CN105084408B - Preparing method for copper oxide powder - Google Patents
Preparing method for copper oxide powder Download PDFInfo
- Publication number
- CN105084408B CN105084408B CN201510477775.2A CN201510477775A CN105084408B CN 105084408 B CN105084408 B CN 105084408B CN 201510477775 A CN201510477775 A CN 201510477775A CN 105084408 B CN105084408 B CN 105084408B
- Authority
- CN
- China
- Prior art keywords
- oxide powder
- copper
- copper oxide
- cupric oxide
- carbonate
- 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
Links
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a preparing method for copper oxide powder. The preparing method comprises the following steps that 1, copper powder, hydrogen peroxide and sulfuric acid react to generate a mixed water solution; 2, under existence of a polyethylene glycol template addition agent, sodium bicarbonate, sodium carbonate and the mixed water solution react to generate basic cupric carbonate; 3, the basic cupric carbonate is decomposed at high temperature to generate copper oxide powder; 4, the copper oxide powder is placed into volatile solvent to be treated ultrasonically, the solvent is volatilized after ultrasonic treatment, and the copper oxide powder with the morphology changed is obtained finally. The method comprises two morphology control processes of the copper oxide powder, the first process is the copper oxide growth morphology control process, and the second process is the copper oxide agglomeration morphology control process. The preparing method is simple and convenient, the problem that the morphology is difficult to change after copper oxide is synthesized is solved, and multi-way application of the copper oxide of different morphologies can be expanded easily.
Description
Technical field
The invention belongs to printed circuit field of electronic materials, especially a kind of preparation side of inorganic material cupric oxide powder
Method.
Background technology
Copper oxide belongs to transition metal oxide, and the characteristic such as light, electricity, magnetic and catalysis that it possesses determines in many fields
There is potential using value.In lithium ion battery electrode material application, lobate, prismatic copper oxide is less due to having
Specific surface, shows higher initial coulomb efficiency but relatively low discharge capacity；The copper oxide of dendritic hollow then shows larger
Specific surface, initial capacity is big at constant current, and average coulombic effect is high.The mechanism that copper oxide is used for gas sensor is it
Can adsorbed gas or chemical reaction occurs with gas, this process then can produce the change of resistance, and instrument passes through monitoring electricity
That hinders changes numerical value and is converted into the information of gas；The copper oxide microcosmic combination of this kind of gas sensor application need to meet larger ratio
The requirement on surface, pattern is mostly bar-shaped, porous hollow is spherical, wire, lamellar, cellular.Copper oxide is also that a kind of p-type is partly led
Body, band gap is 1.2ev～2.1ev, is commonly used for solar pond absorbing material, and the microstructure of this kind of copper oxide presents bar-shaped
Array, needle-like array, line array；As the less quasiconductor of band gap, copper oxide be also used for photodetector with can
Depending on switch, pattern assumes line array.Copper oxide also shows outstanding catalysis characteristicses, especially the copper oxide of nanostructured due to
Possesses more Large ratio surface, catalysis characteristicses are better than the block, granule of micrometer structure；The copper oxide pattern of this kind of catalytic action presents
For irregular nano-particle, nano belt and nanometer sheet.Nano cupric oxide can be used for nanometer hot-fluid it is therefore an objective to improve system
Thermal conductivity, the suspension that this kind of copper oxide can be good in liquid, microstructure mostly is Nanoparticulate, threadiness, tubulose.Except this
Outside, the copper oxide of special appearance also has in Field Emission Display, super hydrophobic surface, arsenic removal and organic contamination, high energy material etc.
Application.
Existing copper oxide synthetic method relate generally to hydro-thermal method, chemical precipitation method, solid thermal decomposition method, electrochemical method,
Thermal oxidation process, sonochemistry method, microwave process for synthesizing, template auxiliary law, sol-gal process, microemulsion method, Electrospinning, spraying
Pyrolysismethod and thermal chemical vapor deposition method etc., but when synthesizing copper oxide, research worker can pay the utmost attention to its morphology control
Problem, reason is that copper oxide microscopic appearance characteristic will affect the application effect of specific area.In order to realize copper oxide specific certain
Presenting of pattern, except selecting special technical process, also can add some additives in synthetic system, such as dodecyl sulfur
Sour sodium, cetrimonium bromide, ethylene glycol, cetyl phenyl-hydrogen-sulfate are received, sulfur dodecyl gallate, hexamethylene diamine, poly- (4- benzene second
Alkene sulfonic acid is received), Polyvinylpyrrolidone etc..
