agitation
Middle reaction, wherein mixing speed 600-1000r/min, reaction time 1-2h.
Further preferably, the centrifugal speed being centrifugated in step 2) is 1500-3000rmp.
Further preferably, sediment described in step 3) is cleaned 3-6 times using deionized water, is burnt under the conditions of 70-110 DEG C
Burn 20-28h, obtains product.
The preparation method of modifying titanium dioxide provided by the invention, by by the part functional group of dispersing agent and coupling agent branch
It is connected on titanium dioxide, reduces the molecule of titanium dioxide in the liquid phase and reunite, to realize the modification of titanium dioxide, and then improve two
The dispersibility of titanium oxide, drug used in the preparation method is simple, cheap, and modified condition is mild, is suitable for batch production and work
Industry application has many advantages, such as that method is simple, easily operated, low in cost.
It should be understood that above general description and following detailed description be only it is exemplary and explanatory, not
The present invention can be limited to disclose.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and be used to explain the principle of the present invention together with specification.
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, for those of ordinary skill in the art
Speech, without creative efforts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the XRD diagram picture of modified titanium dioxide；
Fig. 2 is the XRD diagram picture of titanium dioxide before modified；
Fig. 3 be before modified with the infrared comparison spectrogram of modified titanium dioxide.
Specific embodiment
Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to
When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment
Described in embodiment do not represent all embodiments consistented with the present invention.On the contrary, they be only with it is such as appended
The example of method being described in detail in claims, some aspects of the invention are consistent.
In order to improve the dispersibility of titanium dioxide in the liquid phase, present embodiment provides a kind of systems of modifying titanium dioxide
Preparation Method, specific as follows:
1) ionized water is removed, nano-titanium dioxide is added into deionized water, configuration obtains nanometer titanium dioxide titanium solution；
2) under the conditions of temperature is 50-70 DEG C, dispersing agent and coupling agent is added in nanometer titanium dioxide titanium solution and reacted, is obtained
Obtain sediment；
3) by sediment undergoes washing, burn after obtain product.
Wherein, dispersing agent is one of calgon, diethanol amine or sodium metasilicate, and coupling agent is silane coupling agent,
Preferably coupling agent is 3- (methacryloxypropyl) propyl trimethoxy silicane or γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy
Base silane.
The preparation method of above-mentioned modifying titanium dioxide is to hydrolyze to form silicon aldehyde by coupling agent under the auxiliary of dispersing agent,
It is condensed with titanium dioxide hydroxyls dehydrate, effectively titanium dioxide to be prevented to reunite, and then improves the dispersion of titanium dioxide in the liquid phase
Property.
In above-mentioned modifying titanium dioxide preparation method, the mass ratio of dispersing agent, coupling agent and nano-titanium dioxide is 3:
The mass percent of 3:20, the nanometer titanium dioxide titanium solution of configuration are 5%-15%, and titanium dioxide is preferably 98% or more purity
Anatase titanium dioxide.
Titanium dioxide can sufficiently dissolve in nanometer titanium dioxide titanium solution in order to make configuration, as the improvement of technical solution,
When carrying out nano-titanium dioxide solution allocation, handled using stirring and ultrasonic oscillation, wherein ultrasonic oscillation frequency is
40KHz, pH value 4-8, configuration temperature are 15-30 DEG C.
In order to keep dispersing agent, coupling agent and nano-titanium dioxide solution reaction abundant, as the improvement of technical solution, on
It states dispersing agent and coupling agent and is added in nanometer titanium dioxide titanium solution under agitation and reacted, wherein mixing speed 600-
1000r/min, reaction time 1-2h obtain sediment using centrifuge separation mode after reaction, wherein centrifugal speed is
1500-3000rmp。
In order to improve the purity for obtaining modifying titanium dioxide, as the improvement of technical solution, sinking acquisition in step 3)
Starch is cleaned 3-6 times using deionized water, and when solid is dissolved in water cleaning, solution is creamy white until no other impurities, then
20-28h is burnt under the conditions of 70-110 DEG C, obtains product.
