CN105084408A - Preparing method for copper oxide powder - Google Patents
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- CN105084408A CN105084408A CN201510477775.2A CN201510477775A CN105084408A CN 105084408 A CN105084408 A CN 105084408A CN 201510477775 A CN201510477775 A CN 201510477775A CN 105084408 A CN105084408 A CN 105084408A
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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 electronic circuit field of electronic materials, especially a kind of preparation method of inorganic materials cupric oxide powder.
Background technology
Cupric oxide belongs to transition metal oxide, it possess optical, electrical, the characteristic such as magnetic and catalysis determines has potential using value in a lot of fields.In lithium ion battery electrode material application, the cupric oxide of lobate, prismatic, owing to having less specific surface, shows higher initial coulomb efficiency but lower loading capacity; The cupric oxide of dendritic hollow then shows larger specific surface, and initial capacity is large at constant current, and average coulombic effect is high.Cupric oxide be used for the mechanism of gas sensor be its can adsorbed gas or with gas generation chemical reaction, this process then can produce the change of resistance, and instrument converts the information of gas to by the change numerical value of monitoring resistor; The cupric oxide microcosmic of this kind of gas sensor application combines the requirement that need meet compared with large specific surface, and pattern mostly is bar-shaped, porous hollow is spherical, wire, sheet, cellular.Cupric oxide is also a kind of p-type semiconductor, and band gap is 1.2eV ~ 2.1eV, is commonly used for solar pond absorbing material, and the microtexture of this kind of cupric oxide presents bar array, needle-like array, line array; As the semi-conductor that band gap is less, cupric oxide is also used to photodetector and visual switch, and pattern presents line array.Cupric oxide also shows outstanding catalysis characteristics, and especially the cupric oxide of nanostructure is owing to possessing more large specific surface, and catalysis characteristics is more better than the particle of bulk, micrometer structure; The cupric oxide pattern of this kind of katalysis is rendered as irregular nano particle, nano belt and nanometer sheet.Nano cupric oxide can also be used for nanometer hot-fluid, and object is the thermal conductivity of raising system, and the suspension that this kind of cupric oxide can be good at liquid, microtexture mostly is Nanoparticulate, threadiness, tubulose.In addition, the cupric oxide of special appearance also has application at Field Emission Display, super hydrophobic surface, arsenic removal and organic contamination, high energy material etc.
Existing cupric oxide synthetic method relates generally to hydrothermal method, chemical precipitation method, solid thermal decomposition method, electrochemical method, thermal oxidation process, sonochemistry method, microwave process for synthesizing, template auxiliary law, sol-gel method, micro emulsion method, Electrospinning, spray pyrolysis and thermal chemical vapor deposition method etc., but when synthesizing cupric oxide, researchist can pay the utmost attention to its morphology control problem, and reason is that cupric oxide microscopic appearance characteristic will affect the effect of specific area.In order to realize presenting of cupric oxide certain pattern specific, except selecting special technological process, also can add some additive in synthetic system, as sodium lauryl sulphate, cetrimonium bromide, ethylene glycol, hexadecyl phenyl-hydrogen-sulfate receive, sulphur dodecyl gallate, hexanediamine, poly-(4-styrene sulfonic acid is received), polyvinylpyrrolidone etc.
Hydrothermal method is synthesis cupric oxide modal method, and this is because synthesizing inorganic salt has good water soluble characteristic mostly, and the polarity of water molecules can the lattice growth direction of induced oxidation copper.The situation that precipitation temperature is constant, Cu (NO
3)
2.3H
2the hydro-thermal reaction system of O and NaOH composition can generate the copper oxide particle of sheet structure.Organic salt acetylacetone copper [Cu (C
5h
7)
2: Cu (AA)
2] and inorganic salt Cu (NO
3)
2.3H
2o then generates flower-shaped cupric oxide under hydrothermal conditions.Cupric oxide nano-rod Hydrothermal Synthesis formula has respectively: CuCl
2, NaOH, Cu (OH)
4 2-with cetrimonium bromide; Cu (NO
3)
2, lactic acid and NaOH; CuSO
4, lactic acid receives and NaOH; Cu (NO
3)
2with NaOH.
