CN101805011B - Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof - Google Patents

Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof Download PDF

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CN101805011B
CN101805011B CN2010101395359A CN201010139535A CN101805011B CN 101805011 B CN101805011 B CN 101805011B CN 2010101395359 A CN2010101395359 A CN 2010101395359A CN 201010139535 A CN201010139535 A CN 201010139535A CN 101805011 B CN101805011 B CN 101805011B
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王翠萍
吴建林
刘兴军
黄艺雄
张锦彬
马云庆
施展
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Xiamen University
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Abstract

The invention discloses Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as a preparation method thereof, relating to the preparation method of the nano-particles. A whole reaction mixed liquid is divided into two phases through regulating the proportion of each substance in a reaction system, wherein one phase contains metal salt while the other phase contains a reducing agent. The metal salt is released to the phase containing the reducing agent, and contacted with the reducing agent at a part close to the interface of two phases to carry out reduction reaction, and the release action and a protecting agent in the reaction system commonly act in the whole reaction system so as to achieve the aim of controlling the appearances and the sizes of the product Cu2O ultra-fine nano-particles. The Cu2O ultra-fine nano-particles can be prepared by using the release method; if the reaction mixed liquid containing the Cu2O ultra-fine nano-particles continuously keeps the temperature for certain time at certain temperature, Cu2O self-assembly nanospheres with larger particle sizes formed by self-assembling the Cu2O ultra-fine nano-particles are prepared due to the Ostwald maturating action.

Description

Cu＜sub〉2＜/sub〉O superfine nano particle and self-assembled nanometer microballoon and preparation method thereof
Technical field
The present invention relates to a kind of nanometer particle process method, relate in particular to a kind of by sustained release method control principal reaction medicine adding speed so that prepare ultra-fine Cu respectively 2The method of O nanoparticle and self-assembled nanometer microballoon thereof.
Background technology
Nanoparticle is because its size less (from a nanometer to the hundreds of nanometer), and caused small-size effect.This effect makes the character of nanoparticle compare with massive material qualitative change has taken place, thereby caused the generation of a series of peculiar physical phenomenons, and this also makes nanoparticle possess the potentiality of using in frontier.Cu 2The O nanoparticle, especially ultra-fine Cu 2O nanoparticle (particle diameter is below 10nm), as a kind of P-type semiconductor, (1.Maji T.K. has a wide range of applications in fields such as magnetic devices, solar energy converting, catalyzer, electrode materialss, Matasuda R., Kitagawa S, Nat.Mater.2007,6,142.; 2.Sander M.S., Cote M.J., Gu W., Kile B.M., Tripp C.P., Adv.Mater.2004,16,2052; 3.Liu J., Xue D., Adv.Mater.2008,20,2622.); In addition, ultra-fine Cu 2The Nano microsphere that the self-assembly of O nanoparticle forms, because its general nanoparticle than same particle size, have much bigger specific surface area, this makes it have stronger surfactivity, thereby can be applied in catalytic field better and be applied to biomedical sector as the DNA detection electrode.Therefore, Cu in recent years 2The preparation and the sign of O nanoparticle are subjected to extensive concern.Some research institutions have attempted preparing Cu 2The O nanoparticle is explored some preparation Cu 2The method of O nanoparticle is as (Mehmet ZahmakIran, Saim such as mechanical process, spray-drying process, sol-gel method, electrochemical deposition method and microemulsion methods
Figure GSA00000072508400011
Et al, Material Letters 2009,63,400).Though wherein mechanical process, spray-drying process, sol-gel method and electrochemical process operate relative simplyr, can not control Cu well 2The pattern of O nanoparticle and particle diameter obtain the uniform Cu of size distribution in can not be on a large scale 2The O nanoparticle; And microemulsion method is restive because of its reaction system too complex, and cost is higher, so be not suitable for large-scale industrial production Cu 2The O nanoparticle.
Have some about Cu 2The patent application of O nano material preparation aspect, as:
Publication number provides a kind of Cu for the application for a patent for invention of CN1693204 2The O nanometer particle process method, the solvent that its weak point is used in being to prepare is water, can not solve the too strong agglomeration traits that causes of polarity owing to water, thereby can not prepare ultra-fine Cu 2The O nanoparticle; In addition, the reductive agent that uses in this method is hydrazine hydrate, because hydrazine hydrate has extremely strong reductibility, organism there is intensive toxicity, so use hydrazine hydrate as raw material, not only the health to operator constitutes a threat to, and owing to must carrying out the complicacy that extra protection has increased production technique and production unit to personnel and equipment, and environment structure is endangered in the production process.
