CN104671283B - Supercritical ultrasonics technology and ultrasonic molten-salt growth method synthesis copper molybdate nanometer sheet antimicrobial powder - Google Patents

Abstract

Nanometer sheet crystal with its unique structure have many unusual physics, chemically and electrically etc. performance and receive much concern.The present invention is with Na₂MoO₄、Cu(NO₃)₂For raw material, CuMoO is prepared using supercritical ultrasonics technology and ultrasonic molten-salt growth method₄Nanometer sheet antimicrobial powder.Using temperature control during supercritical ultrasonics technology at 30 60 DEG C, ultrasonic time 15 45min；Ultrasonic molten-salt growth method is with the CuMoO of ultrasonic method preparation₄Nanometer sheet is raw material, and sodium nitrate and lithium nitrate are complex salt, 210 360 DEG C of reaction temperature.The sem analysis of powder body show, the CuMoO of supercritical ultrasonics technology preparation₄Nanometer sheet thickness about in 50nm, length × a width of 250nm × 400nm；The CuMoO of ultrasonic molten-salt growth method preparation₄Receive chip size thickness about in 100nm, long × 2.5 μm of a width of 0.7 μ m；This nanometer sheet antimicrobial powder can be used for the fields such as anti-bacteria paper and antimicrobial coating.

Description

Supercritical ultrasonics technology and ultrasonic-molten-salt growth method synthesis copper molybdate nanometer sheet antimicrobial powder

Technical field

The invention belongs to the technology of preparing of powder body, it is related to using the sonochemistry sedimentation method and ultrasonic-molten-salt growth method synthesis The method of copper molybdate nanometer sheet antimicrobial powder.

Background technology

Nano flake crystal has many unusual physics, the performance such as chemically and electrically with its unique structure, has weight The scientific research meaning wanted and be widely applied prospect, its research arouses great concern.

Preparing copper molybdate powder body by supercritical ultrasonics technology, to mainly use ultrasonic wavelength short and be easy to improve focusing power Feature, its principal character and the mechanism of action are：1. wavelength is short, is similar to straightline propagation, propagation characteristic and the property processing medium Closely related.2. energy is easily concentrated, thus can form very big intensity, within the extremely short time produce high temperature, high pressure and Violent vibration, produces cavitation effect.The cavitation of ultrasound wave is compared with tradition stirring hybrid technology and is easily realized uniformly Mixing, eliminates local concentration inequality, improves chemical reaction velocity, stimulate generation, the growth of crystal and the reunion of granule of cenotype It is controlled effectively.The grain shape of powder body and size can more easily be controlled by supercritical ultrasonics technology hence it is evident that changing crystal grain Pattern and size.

In molten-salt growth method, the melt of salt serves the effect of flux and reaction medium, compared with traditional solid phase method, fused salt Method can significantly reduce synthesis temperature and shorten the response time, and this can be attributed to due to the formation of the melt of salt, so that reaction is become Mobility in the liquid phase is divided to strengthen, diffusion rate significantly improves.Molten-salt growth method generally can adopt the salt of one or several low melting points Class is as reaction medium.MoO₄ ^2-And Cu²⁺There is certain dissolubility in fused salt, ratio is passing in fused salt due to its mobility High in the solid state reaction of system, no significantly reaction interface presence etc., therefore CuMoO is greatly reduced₄Crystalline formation activation energy, Product crystalline phase can be formed under relatively low reaction temperature.After reaction terminates, using suitable solvent, salt is dissolved, through diafiltration The product synthesizing can be obtained after washing.

Molten-salt growth method, for traditional solid phase method, has process is simple, synthesis temperature is low, temperature retention time is short, synthesis Powder body chemical composition uniform, the advantages of crystal morphology is good, thing phase purity is high.In addition, salt is easily separated, also reusable.No With fused salt also closely not identical to the contribution of product, the present invention adopts the mixture of sodium nitrate and lithium nitrate as composite fused salt, To the pattern with different burden control copper molybdate crystal grain.Because molten-salt growth method is in the higher temperature of supercritical ultrasonics technology and spy relatively Compound is synthesized, the copper molybdate product structure that molten-salt growth method obtains is more more stable than the powder structure that ultrasonic method obtains under fixed condition.