The present invention is further illustrated with specific embodiment below, but is not limited to this hair
Bright protection scope.
Embodiment 1
1) 100 ml deionized waters are taken, 0.5 gram of titania powder is added thereto, is configured to titania solution；
2) lauryl sodium sulfate, polyethylene glycol 400, polyethylene glycol are separately added into above-mentioned titania solution
2000, polyacrylamide and calgon, wherein additional amount is 0.02 gram, magnetic agitation 30 minutes, then supersonic oscillations
30 minutes, obtain dispersion liquid；
3) dispersion liquid is stood into one day survey granularity, the results are shown in Table 1.
Table 1:
Embodiment 2
1) it takes 100 ml deionized waters to adjust different pH value, 1 gram of titanium dioxide is added thereto, stir 30 minutes, surpass
Sonication 30 minutes, 0.1 gram of coupling agent is added --- 3- (methacryloxypropyl) propyl trimethoxy silicane reacts at room temperature
1 hour, washing of precipitate calcination is taken, sample is obtained.
2) sample is dissolved in deionized water, is stirred, ultrasonic treatment stands one day, and measurement partial size is shown in Table 2.
Table 2:
| pH | 2 | 4 | 6 | 8 | 10 | 12 |
| Partial size/nm | 136.5 | 98.4 | 86.5 | 90.5 | 128.9 | 149.2 |
Embodiment 3
1) it takes 100 ml deionized waters to adjust pH value=6,1 gram of titanium dioxide is added thereto, stir 30 minutes, ultrasound
Processing 30 minutes, same amount coupling agent --- 3- (methacryloxypropyl) propyl trimethoxy silicane does not react 1 at room temperature for addition
Hour, washing of precipitate calcination is taken, sample is obtained.
2) sample is dissolved in deionized water, is stirred, ultrasonic treatment stands one day, and measurement partial size is shown in Table 3.
Table 3:
Embodiment 4
1) it takes 100 ml deionized waters to adjust pH value=6,1 gram of titanium dioxide is added thereto, stir 30 minutes, ultrasound
Processing 30 minutes, is added 0.15 gram of coupling agent --- and 3- (methacryloxypropyl) propyl trimethoxy silicane controls the reaction time,
Take washing of precipitate calcination.
2) sample is dissolved in deionized water, is stirred, ultrasonic treatment stands one day, and measurement partial size is shown in Table 4.
Table 4:
| Reaction time/h | 0.5 | 1 | 1.5 | 2 | 2.5 |
| Partial size/nm | 132.5 | 75.8 | 83.6 | 88.4.7 | 126.5 |
Embodiment 5
1) it takes 100 ml deionized waters to adjust pH value=6,1 gram of titanium dioxide is added thereto, stir 30 minutes, ultrasound
Processing 30 minutes, is added 0.15 gram of coupling agent --- and 3- (methacryloxypropyl) propyl trimethoxy silicane reacts 1 hour, control
Reaction temperature processed takes washing of precipitate calcination.
2) sample is dissolved in deionized water, is stirred, ultrasonic treatment stands one day, and measurement partial size is shown in Table 5.
Table 5:
| Reaction temperature/DEG C | 40 | 50 | 60 | 70 | 80 |
| Partial size/nm | 135.7 | 80.4 | 76.2 | 88.6 | 156.9 |
Embodiment 6
1) it takes 100 ml deionized waters to adjust pH value=6,1 gram of titanium dioxide is added thereto, stir 30 minutes, ultrasound
Processing 30 minutes, is added 0.15 gram of dispersing agent --- calgon and 0.15 gram of coupling agent --- 3- (methacryloxypropyl) third
Base trimethoxy silane reacts at room temperature 1 hour, takes washing of precipitate calcination.
2) sample is dissolved in deionized water, is stirred, ultrasonic treatment stands one day, and measurement partial size is shown in Table 6.
