CN102942208A - Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly - Google Patents

Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly Download PDF

Info

Publication number
CN102942208A
CN102942208A CN2012104667284A CN201210466728A CN102942208A CN 102942208 A CN102942208 A CN 102942208A CN 2012104667284 A CN2012104667284 A CN 2012104667284A CN 201210466728 A CN201210466728 A CN 201210466728A CN 102942208 A CN102942208 A CN 102942208A
Authority
CN
China
Prior art keywords
zno
assembly
carbon
doped mesoporous
solution
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
Application number
CN2012104667284A
Other languages
Chinese (zh)
Other versions
CN102942208B (en
Inventor
胡勇
周墨娇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Normal University CJNU
Original Assignee
Zhejiang Normal University CJNU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Normal University CJNU filed Critical Zhejiang Normal University CJNU
Priority to CN201210466728.4A priority Critical patent/CN102942208B/en
Publication of CN102942208A publication Critical patent/CN102942208A/en
Application granted granted Critical
Publication of CN102942208B publication Critical patent/CN102942208B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention discloses a method for easily and conveniently preparing a carbon doped mesoporous ZnO Hamburg structure nanometer assembly. The method comprises the following steps of: adding structure-directing agent glucose by taking ethylene glycol as a reaction solvent and inorganic salt zinc acetate of a transition metal and excess alkali source as reaction precursors, and performing induced polymerization and twin crystal polar field driving to realize self-assembly of the carbon doped ZnO nanoparticles, thereby obtaining high-quality and high-yield Hamburg type carbon doped mesoporous ZnO assembly. By using the Hamburg structure carbon doped mesoporous ZnO prepared by the invention, the diameter range of the assembly is 400-500 nm, the particle size of the ZnO nanoparticles is about 5.8 nm, and the mesoporous radius is averagely 7.6 nm. The Hamburg type carbon doped mesoporous ZnO prepared by the invention has the advantages of low product cost, easiness in control, high uniformity, high yield, high repeatability, suitability for large-scale production and the like.