Content of the invention

The present invention one is to synthesize copper molybdate nanometer sheet antimicrobial powder using the sonochemistry sedimentation method；Two is to be sunk with sonochemistry The copper molybdate powder body of shallow lake method synthesis makees the antimicrobial powder that raw material synthesizes copper molybdate nanometer sheet again with molten-salt growth method.

The primary chemical precipitation being related in copper molybdate antimicrobial powder course of reaction：

Na₂MoO₄+Cu(NO₃)₂=CuMoO₄↓+2NaNO₃(precipitation color is fluorescent green)

Above-mentioned reaction can comprise the following steps：

1. supercritical ultrasonics technology preparation copper molybdate powder body (hereinafter referred to as CM1)

By Na₂MoO₄With Cu (NO₃)₂It is configured to the aqueous solution that concentration is 0.2-0.4mol/L respectively, then by Na₂MoO₄Molten Liquid is poured slowly into Cu (NO₃)₂In aqueous solution, in molar ratio for 1: 1-2 mixing, configure 60～120ml mixed solution altogether；Ultrasonic plus Hot temperature 30-60 DEG C, response time 15-45 minute, so that this mixed solution is sufficiently mixed simultaneously and complete chemical precipitation reaction, mixing Afterwards, mixed solution has fluorescent green precipitate to generate；Then mixed liquor is centrifuged remaining precipitate, and distilled water wash Precipitate, then dry 8-12h in temperature 70-90 DEG C, can get fluorescent green CuMoO₄Antimicrobial powder, i.e. CM1.

2. ultrasonic-molten-salt growth method preparation copper molybdate powder body (hereinafter referred to as CM2)

The CM1 powder body of above-mentioned preparation is raw material, sodium nitrate and lithium nitrate are complex salt, the mass ratio of complex salt is 1: 1.2-2；The ratio mixing being 1-3: 10-20 in material, salt mass ratio again, and add appropriate dehydrated alcohol to grind 1- in mortar 3h, makes raw material and complex salt be sufficiently mixed uniformly；Afterwards this mixture is put in crucible, be dried after 2-5h through 70-110 DEG C, then Put in electric furnace and be incubated 3-7h after temperature 210-360 DEG C calcining；Then fully soaked, washed mistake after cured product with distilled water Filter, dry, the remaining fused salt of removing, can get drabon color CuMoO₄Powder body, i.e. CM2.

Fig. 1 is to test copper molybdate antimicrobial powder antibacterial circle diameter variation diagram, as shown in Figure 1, molybdenum with staphylococcus aureuses The antibacterial effect of sour copper powder body is all good, and wherein the antibacterial circle diameter of ultrasonic method is slightly larger than ultrasonic-molten-salt growth method；Fig. 2 is ultrasonic Method and ultrasonic-molten-salt growth method preparation CuMoO₄The XRD of antimicrobial powder；As seen from Figure 2, ultrasonic method (a) and ultrasonic-molten-salt growth method B CuMoO that () is obtained₄The crystal diffraction characteristic peak of the XRD of powder body is similar, shows that crystal existing defects are abnormal miscellaneous peak in diffraction maximum more Become and amorphous state structure, the diffraction maximum of ultrasonic method tends to more unstable configuration, and therefore activity is higher is embodied in antibacterial Aspect of performance is also preferable.I.e. the anti-microbial property of ultrasonic method is slightly better than ultrasonic-molten-salt growth method.Fig. 3 ultrasonic method and ultrasonic-fused salt legal system Standby C_uMoO₄The SEM figure of antimicrobial powder；From Fig. 3 (a), the CM1 of ultrasonic method preparation is more uniform flat crystal,；Platelet Dimensional thickness in 50nm, length × a width of 250nm × 400nm；From Fig. 3 (b), the CM2 sheet-shaped of ultrasonic-molten-salt growth method preparation Looks more highlightedly develop to two-dimensional directional, platelet dimensional thickness in 100nm, long × 2.5 μm of a width of 0.7 μ m；Activity is relatively High unstability laminated structure may make it have preferable anti-microbial property.

