CN102992411B - Hollow silkworm cocoon-shaped porous nickel oxide nano material and preparation method thereof - Google Patents

Hollow silkworm cocoon-shaped porous nickel oxide nano material and preparation method thereof Download PDF

Info

Publication number
CN102992411B
CN102992411B CN201210374829.9A CN201210374829A CN102992411B CN 102992411 B CN102992411 B CN 102992411B CN 201210374829 A CN201210374829 A CN 201210374829A CN 102992411 B CN102992411 B CN 102992411B
Authority
CN
China
Prior art keywords
nickel oxide
oxide nano
nano material
silk cocoon
porous nickel
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.)
Expired - Fee Related
Application number
CN201210374829.9A
Other languages
Chinese (zh)
Other versions
CN102992411A (en
Inventor
胡寒梅
邓崇海
卢君然
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.)
Anhui University of Architecture
Original Assignee
Anhui University of Architecture
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 Anhui University of Architecture filed Critical Anhui University of Architecture
Priority to CN201210374829.9A priority Critical patent/CN102992411B/en
Publication of CN102992411A publication Critical patent/CN102992411A/en
Application granted granted Critical
Publication of CN102992411B publication Critical patent/CN102992411B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

The invention discloses a hollow silkworm cocoon-shaped porous nickel oxide nano material and a preparation method thereof. The method comprises the following steps of: weighing a proper amount of NiCl2.6H2O and adding the weighed NiCl2.6H2O into 50mL deionized water, and adding a proper volume of N2H4.H2O; in magnetic stirring, adding a proper amount of (NH4)2C2O4, stirring for 10-20 minutes, placing the product in a microwave oven, and heating at a low fire level for 8-12 minutes; cooling down the product to room temperature, and standing overnight to obtain a blue precipitate; and placing the dried blue precipitate into a resistance furnace, setting the temperature to 400-600 DEG C, and performing thermal treatment for 0.5-2 hours to obtain the hollow silkworm cocoon-shaped porous nickel oxide nano material. The long diameter of the nickel oxide nano silkworm cocoon is 280-650nm, the short diameter is 120-350nm, and the wall thickness is 30-80nm; and the surface is rich in pore structures, and the pore structure is formed by nano particles with particle size of 10-20nm. The method disclosed by the invention has simple technology and good repeatability, and is convenient to operate and is green, environment-friendly and energy-saving.