Hydro-thermal method is the synthesis modal method of copper oxide, and this is because synthesizing inorganic salt has good water-soluble spy mostly
Property, and the polarity of hydrone can be with the lattice growth direction of induced oxidation copper.The constant situation of precipitation temperature, cu (no3)2.3h2The hydro-thermal reaction system of o and naoh composition can generate the copper oxide particle of laminated structure.Organic salt acetylacetone copper [cu
(c5h7)2:cu(aa)2] and inorganic salt cu (no3)2.3h2O then generates flower-shaped copper oxide under hydrothermal conditions.Cupric oxide nano
Excellent Hydrothermal Synthesiss formula has respectively: cucl2、naoh、cu(oh)4 2-With cetrimonium bromide；cu(no3)2, lactic acid with
naoh；cuso4, lactic acid receives and naoh；cu(no3)2With naoh.
Another kind of method that aqueous systems are synthesized copper oxide is chemical precipitation method, this method and hydro-thermal method more phase
Seemingly, simply the temperature needed for course of reaction is relatively low, and main synthesizing formula has respectively: cu (no3)2.3h2O and naoh；cu(oac)2.h2O and naoh；cu(no3)2.3h2O and na2co3.The particle surface energy that chemical precipitation method is generated is high, and agglomeration is serious,
Would generally be using ultrasonic method discrete particles in building-up process, document shows that synthesized oxidation steel structure can be cotton-shaped, bundle
Shape, flower-shaped etc.；The ph value controlling chemical precipitation process can also obtain the different copper oxide of microstructure in same formula
Grain；Even add (nh in chemical precipitation process4)2s2o8、k2s2o8, so that lamellar, palpus shape to be settled out on the copper base of pickling
Copper oxide particle.
Electrochemical process is also one kind more widely used metal-oxide synthetic method, return its reason be prepare simple,
Operation temperature is low, motility is big, and controls the parameter of electro-deposition, such as deposition voltage, electric current density and temperature etc., just can give birth to
Become different-shape, the granule of size.Preparation process is to be used copper sheet as anode, then copper sheet is immersed in nano3Or koh electricity
In electrolyte solution, after applying electrochemical reaction parameters, predecessor cu (oh) can be generated2Deng can get copper oxide after pyrolysis
Grain.It is lobate, cellular and bar-shaped that document report shows that the copper oxide microstructure synthesized by electrochemical process can present.
Thermal oxidation method only need to heat to copper sheet under air or oxygen atmosphere, the pre-treatment of copper sheet, oxidizing temperature,
Time, airflow rate have conclusive impact to the pattern of copper oxide.The microstructure of the copper oxide synthesized by this method
It is most common with wire.
Solid thermal decomposition method prepares copper oxide particle with chemical precipitation method very close to the solid precursors simply being used
Need to decompose generation copper oxide, these solid precursors such as basic copper carbonate [cu through high temperature2(oh)2co3]、cu2cl
(oh)3、cuc2o4And cu (oh)2Deng.Copper oxide synthesized by excessively this method of document report can assume lamellar, flower-shaped, rib
Shape, ellipticity, lenticular etc..The feature that thermal decomposition method synthesizes copper oxide is simple, efficient and safety.
Above 5 kinds of methods are to synthesize the main method of copper oxide although constantly there being some different process synthetic methods to occur,
As sonochemistry method, microwave process for synthesizing, template auxiliary law, sol-gal process, microemulsion method, Electrospinning, spray pyrolysis with
And thermal chemical vapor deposition method etc., but the study on the synthesis of all these document report typically only rests on the rank of laboratory synthesis
Section, is difficult to meet the requirement of large-scale production.