Publication number provides a kind of reduction method to prepare Cu for the application for a patent for invention of CN1384055 2The method of O nano wire, its shortcoming and publication number are that the method for CN1693204 is identical, also are to use hydrazine hydrate as reductive agent, and environment is worked the mischief.
Generally speaking, existing C u 2The preparation and the application of O nanoparticle are scarcely out of swaddling-clothes.
Summary of the invention
The object of the present invention is to provide a kind of employing liquid phase reduction, can be by sustained release method to Cu 2The formation of O nanoparticle and process of growth are carried out fine control, simple, the environmental protection of method, Cu that can scale operation 2O superfine nano particle and self-assembled nanometer microballoon and preparation method thereof.
Technical scheme of the present invention is by adding specific chemical in reaction system, makes the reaction mixture body be divided into phase I and two phases of II mutually.In this two-phase, phase I be oil phase on the upper strata, color is a mazarine, wherein contains the reactant cupric; Phase II is the ethylene glycol phase, is distributed in lower floor, and color wherein contains the reductive agent xitix near colourless.Cupric is discharged into the phase II from phase I lentamente, contacts with reductive agent in the zone near two-phase interface, and reduction reaction takes place.By the method (sustained release method) that this reaction medicine slowly discharges, controlled the nucleation and growth process of nanoparticle in the reaction (being fast nucleation, growth slowly) well, can prepare ultra-fine Cu 2The O nanoparticle; If will contain ultra-fine Cu 2The reaction system of O nanoparticle is incubated 10～20min under 80 ℃ of temperature, can prepare by ultra-fine Cu 2The Cu that the self-assembly of O nanoparticle forms 2The O Nano microsphere.
Cu of the present invention 2The particle diameter of O superfine nano particle is 4～8nm, and shape is subsphaeroidal.
Cu of the present invention 2The preparation method of O superfine nano particle may further comprise the steps:
1) in mantoquita, adds cupric ion wedding agent and solvent successively, get solution A;
2) protective material is dissolved in NaOH and the solvent solution, adds solution A again, get mixed liquor A;
3) mixed liquor A is warming up to mixed liquor A and is divided into two-phase up and down, add reductive agent again, get mixed liquid B, temperature reaction again gets colloid, behind colloid insulation 10～30min, adds precipitation agent in colloid, and vibration disperses, the centrifugal throw out A that gets;
4) with throw out A organic solvent washing, recentrifuge gets sediment B, and the supernatant liquid after repeated washing and centrifugation step are extremely centrifugal becomes till the water white transparency throw out C after obtaining washing;
5) the throw out C drying after will washing, Cu 2O superfine nano particle.
In step 1), described mantoquita is metal-salt Copper dichloride dihydrate or copper sulfate etc., and described cupric ion wedding agent can be selected from oleic acid (OA) or oleyl amine etc., and described solvent can be selected from ethylene glycol, glycerol or water etc.
In step 2) in, described protective material is optional from polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) etc., and the pH value of described NaOH and ethylene glycol mixing solutions can be 11～13; Described solvent can be selected from ethylene glycol, glycerol or water etc.
In step 3), the temperature of described intensification can be 60～70 ℃; Described reductive agent can be selected from xitix or sodium formaldehyde sulphoxylate (SFS) etc.; The temperature of described temperature reaction again can be 70～90 ℃; Described precipitation agent can be dehydrated alcohol or methyl alcohol etc.; Described vibration disperses to adopt ultrasonic vibration to disperse, and described throw out A is light green.
In step 4), described organic solvent can be selected from hexanaphthene, tetrahydrofuran (THF) or acetone etc.; Described throw out C is light green.
Described mantoquita, cupric ion wedding agent, solvent, protective material, NaOH and reductive agent, consumption by mass percentage can be mantoquita 2%～4%, cupric ion wedding agent 10%～20%; protective material 1%～5%; NaOH1%～5%, reductive agent 4%～8%, surplus is solvent.
Cu of the present invention 2The particle diameter of O self-assembled nanometer microballoon is 50nm, is formed by the superfine nano particle aggregation of size distribution at 4～8nm, and shape is subsphaeroidal.
Cu of the present invention 2The preparation method of O self-assembled nanometer microballoon may further comprise the steps:
1) in mantoquita, adds cupric ion wedding agent and solvent successively, get solution A;
2) protective material is dissolved in NaOH and the solvent solution, adds solution A again, get mixed liquor A;
3) mixed liquor A is warming up to mixed liquor A and is divided into two-phase up and down, add reductive agent again, get mixed liquid B, temperature reaction again gets colloid, with colloid insulation 30～60min, adds precipitation agent in colloid, and vibration disperses, the centrifugal throw out A that gets;
4) with throw out A organic solvent washing, recentrifuge gets sediment B, and the supernatant liquid after repeated washing and centrifugation step are extremely centrifugal becomes till the water white transparency throw out C after obtaining washing;
5) the throw out C drying after will washing, Cu 2O self-assembled nanometer microballoon.