Description

A kind of hollow silk cocoon shape porous nickel oxide nano material and preparation method thereof
Technical field
The present invention relates to belong to nano material preparing technical field, specifically, relate to a kind of hollow silk cocoon shape porous nickel oxide nano material and preparation method thereof.
Background technology
Nano-nickel oxide (NiO) is a kind of important p-type semiconductor material, there is unique electricity, magnetics and catalysis characteristics, be widely used in the fields such as catalyzer, dye cell, gas sensor, magneticsubstance, electroplated film disk, photoelectric conversion material, be a kind of up-and-coming functional type inorganic materials, caused material scholar's extensive concern.Relation between synthetic and appearance structure and the performance of nickel oxide nano material is two main aspects of nickel oxide nano investigation of materials, and the nickel oxide nano material that processability is good the relation between its appearance structure and performance understood fully are to the extremely important theoretical and practical significance of having further developed of nickel oxide nano material.
In recent years, number of chemical and physicochemical method are used to prepare the nickel oxide nano material of specific morphology.The loyal grade of the Li Chun of East China University of Science reported a kind of preparation method who spends shape nickel oxide, take vulkacit H, Nickelous nitrate hexahydrate and deionized water as raw material, be mixed with mixing solutions, at 80～150 ℃ of temperature, hydro-thermal reaction is 4～20 hours, reacted solution centrifugal is separated, washing is precipitated thing, dried product is ground to rear 300 ℃ of roastings 2 hours, obtain flower shape nickel oxide (a kind of preparation method who spends shape nickel oxide, Chinese invention patent, the patent No.: CN200810037009.4, publication number: CN101269850).The Cao Hua of Tsing-Hua University waits by force the preparation method who has reported a kind of nickel oxide nanowires, multiaperture pellumina is immersed in previously prepared good nickel sol, at pressure, be under 1.25～1.3MPa, to pressurize 3～5 hours, the film of treated mistake is taken out from colloidal sol, under infrared lamp, dry, roasting 3～5 hours under 500～700 ℃, inert atmosphere normal pressure again, obtain nickel oxide nanowires (a kind of synthetic method of nickel oxide nanowires, Chinese invention patent, the patent No.: CN02156897.9, publication number: CN1413946).Nickel oxide hollow microsphere preparation method has been reported in the high Lian of Shanghai Silicate Inst., Chinese Academy of Sciences etc., take nickeliferous inorganic salt as nickel source, take polyvalent alcohol as solvent, under the condition existing at the sodium-acetate containing crystal water, at 160～190 ℃, solvent thermal reaction obtains diameter 500～800nm, and outer wall is by a large amount of softnesses, α-Ni that 20 interlaced～40nm is thick (OH) 2α-Ni (OH) that nanometer sheet forms 2tiny balloon, gained throw out can make NiO tiny balloon (without the wet chemical preparation method of the nickel oxide hollow microsphere of template, Chinese invention patent, the patent No.: CN200810202802.5, publication number: CN101417823) after calcining process.The Wang Cong of BJ University of Aeronautics & Astronautics etc. has reported a kind of preparation method of vesicular structure nickel oxide nano flake, take nickel salt, ammoniacal liquor and tensio-active agent as raw material, first hydro-thermal reaction obtains nickel hydroxide presoma, then at 350～500 ℃ of roasting 2～4h, obtain the nickel oxide nano flake of vesicular structure, the diameter in hole is 30～40nm, the diameter of NiO nano flake is 300～400nm (evenly, preparation method of the nickel oxide nano flake of central hole structure, Chinese invention patent, the patent No.: CN200910237799.5, publication number: CN101704558A).Under nano materials research worker's unremitting effort, prepared the nickel oxide nano structure of different morphologies, as nano particle, nanometer rod, nanometer sheet, nano wire, nano flower and tiny balloon etc.But with regard to literature survey, yet there are no the report of hollow silk cocoon shape nickel oxide nano structure.
Summary of the invention
The object of the present invention is to provide a kind of hollow silk cocoon shape porous nickel oxide nano material and preparation method thereof, to fill up the blank of prior art, for nickel oxide nano structured material adds new variety.
The object of the invention is to realize by following technical solution.
