CN101823703A - Controllable preparation method for petaliform tin oxide nano powder - Google Patents
Controllable preparation method for petaliform tin oxide nano powder Download PDFInfo
- Publication number
- CN101823703A CN101823703A CN200910096575A CN200910096575A CN101823703A CN 101823703 A CN101823703 A CN 101823703A CN 200910096575 A CN200910096575 A CN 200910096575A CN 200910096575 A CN200910096575 A CN 200910096575A CN 101823703 A CN101823703 A CN 101823703A
- Authority
- CN
- China
- Prior art keywords
- naoh
- until
- powder
- sno
- suspension liquid
- 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.)
- Granted
Links
Images
Abstract
The invention discloses a controllable preparation method for petaliform tin oxide nano powder, which is mainly characterized in that SnCl2 and NaOH serve as raw materials. The method comprises the following detailed steps: dissolving the SnCl2 and NaOH in deionized water respectively to prepare a tin salt suspension of which the concentration is 0.2 to 0.4mol/L and NaOH solution of which the concentration is 0.3 to 1mol/L; under magnetic stirring, uniformly dripping the NaOH solution into the tin salt solution until the pH value is between 11 and 13, and stirring the solution for 2 to 3 hours to obtain SnO2 precursor; pouring the precursor into a water heating reaction kettle for water heating treatment for 12 to 24 hours at the temperature of 160 to 200 DEG C; and washing and drying the obtained product, and obtaining the petaliform SnO2 powder consisting of single crystal nano sheets of which the thickness is about 3 to 10nm. No any surfactant is added. The method has the characteristics of high quality and yield of the product, low cost, massive production and the like, and is an environment-friendly synthetic method.
Description
Technical field
The present invention relates to a kind of colored sheet SnO
2The preparation method of nano-powder, this powder can be applicable to fields such as gas sensor material and photocatalyst material.
Background technology
SnO
2Have fabulous photoelectric characteristic and to the sensitive property of reducing gas, be widely used in gas sensor material and and field such as photocatalyst material at present.Work as SnO
2After the crystal particle scale of material entered nano level, owing to the exclusive dimensional effect of nano material, quantum size effect and surface effects etc. show many special physicochemical character, its gas-sensitive property and catalysis characteristics all had significantly lifting.Therefore, to SnO
2The controlled preparation of the microscopic appearance of nano material, particle diameter and crystalline structure is most important to improving its gas-sensitive property and catalysis characteristics.
In recent years, researcher has been prepared the SnO of multiple patterns such as particulate state, nano wire/nanometer rod/nanoneedle, hollow ball, nanometer plate
2Nano material.Related preparation method has the physics method that comprises magnetron sputtering, atomic beam deposition, electron beam deposition and high-temp combustion synthesis method etc., and comprise chemical gas phase oxidation, direct chemical method such as synthetic, collosol and gel of precipitation, hydro-thermal and template, the synthetic SnO of institute
2The shape major part of nano material is particulate state, one dimension wire and hollow ball structure, and only a few presents sheet or flower-shaped.For example, Journa of American Chemical Society, 2002,124, " Growth and Structure Evolution of Novel Tin Oxide Diskettes " reported with the vapor coating legal system and has been equipped with SnO among the 8673-8680
2The technology of nanometer monocrystalline dish, the investigator is that the mode that starting material pass through high temperature oxidation forms monocrystalline SnO with the SnO powder
2Nanometer plate.Sensors andActuators B in 2006,2006,113, " High ethanol sensitive SnO2 microspheres " reported a kind of with SnCl among the 937-943
2With the sulphur powder be that raw material at high temperature is oxidized to SnS flower-shaped SnO with chemical Vapor deposition process
2The method of microballoon.Compare prepared by physical method SnO
2Higher to equipment requirements, be used for film preparation more; And the cost of chemical method is relatively low, and is easy to operate, is suitable for industrial production in enormous quantities.Yet though the above-mentioned chemical Vapor deposition process easily-controlled reaction conditions of using, Technology complexity, cost height, one-time investment are big.
