CN105016354A - Method for preparing submicron all-silicon DD3R molecular sieve - Google Patents
Method for preparing submicron all-silicon DD3R molecular sieve Download PDFInfo
- Publication number
- CN105016354A CN105016354A CN201510390345.7A CN201510390345A CN105016354A CN 105016354 A CN105016354 A CN 105016354A CN 201510390345 A CN201510390345 A CN 201510390345A CN 105016354 A CN105016354 A CN 105016354A
- Authority
- CN
- China
- Prior art keywords
- silicon
- molecular sieve
- dd3r molecular
- dd3r
- template 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
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a method for preparing a submicron all-silicon DD3R molecular sieve. The method comprises the following steps: 1) mixing a silicon source, amantadine, water and an auxiliary template agent to obtain crystal synthesis mother liquor and stirring and ageing the crystal synthesis mother liquor; and 2) adding 0.01-5% by mass of seed crystals into the crystal synthesis mother liquor and heating the crystal synthesis mother liquor with the seed crystals at 120-220 DEG C, wherein the auxiliary template agent is one or more selected from the group consisting of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetraethyl ammonium fluoride, tetraethyl ammonium bromide, tetrabutyl ammonium hydroxide and tetrabutyl ammonium bromide. According to the present invention, by adopting the method of mixing the template agent and adding the seed crystals, an induction period in a crystallization process is greatly shortened, a crystallization rate is increased and a synthesis period of the DD3R molecular sieve is shortened, so that the synthesis period of the submicron all-silicon DD3R molecular sieve is shortened from 25 days in the prior art to 3 hours; and the prepared DD3R molecular sieve is uniform in crystal size, has a particle size less than 1 micrometer, has a yield rate close to 100%, and has great application potential in adsorption and separation fields.
Description
Technical field
The present invention relates to chemical field, specifically disclose a kind of method preparing submicron total silicon DD3R molecular sieve.
Background technology
Zeolite molecular sieve has the advantages such as the homogeneous and material transferring in chemical stability, thermostability, mechanical stability, aperture is fast, has been widely used in gas adsorption and has been separated in Application Areas.The structural code of DD3R molecular sieve is DDR, and this molecular sieve is a kind of small pore molecular sieve, and the pore size of its octatomic ring is 0.36 × 0.44nm, and the kinetic diameter of the close micro-molecular gas common in a large number of this numerical value, so at CO
2-CH
4be separated and O
2/ N
2deng there being great application prospect in sepn process.And total silicon DD3R skeleton structure is not containing aluminium, for the skeleton structure of full Si, therefore it has very strong hydrothermal stability, chemical stability and solvent stability and strong-hydrophobicity, under the environment that high temperature, high pressure, solvent exist, still keep original skeleton structure and desirable adsorption selectivity, be separated Application Areas in multiple gas adsorption and show huge potential value.
But the synthesis cost of its costliness, technique is loaded down with trivial details and product yield is low, the not high factor of quality greatly hinders further investigation to DD3R zeolite molecular sieve and industrial applications.Pure phase, homogeneous DD3R crystal are very crucial for absorption and diffusion research, so, seek a kind of high yield, high-repetition-rate, homogeneous DD3R molecular sieve fast synthesis method be beneficial to the scale operation of DD3R and fractionation by adsorption application.
Summary of the invention
The object of the invention is to the defect overcoming prior art, there is provided a kind of method of Fast back-projection algorithm submicron order total silicon DD3R molecular sieve, overcome DD3R synthesis difficulty in prior art, generated time is long, cost intensive, technique are loaded down with trivial details, the low and defect of poor repeatability of product yield.
In order to realize above object and other objects, the present invention realizes by comprising following technical scheme:
Prepare a method for submicron total silicon DD3R molecular sieve, comprise the following steps:
1) silicon source, amantadine, water and auxiliary template agent are mixed to get Opacity in lens mother liquor, stir aging;
2) add the crystal seed that massfraction is 0.01 ~ 5%, heat under the condition of 120 ~ 220 DEG C;
Described auxiliary template agent be selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetraethyl ammonium fluoride, tetraethylammonium bromide, TBAH and Tetrabutyl amonium bromide one or more.