The another kind of method of aqueous systems Reactive Synthesis cupric oxide is chemical precipitation method, and this method and hydrothermal method are comparatively similar, and the temperature just needed for reaction process is lower, and main synthesizing formula has respectively: Cu (NO
3)
2.3H
2o and NaOH; Cu (OAc)
2.H
2o and NaOH; Cu (NO
3)
2.3H
2o and Na
2cO
3.The particle surface energy that chemical precipitation method generates is high, and agglomeration is serious, usually can use ultrasonic method discrete particles in building-up process, and the cupric oxide structure synthesized by document display can be cotton-shaped, pencil, flower-shaped etc.; The pH value controlling chemical precipitation process also can obtain the different copper oxide particle of microtexture at same formula; Even add (NH in chemical precipitation process
4)
2s
2o
8, K
2s
2o
8, to be settled out the copper oxide particle of sheet, palpus shape on the copper base of pickling.
Electrochemical process is also the more widely used metal oxide synthetic method of one, its reason is returned to be that preparation is simple and easy, service temperature is low, handiness is large, and control the parameter of galvanic deposit well, as deposition voltage, current density and temperature etc., the particle of different-shape, size just can be generated.Preparation process uses copper sheet as anode, then copper sheet is immersed in NaNO
3or in KOH electrolyte solution, after applying electrochemical reaction parameters, precursor C u (OH) can be generated
2deng, can copper oxide particle be obtained after pyrolysis.The cupric oxide microtexture of bibliographical information display synthesized by electrochemical process can present lobate, cellular and bar-shaped.
Thermal oxidation method only need heat copper sheet under air or oxygen atmosphere, and the pre-treatment of copper sheet, oxidizing temperature, time, the pattern of airflow rate on cupric oxide have conclusive impact.The microtexture of the cupric oxide synthesized by this method is the most common with wire.
Solid thermal decomposition method prepares the very close of copper oxide particle and chemical precipitation method, and be that used solid precursors needs could decompose through high temperature to generate cupric oxide, these solid precursors are as ventilation breather [Cu
2(OH)
2cO
3], Cu
2cl (OH)
3, CuC
2o
4and Cu (OH)
2deng.The bibliographical information cupric oxide crossed synthesized by this method can present sheet, flower-shaped, prismatic, ellipticity, lenticular etc.The feature of thermal decomposition method synthesis cupric oxide is simple, efficient and safety.
Above 5 kinds of methods are main method of synthesis cupric oxide; although constantly there are some different process synthetic methods to occur; as sonochemistry method, microwave process for synthesizing, template auxiliary law, sol-gel method, micro emulsion method, Electrospinning, spray pyrolysis and thermal chemical vapor deposition method etc.; but the study on the synthesis of all these bibliographical informations generally only rests on the stage of laboratory synthesis, is difficult to the requirement meeting large-scale production.