Compare with general wet-chemical reaction method, hydrothermal method can directly generate crystal, and prepared powder granule is even, the degree of crystallinity height, and crystalline state is complete, thereby makes one of its important technology that becomes multiple nano oxide powder preparation.Journal of Nanoparticle Research, 2006,8, " Facile synthesis and optical property of SnO2 flower-like architectures " reported with KBrO3, NaOH and tinfoil paper to be that raw material has synthesized the flower-shaped SnO of class with hydrothermal method among the 1065-1069
2Method.In addition, Journal of Crystal Growth, 2006,291, " Hydrothemalsynthesis and characterization of novel flower-like zinc-doped SnO2 nano-crystals " reported with SnCl among the 258-261
4With NaOH be that raw material passes through ZnCl
2Doping the has utilized Hydrothermal Preparation flower-shaped SnO that forms by nanoneedle
2According to Materials Letter, 2007,61, " Synthesis of novel hexagon SnO2 nanosheets in ethanol/water soltion by hydrothermal process " report of 3705-3707 is by regulating and control water and alcoholic acid volume ratio with SnCl
4, NaOH and template CTAB be that raw material has been realized SnO
2The controlled preparation of nanometer sheet shape and size.With reported method is different before, the present invention is mainly directly with SnCl
2With NaOH be that raw material adopts the non-template hydrothermal method to realize the colored sheet SnO that is self-assembled into by single crystal nanoplate
2The controlled preparation of nano-powder can be controlled SnO by regulation and control water and alcoholic acid volume ratio
2The thickness of nanometer sheet and the yardstick on the two-dimensional direction.Present method is not added any tensio-active agent, have product quality height, productive rate height, cost is low and can scale production etc. characteristics, be a kind of environmentally friendly synthetic method.The colored sheet SnO that obtains
2Be rutile phase structure and monolithic SnO
2Be monocrystalline.By sign, find that this powder has special photoabsorption peak position, might improve SnO greatly to the ultraviolet-visible optical absorption characteristics of powder
2Photoelectric characteristic.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of directly with SnCl at the above-mentioned state of the art
2With NaOH be that raw material adopts the non-template hydrothermal method to realize the colored sheet SnO that is self-assembled into by single crystal nanoplate
2The controllable method for preparing of nano-powder, it can control SnO by regulation and control water and alcoholic acid volume ratio
2The thickness of nanometer sheet and the yardstick on the two-dimensional direction, and do not add any tensio-active agent, have product quality height, productive rate height, cost is low and can scale production etc. characteristics, be a kind of environmentally friendly synthetic method.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of controllable method for preparing of spending the sheet tin oxide nano-powder is characterized in that steps in sequence is:
A. with SnCl
2Be dissolved into ethanol and water volume ratio and be in 0~1 the alcohol-water mixture or the aqueous solution, be stirred to the white suspension liquid that forms 0.2~0.4mol/L then; NaOH is dissolved in the water as a certain amount of deionized water in, stir then until the NaOH solution that forms 0.4~1mol/L;
B. under strong mixing, NaOH solution is dropped in the above-mentioned white suspension liquid uniformly, between 11~13, and then stir 2~3h, form presoma suspension liquid with black precipitate until the pH value;
C. above-mentioned presoma suspension liquid is transferred in the hydrothermal reaction kettle,, naturally cooled to room temperature then at 160~200 ℃ of following hydrothermal treatment consists 12~24h;
D. successively with the hydrothermal product washing for several times, until with Cl with deionized water and ethanol
-Remove fully, 70~90 ℃ of oven dry 1~2h obtain khaki SnO under the condition of vacuumizing
2Nano-powder.
Described washing is with deionized water and ethanol hydrothermal product to be washed respectively for several times successively, generally uses deionized water wash 4 times, with washing with alcohol 2 times, until with Cl
-Remove fully.
Concrete washing methods is:
A. product is moved into respectively in the centrifuge tube equably, then, in centrifuge tube, inject the deionized water of suitable volumes;
B., the symmetric supercentrifuge of putting into of centrifuge tube of product and deionized water will be housed, set rotating speed (being generally 6000~8000 rev/mins) and time (general 10~15 minutes/time), and start whizzer and finish once washing;
C. next according to identical operations, use deionized water and washing with alcohol for several times successively, until with Cl
-Remove fully.
