CN102320645B - Preparation method of solid or hollow Cu4O3 microballoons - Google Patents

Preparation method of solid or hollow Cu4O3 microballoons Download PDF

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CN102320645B
CN102320645B CN201110243938.2A CN201110243938A CN102320645B CN 102320645 B CN102320645 B CN 102320645B CN 201110243938 A CN201110243938 A CN 201110243938A CN 102320645 B CN102320645 B CN 102320645B
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preparation
alcohol
reaction
microballoon
solid
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CN102320645A (en
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苏发兵
赵丽润
车红卫
王莹利
翟世辉
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Jiangxi Rare Earth Research Institute, Chinese Academy of Sciences
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Institute of Process Engineering of CAS
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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, as Multifunctional fine inorganic materials, have purposes very widely in industrial production, such as being widely used in field of functional materials such as catalysis, photolysis, electromagnetic materials.
Except the cupric oxide of widespread use, Red copper oxide, also there is a kind of oxide compound: Cu in copper oxide 4o 3.Cu 4o 3in late 1870s, be found in copper mine at first, general and cupric oxide, Red copper oxide coexist, and seldom with pure material, exist.Cu 4o 3be a kind of metastable state material, because Cu (I) and Cu (II) exist simultaneously, structural instability, is therefore difficult to synthetic.
People are for synthetic pure Cu in recent years 4o 3, attempted a lot of methods.At present by chemical Vapor deposition process and magnetron sputtering method, prepare pure Cu 4o 3film, and to pure Cu 4o 3the optics of film, magnetics and electric property are studied.Xiao Ronghui etc. (" impact of oxygen flow on reaction magnetocontrol sputtering copper oxide membrane structure and optical property ", Xiao Ronghui etc., " Zhangzhou Normal College's journal: natural science edition, the 3rd phase in 2010) by reaction magnetocontrol sputtering method, deposited copper sull on glass substrate, has studied the impact of oxygen flow on membrane structure and optical property.Result shows, in film deposition process, along with the increase of oxygen flow, copper oxidation resultant is from Cu 2o is progressively transitioned into Cu 4o 3, be finally CuO.
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) with strong aqua, in copper mine, extract the oxide compound of copper or copper, 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 to burn the copper in secondary deionized water or cupric oxide, with laser ablation method, prepare Cu such as Amikura 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 needs to develop new preparation method.Solvent thermal reaction is a Material Field large study hotspot in recent years, compares with other syntheti c routes, and the distinguishing feature of solvent thermal reaction is reaction conditions as mild as a dove, can stablize metastable phase, prepares novel substance, develop new syntheti c route etc.The synthetic technology of solvent thermal pressurized heat can be prepared metastable phase that just can make in extreme condition, that could exist under hyperpressure conventionally under relatively low temperature and pressure.In solvent thermal reaction, one or more presomas are dissolved in non-aqueous solvent, under liquid phase or super critical condition, reactant be dispersed in solution and become more active, reaction occurs, product slowly generates.This process is relatively simple and be easy to control, and in enclosed system, can effectively prevent volatilization and the presoma of preparation to air-sensitive of toxic substance.In addition, the formation of phase, the size of particle diameter, form also can be controlled, and the dispersiveness of product is better.Under solvent thermal condition, the character of solvent (density, viscosity, dissemination) influences each other, alter a great deal, and differ greatly under its character and usual conditions, accordingly, dissolving, dispersion process and the chemical reactivity of reactant (normally solid) improve greatly or strengthen, and this just makes reaction at lower temperature, to occur.
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 by SICL 4, NAN 3mix with magnesium powder, or take iron powder as reductive agent 5.8-6.0 in molar ratio: 1: the amount of 0.58-0.60 is by SICL 4, NAN 3mix with iron powder, be sealed in autoclave, in 200 ℃-300 ℃ reactions 10 hours ± 0.5 hour; Product, through pickling, washing, centrifugation and dry, obtains silicon nitride micro Nano material.Prepared B-SI 3n 4nanometer rod diameter is about 100 nanometer～800 nanometers, and the diameter of nano wire is 30 nanometer-125 nanometers; A-SI 3n 4the diameter of nano wire is 50 nanometer-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 by SiCl 4and Mg 3n 2mix, be sealed in 550-700 ℃ of reaction more than 5 hours, product, through pickling and washing, centrifugation and dry, obtains α-Si 3n 4nano wire powder, the α-Si making 3n 4nano wire mean diameter is about 35 nanometers, the approximately several microns of length.