The method that the present invention mainly utilizes hydrothermal deposition to combine with thermolysis synthesizes cupric oxide, and template contral precursor ventilation breather crystal growth and thermolysis ventilation breather are the building-up process of first time morphology control.Although have lot of documents, patent reports the synthetic route of ventilation breather, but be showed no and synthesis control has been carried out to its pattern, as: Chinese invention patent CN201310193323.2 proposes to react with gas atomized spherical cupric sulfate pentahydrate and sodium carbonate the method generating spherical basic cupric carbonate powder, but the gas atomization size prepared by this method is uncontrollable, cannot form homogeneous formulation pattern, and atomization process is difficult to the purity ensureing basic cupric carbonate powder; Chinese invention patent CN201210559033.0, CN201210559102.8 and CN201210559223.2 all adopt centrifugal evaporator to prepare high-purity alkali type copper carbonate, this method is owing to using liquefied ammonia as reaction intermediate, synthesized ventilation breather can be subject to polluted by nitrogen, and Chinese invention patent CN201210026076.2 and CN201210559117.4 equally also produces polluted by nitrogen problem; Chinese invention patent CN201010229534.3 only provides sodium bicarbonate and copper sulfate to synthesize the simple route of ventilation breather, does not control effectively to its pattern; Chinese invention patent CN201110146202.3 has synthesized ventilation breather with cupric nitrate and sodium carbonate for reactive agent, but does not propose the method that controls its pattern in synthetic route; Chinese invention patent CN201310123585.1 proposes using cupric chloride, copper sulfate as raw material and CO
3 2-with the solution of OH-with containing CH
3cOO
-solution reaction generate ventilation breather, but cupric chloride derives from waste liquid, copper sulfate derives from copper mine or waste cupron, is all unfavorable for the purity of ventilation breather, and does not make any morphology control to compounding design; Chinese invention patent CN200710047801.3 then points out that ventilation breather can be obtained by alkali type nantokite or copper hydroxide and sodium bicarbonate solid state reaction, although reaction scheme is simple, too high temperature of reaction causes ventilation breather pattern wayward.In addition, document also see report by synthesis ventilation breather be heated the method resolving into cupric oxide again.Chinese invention patent CN201410550840.5, CN201210559223.2, CN201210559066.5 and CN201410200323.5 all adopt the method for copper, liquefied ammonia and bicarbonate of ammonia or carbonic acid gas to synthesize ventilation breather, its polluted by nitrogen produced directly is retained in inside the cupric oxide of pyrolysis ventilation breather generation, is unfavorable for control of purity; Chinese invention patent CN201310138761.9 proposition bluestone waste synthesizes ventilation breather, then decomposes and obtains cupric oxide, because impurity component in waste liquid is uncertain and content is high, be not suitable for the application of electronic product; Document [plating and covering with paint, 2012,9:8 ~ 11] adopts copper sheet, ammoniacal liquor synthesizes ventilation breather with the method for bicarbonate of ammonia and thermal degradation becomes cupric oxide, but owing to using copper sheet as reaction raw materials, reaction efficiency is slow, and describes there are no morphology control; Document [electronic science and technology, 2015,2 (1): 43 ~ 48] uses copper sulfate and sodium bicarbonate to synthesize ventilation breather, cupric oxide is obtained again by thermolysis process, although can realize the synthesis of cupric oxide fast, pattern is uncontrollable, is unfavorable for the multidirectional application of cupric oxide; Document [TheJournalofPhysicalChemistryB, 2005,109:17157 ~ 17161] propose to synthesize ventilation breather with copper sulfate and salt of wormwood, change the condition such as temperature, pressure to control ventilation breather pattern in building-up process, but not mentioned any use template controls the method for pattern.
Summary of the invention
The present invention is directed to the uppity technical problem of existing thermal synthesis cupric oxide pattern, provide a kind of preparation method of cupric oxide powder.
Technical scheme of the present invention is as follows:
A preparation method for cupric oxide powder, comprises the steps: that (1) makes copper powder, hydrogen peroxide and sulfuric acid three react generation mixed aqueous solution; (2) under polyoxyethylene glycol template additive exists, sodium bicarbonate, sodium carbonate and described mixed aqueous solution three is made to react generation ventilation breather; (3) ventilation breather pyrolytic decomposition generates cupric oxide powder; (4) cupric oxide powder is put in volatile solvent carry out supersound process, solvent flashing after supersound process, finally obtain the cupric oxide powder that pattern changes.
Aforesaid method comprises the morphology control process of twice cupric oxide powder, be the control of cupric oxide growth morphology for the first time, control method is mainly polyoxyethylene glycol and serves as nucleus growth template and the direction of growth and the speed of optimizing solid nucleus, and thermolysis ventilation breather is conducive to the cupric oxide forming porous appearance structure.Second time is the control of cupric oxide reunion pattern, and control method is that volatile solvent and cupric oxide form special interaction, and ultrasonic energy drives the pattern of cupric oxide to change.