Compared with prior art, the invention has the advantages that:
A. the colored sheet SnO that obtains
2Nano-powder has single tetragonal system rutile-type structure, is assembled into flower-shapedly by single crystal nanoplate, and the thickness of sheet is in 3~10nm scope, and is and controlled;
B.SnO
2Nano-powder has higher specific surface area and unique optical absorption characteristics, and specific surface area is at 42.6~93.2m
2Between/the g, the optical absorption peak corresponding wavelength is 331nm, sees accompanying drawing 4;
C. raw material is simple and easy to, and cost is low, and technology is simply pollution-free, suitability for industrialized production.
Description of drawings
Fig. 1. be flower sheet SnO
2The X-ray diffractogram of nano-powder, sample purity height as can be seen, good crystallinity, and with JCPDS card 41-1445 (space group:P42/mnm, a
o=4.74
c
o=3.19
) each peak correspondence (be rutile-type structure, belong to tetragonal system).
Fig. 2 a and 2b. are flower sheet SnO
2The field emission scanning electron microscope figure of nano-powder, the SnO of monolithic as can be seen
2The thickness of nanometer sheet is between 3~5nm, SnO
2Nanometer sheet and be self-assembled into micron-sized floriform appearance.
Fig. 3. be flower sheet SnO
2The transmission electron microscope picture of nano-powder, monolithic SnO as can be seen
2Being about on two-dimensional directional is 1 μ m, the wide 500nm that is about.Upper left high resolution TEM correspondence (110) crystal face, bottom-right SAED correspondence [001] crystal orientation.
Fig. 4. be flower sheet SnO
2The optical absorption characteristics of nano-powder correspondence has the absorption peak of the last one as can be seen at the 331nm place, usually SnO
2Absorption peak be 306nm, its absorption peak generation red shift is promptly moved to high wavelength significantly as can be seen.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Concrete embodiment 1:
A. the anhydrous SnCl of weighing 1.3539g
2Be dissolved in the 20ml water, then 10 minutes white suspension liquids of magnetic agitation until formation 0.3mol/L.The NaOH of weighing 0.8g is dissolved in the 20ml deionized water, and magnetic agitation is to the transparent NaOH solution that forms 1.0mol/L then.
B. under strong magnetic agitation, transparent NaOH solution being dropped in the above-mentioned white suspension liquid uniformly, is 11 until the pH value, and then magnetic agitation 3h, forms the presoma suspension liquid with black precipitate.
C. above-mentioned presoma suspension liquid is transferred to in the 100ml reactor,, naturally cooled to room temperature then at 200 ℃ of following hydrothermal treatment consists 24h.
D. successively with the hydrothermal product washing for several times, until with Cl with deionized water and ethanol
-Remove fully, 70 ℃ of oven dry 1h obtain khaki SnO under the condition of vacuumizing
2Nano-powder, its specific surface area are 51.6m
2/ g.SnO
2The thickness of nanometer sheet is about 3~5nm, the wide 500nm that is about, and being about is 1 μ m.
Concrete embodiment 2:
A. the anhydrous SnCl of weighing 1.3539g
2Separate in the mixed solution of 5ml ethanol and 15ml water (volume ratio is 1: 3), then 10 minutes white suspension liquids of magnetic agitation until formation 0.3mol/L.Weighing 0.8g NaOH is dissolved in the 50ml deionized water, and magnetic agitation forms the transparent NaOH solution of 0.4mol/L then.
B. under strong magnetic agitation, transparent NaOH solution being dropped in the above-mentioned white suspension liquid uniformly, is 13 until the pH value, and then magnetic agitation 2h, forms the presoma suspension liquid with black precipitate.
C. above-mentioned presoma suspension liquid is transferred to in the 100ml reactor,, naturally cooled to room temperature then at 180 ℃ of following hydrothermal treatment consists 12h.
D. successively with the hydrothermal product washing for several times, until with Cl with deionized water and ethanol
-Remove fully, 70 ℃ of oven dry 1h obtain khaki SnO under the condition of vacuumizing
2Nano-powder, its specific surface area are 93.2m
2/ g.SnO
2The thickness of nanometer sheet is about 5~10nm, and the wide 200nm that is about is about and is 500nm.