The method synthesis copper oxide that the present invention is mainly combined with thermal decomposition using hydrothermal deposition, template contral forerunner's alkaloids
The building-up process that formula curpic carbonate crystal growth is first time morphology control with thermal decomposition basic copper carbonate.Although have lot of documents,
The patent report synthetic route of basic copper carbonate, but be showed no and its pattern carried out synthesize control, such as: Chinese invention patent
Cn201310193323.2 proposes to react generation spherical basic cupric carbonate powder with gas atomized spherical copper sulphate pentahydrate and sodium carbonate
Method, but the gas atomization size prepared by this method uncontrollable it is impossible to form homogeneous formulation pattern, and
Atomization process is it is difficult to ensure that the purity of basic cupric carbonate powder；Chinese invention patent cn201210559033.0,
Cn201210559102.8 and cn201210559223.2 all adopt centrifugal evaporator preparation high-purity alkali type copper carbonate, the method by
In being used liquefied ammonia as reaction intermediate, synthesized basic copper carbonate can be subject to polluted by nitrogen, Chinese invention patent
Cn201210026076.2 and cn201210559117.4 equally also produces polluted by nitrogen problem；Chinese invention patent
Cn201010229534.3 provides only sodium bicarbonate and copper sulfate synthesizes the simple route of basic copper carbonate, its pattern is not entered
Row effective control；Chinese invention patent cn201110146202.3 has synthesized alkali formula with copper nitrate and sodium carbonate as reactive agent
Curpic carbonate, but do not suggest that the method that its pattern is controlled in synthetic route；Chinese invention patent
Cn201310123585.1 proposes using copper chloride, copper sulfate as raw material and co3 2-With the solution of oh- and contain ch3coo-Molten
Liquid reaction generates basic copper carbonate, but copper chloride derives from waste liquid, copper sulfate derives from copper mine or waste cupron, is all unfavorable for alkali
The purity of formula curpic carbonate, and compounding design is not made with any morphology control；Chinese invention patent cn200710047801.3 then refers to
Go out basic copper carbonate to obtain although reaction scheme is simple with sodium bicarbonate solid-state reaction by alkali type nantokite or Copper hydrate
Single, but too high reaction temperature causes basic copper carbonate pattern wayward.In addition, document is also shown in reporting by synthetic alkali formula
Curpic carbonate is heated the method resolving into copper oxide again.Chinese invention patent cn201410550840.5,
Cn201210559223.2, cn201210559066.5 and cn201410200323.5 all using copper, liquefied ammonia and ammonium hydrogen carbonate or
The method synthesis basic copper carbonate of carbon dioxide, the polluted by nitrogen that it produces directly is retained in the oxidation that pyrolysis basic copper carbonate generates
Inside copper, it is unfavorable for control of purity；Chinese invention patent cn201310138761.9 proposes to use bluestone waste synthetic alkali formula carbon
Sour copper, then decomposes and obtains copper oxide, because impurity component does not know and content is high in waste liquid, is not suitable for answering of electronic product
With；Document [plating and covering with paint, 2012,9:8～11] synthesizes basic copper carbonate simultaneously using the method for copper sheet, ammonia and ammonium hydrogen carbonate
Heat resolve becomes copper oxide, but due to being used copper sheet as reaction raw materials, reaction efficiency is slow, and there are no morphology control description；
Document [electronic science and technology, 2015,2 (1): 43～48] uses copper sulfate to synthesize basic copper carbonate with sodium bicarbonate, then passes through
Thermolysis process is obtained copper oxide although the synthesis of copper oxide can quickly be realized, but pattern is uncontrollable, is unfavorable for copper oxide
Multidirectional application；Document [the journal of physical chemistry b, 2005,109:17157～17161] carries
Go out and basic copper carbonate is synthesized with potassium carbonate with copper sulfate, change the conditions such as temperature, pressure to control basic carbonate in building-up process
Copper pattern, but do not refer to the method that any use template controls pattern.
Content of the invention
The present invention is directed to the uppity technical problem of existing thermal synthesis copper oxide pattern, there is provided a kind of cupric oxide powder
Preparation method.
Technical scheme is as follows:
A kind of preparation method of cupric oxide powder, comprises the steps: that (1) makes copper powder, hydrogen peroxide and sulphuric acid three anti-
Mixed aqueous solution should be generated；(2) in the presence of Polyethylene Glycol template additive, sodium bicarbonate, sodium carbonate and described mixing water are made
Solution three reaction generates basic copper carbonate；(3) basic copper carbonate pyrolytic generates cupric oxide powder；(4) by cupric oxide powder
End is put in volatile solvent and is carried out supersound process, and solvent flashing after supersound process finally gives the oxidation that pattern changes
Copper powders.
