CN104445414B - The preparation method of nanometer Cupric wolframate. antimicrobial powder - Google Patents
The preparation method of nanometer Cupric wolframate. antimicrobial powder Download PDFInfo
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- CN104445414B CN104445414B CN201410601596.0A CN201410601596A CN104445414B CN 104445414 B CN104445414 B CN 104445414B CN 201410601596 A CN201410601596 A CN 201410601596A CN 104445414 B CN104445414 B CN 104445414B
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention belongs to the technology of preparing of powder body, during preparation nanometer Cupric wolframate. antimicrobial powder, it is related to two methods of ultrasonic method and molten-salt growth method.Cupric wolframate. has a wide range of applications at aspects such as photocatalysis, gas sensor, magnetic materials, but the application in terms of antibacterial is rarely reported.It is that raw material is obtained Cupric wolframate. antimicrobial powder with sodium tungstate and copper nitrate, reduce antibacterial cost, increased antibacterial family newcomer.The method that the present invention prepares nanometer Cupric wolframate. antimicrobial powder is different from common sol-gal process, hydrothermal synthesis method, carrier adsorption method etc..The present invention one is the Cupric wolframate. antiseptic nano powder using ultrasound cavitation effect preparation containing water of crystallization, and two is that the Cupric wolframate. antimicrobial powder containing water of crystallization prepares final nanometer Cupric wolframate. antimicrobial powder with molten-salt growth method again as presoma first with ultrasound cavitation effect preparation.Such antibacterial can be applicable to papermaking and the industries such as plastics.
Description
Technical field
The invention belongs to the technology of preparing of powder body, during preparation nanometer Cupric wolframate. antimicrobial powder, it is related to ultrasonic method and fused salt
Two methods of method.
Background technology
Silver-series antibacterial agent application at present is relatively broad.Because the cost of silver-series antibacterial agent is higher, therefore anti-microbial property is good
Good non-silver antibacterial agent becomes one of study hotspot.The anti-biotic material of nano-particle level has the medicine of higher specific surface area and Geng Gao
Thing load capacity, therefore more preferable antibacterial effect can be shown.Nano-particle anti-biotic material reaches bacterium surface and can make cell membrane
Saturatingization, is that nano-particle plays one of most important process of antimicrobial effect.
Cupric wolframate. has a wide range of applications at aspects such as photocatalysis, gas sensor, magnetic materials, but in terms of antibacterial
Application be rarely reported.The present invention one is to prepare the antiseptic nano powder of Cupric wolframate. containing water of crystallization using ultrasound cavitation effect, and two are
Prepare Cupric wolframate. containing water of crystallization (CuWO4 2H2O) antimicrobial powder first with ultrasound cavitation effect and use fused salt again as presoma
Method prepares nanometer Cupric wolframate. (CuWO4) antimicrobial powder.
During tradition preparation chemosynthesis powder body, generally so that response speed is accelerated using temperature constant magnetic stirring method and reach uniformly
Reaction, typically takes in several hours to more than ten hour, therefore equipment and operation is required higher, and is difficult to obtain nanoscale powder
Body.During present invention synthesis Cupric wolframate. antimicrobial powder, dozens of minutes is only needed using supercritical ultrasonics technology, greatlys save the time, and ultrasonic
More preferably, particle size distribution is evenly for the powder body antibacterial effect that ripple method is obtained.Powder granule diameter is in nano-scale range, ultrasonic method principle
It is when ul-trasonic irradiation is in liquid, the rapid nucleation of the microbubble in liquid, growth, vibration, when acoustic pressure power is sufficiently large, gas
Bubble collapse can produce microjet and the shock wave of high speed, simultaneously within the extremely short time, in the little space around cavitation bubble
Produce and be up to the high temperature of more than 5000K and the high pressure of 100MPa, it is special that these constitute that material chemically and physically changed
Environment.When this effect occurs in the surface of solids, shock wave and microjet can invade the surface of solids, break down solids.Meanwhile, by
Strong immixture in granule surrounding liquid, accelerates conduction of heat and material transmittance process, promotes material solid
Diffusion in body space.
During molten-salt growth method also is applied to prepare nanometer Cupric wolframate. antimicrobial powder by the present invention, because fused salt is applied in generation
Powder granule between, being connected with each other between granule can be stoped, make the good dispersion of the powder body of synthesis, with traditional solid phase
Reaction sintering is compared, and is easier to obtain nanometer grade powder, and significantly reduces synthesis temperature, process is simple, equipment requirements
Low, environmental friendliness is it is easy to large-scale production.