In step 1), described mantoquita is metal-salt Copper dichloride dihydrate or copper sulfate etc., and described cupric ion wedding agent can be selected from oleic acid (OA) or oleyl amine etc., and described solvent can be selected from ethylene glycol, glycerol or water etc.
In step 2) in, described protective material is optional from polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP) etc., and the pH value of described NaOH and ethylene glycol mixing solutions can be 11～13; Described solvent can be selected from ethylene glycol, glycerol or water etc.
In step 3), the temperature of described intensification can be 60～70 ℃; Described reductive agent can be selected from xitix or sodium formaldehyde sulphoxylate (SFS) etc.; The temperature of described temperature reaction again can be 70～90 ℃; Described precipitation agent can be dehydrated alcohol or methyl alcohol etc.; Described vibration disperses to adopt ultrasonic vibration to disperse, and described throw out A is light green.
In step 4), described organic solvent can be selected from hexanaphthene, tetrahydrofuran (THF) or acetone etc.; Described throw out C is light green.
Described mantoquita, cupric ion wedding agent, solvent, protective material, NaOH and reductive agent, consumption by mass percentage can be mantoquita 2%～4%, cupric ion wedding agent 10%～20%; protective material 1%～5%; NaOH1%～5%, reductive agent 4%～8%, surplus is solvent.
Because the prepared Cu of the present invention 2O superfine nano particle and Cu 2O self-assembled nanometer microballoon is pure Cu 2Therefore the O phase, can think that the purity of these two kinds of products is higher, can reach more than 99%.
Outstanding advantage of the present invention is:
1) technology is simple, and environmental protection, promptly utilizes the method for reactant slowly-releasing in the preparation process, easily entire reaction course is controlled, and has been used environment amenable xitix as reductive agent.In preparation process, creatively, make reaction system be divided into the two-phase that respectively contains a kind of principal reaction thing, thereby realized the slowly-releasing of reactant by the proportioning of various materials in the conditioned reaction system, finally reached control to entire reaction.
2) can obtain required Cu by controlling reaction time 2O superfine nano particle and self-assembled nanometer microballoon, if add make behind the reductive agent colloid soaking time short (10～30min), then can obtain Cu 2O superfine nano particle; If add make behind the reductive agent colloid soaking time long (30～60min), then can obtain Cu 2O self-assembled nanometer microballoon.These are by Cu 2The Cu that the self-assembly of O superfine nano particle forms 2The particle diameter of O self-assembled nanometer microballoon is big (about 50nm), with the common Cu of same particle size 2The O nanoparticle is compared and since the former be by a lot of small-particles (4～8nm) under the effect of Ostwald slaking loosely reunite and to form, enlarge markedly than the surface-area of its particle of the latter, therefore the Cu that forms by self-assembly 2O self-assembled nanometer microballoon has very strong surfactivity, thereby at aspects such as catalytic field and electrode materialss good application prospects is arranged.
3) the present invention is suitable for large-scale production in batches.
Description of drawings
Fig. 1 is for adding reductive agent (xitix) before, and reaction mixture is divided into the photo of two-phase (phase I with II) mutually.As can be seen from Figure 1, the upper strata of reaction mixture is phase I, and its color is a mazarine, and lower floor is phase II, and its color is near colourless.
The Cu that Fig. 2 prepares for embodiment 2O superfine nano particle and Cu 2The XRD figure of O self-assembled nanometer microballoon.In Fig. 2, (a) be Cu 2The XRD figure of O superfine nano particle; (b) be Cu 2The XRD figure of O self-assembled nanometer microballoon; X-coordinate is diffraction angle 2 θ/degree, and ordinate zou is a diffraction peak intensity; In Fig. 2 (a) and Fig. 2 (b), the characteristic peak of Chu Xianing is followed successively by cubic oxide cuprous (111), (200), (220) and (311) peak from left to right.