Said method includes the morphology control process of cupric oxide powder twice, for the first time for the control of copper oxide growth morphology
System, control method is mainly Polyethylene Glycol and serves as nucleus growth template and optimize the direction of growth and the speed of solid nucleus, heat point
Solution basic copper carbonate advantageously forms the copper oxide of porous appearance structure.It is for second the control of copper oxide reunion pattern, control
Method is that volatile solvent forms special interaction with copper oxide, and ultrasonic energy drives the pattern of copper oxide to change.
It is preferred that, described step (1) is further: the hydrogenperoxide steam generator being 30% with volumetric concentration first with
Volumetric concentration is that 98% sulfuric acid solution is configured to mixed aqueous solution, and in every liter of mixed aqueous solution, hydrogenperoxide steam generator, sulphuric acid are molten
The percent by volume of liquid and deionized water three is (20～25): (30～35): (45～50)；Then in every liter of mixed aqueous solution
The pure copper powder of the purity >=99wt% of middle addition 0.7～1.0mol, treats that copper powder is completely dissolved reaction post-heating and protects to 50～60 DEG C
Hold 10min, after being cooled to room temperature, be filtrated to get copper-bath.
It is preferred that, described step (2) is further: adds 0.2～0.3mol in every liter of described mixed aqueous solution
Sodium bicarbonate and 0.15～0.3mol sodium carbonate, then add 0.5～1g Polyethylene Glycol in every liter of mixed aqueous solution, persistently stir
Mix lower heated solution system to 70～80 DEG C, question response stops heating and standing 30～40min completely afterwards, stays after outwelling aqueous solution
Under thick shape solid sediment cleaned 3 times with ethanol and pure water respectively again, isolate green thick shape solid precipitation with centrifuge
Thing basic copper carbonate.
It is preferred that, described step (3) is further: basic copper carbonate puts 500～600 DEG C of revolution into after being dried
Formula incinerator carries out pyrolysis, finally gives the fine cupric oxide powder of black.
Temperature is too low, and decomposition efficiency is very low or does not decompose；Temperature is too high, and copper oxide is likely to become Red copper oxide.
The black fine powder copper oxide microscopic appearance obtaining assumes porous flake granule loosely-packed chondritic.
It is preferred that, described step (4) is further: the cupric oxide powder being dried has been added lid plastic bottle, so
After pour volatile solvent into and form solid-liquid mixing system, the volatility of every 1g cupric oxide powder addition 5ml in solid-liquid mixing system
Solvent；Capping is placed in supersonic generator after tightening and carries out supersound process 10～15min, and the condition of supersound process is power
120-150w and supersonic frequency 40-50khz；After supersound process, solid-liquid mixing system is inverted on sheet glass, natural under room temperature
Solvent flashing, finally gives the cupric oxide powder that pattern changes.
It is preferred that, described volatile solvent is ethanol, ether, methanol, butanone one kind therein.
Volatile solvent and the fine cupric oxide powder of black form special interaction, and ultrasonic energy drives cupric oxide powder
The pattern at end changes；When volatile solvent is the non-polar solvens such as ether, it is tight that cupric oxide powder pattern is changed into porous flake granule
Closs packing chondritic；When volatile solvent is ethanol polar solvent, it is complete that cupric oxide powder pattern is changed into porous flake granule
Approximate shceme structure.
It is preferred that, the mean molecule quantity of described Polyethylene Glycol is 2000-6000.
Polyethylene Glycol mean molecule quantity is too little, template action effect on driving birds is not good；Molecular weight is bigger, and the viscosity of solution system is too
Greatly, reaction is hindered to occur
The invention mainly relates to physical and chemical process and principle as follows:
It is copper-bath that pure copper powder, hydrogen peroxide and sulphuric acid three react the mixed aqueous solution generating；In Polyethylene Glycol
In the presence of template additive, it is alkali formula carbon that sodium bicarbonate, sodium carbonate and copper sulfate three react the thick shape solid sediment generating
Sour copper；Basic copper carbonate pyrolytic generates the fine cupric oxide powder of black, and it is loose that its microscopic appearance assumes porous flake granule
Pile up chondritic；Cupric oxide powder is put in volatile nonpolar solvents (as ether), and ultrasonication during supersound process causes
Cavitation bubble produce transient state and be separated, the collapse of the cavitation bubble that and then occurs then cause copper oxide lamellar short grained interior to effect
Power, thus results in more close packed structures, it is tightly packed that supersound process rear oxidation copper powders pattern is changed into porous flake granule
Chondritic, principle such as Fig. 1；
Cupric oxide powder is put in volatile polar solvent (as ethanol), functional group's-oh shape of cupric oxide powder and ethanol
Hydrogen bond is become to cause ethanol to be not easy to be desorbed copper oxide particle, ultrasonic energy acts on cupric oxide powder and will cause little of lamellar
Grain can depart from mutual Van der Waals force and become discrete state, and supersound process rear oxidation copper powders pattern is changed into porous flake
The complete discrete topology of granule, principle such as Fig. 2.