Technical scheme of the present invention be adopt the synthetic and roasting heat of microwave chemical to decompose two-step approach to prepare hollow silk cocoon shape porous NiO nanocrystalline, its concrete technology flow process is as follows:
(1) take Nickel dichloride hexahydrate (NiCl 26H 2o) in the beaker of 100 milliliters, add 50 ml deionized water, after stirring and dissolving, add a certain amount of hydrazine hydrate (N 2h 4h 2o, 85%);
(2) take oxamide (NH 4) 2c 2o 4join in above-mentioned solution;
(3) reaction mixture continues to stir 10～20 minutes, with polyethylene film, rim of a cup is covered, and is placed on microwave oven, and low fire screen heating 8～12 minutes are set;
(4) naturally cool to room temperature, standing overnight, filtering precipitate, uses respectively deionized water and absolute ethanol washing 3～5 times, throw out is placed in to vacuum drying oven and heats 6～12 hours, and temperature is 40～60 ℃;
(5) the blue throw out of drying is put into resistance furnace, thermal treatment 0.5～2 hour, obtains hollow silk cocoon shape porous nickel oxide nano material of the present invention;
In technique scheme, the volume of described hydrazine hydrate is 0.1～0.3mL.
The mol ratio of described Nickel dichloride hexahydrate and oxamide is 1: 2.
Described thermal treatment temp is 400～600 ℃,
Described microwave oven is commercialization household microwave oven, microwave output power 800W.
The hollow silk cocoon shape porous nickel oxide that the present invention obtains is a kind of semiconductor nano material, can in the fields such as photochemical catalysis, dye cell, gas sensor, magneticsubstance, be developed and applied.Described preparation technology's equipment is simple, and the reaction times is fast, easy and simple to handle, reproducible; Do not adopt organic solvent and tensio-active agent, the clean energy of environmental protection; Raw material is easy to get, with low cost, and suitability for industrialized is produced.
Compare with existing nickel oxide nano structure and technology of preparing thereof, beneficial effect of the present invention is embodied in:
(1) the present invention adopts microwave, and synthetic-thermal treatment two-step approach has been prepared novel hollow silk cocoon shape porous nickel oxide nanostructure.
(2) the nanocrystalline dispersiveness of hollow silk cocoon shape porous nickel oxide that the inventive method is prepared is better, evenly, major diameter is distributed between 280～650nm size, and minor axis is distributed between 120～350nm, wall thickness is 30～80nm, and rich surface contains a large amount of pore textures.
(3) the inventive method adopts Microwave Radiation in Manufacturing, simple to operate, is swift in response, and cost is low, and suitability for industrialized is produced.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction analysis (XRD) figure of the hollow silk cocoon shape of the present invention porous nickel oxide nano material;
Fig. 2 is field emission scanning electron microscope (FESEM) photo of the hollow silk cocoon shape of the present invention porous nickel oxide;
Fig. 3 is transmission electron microscope (TEM) photo of the hollow silk cocoon shape of the present invention porous nickel oxide;
Embodiment
By specific embodiment, technical scheme of the present invention is done below the description of further detailed complete.Following embodiment further illustrates of the present invention, and does not limit the scope of the invention.
Embodiment 1
Hollow silk cocoon shape porous nickel oxide nano material of the present invention adopts synthesize-thermolysis two-step approach of microwave to prepare, and its concrete technology flow process is as follows:
(1) take 1mmol Nickel dichloride hexahydrate (NiCl 26H 2o) in the beaker of 100 milliliters, add 50 ml deionized water, after stirring and dissolving, add the hydrazine hydrate (N of 0.15mL 2h 4h 2o, 85%);
(2) take 2mmol oxamide (NH 4) 2c 2o 4join in above-mentioned solution;
(3) reaction mixture continues to stir 10 minutes, with polyethylene film, rim of a cup is covered, and is placed on microwave oven, and low fire screen heating 10 minutes are set;
(4) naturally cool to room temperature, standing overnight, filtering precipitate, uses respectively deionized water and absolute ethanol washing 3～5 times, throw out is placed in to vacuum drying oven and heats 6 hours, and temperature is 60 ℃;
(5) the blue throw out of drying is put into resistance furnace, set temperature is 500 ℃, and thermal treatment 1 hour obtain hollow silk cocoon shape porous nickel oxide nano material of the present invention.
Referring to accompanying drawing 1, X-ray diffraction (XRD) figure of the hollow silk cocoon shape porous nickel oxide making by the method described in embodiment 1, in figure, spectral line peak position is corresponding one by one with the diffraction peak of JCPDS card (78-0643) nickel oxide, is indicated as the nickel oxide of pure Emission in Cubic structure.