Description

The method of the carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly
Technical field
The invention belongs to inorganic mesoporous technical field of material, particularly the method for the carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly.
Background technology
Nano zine oxide (ZnO) has good conduction and thermal conductivity, chemical stability, non-migrating, fluorescence, absorption and scatters ultraviolet ability etc. as a kind of multifunctional semiconductor.It has important using value at aspects such as piezoelectric, optics, gas sensor, coating, environmental improvements, in addition abundant raw materials, low price, nontoxic to environment, show especially boundless application prospect, " physical chemistry " magazine (2011,13597 pages of 115 volumes) and " material wall bulletin " magazine (2012,90 pages of 68 volumes) in the U.S. had report.Mesoporous material is because having special aperture, larger pore volume, the abundant microtextures such as ion-exchange site, add that its specific surface area is large, adsorptive power forces it to be widely used in fields such as heterogeneous catalyst, the energy, biotechnology, nano-device, water treatments, " hazardous material " magazine (2010,204 pages of 181 volumes) in the U.S. had report.At present, the method that existing bibliographical information prepares various mesoporous materials has: template, sol-gel method, sedimentation, thermal expansion gaseous diffusion process, structure directing method etc., wherein inorganic materials is also with mesoporous SiO 2, TiO 2In the majority with mesoporous carbon material, patent 200610011885.0,200410065441.6,200910050884.0 etc. discloses these synthetic methods.Meso-porous ZnO is difficult to form as the same tridimensional network with Ti-O of Si-O because of Zn ion facile hydrolysis, so be difficult to obtain by traditional evaporation conduction self assembling process.The cage shape polyhedron that utilizes vacuum thermal evaporation sedimentation making ZnO particle to assemble has been reported in " JACS " (2003,11299 pages of 125 volumes), shows the feature of meso-hole structure because of the gap that has nano-scale between the particle.But the method temperature of reaction reaches 1150 ° of C, and is vacuum condition, to the plant and instrument requirement condition is high, control condition is harsh, production cost is high, is difficult to realize industrialization.
Summary of the invention
The objective of the invention is for existing, control condition harsh, the production cost high weak point high to the plant and instrument requirement condition of existing preparation meso-porous ZnO, provide a kind of to plant and instrument less demanding, simple to operate easy to control, production cost is low, the product homogeneity high, can be mass, the method for the carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly of good reproducibility.
The present invention is achieved through the following technical solutions: the method for the carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly, and take ethylene glycol (EG) as reaction solvent, with the inorganic salt zinc acetate (Zn (Ac) of transition metal 22H 2O) and excessive alkali source (NaOH) be pre-reaction material, add structure directing agent glucose, drive the ZnO nano particle self-assembly that has realized that carbon (C) mixes by induced polymerization and twin polarity field, thereby obtain the carbon-doped mesoporous ZnO assembly of hamburger type of high quality, high yield.
In the method for the carbon-doped mesoporous ZnO of described a kind of simple preparation hamburger structure nano assembly, the method for preparing carbon-doped mesoporous ZnO hamburger structure nano assembly may further comprise the steps:
⑴ Zn (OH) 4 2-The preparation of sol precursor
Get raw material zinc acetate (Zn (Ac) 22H 2O) and ethylene glycol (EG), be made into Zn 2+Volumetric molar concentration is the colourless transparent solution A of 0.1～0.4M, carries out magnetic agitation under the room temperature; Get sodium hydroxide (NaOH) and EG, be made into the solution B take the NaOH volumetric molar concentration as 0.4～0.8M, dropwise add solution B in the solution A, through reaction, solution becomes gradually muddy and becomes clear again, treats that solution B drips end, taking by weighing 0.02～0.08M glucose is dissolved in wherein, continue to stir 10～20 minutes, solution becomes near transparent oyster white, and the mixed solution of gained is Zn (OH) 4 2-Sol precursor;
⑵ the preparation of carbon-doped mesoporous ZnO hamburger structure nano assembly
Mixed solution is transferred in the reactor, and through 160～180 ° of C, after 12～24 hours, centrifuge washing, oven dry namely obtain carbon-doped mesoporous ZnO hamburger structure nano assembly.