The present invention is obtained non-silver nanoparticle Cupric wolframate. antimicrobial powder, reduces antibacterial cost, expands antibacterial family member.Should
Antimicrobial powder can be widely applied to the fields such as anti-bacteria paper, antimicrobial coating and antibiotic plastic.
It is now recognized that Cupric wolframate. powder body Antibacterial Mechanism is the Cu2+ active antibacterial mechanism according to copper system antibacterial；CuWO4 exists
During use Cu2+ can gradual separate out, when micro Cu 2+ reach microbial cell film when, because the latter is negatively charged, according to
The two is made firmly to adsorb by Coulomb attraction.Cu2+ penetration cell wall enters intracellular and anti-with the sulfydryl (- SH base) in cell
Should, make protein denaturation, destroy the activity of cell synzyme, thus cell loss division growth ability and dead.Thin killing
After bacterium, Cu2+ can from cell separate out, then contact with other antibacterials, go round and begin again.
Content of the invention
The present invention one is that using ultrasound condition, the ultrasound cavitation effect preparation of mixed solution is contained with the Cupric wolframate. of water of crystallization
(CuWO4 2H2O) antimicrobial powder, two is the Cupric wolframate. (CuWO4 2H2O) first with ultrasound cavitation effect preparation containing water of crystallization
Antimicrobial powder prepares nanometer Cupric wolframate. (CuWO4) antimicrobial powder with molten-salt growth method again as presoma.Powder body diameter is in nanoscale model
Enclose and uniformity is preferable.
The dominant response being related in Cupric wolframate. antimicrobial powder course of reaction：
Na2WO4+Cu (NO3) 2=CuWO4 ↓+2NaNO3 (color of precipitation is fluorescence green)
Cupric wolframate. nano-class antibacterial powder body can be obtained by following two steps：
(1) ultrasonic method preparation nanometer CuWO4 2H2O antimicrobial powder (hereinafter referred to as this CuWO4 2H2O antimicrobial powder is C1)
Na2WO4 and Cu (NO3) 2 is configured to the solution that concentration is 0.2-1.0mol/L respectively；Then by Na2WO4 solution
It is poured slowly in the aqueous solution of Cu (NO3) 2, in molar ratio for 1: 1-2 mixing, configure 60-120ml mixed solution altogether；60-90℃
Ultrasonic Heating reacts 30-60min, makes this mixed solution fully react mixing.There is cotton-shaped fluorescence green precipitation in mixed liquor after mixing
Generate.Mixed solution is centrifuged, distilled water wash, then dries 8-12h at 70-90 DEG C DEG C, can get C1.
(2) ultrasonic molten-salt growth method preparation nanometer CuWO4 antimicrobial powder (hereinafter referred to as this CuWO4 antimicrobial powder is C2)
C1 is mixed for 1: 3-14 in mass ratio with fused salt (as LiNO3 etc.), adds appropriate dehydrated alcohol to grind in mortar
Mill 1-2h, makes C1 be sufficiently mixed uniformly with the fused salt as reaction medium.Mixture loads in crucible, through 80-100 DEG C of drying 3-
After 5h, put into and be incubated 2-6h after calcining at 210-340 DEG C in electric furnace, after cooling, obtain cured product.Fully soaked with distilled water
Foam washing washs cured product, then passes through centrifugation, distilled water wash, is dried, and removes remaining fused salt, you can obtain C2.
The inhibition zone that the Cupric wolframate. antimicrobial powder of above-mentioned 2 kinds of distinct methods preparation is carried out resisting gold-coloured staphylococci is surveyed
Examination, anti-bacteria test result is as shown in table 1.
The color of CuWO4 being obtained under table 1 different technology conditions and antibacterial circle diameter
As shown in Table 1, during the different response time under ultrasound condition, of different sizes, the different preparation works of C1 inhibition zone
As only also differed with the size of ultrasonic method and the C2 inhibition zone first prepared with molten-salt growth method again with ultrasonic method under the conditions of skill, inhibition zone
Average diameter, about between 15-19mm, has preferable anti-microbial property.Fig. 1 a, b are preparation C1 and C2 under different time respectively
Inhibition zone.As can be seen that C1 has more preferable antibacterial effect compared with C2 from table 1 and Fig. 1.Fig. 2 a, b are the XRD figure of C1 and C2, from
Find out in Fig. 2 a that the powder body of synthesis is in the state of the higher shakiness containing crystallization crystalline lenss of activity, its XRD diffraction maximum is
CuWO4 2H2O crystal；Fig. 2 b is the XRD figure of Cupric wolframate. antimicrobial powder C2, finds out the Cupric wolframate. of synthesis from the XRD figure of Fig. 2 b
Substantially, all of XRD diffraction maximum is all fitted like a glove crystal peak feature with the peak of standard CuWO4, is the stable CuWO4 of crystal structure
Crystal.