Table 6:
| pH | 2 | 4 | 6 | 8 | 10 | 12 |
| Partial size/nm | 136.2 | 89.4 | 77.6 | 90.0 | 115.6 | 158.9 |
Embodiment 7
1) it takes 100 ml deionized waters to adjust pH=6 value, 1 gram of titanium dioxide is added thereto, stir 30 minutes, ultrasound
Processing 30 minutes, is added 0.15 gram of dispersing agent and agent dosage, and reaction time 1h controls reaction temperature, takes washing of precipitate calcination.
2) sample is dissolved in deionized water, is stirred, ultrasonic treatment stands one day, and measurement partial size is shown in Table 7.
Table 7:
| Reaction temperature/DEG C | 30 | 40 | 50 | 60 | 70 | 80 |
| Partial size/nm | 145.6 | 100.3 | 71.5 | 69.2 | 73.1 | 150.3 |
Embodiment 8
1) it takes 100 ml deionized waters to adjust pH=6 value, 1 gram of titanium dioxide is added thereto, stir 30 minutes, ultrasound
0.15 gram of dispersing agent and agent dosage is added in processing 30 minutes, controls the reaction time, takes washing of precipitate calcination.
2) sample is dissolved in deionized water, is stirred, ultrasonic treatment stands one day, and measurement partial size is shown in Table 8.
Table 8:
| Reaction time/h | 0.5 | 1 | 1.5 | 2 | 2.5 |
| Partial size/nm | 69.2 | 40.5 | 44.2 | 45.2 | 89.4 |
Embodiment 9
1) 100ml deionized water is taken, under the conditions of temperature is 15-30 DEG C, 1g nanometer titanium dioxide is added into deionized water
PH value is transferred to 6 by titanium, and with magnetic stirrer 30min, the ultrasonic oscillation that reuse frequency is 40KHz handles 30min, matches
It sets and obtains nanometer titanium dioxide titanium solution；
2) under the conditions of temperature is 50-70 DEG C, by the 3- (methacryloxypropyl) third of 0.15g calgon and 0.15g
Base trimethoxy silicon, which is added in nanometer titanium dioxide titanium solution, to react, and obtains sediment, wherein reaction temperature is 60 DEG C, when reaction
Between be 1h, then solution sediment will be obtained with 1500-3000rmp centrifugal treating after reaction；
3) sediment is cleaned 5 times with deionized water, the solid after cleaning is burnt at 100 DEG C for 24 hours to get to purpose
Product.
Above-mentioned product (modified) and blank sample (before modified) are characterized, are shown in Table 9.
Table 9:
| pH | 2 | 4 | 6 | 8 | 10 | 12 |
| Blank Zeta potential | 17.6 | 9.33 | 0.18 | -4.6 | -8.8 | -10.5 |
| Embodiment 9Zeta current potential | 23.5 | 20.1 | 15.4 | 0.98 | -22.9 | -24.8 |
Above-mentioned product and blank sample are subjected to XRD diagram picture, referring to Fig. 1, Fig. 2, from Fig. 1, Fig. 2 as it can be seen that the two XRD diagram picture
Substantially do not change, illustrate that the crystal form of titanium dioxide does not change.
It is the infrared spectrogram with modified titanium dioxide before modified referring to Fig. 3, wherein B curve is titanium dioxide before modified
Titanium curve, C curve are titanium dioxide curve before modified.As seen from Figure 3, the hydrone and hydroxyl on nano-titanium dioxide surface before modified
The stretching vibration of base is absorbed in 3200-3800cm-1, 1560cm-1Place.In 3420cm-1The peak at place is titanium alcohol radical and adsorption hydrogen
The vibration peak of key association, by modification, peak obviously weakens herein, illustrates that most of nano-titanium dioxide is sent out with silane coupling agent
Raw condensation reaction.2920cm-1There is an apparent peak in place, illustrates modifying process 3- (methacryloxypropyl) propyl trimethoxy
In silane scion grafting to titanium dioxide.Lower than 700cm-1Absorption peak be supersaturation absorb the peak Ti-O and Ti-O-Ti, can neglect
Slightly.