Adopt the doped meso-porous ZnO of hamburger structural carbon of the present invention's preparation, its assembly diameter range is at 400～500nm, ZnO nano grain diameter size is about 5.8nm, the advantages such as mesoporous radius average out to 7.6nm, the carbon-doped mesoporous ZnO of hamburger type of the present invention preparation have that product cost is low, easy to control, homogeneity is high, output is large, good reproducibility and suitable scale operation.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of carbon-doped mesoporous ZnO hamburger structure nano assembly of preparation among the embodiment 1 that surveys of the Dutch PW3040/60 of PHILIPS Co. type x-ray diffractometer, wherein: X-coordinate X is angle of diffraction (2 θ), and ordinate zou Y is relative diffracted intensity.Illustration is its little angle x-ray diffraction pattern.
Fig. 2 is the shape appearance figure of carbon-doped mesoporous ZnO hamburger structure nano assembly of preparation among the S-4800 of HIT type field emission scanning electron microscope (FE-SEM) the observation embodiment 1, and illustration is its partial enlarged drawing.
Fig. 3 is carbon-doped mesoporous ZnO hamburger structure nano assembly internal structure picture of preparation among the embodiment 1 that observes of the JEM-2100F of Jeol Ltd. type transmission electron microscope (TEM).
Fig. 4 is the adsorption isothermal line of carbon-doped mesoporous ZnO hamburger structure nano assembly among the embodiment 1 that provides of the ASAP of Micromeritics Instrument Corp. U.S.A 2020 type physical adsorption appearances, and illustration is its graph of pore diameter distribution.
Fig. 5 is the x ray photoelectron spectroscopic analysis figure (XPS) of C 1s in the structure nano assembly of carbon-doped mesoporous ZnO hamburger.
Fig. 6 is carbon-doped mesoporous ZnO hamburger structure nano assembly and each 50mg of commercial ZnO(among the embodiment 1) to the adsorption effect comparison diagram of the Congo red solution of 30mL (100mg/L).
Fig. 7 is the meso-porous ZnO nanometer assembly shape appearance figure of preparation among the S-4800 of HIT type field emission scanning electron microscope (FE-SEM) the observation embodiment 2, and product presents porous but without fixing exterior appearance, illustration is its partial enlarged drawing.
Fig. 8 is the carbon doping zinc oxide nanometer granule-morphology figure of preparation among the S-4800 of HIT type field emission scanning electron microscope (FE-SEM) the observation embodiment 3.The inhomogeneous pattern irregularity of product size.
Embodiment
Below by embodiment the method for the carbon-doped mesoporous ZnO of a kind of simple preparation of the present invention hamburger structure nano assembly is made further and to be specified.
Embodiment 1
Take by weighing the Zn (Ac) of 0.48g(2.2 * 10-3mol) 22H 2O is dissolved in the 22mL ethylene glycol, obtains colourless transparent solution A, carries out magnetic agitation under the room temperature; Get NaOH and ethylene glycol, be made into take the NaOH volumetric molar concentration as 0.6M, volume is the solution B of 10mL, solution B is dropwise added in the solution A, and reaction for some time, solution becomes gradually muddy and becomes clear again, wait to drip and finish, take by weighing 0.2g glucose and be dissolved in wherein, continue to stir 15～20 minutes, solution is the colloidal sol shape.Above-mentioned gained colloidal sol is transferred in the 40mL reactor, after 160 ° of C react 24 hours, centrifuge washing, 60 ° of C oven dry are done X-ray diffraction, field emission scanning electron microscope, tem study, pore structure analysis, x ray photoelectron spectroscopic analysis and absorption property test to products obtained therefrom.
Do the X-ray diffraction analysis for the carbon-doped mesoporous ZnO hamburger structure nano assembly for preparing in the present embodiment, the result as shown in Figure 1, its X-coordinate X is angle of diffraction (2 θ), ordinate zou Y is relative diffracted intensity, all diffraction peaks can change into by the face-centred cubic structure index JCPDS in (100), (101), (002) and (102) etc. and the international standard powder X-ray RD diffraction card among the figure, and 89-0511 is consistent.Calculating as can be known by formula, its size is about 5.8nm.Illustration is its little angle x-ray diffraction pattern, is 1.468 ° at 2 θ angles and locates, and the not high broadening peak of an intensity is arranged, and illustrate that it is mesoporous material, but the mesoporous degree of order is not high.
Do the field emission scanning electron microscope analysis for the carbon-doped mesoporous ZnO hamburger structure nano assembly for preparing in the present embodiment, the electromicroscopic photograph that obtains as shown in Figure 2, can find out the symmetrical configuration of hamburger shape ZnO, appearance and size is even, diameter is greatly about 400～500nm, rough, for small-particle forms.
Do tem study for the carbon-doped mesoporous ZnO hamburger structure nano assembly for preparing in the present embodiment.As can be seen from Figure 3, carbon-doped mesoporous ZnO hamburger structure nano assembly integral body of present embodiment preparation is to be piled up by small-particle to form, and has the cave-shaped pore space structure of ant.