From table 1 and Fig. 1, C1 antibacterial effect is better than C2.And test discovery due to the activity of C1 powder body larger, and prepare
Process is simple is it is adaptable to the preparation of the preparation such as anti-bacteria paper and antibiotic plastic of the anti-biotic material in room temperature to 300 DEG C of scopes for the temperature
In, now C1 has more preferable anti-microbial property.When the preparation in higher preparation temperature 300-1000 DEG C of scope such as antimicrobial coating etc.
When, because this antimicrobial powder is in the more stable state of crystal, select the stable C2 of crystal structure more preferable.
Fig. 3 is the SEM figure of C1 and C2.Be can be seen that by Fig. 3 a：The granule of C1 is relatively regular, but particle diameter is less, average grain
Footpath is about 100nm, and population distribution is more uniform.Powder granule diameter reaches nanoscale.Fig. 3 b is the SEM figure of C2.Permissible by Fig. 3
Find out：C2 granule is relatively regular, and its particle diameter is little compared with C1, and mean diameter is about 60nm, more uniformly spreads, and no substantially reunites
Phenomenon.This is, can to stop so that preparing between the powder granule making fused salt be applied in generation during powder body due to using molten-salt growth method
Being connected with each other between granule, makes the good dispersion of the powder body of synthesis.
The feature of the present invention：
The present invention is applied to a nanometer Cupric wolframate. antibacterial powder using two kinds of different synthetic methods of Ultrasonic Heating method and molten-salt growth method
In the preparation of body, experiment shows, of good performance Cupric wolframate. antiseptic nano powder all can be obtained under the conditions of two kinds, not only makes work
Skill is simple, and antibacterial effect is excellent, can be respectively used under different use conditions；If for use temperature when room temperature and low temperature
Down it is proposed that being prepared by ultrasonic method chemosynthesis and the more preferable C1 of antibacterial effect using simplest method.If for higher
Use at a temperature of it is proposed that antimicrobial powder C2 using first ultrasonic rear molten-salt growth method preparation.The present invention has been obtained non-silver nanoparticle wolframic acid
Copper antimicrobial powder, that is, reduce antibacterial cost, expands antibacterial family member again.This process is simple, reduce synthesis temperature
Degree, equipment requirements are low, environmental friendliness, and cheap, antibacterial effect is preferable.
The present invention can be widely applied to the fields such as anti-bacteria paper, antibiotic plastic and antimicrobial coating.Respectively by C1 and C2 antibacterial
Agent 1-2wt% is applied to anti-bacteria paper and antibiotic plastic be obtained in paper industry and plastic industry, and it is to escherichia coli and golden yellow
Staphylococcic bacteriostasis rate, all more than 90%, improves antibacterial effect.
Brief description
The inhibition zone of C1 and C2 is prepared under Fig. 1 different time：The inhibition zone of a.C1；The inhibition zone of b.C2
The XRD figure of Fig. 2 C1 and C2：The XRD figure of a.C1；The XRD figure of b.C2；
The SEM figure of Fig. 3 C1 and C2：The SEM figure of a.C1；The SEM figure of b.C2
Specific embodiment
Embodiment 1：
Ultrasonic method preparation nanometer CuWO4 2H2O antimicrobial powder (hereinafter referred to as this CuWO4 2H2O antimicrobial powder is C1)
Na2WO4 and Cu (NO3) 2 is configured to the aqueous solution that concentration is 0.3mol/L respectively, then Na2WO4 solution is delayed
Slowly pour in Cu (NO3) 2 aqueous solution, in molar ratio for 1: 2 mixing, configure 60-120ml mixed solution altogether；Super during 80 DEG C of temperature
Acoustic heating reacts 35min, makes this mixed solution fully react mixing.Cotton-shaped fluorescence green precipitation is had to generate in mixed liquor after mixing.
Mixed solution is centrifuged, distilled water wash, then dries 10h at 80 DEG C, can get C1.