In addition, the wiring solution-forming under the same conditions of the nano-titanium dioxide after before modified is surveyed with nano particle size instrument afterwards for 24 hours
Measure the granularity of solution.The solution granularity that modified nano-titanium dioxide is configured obviously becomes smaller.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to of the invention its
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the present invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following
Claim is pointed out.
It should be understood that the present invention is not limited to the precise structure already described above and shown in the accompanying drawings, and
And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is limited only by the attached claims.
Claims (10)
1. a kind of preparation method of modifying titanium dioxide, which comprises the steps of:
1) ionized water is removed, nano-titanium dioxide is added in Xiang Suoshu deionized water, configuration obtains nanometer titanium dioxide titanium solution；
2) under the conditions of temperature is 50-70 DEG C, dispersing agent and coupling agent is added in the nanometer titanium dioxide titanium solution and reacted, from
Sediment is obtained after heart separation；
3) by the sediment undergoes washing, burn after obtain product.
2. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that the dispersing agent is hexa metaphosphoric acid
One of sodium, diethanol amine or sodium metasilicate.
3. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that the coupling agent is silane coupled
Agent.
4. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that the coupling agent is 3- (methyl
Acryloyl-oxy) propyl trimethoxy silicane or γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane.
5. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that dispersing agent, coupling in step 2)
The mass ratio of agent and nano-titanium dioxide is 3:3:20.
6. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that nano-silica described in step 1)
The mass percent for changing titanium solution is 5%-15%.
7. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that configure nano-silica in step 1)
It when changing titanium solution, is handled using stirring and ultrasonic oscillation, wherein ultrasonic oscillation frequency is 40KHz, pH value 4-8, configuration
Temperature is 15-30 DEG C.
8. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that dispersing agent described in step 2) and
Coupling agent, which is added under agitation in nanometer titanium dioxide titanium solution, to react, wherein mixing speed 600-1000r/min, instead
It is 1-2h between seasonable.
9. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that be centrifugated in step 2) from
Heart speed is 1500-3000rmp.
10. the preparation method of modifying titanium dioxide according to claim 1, which is characterized in that sediment described in step 3)
It is cleaned 3-6 times using deionized water, 20-28h is burnt under the conditions of 70-110 DEG C, obtain product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910162140.1A CN109759040A (en) | 2019-03-05 | 2019-03-05 | A kind of preparation method of modifying titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910162140.1A CN109759040A (en) | 2019-03-05 | 2019-03-05 | A kind of preparation method of modifying titanium dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109759040A true CN109759040A (en) | 2019-05-17 |
Family
ID=66457604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910162140.1A Pending CN109759040A (en) | 2019-03-05 | 2019-03-05 | A kind of preparation method of modifying titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109759040A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647312A (en) * | 2020-07-13 | 2020-09-11 | 江苏艾森半导体材料股份有限公司 | Ultraviolet curing ink-jet printing ink with good sedimentation resistance |
| CN117511309A (en) * | 2023-11-27 | 2024-02-06 | 几何智慧(常州)光伏电站运维管理有限公司 | Preparation process of water-based paint applied to photovoltaic panel |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02138349A (en) * | 1988-04-29 | 1990-05-28 | Toyoda Gosei Co Ltd | Fiber-reinforced polypropylene resin composition |
| CN101487795A (en) * | 2008-01-15 | 2009-07-22 | 中国科学院化学研究所 | Method for characterizing surface finishing status of inorganic material with mesoporous |
