CN102320645A - Preparation method of solid or hollow Cu4O3 microballoons - Google Patents

Preparation method of solid or hollow Cu4O3 microballoons Download PDF

Info

Publication number
CN102320645A
CN102320645A CN201110243938A CN201110243938A CN102320645A CN 102320645 A CN102320645 A CN 102320645A CN 201110243938 A CN201110243938 A CN 201110243938A CN 201110243938 A CN201110243938 A CN 201110243938A CN 102320645 A CN102320645 A CN 102320645A
Authority
CN
China
Prior art keywords
preparation
reaction
alcohol
preferred
microballoon
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
CN201110243938A
Other languages
Chinese (zh)
Other versions
CN102320645B (en
Inventor
苏发兵
赵丽润
车红卫
王莹利
翟世辉
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.)
Jiangxi Rare Earth Research Institute, Chinese Academy of Sciences
Original Assignee
Institute of Process Engineering of CAS
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 Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201110243938.2A priority Critical patent/CN102320645B/en
Publication of CN102320645A publication Critical patent/CN102320645A/en
Application granted granted Critical
Publication of CN102320645B publication Critical patent/CN102320645B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a preparation method of solid or hollow Cu4O3 microballoons by a solvothermal technology. The preparation method comprises the following steps that 1, at least one copper salt is dissolved in a mixed solvent containing an alcohol and at least one amide to form a solution with copper ion concentration of 0.05 to 0.2M; and 2, the prepared solution is transferred into a reactor to undergo a reaction at a temperature of 100 to 250 DEG C for 2 to 20 hours to produce black precipitates and the black precipitates are dried to form Cu4O3 microballoons. The Cu4O3 microballoons prepared by the preparation method are solid or hollow, wherein the solid Cu4O3 microballoons have particle sizes of 2 to 5 micrometers and the hollow Cu4O3 microballoons have particle sizes of 500 nanometers to 2 micrometers. The preparation has a simple technical route, convenient operation processes and a fast reaction rate, does not need any complicated experimental equipment, and is easy for large-scale production.