The strong mixing that relates in the building-up process does not have specific requirement, and generally speaking, the stirring intensity when dripping NaOH solution is bigger than other processes.
The sign of powder: Fig. 1-3 is respectively a typical production and obtains flower sheet SnO
2The X-ray diffractogram of nano-powder (XRD), field emission scanning electron microscope figure (FESEM), transmission electron microscope picture (TEM).
Claims (2)
1. controllable method for preparing of spending the sheet tin oxide nano-powder is characterized in that steps in sequence is:
A. with SnCl
2Be dissolved into ethanol and water volume ratio and be in 0~1: 1 the alcohol-water mixture or the aqueous solution, stir then until the white suspension liquid that forms 0.2~0.4mol/L; NaOH is dissolved in the water, stirs then until the NaOH solution that forms 0.4~1mol/L;
B. under strong mixing, NaOH solution is dropped in the above-mentioned white suspension liquid uniformly, between 11~13, and then stir 2~3h, form presoma suspension liquid with black precipitate until the pH value;
C. above-mentioned presoma suspension liquid is transferred in the hydrothermal reaction kettle,, naturally cooled to room temperature then at 160~200 ℃ of following hydrothermal treatment consists 12~24h;
D. successively with the hydrothermal product washing for several times, until with Cl with deionized water and ethanol
-Remove fully, 70~90 ℃ of oven dry 1~2h obtain khaki SnO under the condition of vacuumizing
2Nano-powder.
2. controllable method for preparing according to claim 1 is characterized in that washing is with deionized water and ethanol hydrothermal product to be washed several respectively successively, until with Cl
-Remove fully.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009100965757A CN101823703B (en) | 2009-03-06 | 2009-03-06 | Controllable preparation method for petaliform tin oxide nano powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2009100965757A CN101823703B (en) | 2009-03-06 | 2009-03-06 | Controllable preparation method for petaliform tin oxide nano powder |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101823703A true CN101823703A (en) | 2010-09-08 |
CN101823703B CN101823703B (en) | 2012-07-04 |
Family
ID=42687904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2009100965757A Expired - Fee Related CN101823703B (en) | 2009-03-06 | 2009-03-06 | Controllable preparation method for petaliform tin oxide nano powder |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101823703B (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102080261A (en) * | 2010-12-15 | 2011-06-01 | 哈尔滨师范大学 | Method for synthesizing porous SnO2 nano-wire harness |
CN102128868A (en) * | 2010-12-30 | 2011-07-20 | 华东师范大学 | SnO2/Au modified glucose oxidase electrode and preparation method and application thereof |
CN102213688A (en) * | 2011-04-11 | 2011-10-12 | 大连理工大学 | Method of electrochemically measuring permanganate index by virtue of stannic oxide nanometer electrode |
CN102357365A (en) * | 2011-09-07 | 2012-02-22 | 复旦大学 | Preparation method for titanium oxynitride photocatalyst |
CN103043710A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院福建物质结构研究所 | Method for heterogeneously growing nano SnO2 on surface of alpha-Fe2O3 nanocrystalline |
CN103101967A (en) * | 2011-11-14 | 2013-05-15 | 南开大学 | Preparation method three-dimensional multistage SnO2 nanoflowers |
CN103864139A (en) * | 2014-02-18 | 2014-06-18 | 上海大学 | Preparation method of three-dimensional layered multilevel flower-shaped stannic oxide microsphere |
CN104213098A (en) * | 2013-06-04 | 2014-12-17 | 西安邮电大学 | Nano wall structure composed of flaky tin oxide and preparation method thereof |
CN104528808A (en) * | 2014-12-27 | 2015-04-22 | 陕西科技大学 | Preparation method of hollow tin dioxide microsphere |
CN105000592A (en) * | 2015-07-01 | 2015-10-28 | 盐城工学院 | Black stannic oxide and preparation method thereof |