As optimal way, described step (1) is further: first with volumetric concentration be 30% hydrogen peroxide and volumetric concentration be 98% sulfuric acid be mixed with mixed aqueous solution, the volume percent of hydrogen peroxide in often liter of mixed aqueous solution, sulfuric acid and deionized water three is (20 ~ 25): (30 ~ 35): (45 ~ 50); Then in often liter of mixed aqueous solution, add the pure copper powder of the purity >=99wt% of 0.7 ~ 1.0mol, treat that copper powder complete solubilizing reaction post-heating to 50 ~ 60 DEG C keep 10min, filter after being cooled to room temperature and obtain copper-bath.
As optimal way, described step (2) is further: add 0.2 ~ 0.3mol sodium bicarbonate and 0.15 ~ 0.3mol sodium carbonate in often liter of described mixed aqueous solution, then in often liter of mixed aqueous solution, 0.5 ~ 1g polyoxyethylene glycol is added, heated solution system to 70 ~ 80 DEG C under Keep agitation, question response stops heating and leaving standstill 30 ~ 40min completely afterwards, the thick shape solid sediment stayed after outwelling the aqueous solution cleans 3 times with ethanol and pure water more respectively, isolates green thick shape solid sediment ventilation breather with whizzer.
As optimal way, described step (3) is further: the rotary type incinerator putting 500 ~ 600 DEG C after ventilation breather drying into carries out pyrolysis, finally obtains the meticulous cupric oxide powder of black.
Temperature is too low, and decomposition efficiency is very low or do not decompose; Temperature is too high, and cupric oxide may become Red copper oxide.
The black fine powder cupric oxide microscopic appearance obtained presents porous flake loose particles and piles up ball-like structure.
As optimal way, described step (4) is further: the cupric oxide powder of drying has been added lid Plastic Bottle, then pour volatile solvent into and form solid-liquid mixing system, in solid-liquid mixing system, every 1g cupric oxide powder adds the volatile solvent of 5mL; Capping is placed in ultrasonic generator after tightening carries out supersound process 10 ~ 15min, and the condition of supersound process is power 120-150W and ultrasonic frequency 40-50kHz; Be inverted on sheet glass by solid-liquid mixing system after supersound process, natural solvent flashing under room temperature, finally obtains the cupric oxide powder that pattern changes.
As optimal way, described volatile solvent is ethanol, ether, methyl alcohol, butanone one wherein.
Volatile solvent and the meticulous cupric oxide powder of black form special interaction, and ultrasonic energy drives the pattern of cupric oxide powder to change; When volatile solvent is the non-polar solvents such as ether, cupric oxide powder pattern becomes the tightly packed ball-like structure of porous flake particle; When volatile solvent is ethanol polar solvent, cupric oxide powder pattern becomes the complete discrete topology of porous flake particle.
As optimal way, the molecular-weight average of described polyoxyethylene glycol is 2000-6000.
Polyoxyethylene glycol molecular-weight average is too little, template action poor effect; Molecular weight is larger, and the viscosity of solution system is too large, hinders reaction to occur
The physical and chemical process that the present invention relates generally to and principle as follows:
The mixed aqueous solution that pure copper powder, hydrogen peroxide and sulfuric acid three react generation is copper-bath; Under polyoxyethylene glycol template additive exists, the thick shape solid sediment that sodium bicarbonate, sodium carbonate and copper sulfate three react generation is ventilation breather; Ventilation breather pyrolytic decomposition generates the meticulous cupric oxide powder of black, and its microscopic appearance presents porous flake loose particles and piles up ball-like structure; Cupric oxide powder is put in volatile nonpolar solvents (as ether), the cavitation bubble that during supersound process, ultrasonication causes produces transient state and is separated, and then the cavitation bubble collapse occurred then causes cupric oxide sheet short grained interior to reactive force, thus packed structures is more closely caused, supersound process rear oxidation copper powder pattern becomes the tightly packed ball-like structure of porous flake particle, and principle is as Fig. 1;
Cupric oxide powder is put in volatile polar solvent (as ethanol), functional group-the OH of cupric oxide powder and ethanol forms hydrogen bond and causes ethanol to be not easy desorption copper oxide particle, ultrasonic energy acts on cupric oxide powder and sheet small-particle will be caused can to depart from mutual Van der Waals force and become discrete state, supersound process rear oxidation copper powder pattern becomes the complete discrete topology of porous flake particle, and principle is as Fig. 2.