Description

A kind of solid or hollow Cu 4O 3The preparation method of microballoon
Technical field
The present invention relates to a kind of Cu 4O 3The preparation method of microballoon, particularly a kind of solid or hollow Cu 4O 3The preparation method of microballoon.Solid or the hollow Cu that the present invention is prepared 4O 3Microballoon can be used for catalyzed reaction, photochemical catalysis, lithium ion battery electrode material.
Background technology
Micron cupric oxide and nanometer copper oxide material have good catalysis and electrode activity, are one of emphasis of research because of its superior physics, chemical property always.Micro-nano cupric oxide, Red copper oxide all have purposes very widely as multi-functional meticulous inorganic materials in industrial production, use widely such as having obtained in field of functional materials such as catalysis, photolysis, electromagnetic materials.
Also there is a kind of oxide compound: Cu in copper oxide except the cupric oxide of widespread use, Red copper oxide 4O 3Cu 4O 3Be found in the copper mine in late 1870s at first, general and cupric oxide, Red copper oxide coexist, and seldom exist with pure material.Cu 4O 3Be a kind of metastable state material, because Cu (I) and Cu (II) exist simultaneously, therefore structural instability is difficult to synthetic.
People are for synthetic pure Cu in recent years 4O 3, attempted a lot of methods.At present prepare pure Cu through chemical Vapor deposition process and magnetron sputtering method 4O 3Film, and to pure Cu 4O 3The optics of film, magnetics and electric property are studied.Xiao Ronghui etc. (" oxygen flow is to the influence of reaction magnetocontrol sputtering copper oxide membrane structure and optical property "; Xiao Ronghui etc.; " Zhangzhou Normal College's journal: natural science edition; 2010 the 3rd phases) through the reaction magnetocontrol sputtering method, deposited copper sull on glass substrate has been studied the influence of oxygen flow to membrane structure and optical property.The result shows that in the film deposition process, along with the increase of oxygen flow, copper oxidation resultant is from Cu 2O progressively carries out the transition to Cu 4O 3, be CuO at last.
In the prior art, about Cu 4O 3The research of powder but seldom.According to reports, (Journal of Solid State Chemistry, 1996.121 (1): 33-37) in copper mine, extract the oxide compound of copper or copper with strong aqua, in apparatus,Soxhlet's, prepare Cu such as Morgan 4O 3, Cu 2The mixture of O and CuO; (Applied Surface Science, 2008.254 (21): 6976-6982) utilize pulsed laser that copper or the cupric oxide that is in the secondary deionized water burnt, go out Cu such as Amikura with Prepared with Laser Ablation 4O 3Powder.The shortcoming of aforesaid method is Cu 4O 3Output seldom.
In order to prepare pure Cu 4O 3Powder, the method for prior art is also inapplicable, also need develop new preparation method.Solvent thermal reaction is a field of materials big research focus in recent years, compares with other preparation routes, and the distinguishing feature of solvent thermal reaction is reaction conditions as mild as a dove, can stablize metastable thing phase, preparation novel substance, develop new preparation route etc.The synthetic technology of solvent thermal pressurized heat can prepared metastable phase that just can make in extreme condition, that under hyperpressure, could exist usually under the low relatively temperature and pressure.In solvent thermal reaction, one or more presomas are dissolved in the non-aqueous solvent, under liquid phase or super critical condition, reactant be dispersed in the solution and become more active, reaction takes place, product slowly generates.This process is simple relatively and be easy to control, and in enclosed system, can effectively prevent the volatilization of toxic substance and prepare the presoma to air-sensitive.In addition, the formation of thing phase, the size of particle diameter, form also can be controlled, and the dispersiveness of product better.Under the solvent thermal condition; The character of solvent (density, viscosity, dissemination) influences each other; Alter a great deal, and differ greatly under its character and the usual conditions, corresponding; Dissolving, dispersion process and the chemical reactivity of reactant (normally solid) improve greatly or strengthen, and this just makes reaction under lower temperature, to take place.
CN 101134569A discloses a kind of method of utilizing solvent thermal reaction low temperature synthesizing silicon nitride nano material, and it is 2.8-5.8 in molar ratio: 1: the amount of 0.8-2.7 is with SICL 4, NAN 3Mix with the magnesium powder, or be reductive agent 5.8-6.0 in molar ratio with the iron powder: 1: the amount of 0.58-0.60 is with SICL 4, NAN 3Mix with iron powder, be sealed in the autoclave, in 200 ℃-300 ℃ reactions 10 hours ± 0.5 hour; Product obtains the silicon nitride micro Nano material through pickling, washing, spinning and drying.Prepared B-SI 3N 4The nanometer rod diameter is about 100 nanometers～800 nanometers, and the diameter of nano wire is 30 nanometers-125 nanometers; A-SI 3N 4The diameter of nano wire is 50 nanometers-165 nanometers.
CN 1699639A discloses a kind of α-Si 3N 4The method for solvent thermal reaction preparation of monocrystal nanowire, its in molar ratio 1: 1.5-15 is with SiCl 4And Mg 3N 2Mix, be sealed in 550-700 ℃ of reaction more than 5 hours, product promptly obtains α-Si through pickling and washing, spinning and drying 3N 4The nano wire powder, the α-Si that makes 3N 4The nano wire mean diameter is about 35 nanometers, the several approximately microns of length.