The Cu that Fig. 3 prepares for embodiment 2O superfine nano particle and Cu 2Transmission electron microscope (TEM) figure of O self-assembled nanometer microballoon.In Fig. 3, (a) be Cu 2The TEM image of O superfine nano particle, pictorial display Cu 2O superfine nano particle subglobular, size distribution are at the particle of 4～8nm, and scale is 10nm; (b) be Cu 2The TEM image of O Nano microsphere, insertion portion (b) are the enlarged image of (b) middle white square frame inner compartment, (b) and illustration show Cu 2The particle diameter of O Nano microsphere is approximately 50nm, is formed by the superfine nano particle aggregation of size distribution at 4～8nm, and scale is 50nm (scale in the illustration is 10nm); (c) be Cu 2The high resolution TEM image of O superfine nano particle, scale is 5nm, pictorial display goes out Cu 2The surface of O superfine nano particle is surrounded by (200) crystal face, and its spacing is 0.216nm, and 0.216nm is corresponding to a cube Cu 2The spacing of O (200) crystal face, this has proved from another aspect that also the synthetic nanoparticle is Cu the embodiment 2O superfine nano particle is by forming Cu after the self-assembly 2O self-assembled nanometer microballoon.
Embodiment
Embodiment 1: 0.175g PVP is scattered in the ethylene glycol that 8mL dissolved NaOH (the pH value of this ethylene glycol solution is 12.7), makes PVP solution.The 1.5g xitix is dissolved in the ethylene glycol that 12mL dissolved NaOH (the pH value of this NaOH/ ethylene glycol solution also is 12.7) makes ascorbic acid solution.In container, add 16mL ethylene glycol, 0.4g Copper dichloride dihydrate, 1.5mL oleic acid, violent stirring 40min successively.Add the above-mentioned PVP solution for preparing again in this container, slowly mixing liquid in the container is warming up to 70 ℃, insulation 30min treats that the mixing liquid in the container is divided into two-phase (referring to Fig. 1).Pour in the container the ascorbic acid solution for preparing before this is disposable.Be warming up to 80 ℃, insulation 30min, the reactant in the container becomes green gradually.Add 10mL ethanol in container, centrifugal (8000rpm 8min) isolates the green precipitate thing.With this throw out of washing with acetone, centrifugal again (7000rpm, 6min), the green precipitate thing that finally obtains is in 60 ℃ vacuum drying oven behind the dry 24h, obtain green powder, through XRD (referring to Fig. 2 a) and TEM (referring to Fig. 3 a and Fig. 3 c) detect, determine that the powder for preparing in the experiment is by the ultra-fine Cu of size distribution at 4～8nm 2The O nanoparticle is molecular.
Embodiment 2: 0.175g PVP is scattered in the ethylene glycol that 8mL dissolved a certain amount of NaOH (the pH value of this ethylene glycol solution is 12.7), makes PVP solution.The 1.5g xitix is dissolved in the ethylene glycol that 12mL dissolved NaOH (the pH value of this NaOH/ ethylene glycol solution also is 12.7) makes ascorbic acid solution.In container, add 16mL ethylene glycol, 0.4g Copper dichloride dihydrate, 1.5mL oleic acid, violent stirring 40min successively.Add the above-mentioned PVP solution for preparing again in this container, slowly mixing liquid in the container is warming up to 70 ℃, insulation 30min treats that the mixing liquid in the container is divided into two-phase (referring to Fig. 1).Pour in the container the ascorbic acid solution for preparing before this is disposable.Be warming up to 80 ℃, insulation 30min, the reactant in the container becomes green gradually, continues to be incubated 10min down at 80 ℃, adds 10mL ethanol in container, and it is centrifugal that (6000rpm 4min) isolates the green precipitate thing.With this throw out of washing with acetone, centrifugal again (6000rpm, 3min), the green precipitate thing that obtains finally makes green powder behind the dry 24h in 60 ℃ vacuum drying oven, detects through XRD (referring to Fig. 2 b) and TEM (referring to Fig. 3 b) that to draw this powder be to be Cu about 50nm by particle diameter 2The O Nano microsphere is formed, wherein each Cu 2The O Nano microsphere is by the ultra-fine Cu of several size distribution in 4～8nm 2The loosely gathering under the Ostward maturation of O nanoparticle combines.

Claims (8)

1.Cu 2The preparation method of O superfine nano particle is characterized in that described Cu 2The particle diameter of O superfine nano particle is 4～8nm, and shape is subsphaeroidal;
Described Cu 2The preparation method of O superfine nano particle may further comprise the steps:
1) add cupric ion wedding agent and solvent successively in mantoquita, get solution A, described cupric ion wedding agent is selected from oleic acid or oleyl amine;
2) protective material is dissolved in NaOH and the solvent solution, adds solution A again, get mixed liquor A;
3) mixed liquor A is warming up to mixed liquor A and is divided into two-phase up and down, add reductive agent again, get mixed liquid B, temperature reaction again gets colloid, behind colloid insulation 10～30min, adds precipitation agent in colloid, and vibration disperses, the centrifugal throw out A that gets;
4) with throw out A organic solvent washing, recentrifuge gets sediment B, and the supernatant liquid after repeated washing and centrifugation step are extremely centrifugal becomes till the water white transparency throw out C after obtaining washing;
5) the throw out C drying after will washing, Cu 2O superfine nano particle.