The invention has the beneficial effects as follows: the morphology control process that the present invention includes secondary oxidation copper powder, first time is the control of cupric oxide growth morphology, method is served as nucleus growth template with polyoxyethylene glycol and optimizes the direction of growth and the speed of solid nucleus, forms the cupric oxide of porous appearance structure with thermolysis process; Second time is cupric oxide reunion morphology control, and method is that selective volatilization solvent and cupric oxide form special interaction, and ultrasonic energy drives the pattern of cupric oxide to change.This preparation method is simple and convenient, and after solving cupric oxide synthesis, pattern is difficult to the problem changed, and is conducive to the multidirectional application expanding different-shape cupric oxide.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the present invention selects the preparation method of the non-polar solvents such as ether.
Fig. 2 is the schematic diagram that the present invention selects the preparation method of ethanol polar solvent.
Fig. 3 is the XRD figure of synthesis cupric oxide.
Fig. 4-a is that the cupric oxide SEM that step (1)-step (3) obtains schemes; Fig. 4-b is that the cupric oxide SEM selecting the step (4) of ether non-polar solvent to obtain schemes; Fig. 4-c is that the cupric oxide SEM selecting the step (4) of ethanol polar solvent to obtain schemes.
Fig. 5-a is the cupric oxide particle size distribution figure that step (1)-step (3) obtains; Fig. 5-b is the cupric oxide particle size distribution figure selecting the step (4) of ether non-polar solvent to obtain; Fig. 5-c is the cupric oxide particle size distribution figure selecting the step (4) of ethanol polar solvent to obtain.
Embodiment
Embodiment 1
A preparation method for cupric oxide powder, comprises the steps: that (1) makes copper powder, hydrogen peroxide and sulfuric acid three react generation mixed aqueous solution; (2) under polyoxyethylene glycol template additive exists, sodium bicarbonate, sodium carbonate and described mixed aqueous solution three is made to react generation ventilation breather; (3) ventilation breather pyrolytic decomposition generates cupric oxide powder; (4) cupric oxide powder is put in volatile solvent carry out supersound process, solvent flashing after supersound process, obtain final cupric oxide powder.
Aforesaid method comprises the morphology control process of twice cupric oxide powder, be the control of cupric oxide growth morphology for the first time, control method is mainly polyoxyethylene glycol and serves as nucleus growth template and the direction of growth and the speed of optimizing solid nucleus, and thermolysis ventilation breather is conducive to the cupric oxide forming porous appearance structure.Second time is the control of cupric oxide reunion pattern, and control method is that volatile solvent and cupric oxide form special interaction, and ultrasonic energy drives the pattern of cupric oxide to change.
Embodiment 2
A preparation method for cupric oxide powder, comprises the steps:
(1) first with volumetric concentration be 30% hydrogen peroxide and volumetric concentration be 98% sulfuric acid be mixed with mixed aqueous solution, the volume percent of hydrogen peroxide in often liter of mixed aqueous solution, sulfuric acid and deionized water three is (20 ~ 25): (30 ~ 35): (45 ~ 50); Then in often liter of mixed aqueous solution, add the pure copper powder of the purity >=99wt% of 0.7 ~ 1.0mol, treat that copper powder complete solubilizing reaction post-heating to 50 ~ 60 DEG C keep 10min, filter after being cooled to room temperature and obtain copper-bath.