In the prior art, solvent thermal reaction is mainly used in the preparation of metastable phase material, for Cu 4O 3Thisly cause structural unstable metastable state material, then do not see the report of any employing solvent thermal reaction preparation owing to Cu (I) and Cu (II) exist simultaneously.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is solvent thermal reaction is used for micro-nano Cu 4O 3Preparation, provide solvent thermal reaction to prepare micro-nano Cu 4O 3Processing condition, and successfully prepared micro-nano Cu 4O 3
One of the object of the invention also is to provide a kind of solid or hollow Cu 4O 3The preparation method of microballoon.The present invention is adjusted to product solid or hollow through control reaction temperature.The solid Cu of the present invention's preparation 4O 3Microballoon, its particle diameter are 2-5 μ m; The hollow Cu of the present invention's preparation 4O 3Microballoon, its particle diameter are 500nm-2 μ m.
Solid or hollow Cu of the present invention 4O 3The preparation method of microballoon is a raw material with the mantoquita, adds solvent, after for some time, can make the solid or hollow Cu of micro/nano level in reaction kettle for reaction 4O 3Microballoon.
Solid or hollow Cu of the present invention 4O 3The preparation method of microballoon, preferably after reaction, reaction product is through filtering, wash after drying.
Solid or hollow Cu of the present invention 4O 3The preparation method of microballoon can control the Cu that generates different sizes through changing processing condition such as precursor concentration, solvent ratios, temperature of reaction, reaction times as required 4O 3Microballoon.
Solid or hollow Cu of the present invention 4O 3The preparation method of microballoon, whole technological process is all carried out in hydrothermal reaction kettle, and operational path is succinct, and reaction is a kind of efficient quick, cheap, eco-friendly Cu fast 4O 3The preparation method of microballoon.
Solid or hollow Cu of the present invention 4O 3The preparation method of microballoon, its raw material is a mantoquita, acid amides, alcohol, wherein mantoquita is as initial reactant; Pure and mild acid amides is a mixed solvent, and mantoquita is made into certain density solution, puts into reaction kettle; Add said mixed solvent, adjust the temperature to 100 ℃-250 ℃, reaction times 2-20h; Preferred 4-18h, more preferably 4-12h can make Cu 4O 3Microballoon.The conditioned reaction temperature can preferably be carried out in the thermostatic equipment at baking oven or other heating installations.
According to preparation method of the present invention, behind 100 ℃-250 ℃ reaction 2-20h, obtaining product is black precipitate, can obtain the solid or hollow Cu of micro/nano level after the said black precipitate washing drying 4O 3Microballoon.
According to preparation method of the present invention, said mantoquita is a soluble copper salt, and copper ion concentration is preferably 0.05M-0.2M in the solution, preferred 0.08M-0.18M, more preferably 0.1-0.15M.Said mantoquita is preferably cupric nitrate, cupric chloride, copper sulfate or its mixture, further preferred cupric nitrate.
According to preparation method of the present invention, said alcohol is low-carbon alcohol, and the straight or branched of preferred 1-7 carbon atom is pure, more preferably a kind of in methyl alcohol, ethanol, propyl alcohol, the Virahol, or itself or above mixture.
According to preparation method of the present invention, said acid amides is preferably N, dinethylformamide, N-NMF a kind of, or its mixture.
According to preparation method of the present invention, in said mixed solvent, the shared volume ratio of said alcohol is 10-70%, preferred 20-60%, more preferably 30-50%.
According to preparation method of the present invention, said reaction kettle is any reaction kettle that is suitable for solvent thermal reaction.Preferred liner tetrafluoroethylene of the present invention or enamelled reaction kettle, reaction kettle volume plot ratio is 30-75%, preferred 40-70%, more preferably 40-60%.
According to preparation method of the present invention, controlling said temperature of reaction is 100-170 ℃ (not comprising 170 ℃), the Cu that reaction obtains 4O 3Product is a solid microsphere; Controlling said temperature of reaction is 170-250 ℃ (comprising 170 ℃), the Cu that reaction obtains 4O 3Product is a tiny balloon.
According to preparation method of the present invention, said deposition is preferably carried out drying again after filtering, washing.Said washing preferably adopts deionized water, low-carbon alcohol such as ethanol, or its mixture washing.
According to preparation method of the present invention, said drying is the existing Cu that do not cause 4O 3The drying operation that the product physical and chemical performance changes, its typical case but non-limiting instance comprises that in being lower than 100 ℃, preferred 60 ℃ of down dry for some time, be 4-12 hour preferred time of drying, more preferably 8 hours.
The present invention utilizes in the solvent thermal reaction; One or more precursors are dissolved in the non-aqueous solvent, and under liquid phase or super critical condition, the reactant that is dispersed in the liquid phase is uniformly dispersed and relatively more active at atomic scale; Impel reaction to carry out easily, thereby prepare micro-nano solid or hollow Cu 4O 3Microballoon.Preparing method of the present invention, process are simple relatively and be easy to control, and whole technological process is carried out in reaction kettle, and operational path is succinct, and reaction is a kind of efficient quick, cheap, eco-friendly preparation Cu fast 4O 3The method of microballoon.
Compared to prior art, preparing method's advantage of the present invention is:
1, the Cu of the present invention's preparation 4O 3Microballoon, the experimental technique route is simple, and operation is convenient, and whole technological process is carried out in water heating kettle, need not any complicated experimental installation, and reaction is easy to large-scale production fast;
2, the Cu of the present invention's preparation 4O 3The microballoon favorable reproducibility helps controlling quality product.
Description of drawings
Fig. 1 is the Cu of embodiment 1 preparation 4O 3The XRD figure of microballoon
Fig. 2 is the Cu of embodiment 1 preparation 4O 3The SEM figure of microballoon
Fig. 3 is the Cu of embodiment 1 preparation 4O 3The TEM figure of microballoon
Fig. 4 is the Cu of embodiment 2 preparations 4O 3The XRD figure of microballoon
Fig. 5 is the Cu of embodiment 2 preparations 4O 3The SEM figure of microballoon
Fig. 6 is the Cu of embodiment 2 preparations 4O 3The TEM figure of microballoon
Embodiment
Following examples are used to further specify the present invention, but the present invention is not limited to following examples.
Embodiment one
Take by weighing 0.4g Cu (NO 3) 23H 2O is dissolved in methyl alcohol-N of 30ml, dinethylformamide mixing solutions; The volume ratio that methyl alcohol accounts for mixed solvent is 10%; Be positioned over 160 ℃ of reaction 15h in the 100ml inner liner polytetrafluoroethylene reaction kettle, reaction after finishing is filtered product; Water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.
Cu with above-mentioned preparation 4O 3Material carries out the XRD test on X ' the Pert PRO MPD type multi-functional X-ray diffractometer that Dutch Panalytical company (PANalytical) produces.
Cu with above-mentioned preparation 4O 3The JSM6700 model field emission scanning electron microscope observation surface topography that material is produced in company of NEC.
Cu with above-mentioned preparation 4O 3The JEM-2100 lanthanum hexaborane transmission electron microscopy observation particle information that material is produced in company of NEC.
The Cu that Fig. 1 a obtains for embodiment 1 4O 3The XRD figure of material, b are pure Cu 4O 3Standard card (JCPDS49-1830), can know that by figure prepared product and standard card fit like a glove, this shows that use this method synthetic material is pure Cu 4O 3
The Cu that Fig. 2 obtains for embodiment 1 4O 3The SEM figure of material can know synthetic Cu by figure 4O 3The particle of material is spherical, and particle diameter is about 2-4 μ m.
The Cu that Fig. 3 obtains for embodiment 1 4O 3The TEM figure of material can know this Cu of synthetic by figure 4O 3Material is a solid material.
Embodiment two
Take by weighing 1.5g Cu (NO 3) 23H 2O; Be dissolved in ethanol-N-NMF mixing solutions of 50ml, the volume ratio that ethanol accounts for mixed solvent is 20%, is positioned over 200 ℃ of reaction 10h in the 100ml liner enamel reaction still; After reaction finishes; Product is filtered, and water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.
The Cu that Fig. 4 a obtains for embodiment 2 4O 3The XRD figure of material, b are pure Cu 4O 3Standard card (JCPDS49-1830), can know that by figure prepared product and standard card fit like a glove, this shows that use this method synthetic material is pure Cu 4O 3
The Cu that Fig. 5 obtains for embodiment 2 4O 3The SEM figure of material can know synthetic Cu by figure 4O 3The particle of material is spherical, and particle diameter is about 500nm-1 μ m.
The Cu that Fig. 6 obtains for embodiment 2 4O 3The TEM figure of material can know this Cu of synthetic by figure 4O 3Material is a hollow material.
Embodiment three
Take by weighing 3g Cu (NO 3) 23H 2O is dissolved in propyl alcohol-N of 75ml, N-monomethyl methane amide mixing solutions; The volume ratio that propyl alcohol accounts for mixed solvent is 50%; Be positioned over 250 ℃ of reaction 2h in the 100ml inner liner polytetrafluoroethylene reaction kettle, reaction after finishing is filtered product; Water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is hollow ball shape Cu 4O 3Material, particle diameter are about 500nm-1 μ m.
Embodiment four
Take by weighing 1.0g Cu (NO 3) 23H 2O; Be dissolved in Virahol-N-NMF mixing solutions of 40ml, the volume ratio that Virahol accounts for mixed solvent is 70%, is positioned over 100 ℃ of reaction 20h in the 100ml liner enamel reaction still; After reaction finishes; Product is filtered, and water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is solid spherical Cu 4O 3Material, particle diameter are about 3 μ m-5 μ m.
Embodiment five
Take by weighing 2.8g Cu (NO 3) 23H 2O is dissolved in ethanol-N of 60ml, dinethylformamide mixing solutions; The volume ratio that ethanol accounts for mixed solvent is 40%; Be positioned over 130 ℃ of reaction 12h in the 100ml inner liner polytetrafluoroethylene reaction kettle, reaction after finishing is filtered product; Water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is solid spherical Cu 4O 3Material, particle diameter are about 3 μ m-5 μ m.
Embodiment six
Take by weighing 0.7g Cu (NO 3) 23H 2O; Be dissolved in methyl alcohol-N-NMF mixing solutions of 35ml, the volume ratio that methyl alcohol accounts for mixed solvent is 60%, is positioned over 170 ℃ of reaction 5h in the 100ml liner enamel reaction still; After reaction finishes; Product is filtered, and water, absolute ethyl alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is hollow ball shape Cu 4O 3Material, particle diameter are about 1 μ m-2 μ m.
Applicant's statement; The present invention explains detailed process condition of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process condition and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process condition and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.