Do the test of N2 adsorption desorption for the carbon-doped mesoporous ZnO hamburger structure nano assembly for preparing in the present embodiment, the information that obtains as shown in Figure 4, the sorption isotherm of sample belongs to the IV type and has the H3 hysteresis loop, and these can both prove further that this sample is mesoporous material.Graph of pore diameter distribution in the illustration more intuitively reality goes out sample and has narrower pore size distribution, and pore radius is about 7.6nm.In addition, the BET specific surface area of sample is 88m 2g -1, be 20 times of the commercial ZnO of bibliographical information.
Do the x ray photoelectron spectroscopic analysis for the carbon-doped mesoporous ZnO hamburger structure nano assembly for preparing in the present embodiment.Fig. 5 has shown the wherein further swarming of C 1s power spectrum, by analyze as can be known sample 283.3,284.8,286.2,288.6eV has peak (respectively corresponding Zn-C key, C-C key, O-C-O complex body, C=O and C-O) everywhere, and take C-C key and O-C-O complex body as main.The decolorizing carbon that the image-stone China ink is described exists, and C successfully replaces part Zn position and a small amount of O position, the doping of realization C.
The carbon-doped mesoporous ZnO hamburger structure nano assembly for preparing in the present embodiment is done the absorption property test, the information that obtains as shown in Figure 6, can find out that sample can remove water middle and high concentration organic pollutant (Congo red) at short notice, can reach fast balance, under the same terms, adsorptive capacity is 4 times of commercial ZnO.
Embodiment 2
Take by weighing that 0.48g(2.2 * 10-3mol) Zn (Ac) 22H2O is dissolved in the 22mL ethylene glycol, obtains colourless transparent solution A, carries out magnetic agitation under the room temperature; Get NaOH and EG, be made into take the NaOH volumetric molar concentration as 0.6M, volume is the solution B of 10mL, and solution B is dropwise added in the solution A, and reaction for some time, solution becomes gradually muddy and becomes clear again, waits to drip and finishes, and continues to stir 15～20 minutes, and solution is the colloidal sol shape.Above-mentioned gained colloidal sol is transferred in the 40mL reactor, after 160 ° of C react 24 hours, centrifuge washing, 60 ° of C oven dry.
To in the present embodiment 2 preparation product do the field emission scanning electron microscope analysis, the electromicroscopic photograph that obtains as shown in Figure 7, as can be seen from the figure, the meso-porous ZnO for preparing in the present embodiment is that particle is piled up and formed, present cavernous structure, but its overall dimensions is excessive, and without fixing pattern.Illustrate from the side in the process of embodiment 1 preparation sample that glucose not only is its carbon source that provides carbon to mix, more playing important guiding regulating effect aspect the formation of hamburger profile and the assembly dimensional homogeneity.
Embodiment 3: take by weighing that 0.48g(2.2 * 10-3mol) Zn (Ac) 22H2O is dissolved in the 22mL water, obtains colourless transparent solution A, carries out magnetic agitation under the room temperature; Get NaOH and be made into the aqueous solution B that volumetric molar concentration is 0.6M, volume is 10mL, dropwise adds solution B in the solution A, reaction for some time, solution becomes gradually muddy and becomes clear again, waits to drip and finishes, take by weighing 0.2g glucose and be dissolved in wherein, continue to stir 15～20 minutes, solution is the colloidal sol shape.Above-mentioned gained colloidal sol is transferred in the 40mL reactor, after 160 ° of C react 24 hours, centrifuge washing, 60 ° of C oven dry.
To in the present embodiment 3 preparation product do the field emission scanning electron microscope analysis, the electromicroscopic photograph that obtains as shown in Figure 8, as can be seen from the figure, the sample that obtains take distilled water as medium is irregular nano particle, without the assembling sign.Also illustrate that pure system plays vital effect for the assembling of hamburger shape meso-porous ZnO.
XRD, FE-SEM, TEM, HRTEM, XPS, result and literature search that pore structure and absorption property are measured show: adopt the preparation-obtained carbon-doped mesoporous ZnO of the inventive method hamburger structure nano assembly, it is the sorbing material that successfully synthesizes with present better simply single stage method, it is low that it has a cost, output is high, the appearance and size good uniformity, the circulation ratio high, and merge mesoporous and carbon doping characteristic, it has filled up the blank in the low temperature liquid phase single stage method synthesizing blender meso-porous ZnO field, can play certain pushing effect for batch production and the further Application and Development of this kind good adsorption performance material for water treatment.