The invention has the beneficial effects as follows: the present invention includes the morphology control process of secondary oxidation copper powders, for the first time for oxygen
Change copper growth morphology to control, method is the direction of growth and the speed optimizing solid nucleus so that Polyethylene Glycol serves as nucleus growth template
Rate, forms the copper oxide of porous appearance structure with thermolysis process；It is for second copper oxide reunion morphology control, method is to select
Volatile solvent and copper oxide form special interaction, and ultrasonic energy drives the pattern of copper oxide to change.This preparation method
Simple and convenient, after solving the problems, such as copper oxide synthesis, pattern is difficult to change, and is conducive to expanding the multidirectional of different-shape copper oxide
Application.
Brief description
Fig. 1 is the schematic diagram that the present invention selects the preparation methoies of non-polar solven such as ether.
Fig. 2 is the schematic diagram of the preparation method that the present invention selects ethanol polar solvent.
Fig. 3 is the xrd figure of synthesis copper oxide.
Fig. 4-a is the copper oxide sem figure that step (1)-step (3) obtains；Fig. 4-b is the step selecting ether non-polar solven
Suddenly the copper oxide sem figure that (4) obtain；Fig. 4-c is the copper oxide sem figure selecting the step (4) of ethanol polar solvent to obtain.
Fig. 5-a is the copper oxide particle size distribution figure that step (1)-step (3) obtains；Fig. 5-b is to select ether nonpolar molten
The copper oxide particle size distribution figure that the step (4) of agent obtains；Fig. 5-c is the oxidation selecting the step (4) of ethanol polar solvent to obtain
Copper particle size distribution figure.
Specific embodiment
Embodiment 1
A kind of preparation method of cupric oxide powder, comprises the steps: that (1) makes copper powder, hydrogen peroxide and sulphuric acid three anti-
Mixed aqueous solution should be generated；(2) in the presence of Polyethylene Glycol template additive, sodium bicarbonate, sodium carbonate and described mixing water are made
Solution three reaction generates basic copper carbonate；(3) basic copper carbonate pyrolytic generates cupric oxide powder；(4) by cupric oxide powder
End is put in volatile solvent and is carried out supersound process, and solvent flashing after supersound process obtains final cupric oxide powder.
Said method includes the morphology control process of cupric oxide powder twice, for the first time for the control of copper oxide growth morphology
System, control method is mainly Polyethylene Glycol and serves as nucleus growth template and optimize the direction of growth and the speed of solid nucleus, heat point
Solution basic copper carbonate advantageously forms the copper oxide of porous appearance structure.It is for second the control of copper oxide reunion pattern, control
Method is that volatile solvent forms special interaction with copper oxide, and ultrasonic energy drives the pattern of copper oxide to change.
Embodiment 2
A kind of preparation method of cupric oxide powder, comprises the steps:
(1) hydrogenperoxide steam generator being 30% with volumetric concentration first and volumetric concentration are that 98% sulfuric acid solution is configured to
Mixed aqueous solution, in every liter of mixed aqueous solution, the percent by volume of hydrogenperoxide steam generator, sulfuric acid solution and deionized water three is
(20～25): (30～35): (45～50)；Then in every liter of mixed aqueous solution add 0.7～1.0mol purity >=
The pure copper powder of 99wt%, treats that copper powder is completely dissolved reaction post-heating to 50～60 DEG C of holding 10min, filters after being cooled to room temperature
To copper-bath.