Preferably, step 1) described in the SiO in silicon source
2, water, amantadine and auxiliary template agent mol ratio be 1:15 ~ 300:0.02 ~ 2:0.02 ~ 2.
More preferably, step 1) described in SiO in silicon source
2be 1:30 ~ 100 with the mol ratio of water.
More preferably, step 1) described in SiO in silicon source
2be 2 with the mol ratio of amantadine.
More preferably, step 1) described in SiO in silicon source
2be 2 with the mol ratio of auxiliary template agent.
Preferably, step 1) described in silicon source be selected from positive quanmethyl silicate, tetraethyl orthosilicate, water glass, silicon sol and white carbon black one or more.
More preferably, step 1) described in silicon source be selected from silicon sol, and SiO in described silicon sol
2content be 40wt%.
Preferably, step 1) described in stir digestion time be 0.01 ~ 6 day.
Preferably, step 1) described in stir digestion time be 1 day.
Preferably, step 1) in first by amantadine, tetraethyl-oxyammonia and water mix and blend 0.5 ~ 3 hour, then add silicon sol.
More preferably, described auxiliary template agent is tetraethyl ammonium hydroxide.
Crystal seed described in the present invention is total silicon DD3R molecular sieve crystal seed.
Preferably, with SiO in described silicon source
2quality be benchmark meter, step 2) described in the addition 0.01 ~ 0.5wt% of crystal seed.
More preferably, with SiO in described silicon source
2quality be benchmark meter, step 2) described in the addition 0.046wt% of crystal seed.
Preferably, step 2) described in heating time be 3 ~ 72 hours.
Preferably, step 2) described in heating time be 12h.
Preferably, step 2) described in the temperature of heating be 160 DEG C.
Preferably, step 2) described in heating method be microwave heating.
The invention also discloses a kind of total silicon DD3R molecular sieve, prepared by method as described above, the particle diameter of described total silicon DD3R molecular sieve is 0.4 ~ 1 micron.
Amantadine described in the present invention is master module agent, and described tetraethyl ammonium hydroxide is auxiliary template agent.
The present invention adopts mixed templates and adds the method for crystal seed, shorten the inductive phase in crystallization process greatly, add crystallization velocity, significantly shorten the synthesis cycle of DD3R molecular sieve, make its synthesis cycle shorten to 3 hours by 25 days of the prior art, and obtained DD3R molecular sieve crystal yardstick is homogeneous, particle diameter is less than 1 μm, productive rate, close to 100%, has great application potential in absorption and separation field.
Accompanying drawing explanation
Fig. 1 adds 0.046wt% crystal seed in embodiment 1, and the mol ratio of the silicon in water and described silicon source is the stereoscan photograph of the DD3R molecular sieve that 100,160 DEG C of microwave heatings are synthesized for 12 hours;
Fig. 2 adds 0.046wt% crystal seed in embodiment 1, and the mol ratio of the silicon in water and described silicon source is that the XRD figure of the DD3R molecular sieve that 100,160 DEG C of microwave heatings are synthesized for 12 hours is composed;
Fig. 3 adds 0.046wt% crystal seed in embodiment 2, and the mol ratio of the silicon in water and described silicon source is the stereoscan photograph of the DD3R molecular sieve that 50,160 DEG C of microwave heatings are synthesized for 12 hours;
Fig. 4 adds 0.046wt% crystal seed in embodiment 2, and the mol ratio of the silicon in water and described silicon source is that the XRD figure of the DD3R molecular sieve that 50,160 DEG C of microwave heatings are synthesized for 12 hours is composed;
Fig. 5 is the stereoscan photograph of the DD3R molecular sieve of method synthesis in embodiment 3;
Fig. 6 is the XRD figure spectrum of total silicon DD3R molecular sieve crystal in embodiment 3, consistent with standard diagram.
Fig. 7 is the nitrogen adsorption isotherm of total silicon DD3R molecular sieve crystal in embodiment 3.