With regard to CuMoO₄The growth mechanism of nanometer sheet, the present invention admits following viewpoint：(1) for the nanometer of ultrasonic method preparation The key one of molybdic acid copper sheet is the concentration controlling reactant solution, and two is ultrasound environments temperature, time etc..In Ultrasonic Heating Under the conditions of with Na₂MoO₄、Cu(NO₃)₂Generate CuMoO for raw material mixed solution₄Precipitation in, due to strictly controlling each group Point molar concentration and solution temperature and ultrasonic time, suitable reaction condition will lead to crystalline growth preferred orientation so that Crystal formation process is the nucleation starting to unordered cloud cluster shape so that fusion is lamellar, finally for nanometer chip architecture.(2) For ultrasonic-molten-salt growth method preparation nanometer molybdic acid copper sheet, in addition to above-mentioned condition, also need to control fused salt materials species and join Than, material salt ratio, calcining heat and temperature retention time etc..During by CM1 powder body with fused salt mixed calcining, this powder body is situated between in the fused salt melting Under matter existence condition, Cupric wolframate. nanometer fine grained can be synthesized rapidly, suitable reaction condition will lead to crystalline growth preferentially It is orientated specific crystal face with reference to growth so that wolframic acid copper crystal stretches out on two-dimentional yardstick, finally grow into and there is two dimension knot The lamellar of structure.

CuMoO₄The Antibacterial Mechanism of antimicrobial powder includes three below aspect

(1)Cu²⁺Active antibacterial mechanism：It is now recognized that copper molybdate Antibacterial Mechanism is the Cu according to it²⁺Active antibacterial mechanism； CuMoO₄Cu in use²⁺The gradual separate out of meeting, works as micro Cu²⁺Reach microbial cell film when, because the latter carry negative Electric charge, relies on Coulomb attraction so that the two is firmly adsorbed.Cu²⁺Penetration cell wall enter intracellular, and with cell in sulfydryl (- SH Base) reaction, make protein denaturation, destroy the activity of cell synzyme, thus cell loss division growth ability and dead.Killing Go out after antibacterial, Cu²⁺Can from cell separate out, then contact with other antibacterials, enter next round and kill being circulated throughout of antibacterial Journey.

(2)Cu²⁺Photocatalysis antibacterial mechanism：CuMoO₄It is also good photocatalyst material, Cu²⁺Can play in catalysis activity The effect of the heart, activates the oxygen in air or water in the presence of light, produces hydroxyl radical free radical (OH) and active oxygen ion (O^2-), It can destroy the multiplication capacity of microbial cell, suppression or killing antibacterial.

(3)Cu²⁺The Electrostatic Absorption sterilization mechanism of ion：The germy cell wall of institute and cell membrane typically all carry negative charge (mainly by-COO-, the anionic group such as-S- produces), and Cu²⁺Ion carries positive charge.Because the charges of different polarity are attracting, Cu²⁺Ion is easy to no selectively be adsorbed by various antibacterials, constrains the activity of antibacterial simultaneously, makes the existence microenvironment of antibacterial disorderly Imbalance, suppresses its breathing, ultimately results in bacterial death.

The feature of the present invention：

The present invention is incorporated into CuMoO using Ultrasonic Heating chemical precipitation method and ultrasonic-molten-salt growth method₄Nanometer sheet antimicrobial powder In synthesis, of good performance CuMoO under two methods, all can be obtained₄Nanometer sheet antimicrobial powder, the necessary requirement of preparation nanometer sheet It is：Molar concentration and solution temperature, Ultrasonic Heating time etc. of each component of Reasonable adjustment is needed during the synthesis of the sonochemistry sedimentation method；Super Suitable compound material salt proportioning, raw material and fused salt need to be chosen on the basis of aforementioned ultrasonic synthetic powder during sound-molten-salt growth method synthesis Proportioning and calcining heat and temperature retention time etc..

The copper molybdate nanometer sheet of present invention synthesis can use at different conditions；If during for temperature below 300 DEG C, It is proposed with the antimicrobial powder CM1 of ultrasonic method preparation.If using during temperature 300-900 DEG C it is proposed that adopt ultrasonic-fused salt legal system Standby powder body CM2.Present invention copper compound replaces silver compound, has both reduced antibacterial cost, expands antibacterial family again and becomes Member.This process is simple, equipment requirements are low, environmental friendliness, and cheap, antibacterial effect is preferable.The present invention can extensively answer For fields such as anti-bacteria paper, antibiotic plastic and antimicrobial coatings.