CN105600818A (en) * | 2016-01-12 | 2016-05-25 | 济南大学 | Preparation method of oxygen-vacancy-rich tin dioxide nanometer powder and obtained product |
CN105734481A (en) * | 2014-12-10 | 2016-07-06 | 辽宁法库陶瓷工程技术研究中心 | Preparation method of high-temperature-resistant nano wave absorbing agent and wave absorbing coating |
CN105967225A (en) * | 2016-05-13 | 2016-09-28 | 上海纳米技术及应用国家工程研究中心有限公司 | {0><}0{>Tin dioxide nano flower and preparation method thereof |
CN106238723A (en) * | 2016-08-24 | 2016-12-21 | 武汉工程大学 | A kind of flower-shaped Au SnO2composite and its preparation method and application |
CN110711585A (en) * | 2019-10-18 | 2020-01-21 | 中国地质大学(北京) | Tree crown-shaped anoxic tin oxide nanosheet array structure and preparation method thereof |
CN111003695A (en) * | 2019-12-20 | 2020-04-14 | 河南科技大学 | Superfine nano tin dioxide and preparation method thereof |
CN113277551A (en) * | 2021-05-19 | 2021-08-20 | 郑州大学 | Composite lithium lanthanum titanate material, preparation method and application |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1237007C (en) * | 2003-10-15 | 2006-01-18 | 中国科学院上海硅酸盐研究所 | Method for preparing nano tin anhydride powder |
-
2009
- 2009-03-06 CN CN2009100965757A patent/CN101823703B/en not_active Expired - Fee Related
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102080261B (en) * | 2010-12-15 | 2012-11-21 | 哈尔滨师范大学 | Method for synthesizing porous SnO2 nano-wire harness |
CN102080261A (en) * | 2010-12-15 | 2011-06-01 | 哈尔滨师范大学 | Method for synthesizing porous SnO2 nano-wire harness |
CN102128868A (en) * | 2010-12-30 | 2011-07-20 | 华东师范大学 | SnO2/Au modified glucose oxidase electrode and preparation method and application thereof |
CN102213688A (en) * | 2011-04-11 | 2011-10-12 | 大连理工大学 | Method of electrochemically measuring permanganate index by virtue of stannic oxide nanometer electrode |
CN102213688B (en) * | 2011-04-11 | 2013-06-05 | 大连理工大学 | Method of electrochemically measuring permanganate index by virtue of stannic oxide nanometer electrode |
CN102357365A (en) * | 2011-09-07 | 2012-02-22 | 复旦大学 | Preparation method for titanium oxynitride photocatalyst |
CN103043710B (en) * | 2011-10-17 | 2015-09-16 | 中国科学院福建物质结构研究所 | A kind of at α-Fe 2o 3nanocrystal surface Heteroepitaxy nano SnO 2method |
CN103043710A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院福建物质结构研究所 | Method for heterogeneously growing nano SnO2 on surface of alpha-Fe2O3 nanocrystalline |
CN103101967A (en) * | 2011-11-14 | 2013-05-15 | 南开大学 | Preparation method three-dimensional multistage SnO2 nanoflowers |
CN104213098B (en) * | 2013-06-04 | 2017-07-18 | 西安邮电大学 | A kind of nanometer wall construction being made up of sheet tin oxide and preparation method thereof |
CN104213098A (en) * | 2013-06-04 | 2014-12-17 | 西安邮电大学 | Nano wall structure composed of flaky tin oxide and preparation method thereof |
CN103864139A (en) * | 2014-02-18 | 2014-06-18 | 上海大学 | Preparation method of three-dimensional layered multilevel flower-shaped stannic oxide microsphere |
CN105734481A (en) * | 2014-12-10 | 2016-07-06 | 辽宁法库陶瓷工程技术研究中心 | Preparation method of high-temperature-resistant nano wave absorbing agent and wave absorbing coating |
CN105734481B (en) * | 2014-12-10 | 2018-02-27 | 辽宁法库陶瓷工程技术研究中心 | A kind of preparation method of high-temperature resistant nano wave absorbing agent and microwave absorbing coating |
CN104528808A (en) * | 2014-12-27 | 2015-04-22 | 陕西科技大学 | Preparation method of hollow tin dioxide microsphere |
CN105000592A (en) * | 2015-07-01 | 2015-10-28 | 盐城工学院 | Black stannic oxide and preparation method thereof |
CN105600818A (en) * | 2016-01-12 | 2016-05-25 | 济南大学 | Preparation method of oxygen-vacancy-rich tin dioxide nanometer powder and obtained product |
CN105600818B (en) * | 2016-01-12 | 2017-06-23 | 济南大学 | The method and products obtained therefrom of a kind of stannic oxide nanometer powder prepared rich in Lacking oxygen |