Claims (10)

1. Cu 4O 3The preparation method of microballoon is characterized in that, said method comprising the steps of:
1) mantoquita is dissolved in the mixed solvent of alcohol and acid amides, obtains the solution that copper ion concentration is 0.05M-0.2M;
2) solution that configures is transferred in the reaction kettle, in 100 ℃-250 ℃ reaction 2-20h, preferred 4-18h, more preferably 4-12h obtains black precipitate, and said deposition obtains Cu through drying 4O 3Microballoon.
2. preparation method according to claim 1 is characterized in that copper ion concentration is preferably 0.08M-0.18M in the solution; More preferably 0.1-0.15M; Said mantoquita is a soluble copper salt, the preferred cupric nitrate of said mantoquita, copper sulfate, cupric chloride or its mixture, further preferred cupric nitrate.
3. preparation method according to claim 1 and 2 is characterized in that, said alcohol is low-carbon alcohol, and the straight or branched of preferred 1-7 carbon atom is pure, more preferably a kind of in methyl alcohol, ethanol, propyl alcohol, the Virahol, or itself or above mixture.
4. according to the described preparation method of one of claim 1-3, it is characterized in that said acid amides is N, dinethylformamide, N-NMF a kind of, or its mixture.
5. according to the described preparation method of one of claim 1-4, it is characterized in that in the said mixed solvent, the volume ratio that said alcohol accounts for is 10-70%, preferred 20-60%, more preferably 30-50%.
6. according to the described preparation method of one of claim 1-5, it is characterized in that said reaction kettle is the reaction kettle that is suitable for solvent thermal reaction; Preferred liner tetrafluoroethylene or enamelled reaction kettle; Reaction kettle volume plot ratio is 30-75%, preferred 40-70%, more preferably 40-60%.
7. according to the described preparation method of one of claim 1-6, it is characterized in that said temperature of reaction is 100-170 ℃, do not comprise 170 ℃, obtain Cu 4O 3Product is a solid microsphere; Said temperature of reaction is 170-250 ℃, comprises 170 ℃, the Cu that reaction obtains 4O 3Product is a tiny balloon.
8. according to the described preparation method of one of claim 1-7, it is characterized in that said deposition is carried out drying again after washing, deionized water, low-carbon alcohol or the washing of its mixture are preferably adopted in said washing, and the low-carbon alcohol preferred alcohol is used in said washing.
9. according to the described preparation method of one of claim 1-8, it is characterized in that said deposition is carried out drying again after filtering, washing.
10. according to the described preparation method of one of claim 1-9, it is characterized in that said Cu 4O 3Microballoon is a micro/nano level.
CN201110243938.2A 2011-08-24 2011-08-24 Preparation method of solid or hollow Cu4O3 microballoons Active CN102320645B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110243938.2A CN102320645B (en) 2011-08-24 2011-08-24 Preparation method of solid or hollow Cu4O3 microballoons