2. Cu as claimed in claim 1 2The preparation method of O superfine nano particle is characterized in that,
In step 1), described mantoquita is metal-salt Copper dichloride dihydrate or copper sulfate, and described solvent is selected from ethylene glycol, glycerol or water;
In step 2) in, described protective material is selected from polyvinyl alcohol or polyvinylpyrrolidone, and the pH value of described NaOH and ethylene glycol mixing solutions is 11～13; Described solvent is selected from ethylene glycol, glycerol or water.
3. Cu as claimed in claim 1 2The preparation method of O superfine nano particle is characterized in that,
In step 3), the temperature of described intensification is 60～70 ℃; Described reductive agent is selected from xitix or sodium formaldehyde sulphoxylate; The temperature of described temperature reaction again is 70～90 ℃; Described precipitation agent is dehydrated alcohol or methyl alcohol;
In step 4), described organic solvent is selected from hexanaphthene, tetrahydrofuran (THF) or acetone.
4. Cu as claimed in claim 1 2The preparation method of O superfine nano particle; it is characterized in that described mantoquita, cupric ion wedding agent, solvent, protective material, NaOH and reductive agent; consumption by mass percentage is a mantoquita 2%～4%; cupric ion wedding agent 10%～20%; protective material 1%～5%; NaOH1%～5%, reductive agent 4%～8%, surplus is solvent.
5.Cu 2The preparation method of O self-assembled nanometer microballoon is characterized in that described Cu 2The particle diameter of O self-assembled nanometer microballoon is 50nm, is formed by the superfine nano particle aggregation of size distribution at 4～8nm, and shape is subsphaeroidal;
Described Cu 2The preparation method of O self-assembled nanometer microballoon may further comprise the steps:
1) add cupric ion wedding agent and solvent successively in mantoquita, get solution A, described cupric ion wedding agent is selected from oleic acid or oleyl amine;
2) protective material is dissolved in NaOH and the solvent solution, adds solution A again, get mixed liquor A;
3) mixed liquor A is warming up to mixed liquor A and is divided into two-phase up and down, add reductive agent again, get mixed liquid B, temperature reaction again gets colloid, with colloid insulation 30～60min, adds precipitation agent in colloid, and vibration disperses, the centrifugal throw out A that gets;
4) with throw out A organic solvent washing, recentrifuge gets sediment B, and the supernatant liquid after repeated washing and centrifugation step are extremely centrifugal becomes till the water white transparency throw out C after obtaining washing;
5) the throw out C drying after will washing, Cu 2O self-assembled nanometer microballoon.
6. Cu as claimed in claim 5 2The preparation method of O self-assembled nanometer microballoon is characterized in that,
In step 1), described mantoquita is metal-salt Copper dichloride dihydrate or copper sulfate, and described solvent is selected from ethylene glycol, glycerol or water;
In step 2) in, described protective material is optional from polyvinyl alcohol or polyvinylpyrrolidone, and the pH value of described NaOH and ethylene glycol mixing solutions is 11～13; Described solvent is selected from ethylene glycol, glycerol or water.
7. Cu as claimed in claim 5 2The preparation method of O self-assembled nanometer microballoon is characterized in that,
In step 3), the temperature of described intensification is 60～70 ℃; Described reductive agent is selected from xitix or sodium formaldehyde sulphoxylate; The temperature of described temperature reaction again is 70～90 ℃; Described precipitation agent is dehydrated alcohol or methyl alcohol;
In step 4), described organic solvent is selected from hexanaphthene, tetrahydrofuran (THF) or acetone.
8. Cu as claimed in claim 5 2The preparation method of O self-assembled nanometer microballoon; it is characterized in that described mantoquita, cupric ion wedding agent, solvent, protective material, NaOH and reductive agent; consumption by mass percentage is a mantoquita 2%～4%; cupric ion wedding agent 10%～20%; protective material 1%～5%; NaOH1%～5%, reductive agent 4%～8%, surplus is solvent.
CN2010101395359A 2010-04-06 2010-04-06 Cu2O ultra-fine nano-particles and self-assembly nanospheres as well as preparation method thereof Expired - Fee Related CN101805011B (en)

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