Embodiment
The present invention is set forth further below in conjunction with embodiment.Should be understood that embodiment only for illustration of the present invention, but not limit the scope of the invention.
Embodiment 1
The present embodiment is for adding 0.046wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that 100,160 DEG C of microwaves synthesize total silicon DD3R molecular sieve for 12 hours.
After being mixed with 1.51 grams of amantadines by 1.68 grams of tetraethyl ammonium hydroxides, add 33.1 grams of H
2o stir about 0.5 hour, then slowly drips 3 grams of silicon sol, SiO in described silicon sol
2content be 40wt%, stir after 24 hours and add 20 milligrams of total silicon DD3R crystal seeds, stir 5 minutes, in 160 DEG C of microwave heatings 12 hours.After product takes out, with deionized water wash, centrifugal, after oven dry, obtain total silicon DD3R molecular sieve crystal.
Fig. 1 is the stereoscan photograph of total silicon DD3R molecular sieve crystal in the present embodiment, and total silicon DD3R molecular sieve crystal is the rhomboidan of about 1 micron, and crystallographic dimension is comparatively even, and yield >80% is (with the SiO synthesized
2quality and the SiO that feeds intake
2ratio).Compare with traditional total silicon DD3R synthetic method, the time of Hydrothermal Synthesis shortened to 12 hours from 25 ~ 48 days.
Fig. 2 is the XRD figure spectrum of the total silicon DD3R molecular sieve crystal prepared in the present embodiment, consistent with standard diagram.
Embodiment 2
The present embodiment is for adding 0.046wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that 50,160 DEG C of microwaves synthesize total silicon DD3R molecular sieve for 12 hours.
Be with the difference of embodiment 1, in water and described silicon source, the mol ratio of silicon is 50, all the other steps and parameter identical with embodiment 1.
Fig. 3 is the stereoscan photograph of the total silicon DD3R molecular sieve crystal obtained in the present embodiment, and total silicon DD3R molecular sieve crystal is the rhomboidan of about 0.7 micron, and crystallographic dimension is comparatively even, yield >80%.
Fig. 4 is the XRD figure spectrum of the total silicon DD3R molecular sieve crystal obtained in the present embodiment, consistent with standard diagram.
Embodiment 3
The present embodiment is for adding 0.046wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that total silicon DD3R molecular sieve is synthesized in 30,160 DEG C of microwave heatings for 12 hours.
Be with the difference of embodiment 1, in water and described silicon source, the mol ratio of silicon is 30, all the other steps and parameter identical with embodiment 1.
Fig. 5 is the stereoscan photograph of total silicon DD3R molecular sieve crystal, and total silicon DD3R molecular sieve crystal is the rhomboidan of about 0.4 micron, and crystallographic dimension is comparatively even, and yield >80%, meanwhile, it is 256m that nitrogen adsorption records specific surface area
2/ g.
Fig. 6 is the XRD figure spectrum of total silicon DD3R molecular sieve crystal, consistent with standard diagram.
Fig. 7 is the nitrogen adsorption isotherm of total silicon DD3R molecular sieve crystal.
Embodiment 4
The present embodiment is for adding 0.01wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that total silicon DD3R molecular sieve is synthesized in 15,160 DEG C of microwave heatings for 72 hours.
SiO
2, water, amantadine and auxiliary template agent mol ratio be 1:15:0.02:2.
Described auxiliary template agent is Tetramethylammonium hydroxide.
Described silicon source is positive quanmethyl silicate.
After Tetramethylammonium hydroxide being mixed with amantadine, add H
2o stir about 2 hours.Aging 0.01 day is stirred after adding silicon source.
Embodiment 5
The present embodiment is for adding 2.5wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that total silicon DD3R molecular sieve is synthesized in 150,120 DEG C of microwave heatings for 72 hours.
SiO
2, water, amantadine and auxiliary template agent mol ratio be 1:150:1:1.
Described auxiliary template agent is TBAH.
Described silicon source is tetraethyl orthosilicate.