In the prior art, solvent thermal reaction is mainly used in the preparation of metastable phase material, for Cu 4o 3thisly because Cu (I) and Cu (II) exist simultaneously, cause structural unstable metastable state material, have no report prepared by any employing solvent thermal reaction.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is solvent thermal reaction 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 object of the present invention is also to provide a kind of solid or hollow Cu 4o 3the preparation method of microballoon.The present invention, by controlling temperature of reaction, is adjusted to product solid or hollow.Solid Cu prepared by the present invention 4o 3microballoon, its particle diameter is 2-5 μ m; Hollow Cu prepared by the present invention 4o 3microballoon, its particle diameter is 500nm-2 μ m.
Solid or hollow Cu of the present invention 4o 3the preparation method of microballoon, take mantoquita as raw material, adds solvent, in reaction kettle for reaction, after for some time, can make the solid or hollow Cu of micro/nano level 4o 3microballoon.
Solid or hollow Cu of the present invention 4o 3the preparation method of microballoon, preferably, after reaction, reaction product after filtration, washing is rear is dried.
Solid or hollow Cu of the present invention 4o 3the preparation method of microballoon, can as required, control by changing the processing condition such as precursor concentration, solvent ratios, temperature of reaction, reaction times the Cu that generates different sizes 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 fast, is a kind of efficient quick, cheap, eco-friendly Cu 4o 3the preparation method of microballoon.
Solid or hollow Cu of the present invention 4o 3the preparation method of microballoon, its raw material is mantoquita, acid amides, alcohol, wherein mantoquita is as initial reactant, alcohol and acid amides are mixed solvent, and mantoquita is made into certain density solution, put into reactor, add described mixed solvent, adjust the temperature to 100 ℃-250 ℃, reaction times 2-20h, preferably 4-18h, more preferably 4-12h, can make Cu 4o 3microballoon.Regulate temperature of reaction at baking oven or other heating installations, preferably in thermostatic equipment, to carry out.
According to preparation method of the present invention, after 100 ℃-250 ℃ reaction 2-20h, obtaining product is black precipitate, can obtain the solid or hollow Cu of micro/nano level after described black precipitate washing is dry 4o 3microballoon.
According to preparation method of the present invention, described mantoquita is soluble copper salt, and in solution, copper ion concentration is preferably 0.05M-0.2M, preferably 0.08M-0.18M, more preferably 0.1-0.15M.Described mantoquita is preferably cupric nitrate, cupric chloride, copper sulfate or its mixture, further preferred cupric nitrate.
According to preparation method of the present invention, described alcohol is low-carbon alcohol, the preferred straight or branched alcohol of 1-7 carbon atom, more preferably a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, or itself or above mixture.
According to preparation method of the present invention, described acid amides is preferably a kind of of DMF, N-METHYLFORMAMIDE, or its mixture.
According to preparation method of the present invention, in described mixed solvent, the shared volume ratio of described alcohol is 10-70%, preferably 20-60%, more preferably 30-50%.
According to preparation method of the present invention, described reactor is any reactor that is suitable for solvent thermal reaction.The reactor of preferred liner tetrafluoroethylene of the present invention or enamel, reactor volume plot ratio is 30-75%, preferably 40-70%, more preferably 40-60%.
According to preparation method of the present invention, controlling described temperature of reaction is 100-170 ℃ (not comprising 170 ℃), the Cu that reaction obtains 4o 3product is solid microsphere; Controlling described temperature of reaction is 170-250 ℃ (comprising 170 ℃), the Cu that reaction obtains 4o 3product is tiny balloon.
According to preparation method of the present invention, described precipitation preferably after filtration, washing after be dried again.Described washing preferably adopts deionized water, low-carbon alcohol such as ethanol, or its mixture washing.