CN105967225A (en) * | 2016-05-13 | 2016-09-28 | 上海纳米技术及应用国家工程研究中心有限公司 | {0><}0{>Tin dioxide nano flower and preparation method thereof |
CN105967225B (en) * | 2016-05-13 | 2018-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of stannic oxide nanometer flower and preparation method thereof |
CN106238723A (en) * | 2016-08-24 | 2016-12-21 | 武汉工程大学 | A kind of flower-shaped Au SnO2composite and its preparation method and application |
CN110711585A (en) * | 2019-10-18 | 2020-01-21 | 中国地质大学(北京) | Tree crown-shaped anoxic tin oxide nanosheet array structure and preparation method thereof |
CN110711585B (en) * | 2019-10-18 | 2020-09-11 | 中国地质大学(北京) | Tree crown-shaped anoxic tin oxide nanosheet array structure and preparation method thereof |
CN111003695A (en) * | 2019-12-20 | 2020-04-14 | 河南科技大学 | Superfine nano tin dioxide and preparation method thereof |
CN113277551A (en) * | 2021-05-19 | 2021-08-20 | 郑州大学 | Composite lithium lanthanum titanate material, preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN101823703B (en) | 2012-07-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101823703B (en) | Controllable preparation method for petaliform tin oxide nano powder | |
CN102086044B (en) | Method for preparing hollow spherical stannic oxide nano powder | |
CN103435096B (en) | Method for preparing size controllable nano stannic oxide | |
CN101585544B (en) | Method for preparing aluminum borate nanowire | |
CN102336431B (en) | SnO2 flowerlike structure nano material and hydrothermal preparation method for the same | |
CN107557908B (en) | A kind of bead chain shape CuMn2O4The preparation method and products obtained therefrom of/ZnO composite fibre | |
CN102795664B (en) | Preparation method of mesoporous titanium dioxide microballoons with controllable particle size | |
CN106745231B (en) | A kind of taper titanium dioxide nano-rod and preparation method thereof | |
CN102267718A (en) | Synthesis method of tin dioxide nanometer material | |
CN105016382B (en) | Method for preparing pure gold redstone type titanium dioxide nanorod | |
CN102161498A (en) | Preparation method of uniformly dispersed nano lanthanum oxide | |
CN113443650B (en) | Method for preparing nano titanate by utilizing self-release of crystal water | |
CN105727922B (en) | A kind of Li adulterates SrTiO3The preparation method and product of ten octahedron nanometer particles | |
CN105883910B (en) | A kind of perovskite SrTiO3The preparation method and product of porous nano particle | |
CN103922402B (en) | Method for preparing NH4V3O8 nanoribbon | |
CN112456556A (en) | Method for preparing tantalum oxide nanospheres | |
CN112978687A (en) | Preparation method of tantalum nitride mesoporous nanospheres | |
CN102491416A (en) | Method for preparing Eu2Zr207 nanometer powder | |
CN108654663A (en) | A kind of mixed nitrate molten-salt growth method prepares the nitrogen co-doped single-crystal meso-pore TiO of boron2The method of catalysis material | |
CN102502785A (en) | Preparation method of basic zinc carbonate nano powder with hexagonal and laminary structure | |
CN105776326B (en) | A kind of polyhedral preparation method of titanium dioxide being made up of hollow six prism and products obtained therefrom | |
CN101805017B (en) | Preparation method of rutile type titanium dioxide nano particle | |
CN110216295B (en) | Room temperature water phase preparation method of silver nano flowers and glucose electrocatalytic oxidation thereof | |
CN102502859A (en) | Preparation method for iron molybdate nanocone material with sheet-layer structure | |
CN115090281B (en) | Three-dimensional flaky Na-alpha-MnO 2 Preparation method of (C) and application of (C) in catalytic combustion of VOCs |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120704 Termination date: 20150306 |
|
EXPY | Termination of patent right or utility model |