(2) 0.2～0.3mol sodium bicarbonate and 0.15～0.3mol sodium carbonate are added in every liter of described mixed aqueous solution, so
Add 0.5～1g Polyethylene Glycol afterwards in every liter of mixed aqueous solution, continuously stirred lower heated solution system, to 70～80 DEG C, is treated anti-
Should stop afterwards completely heating and standing 30～40min, the thick shape solid sediment staying after outwelling aqueous solution uses ethanol more respectively
Clean 3 times with pure water, isolate green thick shape solid sediment basic copper carbonate with centrifuge；Centrifuge speed be 1000～
1500rpm, centrifugation time is 10～15min；
(3) basic copper carbonate is put 500～600 DEG C of swinging incinerator into and is carried out pyrolysis after being dried, final
To the fine cupric oxide powder of black.
The black fine powder cupric oxide powder microscopic appearance obtaining assumes porous flake granule loosely-packed chondritic.
(4) cupric oxide powder being dried has been added lid plastic bottle, be subsequently poured into volatile solvent and form solid-liquid mixture
System, in solid-liquid mixing system, every 1g cupric oxide powder adds the volatile solvent of 5ml；Capping is placed on ultrasound wave and occurs after tightening
Carry out supersound process 10～15min, the condition of supersound process is power 120-150w and supersonic frequency 40-50khz in device；Ultrasonic
After process, solid-liquid mixing system is inverted on sheet glass, under room temperature, natural solvent flashing, obtains final cupric oxide powder.
Described volatile solvent is ethanol, ether, methanol, butanone one kind therein.
Volatile solvent and the fine cupric oxide powder of black form special interaction, and ultrasonic energy drives cupric oxide powder
The pattern at end changes；When volatile solvent is the non-polar solvens such as ether, it is tight that cupric oxide powder pattern is changed into porous flake granule
Closs packing chondritic；When volatile solvent is ethanol polar solvent, it is complete that cupric oxide powder pattern is changed into porous flake granule
Approximate shceme structure.
The mean molecule quantity of described Polyethylene Glycol is 2000-6000.
The physical and chemical process that the present embodiment relates generally to and principle are as follows:
It is copper-bath that pure copper powder, hydrogen peroxide and sulphuric acid three react the mixed aqueous solution generating；In Polyethylene Glycol
In the presence of template additive, it is alkali formula carbon that sodium bicarbonate, sodium carbonate and copper sulfate three react the thick shape solid sediment generating
Sour copper；Basic copper carbonate pyrolytic generates the fine cupric oxide powder of black, and it is loose that its microscopic appearance assumes porous flake granule
Pile up chondritic；Cupric oxide powder is put in volatile nonpolar solvents (as ether), and ultrasonication during supersound process causes
Cavitation bubble produce transient state and be separated, the collapse of the cavitation bubble that and then occurs then cause copper oxide lamellar short grained interior to effect
Power, thus results in more close packed structures, it is tightly packed that supersound process rear oxidation copper powders pattern is changed into porous flake granule
Chondritic, principle such as Fig. 1；
Cupric oxide powder is put in volatile polar solvent (as ethanol), functional group's-oh shape of cupric oxide powder and ethanol
Hydrogen bond is become to cause ethanol to be not easy to be desorbed copper oxide particle, ultrasonic energy acts on cupric oxide powder and will cause little of lamellar
Grain can depart from mutual Van der Waals force and become discrete state, and supersound process rear oxidation copper powders pattern is changed into porous flake
The complete discrete topology of granule, principle such as Fig. 2.
Using the lattice growth of the prepared copper oxide of x-ray diffraction instrument analysis, as shown in figure 3, comparison copper oxide card
(jcpds48-1548) understand that synthesized copper oxide is monoclinic crystal structure.
Characterize the morphology change of the copper oxide after morphology control using scanning electron microscope.Step (1)-(3) (i.e. first
Secondary morphology control) afterwards: copper oxide assumes microscopic appearance and assumes porous flake granule loosely-packed chondritic, such as Fig. 4-a.Step
(4) (i.e. second morphology control) afterwards: when volatile solvent is ether non-polar solven, supersound process rear oxidation copper pattern is changed into
The tightly packed chondritic of porous flake granule, as shown in Fig. 4-b；When volatile solvent is ethanol polar solvent, supersound process
Rear oxidation copper pattern is changed into the complete discrete topology of porous flake granule, as shown in Fig. 4-c.