According to preparation method of the present invention, described being dried as the existing Cu that do not cause 4o 3the drying operation that product physical and chemical performance changes, its typical but non-limiting example comprises, in lower than 100 ℃, preferably dry for some time at 60 ℃, be 4-12 hour preferred time of drying, more preferably 8 hours.
The present invention utilizes in solvent thermal reaction, one or more precursors are dissolved in non-aqueous solvent, under liquid phase or super critical condition, are dispersed in reactant in liquid phase and are uniformly dispersed and more active at atomic scale, easily impel reaction to carry out, thereby prepare micro-nano solid or hollow Cu 4o 3microballoon.Preparation method of the present invention, process is relatively simple and be easy to control, and whole technological process is carried out in reactor, and operational path is succinct, and reaction fast, is a kind of efficient quick, cheap, eco-friendly preparation Cu 4o 3the method of microballoon.
Compared to prior art, preparation method's advantage of the present invention is:
1, the Cu that prepared by the present invention 4o 3microballoon, experimental technique route is simple, and operation is convenient, and whole technological process is carried out in water heating kettle, and without any complex experiment equipment, reaction fast, is easy to large-scale production;
2, the Cu that prepared by the present invention 4o 3microballoon favorable reproducibility, is conducive to control quality product.
Accompanying drawing explanation
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 for further illustrating the present invention, but the present invention is not limited to following examples.
Embodiment mono-
Take 0.4g Cu (NO 3) 23H 2o, be 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 100ml inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, dehydrated alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.
By the Cu of above-mentioned preparation 4o 3on X ' the Pert PRO MPD type Multi-functional X ray diffractometer that material is produced in Dutch Panalytical company (PANalytical), carry out XRD test.
By the Cu of above-mentioned preparation 4o 3the JSM6700 model field emission scanning electron microscope observation surface topography that material is produced in NEC company.
By the Cu of above-mentioned preparation 4o 3the JEM-2100 lanthanum hexaborane transmission electron microscopy observation particle information that material is produced in NEC company.
Fig. 1 a is the Cu that embodiment 1 obtains 4o 3the XRD figure of material, b is pure Cu 4o 3standard card (JCPDS49-1830), as seen from the figure, prepared product and standard card fit like a glove, and as can be seen here, with the synthetic material of this method, are pure Cu 4o 3.
Fig. 2 is the Cu that embodiment 1 obtains 4o 3the SEM figure of material, as seen from the figure, synthetic Cu 4o 3the particle of material is spherical, and particle diameter is about 2-4 μ m.
Fig. 3 is the Cu that embodiment 1 obtains 4o 3the TEM figure of material, as seen from the figure, this synthetic Cu 4o 3material is solid material.
Embodiment bis-
Take 1.5g Cu (NO 3) 23H 2o, be dissolved in ethanol-N-METHYLFORMAMIDE mixing solutions of 50ml, the volume ratio that ethanol accounts for mixed solvent is 20%, be positioned over 200 ℃ of reaction 10h in 100ml liner enamel reaction still, after reaction finishes, product is filtered, and water, dehydrated alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.
Fig. 4 a is the Cu that embodiment 2 obtains 4o 3the XRD figure of material, b is pure Cu 4o 3standard card (JCPDS49-1830), as seen from the figure, prepared product and standard card fit like a glove, and as can be seen here, with the synthetic material of this method, are pure Cu 4o 3.
Fig. 5 is the Cu that embodiment 2 obtains 4o 3the SEM figure of material, as seen from the figure, synthetic Cu 4o 3the particle of material is spherical, and particle diameter is about 500nm-1 μ m.
Fig. 6 is the Cu that embodiment 2 obtains 4o 3the TEM figure of material, as seen from the figure, this synthetic Cu 4o 3material is hollow material.
Embodiment tri-
Take 3g Cu (NO 3) 23H 2o, be 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 100ml inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, dehydrated alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is hollow ball shape Cu 4o 3material, particle diameter is about 500nm-1 μ m.