Referring to accompanying drawing 2, field emission scanning electron microscope (FESEM) photo of the hollow silk cocoon shape porous nickel oxide making by the method described in embodiment 1, the output of the hollow nickel oxide nano silk cocoon that visible the method makes is high, better dispersed, major diameter is distributed between 280～650nm, minor axis is distributed between 120～350nm, and wall thickness is 30～80nm, and rich surface contains a large amount of pore textures.
Referring to accompanying drawing 3, transmission electron microscope (TEM) photo of the hollow silk cocoon shape porous nickel oxide making by the method described in embodiment 1, the nanoparticle that the hollow silk cocoon of single nickel oxide is is 10-20nm by median size assembles.
Embodiment 2
Hollow silk cocoon shape porous nickel oxide nano material of the present invention adopts synthesize-thermolysis two-step approach of microwave to prepare, and its concrete technology flow process is as follows:
(1) take 1mmol Nickel dichloride hexahydrate (NiCl 26H 2o) in the beaker of 100 milliliters, add 50 ml deionized water, after stirring and dissolving, add the hydrazine hydrate (N of 0.10mL 2h 4h 2o, 85%);
(2) take 2mmol oxamide (NH 4) 2c 2o 4join in above-mentioned solution;
(3) reaction mixture continues to stir 15 minutes, with polyethylene film, rim of a cup is covered, and is placed on microwave oven, and low fire screen heating 8 minutes are set;
(4) naturally cool to room temperature, standing overnight, filtering precipitate, uses respectively deionized water and absolute ethanol washing 3～5 times, throw out is placed in to vacuum drying oven and heats 8 hours, and temperature is 50 ℃;
(5) the blue throw out of drying is put into resistance furnace, set temperature is 500 ℃, and thermal treatment 2 hours obtain hollow silk cocoon shape porous nickel oxide nano material of the present invention.
Through XRD and FESEM, detect, what by method described in embodiment 2, make is the hollow silk cocoon shape of Emission in Cubic porous nickel oxide nano material.
Embodiment 3
Hollow silk cocoon shape porous nickel oxide nano material of the present invention adopts synthesize-thermolysis two-step approach of microwave to prepare, and its concrete technology flow process is as follows:
(1) take 1mmol Nickel dichloride hexahydrate (NiCl 26H 2o) in the beaker of 100 milliliters, add 50 ml deionized water, after stirring and dissolving, add the hydrazine hydrate (N of 0.20mL 2h 4h 2o, 85%);
(2) take 2mmol oxamide (NH 4) 2c 2o 4join in above-mentioned solution;
(3) reaction mixture continues to stir 10 minutes, with polyethylene film, rim of a cup is covered, and is placed on microwave oven, and low fire screen heating 8 minutes are set;
(4) naturally cool to room temperature, standing overnight, filtering precipitate, uses respectively deionized water and absolute ethanol washing 3～5 times, throw out is placed in to vacuum drying oven and heats 10 hours, and temperature is 50 ℃;
(5) the blue throw out of drying is put into resistance furnace, set temperature is 550 ℃, and thermal treatment 1 hour obtain hollow silk cocoon shape porous nickel oxide nano material of the present invention.
Through XRD and FESEM, detect, what by method described in embodiment 3, make is the hollow silk cocoon shape of Emission in Cubic porous nickel oxide nano material.
Embodiment 4
Hollow silk cocoon shape porous nickel oxide nano material of the present invention adopts synthesize-thermolysis two-step approach of microwave to prepare, and its concrete technology flow process is as follows:
(1) take 1mmol Nickel dichloride hexahydrate (NiCl 26H 2o) in the beaker of 100 milliliters, add 50 ml deionized water, after stirring and dissolving, add the hydrazine hydrate (N of 0.30mL 2h 4h 2o, 85%);
(2) take 2mmol oxamide (NH 4) 2c 2o 4join in above-mentioned solution;
(3) reaction mixture continues to stir 15 minutes, with polyethylene film, rim of a cup is covered, and is placed on microwave oven, and low fire screen heating 12 minutes are set;
(4) naturally cool to room temperature, standing overnight, filtering precipitate, uses respectively deionized water and absolute ethanol washing 3～5 times, throw out is placed in to vacuum drying oven and heats 6 hours, and temperature is 60 ℃;
(5) the blue throw out of drying is put into resistance furnace, set temperature is 450 ℃, and thermal treatment 2 hours obtain hollow silk cocoon shape porous nickel oxide nano material of the present invention.
Through XRD and FESEM, detect, what by method described in embodiment 4, make is the hollow silk cocoon shape of Emission in Cubic porous nickel oxide nano material.