Brief description

Fig. 1 ultrasonic method and ultrasonic-molten-salt growth method preparation CuMoO₄The antibacterial loop graph of antimicrobial powder；

Fig. 2 ultrasonic method and ultrasonic-molten-salt growth method preparation CuMoO₄The XRD figure of antimicrobial powder；(a) ultrasonic method CM1；B () ultrasonic- Molten-salt growth method CM2；

Fig. 3 ultrasonic method and ultrasonic-molten-salt growth method preparation CuMoO₄The SEM figure of antimicrobial powder；(a) ultrasonic method CM1；B () ultrasonic- Molten-salt growth method CM2；

Specific embodiment

Embodiment 1：

Ultrasonic method preparation copper molybdate powder body (hereinafter referred to as CM1)

By Na₂MoO₄With Cu (NO₃)₂It is configured to the aqueous solution that concentration is 0.3mol/L respectively, then by Na₂MoO₄Solution delays Slowly pour Cu (NO into₃)₂In aqueous solution, in molar ratio for 1: 1 mixing, configure 90ml mixed solution altogether；Under the conditions of Ultrasonic Heating, At 70 DEG C, the time, in 35min, makes this mixed solution be sufficiently complete hybrid reaction to temperature control.There is fluorescence in mixed liquor after mixing Green precipitate generates.Mixed liquor is centrifuged remaining precipitate, then uses distilled water wash precipitate, dries at 90 DEG C of temperature 8h, can get CuMoO₄Antimicrobial powder, i.e. CM1.

Embodiment 2：

Ultrasonic-molten-salt growth method preparation copper molybdate powder body (hereinafter referred to as CM2)

With CM1 as raw material, sodium nitrate and lithium nitrate are complex salt, are respectively 1: 1: 10 mixing by material salt mass ratio, and Add appropriate dehydrated alcohol to grind 2h in mortar, so that reaction raw materials and complex salt is sufficiently mixed uniformly.Then mixture is put into In crucible, it is dried after 3h through 90 DEG C, place in electric furnace and be incubated 3h after 360 DEG C of calcinings of temperature.Fully soaked, washed with distilled water Filter after washing cured product, remove remaining fused salt, after drying, can get the molybdic acid copper powder of ultrasonic-molten-salt growth method preparation Body, i.e. CM2 powder body.

Claims (2)

1. a kind of supercritical ultrasonics technology synthesizes the method for copper molybdate nanometer sheet antimicrobial powder it is characterised in that the method includes following step Suddenly：By Na₂MoO₄With Cu (NO₃)₂It is configured to the aqueous solution that concentration is 0.2-0.4mol/L respectively, then by Na₂MoO₄Solution delays Slowly pour Cu (NO into₃)₂In aqueous solution, in molar ratio for 1: 1-2 mixing, configure 60～120ml mixed solution altogether；Ultrasonic Heating temperature 30-60 DEG C of degree, response time 10-45 minute, so that this mixed solution is sufficiently mixed and complete chemical precipitation reaction, mixed solution has Fluorescent green precipitate generates；Mixed liquor is centrifuged filtering lower precipitate afterwards, then uses distilled water wash precipitate, then in temperature 70-90 DEG C of drying 8-12h of degree, can get fluorescent green CuMoO₄Antimicrobial powder, i.e. CM1.

2. a kind of ultrasonic-molten-salt growth method prepares the method for copper molybdate powder body it is characterised in that the method comprises the following steps：With right Require the CuMoO of 1 synthesis₄Antimicrobial powder is raw material, and that is, with CM1 as raw material, sodium nitrate and lithium nitrate are complex salt, complex salt Mass ratio is 1: 1.2-2；The ratio mixing being 1-3: 10-20 in material, salt mass ratio again, and add anhydrous second in right amount in mortar Alcohol grinds 1-3h, so that raw material and complex salt is sufficiently mixed uniformly；Afterwards this mixture is put in crucible, 2- is dried through 70-110 DEG C After 5h, place in electric furnace and be incubated 3-7h after temperature 210-360 DEG C calcining；Then fully soaked, washed solidification with distilled water Filter after product, be dried, remove remaining fused salt, can get drabon color CuMoO₄Antimicrobial powder, i.e. CM2.