Measure the granularity change of the copper oxide after morphology control using laser particle size analyzer.Step (1)-(3) (i.e. first
Secondary morphology control) afterwards: the particle size distribution of copper oxide is 100nm～100 μm, such as Fig. 5-a.Step (4) (i.e. second pattern control
System) afterwards: when volatile solvent is ether non-polar solven, the granularity of supersound process rear oxidation copper is changed into 10 μm～352 μm, such as schemes
Shown in 5-b；When volatile solvent is ethanol polar solvent, the granularity of supersound process rear oxidation copper is changed into 60nm～10 μm, such as schemes
Shown in 5-c.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (7)
1. a kind of preparation method of cupric oxide powder is it is characterised in that comprise the steps: that (1) makes copper powder, hydrogen peroxide and sulfur
Sour three's reaction generates mixed aqueous solution；(2) in the presence of Polyethylene Glycol template additive, sodium bicarbonate, sodium carbonate and institute are made
State mixed aqueous solution three reaction and generate basic copper carbonate；(3) basic copper carbonate pyrolytic generates cupric oxide powder；(4) will
Cupric oxide powder is put in volatile solvent and is carried out supersound process, and solvent flashing after supersound process finally gives pattern and becomes
The cupric oxide powder changed.
2. cupric oxide powder according to claim 1 preparation method it is characterised in that: described step (1) is further:
The hydrogenperoxide steam generator being 30% with volumetric concentration first and the sulfuric acid solution that volumetric concentration is 98% are configured to mixed aqueous solution,
In every liter of mixed aqueous solution, the percent by volume of hydrogenperoxide steam generator, sulfuric acid solution and deionized water three is (20～25): (30
～35): (45～50)；Then add the pure copper powder of the purity >=99wt% of 0.7～1.0mol in every liter of mixed aqueous solution, treat
Copper powder is completely dissolved reaction post-heating to 50～60 DEG C of holding 10min, is filtrated to get copper-bath after being cooled to room temperature.
3. cupric oxide powder according to claim 1 preparation method it is characterised in that: described step (2) is further:
0.2～0.3mol sodium bicarbonate and 0.15～0.3mol sodium carbonate is added in every liter of described mixed aqueous solution, then mixed at every liter
0.5～1g Polyethylene Glycol is added, continuously stirred lower heated solution system, to 70～80 DEG C, is stopped after question response is complete in Heshui solution
Only heat and stand 30～40min, the thick shape solid sediment staying after outwelling aqueous solution uses ethanol and pure water clear more respectively
Wash 3 times, isolate green thick shape solid sediment basic copper carbonate with centrifuge.
4. cupric oxide powder according to claim 1 preparation method it is characterised in that: described step (3) is further:
Basic copper carbonate puts 500～600 DEG C into swinging incinerator after being dried carries out pyrolysis, finally gives the fine oxygen of black
Change copper powders.
5. cupric oxide powder according to claim 1 preparation method it is characterised in that: described step (4) is further:
The cupric oxide powder being dried is added lid plastic bottle, has been subsequently poured into volatile solvent and forms solid-liquid mixing system, solid-liquid mixes
In system, every 1g cupric oxide powder adds the volatile solvent of 5ml；Capping is placed in supersonic generator after tightening and is surpassed
Sonication 10～15min, the condition of supersound process is power 120-150w and supersonic frequency 40-50khz；To consolidate after supersound process
Liquid mixture system is inverted on sheet glass, and under room temperature, natural solvent flashing, finally gives the cupric oxide powder that pattern changes.
6. cupric oxide powder according to claim 1 preparation method it is characterised in that: described volatile solvent be second
Alcohol, ether, methanol, butanone one kind therein.