After TBAH being mixed with amantadine, add H
2o stir about 3 hours.Aging 6 days are stirred after adding silicon source.
Embodiment 6
The present embodiment is for adding 5wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that total silicon DD3R molecular sieve is synthesized in 300,220 DEG C of microwave heatings for 3 hours.
SiO
2, water, amantadine and auxiliary template agent mol ratio be 1:300:2:0.02.
Described auxiliary template agent is tetraethyl ammonium fluoride.
Described silicon source is water glass.
After being mixed with amantadine by tetraethyl ammonium fluoride, add H
2o stir about 0.5 hour.Aging 3 days are stirred after adding silicon source.
Embodiment 7
The present embodiment is for adding 0.046wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that total silicon DD3R molecular sieve is synthesized in 50,160 DEG C of microwave heatings for 48 hours.
SiO
2, water, amantadine and auxiliary template agent mol ratio be 1:50:1:1.
Described auxiliary template agent is tetraethylammonium bromide.
Described silicon source is white carbon black.
After being mixed with amantadine by tetraethylammonium bromide, add H
2o stir about 0.5 hour.Aging 3 days are stirred after adding silicon source.
Embodiment 8
The present embodiment is for adding 0.046wt% crystal seed, and in water and described silicon source, the mol ratio of silicon is that total silicon DD3R molecular sieve is synthesized in 50,160 DEG C of microwave heatings for 48 hours.
SiO
2, water, amantadine and auxiliary template agent mol ratio be 1:50:1:1.
Described auxiliary template agent is Tetrabutyl amonium bromide.
Described silicon source is white carbon black.
After being mixed with amantadine by Tetrabutyl amonium bromide, add H
2o stir about 0.5 hour.Aging 3 days are stirred after adding silicon source.
The above; be only preferred embodiment of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from the inventive method, also can make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, a little change made when utilizing disclosed above technology contents, the equivalent variations of modifying and developing, be Equivalent embodiments of the present invention; Meanwhile, all according to substantial technological of the present invention to the change of any equivalent variations that above-described embodiment is done, modify and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (9)
1. prepare a method for submicron total silicon DD3R molecular sieve, comprise the following steps:
1) silicon source, amantadine, water and auxiliary template agent are mixed to get Opacity in lens mother liquor, stir aging;
2) add the crystal seed that massfraction is 0.01 ~ 5%, heat under the condition of 120 ~ 220 DEG C;
Described auxiliary template agent be selected from Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetraethyl ammonium fluoride, tetraethylammonium bromide, TBAH and Tetrabutyl amonium bromide one or more.
2. method as claimed in claim 1, is characterized in that: step 1) described in the SiO in silicon source
2, water, amantadine and auxiliary template agent mol ratio be 1:15 ~ 300:0.02 ~ 2:0.02 ~ 2.
3. method as claimed in claim 1, is characterized in that: step 1) described in silicon source be selected from positive quanmethyl silicate, tetraethyl orthosilicate, water glass, silicon sol and white carbon black one or more.
4. method as claimed in claim 1, is characterized in that: step 1) described in stir digestion time be 0.01 ~ 6 day.
5. method as claimed in claim 1, is characterized in that: step 1) in first by amantadine, tetraethyl-oxyammonia and water mix and blend 0.5 ~ 3 hour, then add silicon sol.
6. method as claimed in claim 1, is characterized in that: with SiO in described silicon source
2quality be benchmark meter, step 2) described in the addition 0.01 ~ 0.5wt% of crystal seed.
7. method as claimed in claim 1, is characterized in that: step 2) described in time of heating be 3 ~ 72 hours.
8. method as claimed in claim 1, is characterized in that: step 2) described in the method for heating be microwave heating.