| CN102660154A (en) * | 2012-04-28 | 2012-09-12 | 常州大学 | Surface modification method for nanometer titanium dioxide |
| CN103525134A (en) * | 2013-09-22 | 2014-01-22 | 中国水产科学研究院东海水产研究所 | Surface modification method of nano-titanium dioxide |
| CN104449024A (en) * | 2014-12-30 | 2015-03-25 | 马艳荣 | Preparing method for hydrophobicity nanometer titania |
-
2019
- 2019-03-05 CN CN201910162140.1A patent/CN109759040A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02138349A (en) * | 1988-04-29 | 1990-05-28 | Toyoda Gosei Co Ltd | Fiber-reinforced polypropylene resin composition |
| CN101487795A (en) * | 2008-01-15 | 2009-07-22 | 中国科学院化学研究所 | Method for characterizing surface finishing status of inorganic material with mesoporous |
| CN102660154A (en) * | 2012-04-28 | 2012-09-12 | 常州大学 | Surface modification method for nanometer titanium dioxide |
| CN103525134A (en) * | 2013-09-22 | 2014-01-22 | 中国水产科学研究院东海水产研究所 | Surface modification method of nano-titanium dioxide |
| CN104449024A (en) * | 2014-12-30 | 2015-03-25 | 马艳荣 | Preparing method for hydrophobicity nanometer titania |
Non-Patent Citations (1)
| Title |
|---|
| 郭文录等: "纳米TiO2水分散体系稳定性的研究", 《应用化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647312A (en) * | 2020-07-13 | 2020-09-11 | 江苏艾森半导体材料股份有限公司 | Ultraviolet curing ink-jet printing ink with good sedimentation resistance |
| CN117511309A (en) * | 2023-11-27 | 2024-02-06 | 几何智慧(常州)光伏电站运维管理有限公司 | Preparation process of water-based paint applied to photovoltaic panel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104098132B (en) | One kind prepares { 100 } crystal face Anatase TiO2The method of nano particle | |
| CN100503448C (en) | Method for synthesizing anatase type crystallizing titanium dioxide nano nuclear-shell or shell structure material by water phase one-step method | |
| CN109759040A (en) | A kind of preparation method of modifying titanium dioxide | |
| CN103159225B (en) | Synthetic method of ETS-10 titanium silicalite molecular sieve | |
| CN104671282B (en) | A kind of preparation method of composite titania material hollow ball | |
| CN112588283B (en) | Carbon quantum dot/mesoporous Kong Cengzhuang titanium dioxide and preparation method and application thereof | |
| CN101508464A (en) | Process for preparing anatase type nano-titanium dioxide | |
| CN105536850B (en) | A kind of high dispersancy nano composite titania material and preparation method thereof | |
| CN105944738A (en) | Preparation method of TiO2/MoS2 composite material based on surface modification | |
| CN103253704B (en) | Semiconductor porous bismuth oxide nanosphere and preparation method and application thereof | |
| CN102616837B (en) | Method for preparing NH4TiOF3 powder | |
| CN104495868B (en) | A kind of preparation method of big particle diameter HTS | |
| CN101949053B (en) | Method for preparing anatase TiO2 single crystal | |
| CN102432064A (en) | Method for synthesizing nanometer titanium dioxide by reverse microemulsion carbon adsorption titanium tetrachloride hydrolytic system | |
| CN104909405B (en) | Spindle nano titanium oxide based on cellulose base template and preparation method thereof | |
| CN105836796A (en) | Preparation method of bell-type core-shell structured nano-TiO2(at)void(at)SiO2 powder | |
| CN106082201B (en) | The graphene composite nano material and preparation method thereof of ultra-thin TiOx nano piece load | |
| JP2008150232A (en) | Metatitanic acid slurry for raw material of photocatalyst titanium oxide and method for producing the slurry | |
| CN100337740C (en) | Crystal titanium dioxide light catalyst and synthesis thereof | |
| CN107913712A (en) | A kind of titanium dioxide/modification infusorial earth composite material, film and its preparation method and application | |
| CN106268927A (en) | A kind of Ti-beta-molecular sieve obtained by total silicon beta-molecular sieve modification and its preparation method and application | |
| CN105597726A (en) | Composite photocatalyst hydrosol | |
| CN102502808A (en) | Preparation method of nano-grade titanium dioxide | |
| CN107892326B (en) | Rutile Type TiO2The preparation method and product of nano-rod assembly | |
| CN109553128A (en) | Rutile titanium dioxide is nanocrystalline, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190517 |
|
| RJ01 | Rejection of invention patent application after publication |