7. cupric oxide powder according to claim 1 preparation method it is characterised in that: the average mark of described Polyethylene Glycol
Son is measured as 2000-6000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510477775.2A CN105084408B (en) | 2015-08-07 | 2015-08-07 | Preparing method for copper oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510477775.2A CN105084408B (en) | 2015-08-07 | 2015-08-07 | Preparing method for copper oxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105084408A CN105084408A (en) | 2015-11-25 |
| CN105084408B true CN105084408B (en) | 2017-01-25 |
Family
ID=54565863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510477775.2A Expired - Fee Related CN105084408B (en) | 2015-08-07 | 2015-08-07 | Preparing method for copper oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105084408B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112850777B (en) * | 2021-03-30 | 2022-05-03 | 泰兴冶炼厂有限公司 | Preparation method of high-purity nano copper oxide |
| CN114609197B (en) * | 2022-03-25 | 2023-11-21 | 电子科技大学 | Gas-sensitive material, preparation method and NH (NH) thereof 3 Application in gas sensor |
| CN117303430B (en) * | 2023-11-29 | 2024-03-22 | 泰兴冶炼厂有限公司 | Copper oxide powder special for composite current collector and preparation process and method thereof |
| CN117923535B (en) * | 2024-03-21 | 2024-06-04 | 安徽中航纳米技术发展有限公司 | Preparation method of copper oxide porous nanosheets and application of copper oxide porous nanosheets in sodium ion battery anode material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407332B (en) * | 2007-10-12 | 2011-04-27 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| CN101264923B (en) * | 2008-04-22 | 2010-06-23 | 华东师范大学 | CuO straw-shaped nano structure and preparation method thereof |
-
2015
- 2015-08-07 CN CN201510477775.2A patent/CN105084408B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105084408A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tanveer et al. | Template free synthesis of CuS nanosheet-based hierarchical microspheres: an efficient natural light driven photocatalyst | |
| CN105084408B (en) | Preparing method for copper oxide powder | |
| Dong et al. | Hydrothermal synthesis and structure evolution of hierarchical cobalt sulfide nanostructures | |
| CN109205567B (en) | Method for preparing metal oxide multilevel structure by utilizing MOF derived bimetallic oxide template | |
| CN104724734B (en) | A kind of manufacture lightweight, high-specific surface area, the method for bouquet type nano-sized magnesium hydroxide | |
| CN105140517A (en) | Preparation method of non-water-soluble transition metal disulphide nanosheets | |
| Sun et al. | Bottom-up assembly of hierarchical Cu 2 O nanospheres: controllable synthesis, formation mechanism and enhanced photochemical activities | |
| Khorasanizadeh et al. | Ultrasound-accelerated synthesis of uniform DyVO4 nanoparticles as high activity visible-light-driven photocatalyst | |
| CN105129835B (en) | Hexacosahedral cuprous oxide nanometer particle preparation method | |
| CN101920986A (en) | Preparation method of zinc oxide nanosphere | |
| CN105148955A (en) | Preparation process of complex photocatalyst with multiwalled carbon nanotube loading silver/silver phosphate core-shell structure | |
| CN103435089A (en) | Spherical cuprous oxide micro-nano particles with roughness surface and preparation method thereof | |
| Zhang et al. | A novel preparation of Ag-doped TiO2 nanofibers with enhanced stability of photocatalytic activity | |
| Jia et al. | Using sonochemistry for the fabrication of hollow ZnO microspheres | |
| CN102962049A (en) | Method for preparing nanometer photocatalytic material via hydrothermal reaction | |
| CN102694173A (en) | Hydrothermal synthesis method for nanowire/stick-like morphology manganese lithium silicate | |
| Yang et al. | LaCO 3 OH microstructures with tunable morphologies: EDTA-assisted hydrothermal synthesis, formation mechanism and adsorption properties | |
| Wang et al. | Effect of OH− on morphology of Cu2O particles prepared through reduction of Cu (II) by glucose | |
| CN109179515A (en) | Spherical electrocatalysis material and preparation method thereof | |
| CN102107899B (en) | Preparation method of lamellar gamma-phase nano aluminum oxide | |
| Xing et al. | Hydrothermal-assisted homogeneous precipitation synthesis of dumbbell-like MnCO3 nanostructures | |
| Wei et al. | Mulberry-like BiVO 4 architectures: Synthesis, characterization and their application in photocatalysis | |
| CN104609456B (en) | A kind of preparation method of the C/N codope cuprous nanosphere of porous oxidation based on sericin | |
| CN106608653B (en) | A kind of spherical nano molybdenum disulfide of monodisperse and its preparation method and application | |
| Shi et al. | Microwave-assisted one-pot synthesis of SnC2O4/graphene composite anode material for lithium-ion batteries |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170125 Termination date: 20170807 |