9. a total silicon DD3R molecular sieve, prepared by method as described in as arbitrary in claim 1 ~ 9, the particle diameter of described total silicon DD3R molecular sieve is 0.4 ~ 1 micron.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510390345.7A CN105016354A (en) | 2015-07-03 | 2015-07-03 | Method for preparing submicron all-silicon DD3R molecular sieve |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510390345.7A CN105016354A (en) | 2015-07-03 | 2015-07-03 | Method for preparing submicron all-silicon DD3R molecular sieve |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105016354A true CN105016354A (en) | 2015-11-04 |
Family
ID=54406736
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510390345.7A Pending CN105016354A (en) | 2015-07-03 | 2015-07-03 | Method for preparing submicron all-silicon DD3R molecular sieve |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105016354A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105460943A (en) * | 2015-11-25 | 2016-04-06 | 中国科学院上海高等研究院 | Full-silicon DD3R molecular sieve synthesis method |
CN105668578A (en) * | 2016-04-13 | 2016-06-15 | 中国科学院上海高等研究院 | Method for quickly synthesizing DD3R molecular sieve |
CN106823828A (en) * | 2017-02-22 | 2017-06-13 | 郭胤辰 | A kind of synthetic method of molecular screen membrane |
CN107512724A (en) * | 2017-09-24 | 2017-12-26 | 刘庆玉 | One kind is used to remove CO in admixture of gas2Silica zeolite |
CN108697997A (en) * | 2016-02-19 | 2018-10-23 | 日立造船株式会社 | Zeolitic separation membrane and its manufacturing method |
CN109603894A (en) * | 2018-12-29 | 2019-04-12 | 韩旭霞 | A kind of preparation method of purifying formaldehyde material |
CN110605029A (en) * | 2019-08-22 | 2019-12-24 | 上海工程技术大学 | Method for synthesizing DDR molecular sieve membrane |
US11111153B2 (en) | 2018-08-27 | 2021-09-07 | Exxonmobil Research And Engineering Company | Process for making molecular sieves |
US11318450B2 (en) | 2018-08-27 | 2022-05-03 | Exxonmobil Research & Engineering Company | Molecular sieves and a process for making molecular sieves |
US11318451B2 (en) | 2018-08-27 | 2022-05-03 | Exxonmobil Research & Engineering Company | Molecular sieves and a process for making molecular sieves |
US11542446B2 (en) | 2018-08-27 | 2023-01-03 | Exxon Mobil Technology and Engineering Company | Dewaxing using a molecular sieve catalyst |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102786065A (en) * | 2012-08-21 | 2012-11-21 | 浙江师范大学 | Method for preparing full-silicon DD3R zeolite molecular sieve with pure phase and uniform crystal morphology and size |
CN103771451A (en) * | 2014-01-10 | 2014-05-07 | 浙江师范大学 | Synthesis method for preparing pure-phase DD3R (deca-dodecasil 3rhombohedral) zeolite molecular sieve under induction of ultrafine silicon dioxide |
-
2015
- 2015-07-03 CN CN201510390345.7A patent/CN105016354A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102786065A (en) * | 2012-08-21 | 2012-11-21 | 浙江师范大学 | Method for preparing full-silicon DD3R zeolite molecular sieve with pure phase and uniform crystal morphology and size |
CN103771451A (en) * | 2014-01-10 | 2014-05-07 | 浙江师范大学 | Synthesis method for preparing pure-phase DD3R (deca-dodecasil 3rhombohedral) zeolite molecular sieve under induction of ultrafine silicon dioxide |
Non-Patent Citations (1)
Title |
---|
JORGE GASCON ET AL.: ""Accelerated synthesis of all-silica DD3R and its performance in the separation of propylene/propane mixtures"", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105460943A (en) * | 2015-11-25 | 2016-04-06 | 中国科学院上海高等研究院 | Full-silicon DD3R molecular sieve synthesis method |
CN108697997A (en) * | 2016-02-19 | 2018-10-23 | 日立造船株式会社 | Zeolitic separation membrane and its manufacturing method |
CN105668578A (en) * | 2016-04-13 | 2016-06-15 | 中国科学院上海高等研究院 | Method for quickly synthesizing DD3R molecular sieve |