Claims (2)

1. the method for the carbon-doped mesoporous ZnO of simple preparation hamburger structure nano assembly, it is characterized in that preparing in the method for carbon-doped mesoporous ZnO hamburger structure nano assembly at this, take ethylene glycol (EG) as reaction solvent, with the inorganic salt zinc acetate (Zn (Ac) of transition metal 22H 2O) and excessive alkali source (NaOH) be pre-reaction material, add structure directing agent glucose, drive the ZnO nano particle self-assembly that realizes that carbon (C) mixes by induced polymerization and twin polarity field, obtain the carbon-doped mesoporous ZnO assembly of hamburger type.
2. the method for the carbon-doped mesoporous ZnO of a kind of simple preparation according to claim 1 hamburger structure nano assembly is characterized in that the method for preparing carbon-doped mesoporous ZnO hamburger structure nano assembly may further comprise the steps:
⑴ Zn (OH) 4 2-The preparation of sol precursor
Get raw material zinc acetate (Zn (Ac) 22H 2O) and ethylene glycol (EG), be made into Zn 2+Volumetric molar concentration is the colourless transparent solution A of 0.1～0.4M, carries out magnetic agitation under the room temperature; Get sodium hydroxide (NaOH) and EG, be made into the solution B take the NaOH volumetric molar concentration as 0.4～0.8M, dropwise add solution B in the solution A, through reaction, solution becomes gradually muddy and becomes clear again, treats that solution B drips end, taking by weighing 0.02～0.08M glucose is dissolved in wherein, continue to stir 10～20 minutes, solution becomes near transparent oyster white, and the mixed solution of gained is Zn (OH) 4 2-Sol precursor;
⑵ the preparation of carbon-doped mesoporous ZnO hamburger structure nano assembly
Mixed solution is transferred in the reactor, and through 160～180 ° of C, after 12～24 hours, centrifuge washing, oven dry namely obtain carbon-doped mesoporous ZnO hamburger structure nano assembly.
CN201210466728.4A 2012-11-16 2012-11-16 Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly Expired - Fee Related CN102942208B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210466728.4A CN102942208B (en) 2012-11-16 2012-11-16 Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210466728.4A CN102942208B (en) 2012-11-16 2012-11-16 Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly

Publications (2)

Publication Number Publication Date
CN102942208A true CN102942208A (en) 2013-02-27
CN102942208B CN102942208B (en) 2014-07-16

Family

ID=47725231

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210466728.4A Expired - Fee Related CN102942208B (en) 2012-11-16 2012-11-16 Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly

Country Status (1)

Country Link
CN (1) CN102942208B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103496733A (en) * 2013-09-30 2014-01-08 陕西科技大学 Method for preparing carbon doped zinc oxide
CN104445372A (en) * 2014-11-26 2015-03-25 燕山大学 Method for preparing carbon doped zinc oxide nanoparticles
CN109873147A (en) * 2019-03-04 2019-06-11 湘潭大学 A kind of carbon modification porous ZnO nano material and its preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011095589A1 (en) * 2010-02-05 2011-08-11 Grillo Zinkoxid Gmbh ZnO NANOPARTICLES WITH PRISMATIC SHAPE AND THE EFFECT ON OPTICAL PROPERTIES
CN102730747A (en) * 2012-07-16 2012-10-17 河南师范大学 Method for preparing zinc oxide with different microstructures by sol-gel assisted hydrothermal process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011095589A1 (en) * 2010-02-05 2011-08-11 Grillo Zinkoxid Gmbh ZnO NANOPARTICLES WITH PRISMATIC SHAPE AND THE EFFECT ON OPTICAL PROPERTIES
CN102730747A (en) * 2012-07-16 2012-10-17 河南师范大学 Method for preparing zinc oxide with different microstructures by sol-gel assisted hydrothermal process