Claims (5)

1. a hollow silk cocoon shape porous nickel oxide nano material, it is characterized in that, the described nanocrystalline dispersiveness of hollow silk cocoon shape porous nickel oxide is better, major diameter is distributed between 280～650nm, minor axis is distributed between 120～350nm, wall thickness is 30～80nm, and rich surface contains a large amount of pore textures, and the nanoparticle that the hollow silk cocoon of single nickel oxide is is 10-20nm by median size assembles.
2. a preparation method for hollow silk cocoon shape porous nickel oxide nano material claimed in claim 1, is characterized in that, the concrete technology step of described method is as follows:
(1) take Nickel dichloride hexahydrate (NiCl 26H 2o) in the beaker of 100 milliliters, add 50 ml deionized water, after stirring and dissolving, add a certain amount of hydrazine hydrate, the volume of hydrazine hydrate is 0.1～0.3mL;
(2) take oxamide (NH 4) 2c 2o 4join in above-mentioned solution, the mol ratio of Nickel dichloride hexahydrate and oxamide is 1: 2;
(3) reaction mixture continues to stir 10～20 minutes, with polyethylene film, rim of a cup is covered, and is placed on microwave oven, and low fire screen heating 8～12 minutes are set;
(4) naturally cool to room temperature, standing overnight, filtering precipitate, uses respectively deionized water and absolute ethanol washing 3～5 times, throw out is placed in to vacuum drying oven and heats 6～12 hours, and temperature is 40～60 ℃;
(5) the blue throw out of drying is put into resistance furnace, set temperature is 400～600 ℃, and thermal treatment 0.5～2 hour obtain hollow silk cocoon shape porous nickel oxide nano material.
3. the preparation method of hollow silk cocoon shape porous nickel oxide nano material according to claim 2, is characterized in that, in step (1), the volume of hydrazine hydrate is 0.15mL.
4. the preparation method of hollow silk cocoon shape porous nickel oxide nano material according to claim 2, is characterized in that, in step (3), in household microwave oven, low fire screen heating is 10 minutes.
5. the preparation method of hollow silk cocoon shape porous nickel oxide nano material according to claim 2, is characterized in that, in step (5), the blue throw out of drying is put into resistance furnace and heat 1 hour, and temperature is 500 ℃.
CN201210374829.9A 2012-09-25 2012-09-25 Hollow silkworm cocoon-shaped porous nickel oxide nano material and preparation method thereof Expired - Fee Related CN102992411B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210374829.9A CN102992411B (en) 2012-09-25 2012-09-25 Hollow silkworm cocoon-shaped porous nickel oxide nano material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210374829.9A CN102992411B (en) 2012-09-25 2012-09-25 Hollow silkworm cocoon-shaped porous nickel oxide nano material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102992411A CN102992411A (en) 2013-03-27
CN102992411B true CN102992411B (en) 2014-12-03

Family

ID=47921617

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210374829.9A Expired - Fee Related CN102992411B (en) 2012-09-25 2012-09-25 Hollow silkworm cocoon-shaped porous nickel oxide nano material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102992411B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3647271A4 (en) * 2017-06-30 2020-07-08 LG Chem, Ltd. Method for preparing nickel oxide nanoparticle and nickel oxide nanoparticle prepared using same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103193280B (en) * 2013-04-26 2017-03-08 吉林化工学院 Based on the method that double-template prepares nickel oxide nano-crystal combination electrode material
CN110498439B (en) * 2019-09-27 2022-12-23 中国恩菲工程技术有限公司 Method for preparing scandium oxide powder with porous structure
CN113618272A (en) * 2021-09-23 2021-11-09 重庆大学 Flower-shaped core-shell structure composite energetic material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905904A (en) * 2010-07-22 2010-12-08 北京航空航天大学 Preparation method of nickel oxide microspheres consisting of lotus root-like nanosheets
CN102139931A (en) * 2010-01-29 2011-08-03 中国石油化工股份有限公司 Preparation method of nano nickel oxide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8110173B2 (en) * 2009-09-05 2012-02-07 Bahari Molla Mahaleh Yaser Fabrication of NIO nanoparticles and chip-like nanoflakes by solvothermal technique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102139931A (en) * 2010-01-29 2011-08-03 中国石油化工股份有限公司 Preparation method of nano nickel oxide
CN101905904A (en) * 2010-07-22 2010-12-08 北京航空航天大学 Preparation method of nickel oxide microspheres consisting of lotus root-like nanosheets