CN106823828A (en) * | 2017-02-22 | 2017-06-13 | 郭胤辰 | A kind of synthetic method of molecular screen membrane |
CN106823828B (en) * | 2017-02-22 | 2018-02-23 | 郭胤辰 | A kind of synthetic method of molecular screen membrane |
CN107512724A (en) * | 2017-09-24 | 2017-12-26 | 刘庆玉 | One kind is used to remove CO in admixture of gas2Silica zeolite |
US11318450B2 (en) | 2018-08-27 | 2022-05-03 | Exxonmobil Research & Engineering Company | Molecular sieves and a process for making molecular sieves |
US11542446B2 (en) | 2018-08-27 | 2023-01-03 | Exxon Mobil Technology and Engineering Company | Dewaxing using a molecular sieve catalyst |
US11111153B2 (en) | 2018-08-27 | 2021-09-07 | Exxonmobil Research And Engineering Company | Process for making molecular sieves |
US11318451B2 (en) | 2018-08-27 | 2022-05-03 | Exxonmobil Research & Engineering Company | Molecular sieves and a process for making molecular sieves |
CN109603894A (en) * | 2018-12-29 | 2019-04-12 | 韩旭霞 | A kind of preparation method of purifying formaldehyde material |
CN109603894B (en) * | 2018-12-29 | 2021-11-12 | 上海孺子牛环保科技有限公司 | Preparation method of formaldehyde purification material |
CN110605029A (en) * | 2019-08-22 | 2019-12-24 | 上海工程技术大学 | Method for synthesizing DDR molecular sieve membrane |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105016354A (en) | Method for preparing submicron all-silicon DD3R molecular sieve | |
CN104925826A (en) | Method for preparing DD3R molecular sieve | |
CN104986783B (en) | A method of preparing total silicon DD3R molecular sieves | |
CN103121698B (en) | Method for synthesizing SAPO (silicoaluminophosphate)-34 by solid-phase grinding | |
CN104724720B (en) | A kind of synthetic method of the molecular sieves of HZSM 5 | |
CN102311124B (en) | Method for preparing Silicalite-1/ZSM-5 composite molecular sieve | |
CN105439168B (en) | A kind of method for preparing high silica alumina ratio Y type molecular sieve | |
CN107352553A (en) | LSX type zeolites with controlled particle size distribution | |
CN104925825A (en) | Manufacturing method of all-silicon CHA molecular sieve | |
CN111285380A (en) | Preparation method and application of multi-rare earth co-doped boride and nano heat insulation powder thereof | |
Li et al. | Design optimization of CsPbBr 3 nanocrystals into zeolite Beta composites as ultra-stable green emitters for backlight display applications | |
CN106379871B (en) | A kind of method for preparing two selenizing rhenium nanometer sheets | |
CN102330081B (en) | Method for preparing Sm2O3 film by solvent heat method | |
CN101811702B (en) | Preparation method of double-mesopore silicon dioxide transparent gel monolith | |
CN105460943A (en) | Full-silicon DD3R molecular sieve synthesis method | |
CN103771451A (en) | Synthesis method for preparing pure-phase DD3R (deca-dodecasil 3rhombohedral) zeolite molecular sieve under induction of ultrafine silicon dioxide | |
WO2019119513A1 (en) | Non-linear optical crystal monoflurophospate | |
CN109796045B (en) | Method for preparing compound tungstate by adopting self-sacrificial template | |
WO2017201648A1 (en) | Infrared nonlinear optical crystal material, and preparation method therefor and use thereof | |
CN101373669B (en) | Nano porous semiconductor film with upper conversion function for dye sensitization solar cell | |
CN104591202B (en) | A kind of hollow P type zeolite and preparation method thereof | |
CN105129812B (en) | A kind of preparation method of Fast back-projection algorithm DD3R molecular sieves | |
Wang et al. | Single-crystal-to-single-crystal desolvation in a Ti 32 nanoring cluster | |
CN103979515B (en) | A kind of YPO being assisted synthesis by Surfactant CTAB 4nano particle and preparation method thereof | |
CN109694084B (en) | Preparation method of DOH zeolite molecular sieve |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151104 |
|
RJ01 | Rejection of invention patent application after publication |