Embodiment tetra-
Take 1.0g Cu (NO 3) 23H 2o, be dissolved in Virahol-N-METHYLFORMAMIDE mixing solutions of 40ml, the volume ratio that Virahol accounts for mixed solvent is 70%, be positioned over 100 ℃ of reaction 20h in 100ml liner enamel reaction still, after reaction finishes, product is filtered, and water, dehydrated alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is solid spherical Cu 4o 3material, particle diameter is about 3 μ m-5 μ m.
Embodiment five
Take 2.8g Cu (NO 3) 23H 2o, be 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 100ml inner liner polytetrafluoroethylene reactor, after reaction finishes, product filtered, water, dehydrated alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is solid spherical Cu 4o 3material, particle diameter is about 3 μ m-5 μ m.
Embodiment six
Take 0.7g Cu (NO 3) 23H 2o, be dissolved in methyl alcohol-N-METHYLFORMAMIDE mixing solutions of 35ml, the volume ratio that methyl alcohol accounts for mixed solvent is 60%, be positioned over 170 ℃ of reaction 5h in 100ml liner enamel reaction still, after reaction finishes, product is filtered, and water, dehydrated alcohol respectively wash 5 times, 60 ℃ of dry 8h in vacuum drying oven.Prepared product is hollow ball shape Cu 4o 3material, particle diameter is about 1 μ m-2 μ m.
Applicant's statement, the present invention illustrates detailed process condition of the present invention and technical process by above-described embodiment, but the present invention is not limited to above-mentioned detailed process condition and technical process, do not mean that the present invention must rely on above-mentioned detailed process condition and technical process could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (15)

1. a Cu 4o 3the preparation method of micro/nano level 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; In described mixed solvent, the volume ratio that described alcohol accounts for is 10-70%; Described alcohol is the straight or branched alcohol of 1-7 carbon atom; Described acid amides is a kind of of DMF, N-METHYLFORMAMIDE, or its mixture;
2) solution configuring is transferred in reactor, reaction 2-20h, obtains black precipitate, and described precipitation drying obtains Cu 4o 3microballoon;
Temperature of reaction is 100-170 ℃, while not comprising 170 ℃, obtains Cu 4o 3microballoon is solid microsphere; Temperature of reaction is 170-250 ℃, while comprising 170 ℃, and the Cu that reaction obtains 4o 3microballoon is tiny balloon.
2. preparation method as claimed in claim 1, is characterized in that step 2) in reaction times be 4-18h.
3. preparation method as claimed in claim 2, is characterized in that step 2) in reaction times be 4-12h.
4. preparation method according to claim 1, is characterized in that, in solution, copper ion concentration is 0.08M-0.18M, and described mantoquita is soluble copper salt, and described mantoquita is cupric nitrate, copper sulfate, cupric chloride or its mixture.
5. preparation method according to claim 4, is characterized in that, in solution, copper ion concentration is 0.1-0.15M.
6. preparation method according to claim 1, is characterized in that, described mantoquita is cupric nitrate.
7. preparation method according to claim 1, is characterized in that, described alcohol is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, or the mixture more than it.
8. according to the preparation method one of claim 1-4 Suo Shu, it is characterized in that, in described mixed solvent, the volume ratio that described alcohol accounts for is 20-60%.
9. preparation method according to claim 8, is characterized in that, in described mixed solvent, the volume ratio that described alcohol accounts for is 30-50%.
10. according to the preparation method one of claim 1-5 Suo Shu, it is characterized in that, described reactor is the reactor of inner liner polytetrafluoroethylene or enamel, and reactor volume plot ratio is 30-75%.
11. preparation methods according to claim 10, is characterized in that, described reactor volume plot ratio is 40-70%.
12. preparation methods according to claim 11, is characterized in that, described reactor volume plot ratio is 40-60%.
13. according to the preparation method one of claim 1-7 Suo Shu, it is characterized in that, described precipitation is dried after washing again, and described washing adopts deionized water, low-carbon alcohol or the washing of its mixture.
14. preparation methods as claimed in claim 13, is characterized in that, described washing low-carbon alcohol is ethanol.
15. according to the preparation method one of claim 1-7 Suo Shu, it is characterized in that, described precipitation after filtration, washing after be dried again.
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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
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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
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