Embodiment 2：
Ultrasonic molten-salt growth method preparation nanometer CuWO4 antimicrobial powder (hereinafter referred to as this CuWO4 antimicrobial powder is C2)
(1) Na2WO4 and Cu (NO3) 2 is configured to the aqueous solution that concentration is 0.3mol/L respectively, then that Na2WO4 is molten
Liquid is poured slowly in Cu (NO3) 2 aqueous solution, in molar ratio for 1: 2 mixing, configures 60-120ml mixed solution altogether；80 DEG C of temperature
When Ultrasonic Heating reaction 35min, make this mixed solution fully react mixing.There is cotton-shaped fluorescence green precipitation in mixed liquor after mixing
Generate.Mixed solution is centrifuged, distilled water wash, then dries 10h at 80 DEG C, can get C1.
(2) ultrasonic molten-salt growth method prepares CuWO4 antimicrobial powder
C1 is mixed for 1: 3-12 in mass ratio with fused salt (as NaNO3 etc.), adds appropriate dehydrated alcohol to grind in mortar
Mill 2h, makes C1 and reaction medium be sufficiently mixed uniformly.Mixture loads in crucible, dries after 5h through 80 DEG C, put in electric furnace
Calcined under the experiment condition of 320 DEG C of insulation 4h, after cooling, obtained cured product.Solidified with the abundant washing by soaking of distilled water and produce
Thing, is then passed through centrifugation, distilled water wash, is dried, and removes remaining fused salt, you can obtain C2.
Claims (1)
1. the preparation method of nanometer Cupric wolframate. antimicrobial powder is it is characterised in that the method comprises the following steps：
1) ultrasonic method preparation nanometer CuWO4·2H2O antimicrobial powder
By Na2WO4With Cu (NO3)2It is configured to the solution that concentration is 0.2-1.0mol/L respectively, then by Na2WO4Solution slowly falls
Enter Cu (NO3)2Aqueous solution in, in molar ratio for 1: 1-2 mixing, altogether configure 60-120ml mixed solution；Ultrasonic at 60-90 DEG C
Reacting by heating 30-60min, makes this mixed solution fully react mixing, has cotton-shaped fluorescence green precipitation to generate in mixed liquor after mixing；
Mixed solution is centrifuged, distilled water wash, then dries 8-12h at 70-90 DEG C, can get the nanometer of ultrasonic method preparation
CuWO4·2H2O antimicrobial powder, abbreviation C1；
2) molten-salt growth method preparation CuWO4Antimicrobial powder
By C1 and fused salt LiNO3Mixing, its mass ratio is 1: 3-14, adds appropriate dehydrated alcohol to grind 1-2h, make C1 in mortar
It is sufficiently mixed uniformly with the fused salt as reaction medium, mixture loads in crucible, dries after 3-5h through 80-100 DEG C, puts into electricity
It is incubated 2-6h after being calcined at 210-340 DEG C in stove, after cooling, obtain cured product；Fully soaked, washed admittedly with distilled water
Change product, then pass through centrifugation, distilled water wash, drying, remove remaining fused salt, you can obtain ultrasonic-fused salt legal system
Standby nanometer CuWO4Antimicrobial powder, abbreviation C2.
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| CN106051447A (en) * | 2016-06-22 | 2016-10-26 | 江苏东顺新材料科技有限公司 | Antibacterial simulation rattan |
| CN109279654B (en) * | 2018-12-06 | 2021-04-09 | 盐城工学院 | Preparation method of copper tungstic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983930A (en) * | 2010-08-12 | 2011-03-09 | 河北联合大学 | Method for preparing superfine zinc tungstate antibacterial agent by ultrasonic molten salt method |
| CN102645453A (en) * | 2012-03-30 | 2012-08-22 | 中南大学 | Application of copper tungstate and preparation method of copper tungstate gas sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6103392A (en) * | 1994-12-22 | 2000-08-15 | Osram Sylvania Inc. | Tungsten-copper composite powder |
| CN1323527A (en) * | 2000-05-16 | 2001-11-28 | 顾浩 | Inorganic copper and silver antiseptic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101983930A (en) * | 2010-08-12 | 2011-03-09 | 河北联合大学 | Method for preparing superfine zinc tungstate antibacterial agent by ultrasonic molten salt method |
| CN102645453A (en) * | 2012-03-30 | 2012-08-22 | 中南大学 | Application of copper tungstate and preparation method of copper tungstate gas sensor |
Non-Patent Citations (1)
| Title |
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| CuWO4的合成及其电化学性能研究;段连生 等;《电源技术》;20131231;第37卷(第12期);2118-2119，2157 * |
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