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110243938.2A CN102320645B (en) 2011-08-24 2011-08-24 Preparation method of solid or hollow Cu4O3 microballoons

Publications (2)

Publication Number Publication Date
CN102320645A true CN102320645A (en) 2012-01-18
CN102320645B CN102320645B (en) 2014-01-15

Family

ID=45448525

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110243938.2A Active CN102320645B (en) 2011-08-24 2011-08-24 Preparation method of solid or hollow Cu4O3 microballoons

Country Status (1)

Country Link
CN (1) CN102320645B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106698499A (en) * 2017-01-20 2017-05-24 江苏先丰纳米材料科技有限公司 Nano-spherical chain structure copper oxide and preparation method thereof
CN111185171A (en) * 2020-01-18 2020-05-22 中北大学 Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme
CN111373076A (en) * 2017-11-16 2020-07-03 西门子股份公司 Having mixed valence Cu4O3Ethylene selective electrode of catalyst
CN111900353A (en) * 2020-07-30 2020-11-06 北京金博威科技有限公司 Composite material, preparation method, lithium ion battery negative electrode material containing composite material and lithium ion battery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070181A (en) * 2011-01-14 2011-05-25 浙江大学 Preparation method of cuprous oxide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070181A (en) * 2011-01-14 2011-05-25 浙江大学 Preparation method of cuprous oxide