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
《光谱实验室》 20031130 陈松 "乙二醇溶剂中纳米氧化锌的制备" 第937-940页 1-2 第20卷, 第6期 *
《化工新型材料》 20110831 李丽等 "水热法制备高比表面积的多层笼状纳米氧化锌" 第54-56页 1-2 第39卷, 第8期 *
李丽等: ""水热法制备高比表面积的多层笼状纳米氧化锌"", 《化工新型材料》, vol. 39, no. 8, 31 August 2011 (2011-08-31), pages 54 - 56 *
陈松: ""乙二醇溶剂中纳米氧化锌的制备"", 《光谱实验室》, vol. 20, no. 6, 30 November 2003 (2003-11-30), pages 937 - 940 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103496733A (en) * 2013-09-30 2014-01-08 陕西科技大学 Method for preparing carbon doped zinc oxide
CN104445372A (en) * 2014-11-26 2015-03-25 燕山大学 Method for preparing carbon doped zinc oxide nanoparticles
CN104445372B (en) * 2014-11-26 2016-03-02 燕山大学 A kind of method preparing carbon doping Zinc oxide nanoparticle
CN109873147A (en) * 2019-03-04 2019-06-11 湘潭大学 A kind of carbon modification porous ZnO nano material and its preparation method and application
CN109873147B (en) * 2019-03-04 2021-08-24 湘潭大学 Carbon-modified porous ZnO nano material and preparation method and application thereof

Also Published As

Publication number Publication date
CN102942208B (en) 2014-07-16

Similar Documents

Publication Publication Date Title
Deng et al. Protocol for the nanocasting method: preparation of ordered mesoporous metal oxides
Yan et al. Novel self-assembled MgO nanosheet and its precursors
Wang et al. Hydrothermal synthesis and characterization of a novel one-dimensional titanium glycolate complex single crystal: Ti (OCH2CH2O) 2
CN104084186B (en) A kind of Graphene/optically catalytic TiO 2 matrix material and its preparation method
Duan et al. Shape-controlled synthesis of metal carbonate nanostructure via ionic liquid-assisted hydrothermal route: the case of manganese carbonate
CN104148047B (en) Macro preparation method for carbon doped zinc oxide-based visible-light catalyst
CN102649590B (en) Method for preparing mesoporous material NiAl2O4 without specific surface active agent
CN103466702B (en) Method for preparing porous bismuth oxide nano-material without template
CN103433044B (en) Preparation method of cobalt-nickel double metal hydroxide nano composite
CN105621480A (en) Method for preparing zirconium dioxide nano powder by low-temperature calcination of zirconium sol
CN104772136B (en) A kind of pucherite and preparation method and application
CN102583255B (en) Method for preparing mesoporous composite transition metal oxide
CN102910654A (en) Preparation method of fibrous boehmite with large specific surface area and large pore area
CN102942208B (en) Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly
CN102502660B (en) Spiral mesoporous silicon dioxide nanofiber with cracked surface and preparation method thereof
CN104353473B (en) One prepares porous BiVO4the method of/AgCl hybrid microspheres
CN103058265A (en) Preparation method of mesoporous nano flake zinc oxide powder with high specific surface area
CN104226291A (en) Method for synthesizing TiO2/C hollow composite microspheres by hydro-thermal process
CN106986374B (en) A kind of high specific surface area and mesoporous zinc-oxide nano cluster and preparation method thereof
CN108262041A (en) A kind of one pot of method for preparing high activity gold/zinc oxide compound nano cluster of room temperature
CN108017083B (en) A kind of CeO constructed by hollow bead2Porous nano cluster and preparation method thereof
CN112028119B (en) Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal
CN105836796A (en) Preparation method of bell-type core-shell structured nano-TiO2(at)void(at)SiO2 powder
CN103127924A (en) Preparation method of titanium oxide (TiO2) - silicon dioxide (SiO2) visible light compound light catalytic agent
Ahmed et al. The role of cobalt to control the synthesis of nanoscale Co/UiO‐66 composite for photocatalysis

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: 20140716

Termination date: 20151116

EXPY Termination of patent right or utility model