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
US2009/0324486A1A1 2009.12.31 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3647271A4 (en) * 2017-06-30 2020-07-08 LG Chem, Ltd. Method for preparing nickel oxide nanoparticle and nickel oxide nanoparticle prepared using same

Also Published As

Publication number Publication date
CN102992411A (en) 2013-03-27

Similar Documents

Publication Publication Date Title
CN105329876B (en) A kind of preparation method of boron, nitrogen co-doped carbon quantum dot
CN102259936B (en) Preparation method of nano nickel cobalt oxide
CN106637921B (en) A kind of polyacrylonitrile/copper sulfide photo-thermal nano-fiber cloth and its preparation and application
CN102992411B (en) Hollow silkworm cocoon-shaped porous nickel oxide nano material and preparation method thereof
CN104815983B (en) A kind of carbon cladding nickel oxide/metallic nickel and simple method for synthesizing thereof
CN103979608B (en) A kind of preparation method of hollow core-shell Vanadium Pentoxide in FLAKES microballoon
CN103464784B (en) A kind of preparation method of carbon loaded with nano nickel
CN105023762B (en) A kind of foliaceous CuO NiO composite construction nano materials and preparation method thereof
CN105060351B (en) Flower-like cobaltosic oxide material composed of nanoparticles and preparation method thereof
CN103107025A (en) Preparation method of supercapacitor electrode material NiCo2O4
CN101704558A (en) Preparation method of nickel oxide nano flake with uniform and mesoporous structure
CN105084427A (en) In-situ grown three-dimensional multi-structural cobaltosic oxide micro-nanomaterial, controllable preparation and application thereof
CN102674898B (en) Cerium oxide/ aluminium oxide micro-nanostructure ceramic pigment and preparation method thereof
CN104003448A (en) [Alpha]-phase ferric oxide porous core-shell microspheres and controllable synthetic preparation method thereof
CN106128801A (en) A kind of ultracapacitor NiCo2o4the preparation method of based composites
CN109665525B (en) Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon
CN101845668B (en) Method for preparing nano nickel borate whiskers
CN101905904A (en) Preparation method of nickel oxide microspheres consisting of lotus root-like nanosheets
CN110182856A (en) A kind of preparation method of double shells hollow ball-shape nickel cobaltate nano particles
CN105645469A (en) Nano rodlike lanthanum titanate powder and preparation method thereof
CN107352519B (en) A kind of C3N4The preparation method of nano wire
CN104122305A (en) Rare-earth doped modified graphene composite material gas sensitive element for detecting NOx and preparation method of gas sensitive element
CN107572509A (en) A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof
CN105110384A (en) Porous cobaltosic oxide and preparation method thereof
CN103694963B (en) Composite phase-change material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent for invention or patent application
CB02 Change of applicant information

Address after: 230022 No. 856, Jinzhai Road, Hefei, Anhui

Applicant after: Anhui University of Architecture

Address before: 230022 No. 856, Jinzhai Road, Hefei, Anhui

Applicant before: anhui university of architecture

COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: ANHUI BUILDING INDUSTRY COLLEGE TO: ANHUI JIANZHU UNIVERSITY

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: 20141203

Termination date: 20150925

EXPY Termination of patent right or utility model