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JOONG JIAT TEO ET AL.: "Fabrication of Hollow Nanocubes of Cu2O and Cu via Reductive Self-Assembly of CuO Nanocrystal", 《LANGMUIR》 *
YU CHANG ET AL.: "Formation of Colloidal CuO Nanocrystallites and Their Spherical Aggregation and Reductive Transformation to Hollow Cu2O Nanospheres", 《LANGMUIR》 *
周波: "Cu2O/Cu纳米复合材料的控制合成及其光催化性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106698499A (en) * 2017-01-20 2017-05-24 江苏先丰纳米材料科技有限公司 Nano-spherical chain structure copper oxide and preparation method thereof
CN106698499B (en) * 2017-01-20 2018-02-06 江苏先丰纳米材料科技有限公司 A kind of nanosphere chain structure cupric oxide and preparation method thereof
CN111373076A (en) * 2017-11-16 2020-07-03 西门子股份公司 Having mixed valence Cu4O3Ethylene selective electrode of catalyst
CN111185171A (en) * 2020-01-18 2020-05-22 中北大学 Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme
CN111185171B (en) * 2020-01-18 2022-10-21 中北大学 Preparation method of high-activity multi-response carbon-point composite variable-valence copper oxide nanoenzyme
CN111900353A (en) * 2020-07-30 2020-11-06 北京金博威科技有限公司 Composite material, preparation method, lithium ion battery negative electrode material containing composite material and lithium ion battery
CN111900353B (en) * 2020-07-30 2022-02-25 北京金博威科技有限公司 Composite material, preparation method, lithium ion battery negative electrode material containing composite material and lithium ion battery

Also Published As

Publication number Publication date
CN102320645B (en) 2014-01-15

Similar Documents

Publication Publication Date Title
CN109133193A (en) A method of metal hydroxides multilevel structure is prepared using the derivative bimetallic oxide template of MOF
CN109205567B (en) Method for preparing metal oxide multilevel structure by utilizing MOF derived bimetallic oxide template
TW200941804A (en) Homogeneous nanoparticle core doping of cathode material precursors
CN103418316A (en) Preparation method of modified micro-granules
CN105731535B (en) A kind of preparation method of Zinc oxide/titanium dioxide composite nano materials
CN107658527A (en) A kind of high-performance transition metal oxide hollow ball air electrode and preparation method thereof
CN102641736A (en) Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof
CN108840313B (en) Preparation method of multistage spherical nickel diselenide
CN102320645B (en) Preparation method of solid or hollow Cu4O3 microballoons
CN102765707A (en) Micro-and nanoscale ferric phosphate, its solvent extraction-microemulsion preparation method and application thereof
CN104817120A (en) Preparation method of sea urchin-like Ni/Co composite basic carbonate
CN109678193A (en) A kind of preparation method of ceria nanoparticles
CN106492779B (en) Core-shell structure rare earth titanate-dioxide composite nanofiber catalysis material preparation method
CN103950985B (en) Nanometer bismuth tungstate of a kind of middle short side spherical structure and preparation method thereof
CN105084408B (en) Preparing method for copper oxide powder
KR101581331B1 (en) Method for manufacturing metal or metal oxide having micro-nano sizes using ultra-wave and metal or metal oxide thereby
CN101259539A (en) High dispersion metal nano granule and preparation thereof
CN105152192A (en) Preparation method of magnesium oxide/rare-earth oxide core-shell-structure flower-like nano composite material
CN109534383B (en) Synthesis method of cerium dioxide nanosheet
CN103449511A (en) Strontium titanate submicron crystal and preparation method thereof
CN101805013A (en) Synthesis method for grenade-shaped nanometer zinc oxide with low-temperature control
CN106745210A (en) A kind of Li doping SrTiO3The preparation method and product of porous surface nano particle
CN108178191B (en) Uniform ATO nano-particles with good water dispersibility and preparation method thereof
CN102674455B (en) Rare earth samarium zirconate nano material and hydrothermal preparation method thereof
Lee et al. Redox reaction mediated direct synthesis of hierarchical flower-like CuO spheres anchored on electrospun poly (vinylidene difluoride) fiber surfaces at low temperatures

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
TR01 Transfer of patent right

Effective date of registration: 20201117

Address after: 341003 No.36, Huangjin Avenue, Ganzhou economic and Technological Development Zone, Ganzhou City, Jiangxi Province

Patentee after: Jiangxi Rare Earth Research Institute, Chinese Academy of Sciences

Address before: 100190 Beijing, Zhongguancun, north of No. two, No. 1, No.

Patentee before: Institute of Process Engineering, Chinese Academy of Sciences

TR01 Transfer of patent right