(2) 0.2 ~ 0.3mol sodium bicarbonate and 0.15 ~ 0.3mol sodium carbonate is added in often liter of described mixed aqueous solution, then in often liter of mixed aqueous solution, 0.5 ~ 1g polyoxyethylene glycol is added, heated solution system to 70 ~ 80 DEG C under Keep agitation, question response stops heating and leaving standstill 30 ~ 40min completely afterwards, the thick shape solid sediment stayed after outwelling the aqueous solution cleans 3 times with ethanol and pure water more respectively, isolates green thick shape solid sediment ventilation breather with whizzer; Centrifuge speed is 1000 ~ 1500rpm, and centrifugation time is 10 ~ 15min;
(3) the rotary type incinerator putting 500 ~ 600 DEG C after ventilation breather drying into carries out pyrolysis, finally obtains the meticulous cupric oxide powder of black.
The black fine powder cupric oxide powder microscopic appearance obtained presents porous flake loose particles and piles up ball-like structure.
(4) cupric oxide powder of drying has been added lid Plastic Bottle, then pour volatile solvent into and form solid-liquid mixing system, in solid-liquid mixing system, every 1g cupric oxide powder adds the volatile solvent of 5mL; Capping is placed in ultrasonic generator after tightening carries out supersound process 10 ~ 15min, and the condition of supersound process is power 120-150W and ultrasonic frequency 40-50kHz; Be inverted on sheet glass by solid-liquid mixing system after supersound process, natural solvent flashing under room temperature, obtains final cupric oxide powder.
Described volatile solvent is ethanol, ether, methyl alcohol, butanone one wherein.
Volatile solvent and the meticulous cupric oxide powder of black form special interaction, and ultrasonic energy drives the pattern of cupric oxide powder to change; When volatile solvent is the non-polar solvents such as ether, cupric oxide powder pattern becomes the tightly packed ball-like structure of porous flake particle; When volatile solvent is ethanol polar solvent, cupric oxide powder pattern becomes the complete discrete topology of porous flake particle.
The molecular-weight average of described polyoxyethylene glycol is 2000-6000.
The physical and chemical process that the present embodiment relates generally to and principle as follows:
The mixed aqueous solution that pure copper powder, hydrogen peroxide and sulfuric acid three react generation is copper-bath; Under polyoxyethylene glycol template additive exists, the thick shape solid sediment that sodium bicarbonate, sodium carbonate and copper sulfate three react generation is ventilation breather; Ventilation breather pyrolytic decomposition generates the meticulous cupric oxide powder of black, and its microscopic appearance presents porous flake loose particles and piles up ball-like structure; Cupric oxide powder is put in volatile nonpolar solvents (as ether), the cavitation bubble that during supersound process, ultrasonication causes produces transient state and is separated, and then the cavitation bubble collapse occurred then causes cupric oxide sheet short grained interior to reactive force, thus packed structures is more closely caused, supersound process rear oxidation copper powder pattern becomes the tightly packed ball-like structure of porous flake particle, and principle is as Fig. 1;
Cupric oxide powder is put in volatile polar solvent (as ethanol), functional group-the OH of cupric oxide powder and ethanol forms hydrogen bond and causes ethanol to be not easy desorption copper oxide particle, ultrasonic energy acts on cupric oxide powder and sheet small-particle will be caused can to depart from mutual Van der Waals force and become discrete state, supersound process rear oxidation copper powder pattern becomes the complete discrete topology of porous flake particle, and principle is as Fig. 2.
Utilize the lattice growth of the cupric oxide prepared by X-ray diffractometer analysis, as shown in Figure 3, the known synthesized cupric oxide of contrast cupric oxide card (JCPDS48-1548) is monoclinic crystal structure.
Adopt the morphology change of the cupric oxide after scanning electronic microscope sign morphology control.Step (1)-(3) (i.e. first time morphology control) are afterwards: cupric oxide presents microscopic appearance and presents porous flake loose particles and pile up ball-like structure, as Fig. 4-a.Step (4) (i.e. second time morphology control) is afterwards: when volatile solvent is ether non-polar solvent, supersound process rear oxidation copper pattern becomes the tightly packed ball-like structure of porous flake particle, as shown in Fig. 4-b; When volatile solvent is ethanol polar solvent, supersound process rear oxidation copper pattern becomes the complete discrete topology of porous flake particle, as shown in Fig. 4-c.
Utilize the change of granularity of the cupric oxide after laser particle size analyzer measurement morphology control.Step (1)-(3) (i.e. first time morphology control) are afterwards: the size-grade distribution of cupric oxide is 100nm ~ 100 μm, as Fig. 5-a.Step (4) (i.e. second time morphology control) is afterwards: when volatile solvent is ether non-polar solvent, the granularity of supersound process rear oxidation copper becomes 10 μm ~ 352 μm, as shown in Fig. 5-b; When volatile solvent is ethanol polar solvent, the granularity of supersound process rear oxidation copper becomes 60nm ~ 10 μm, as shown in Fig. 5-c.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (7)
1. a preparation method for cupric oxide powder, is characterized in that comprising the steps: that (1) makes copper powder, hydrogen peroxide and sulfuric acid three react generation mixed aqueous solution; (2) under polyoxyethylene glycol template additive exists, sodium bicarbonate, sodium carbonate and described mixed aqueous solution three is made to react generation ventilation breather; (3) ventilation breather pyrolytic decomposition generates cupric oxide powder; (4) cupric oxide powder is put in volatile solvent carry out supersound process, solvent flashing after supersound process, finally obtain the cupric oxide powder that pattern changes.
2. the preparation method of cupric oxide powder according to claim 1, it is characterized in that: described step (1) is further: first with volumetric concentration be 30% hydrogen peroxide and volumetric concentration be 98% sulfuric acid be mixed with mixed aqueous solution, the volume percent of hydrogen peroxide in often liter of mixed aqueous solution, sulfuric acid and deionized water three is (20 ~ 25): (30 ~ 35): (45 ~ 50); Then in often liter of mixed aqueous solution, add the pure copper powder of the purity >=99wt% of 0.7 ~ 1.0mol, treat that copper powder complete solubilizing reaction post-heating to 50 ~ 60 DEG C keep 10min, filter after being cooled to room temperature and obtain copper-bath.
3. the preparation method of cupric oxide powder according to claim 1, it is characterized in that: described step (2) is further: in often liter of described mixed aqueous solution, add 0.2 ~ 0.3mol sodium bicarbonate and 0.15 ~ 0.3mol sodium carbonate, then in often liter of mixed aqueous solution, 0.5 ~ 1g polyoxyethylene glycol is added, heated solution system to 70 ~ 80 DEG C under Keep agitation, question response stops heating and leaving standstill 30 ~ 40min completely afterwards, the thick shape solid sediment stayed after outwelling the aqueous solution cleans 3 times with ethanol and pure water more respectively, green thick shape solid sediment ventilation breather is isolated with whizzer.
4. the preparation method of cupric oxide powder according to claim 1, it is characterized in that: described step (3) is further: the rotary type incinerator putting 500 ~ 600 DEG C after ventilation breather drying into carries out pyrolysis, finally obtain the meticulous cupric oxide powder of black.
5. the preparation method of cupric oxide powder according to claim 1, it is characterized in that: described step (4) is further: the cupric oxide powder of drying has been added lid Plastic Bottle, then pour volatile solvent into and form solid-liquid mixing system, in solid-liquid mixing system, every 1g cupric oxide powder adds the volatile solvent of 5mL; Capping is placed in ultrasonic generator after tightening carries out supersound process 10 ~ 15min, and the condition of supersound process is power 120-150W and ultrasonic frequency 40-50kHz; Be inverted on sheet glass by solid-liquid mixing system D after supersound process, natural solvent flashing under room temperature, finally obtains the cupric oxide powder that pattern changes.
6. the preparation method of cupric oxide powder according to claim 1, is characterized in that: described volatile solvent is ethanol, ether, methyl alcohol, butanone one wherein.
7. the preparation method of cupric oxide powder according to claim 1, is characterized in that: the molecular-weight average of described polyoxyethylene glycol is 2000-6000.
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