CN107159166A - A kind of modified illite loading nano silvery antibacterial material and preparation method thereof - Google Patents
A kind of modified illite loading nano silvery antibacterial material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of modified illite loading nano silvery antibacterial material and preparation method thereof, belong to Chemical Engineering and Technology field, include the preparation of ammonium-bearing illite, the preparation of modified ammonium-bearing illite and the big step of preparation three of antibacterial material.Ammonium-bearing illite prepared by the present invention has good absorption property and ion-exchange capacity compared with illite raw ore.The modification illite loading nano silvery antibacterial material finally obtained shows good fungistatic effect to staphylococcus aureus and Escherichia coli, and Nano Silver is uniform in illite surface distributed, uniform particle diameter, it can be widely applied to prepare the antimicrobial products such as various coating, plastics and cosmetics, with very wide application prospect.
Description
Technical field
The invention belongs to Chemical Engineering and Technology field, a kind of modified illite loading nano silvery is especially related to antibacterial
Material and preparation method thereof.
Background technology
Illite is as a kind of rich potassium high alumina and the clay mineral of rich reserves, and the processing through different modes is widely used
In plastics, papermaking, cosmetics, rubber, wastewater treatment, the field such as heavy metal adsorption.How it efficiently to be utilized, as in recent years
One of the problem of scholars inquire into.There is nano silver particles very high surface-active, bacteriostasis property and catalytic performance extensively should
For catalysis material, battery electrode material, low temperature Heat Conduction Material, electrocondution slurry, anti-biotic material, medical material.Learn at present
Person is attempted differently by silver ion reduction into Nano Silver, and is combined to prepare anti-biotic material with other materials.But Nano Silver
Still belong to blank with illitic combination, therefore illite is combined with nano silver particles prepare a kind of novel nano anti-biotic material,
By with huge potentiality to be exploited and application value.It is easily dispersed in aqueous using illite, with certain adsorptivity,
On nano-silver loaded to illite, the function that bactericidal virus is urged with seizure will can be formed.But common illite Adsorption For Ag
Ion only relies on the electronegativity of itself, and binding ability is weaker, while easily reuniting during Nano Silver is reduced into, causes
Increase Nano Silver particle diameter, fungistatic effect reduction is unfavorable for carrying the illitic application of silver.
Therefore being needed badly among prior art wants a kind of new technical scheme to solve this problem.
The content of the invention
The technical problems to be solved by the invention are：A kind of modified illite loading nano silvery antibacterial material and its system are provided
Preparation Method, the ammonium-bearing illite of preparation has good absorption property and ion-exchange capacity compared with illite raw ore, for solving
Certainly common illite Adsorption For Ag ion binding capacity is weaker, while easily reuniting during Nano Silver is reduced into, presses down
The technical problems such as bacterium effect reduction.
A kind of modified illite loading nano silvery antibacterial material, is gone back by modified ammonium-bearing illite and silver nitrate solution mixing
Original reaction, is made after the solid powder grinding of acquisition.
A kind of preparation method of modified illite loading nano silvery antibacterial material, comprises the following steps, and following steps
Sequentially carry out：
Step 1: taking illite to add in deionized water, suspension, wherein illite are prepared in stirring in water bath 2h at 40 DEG C
Mass ratio with deionized water is (3~5):(40~50)；
After the static flotation 24h of gained suspension, supernatant liquor is abandoned, products therefrom is placed in multiplex vavuum pump of circulating water type
Middle carry out suction filtration, filtered filter cake is cleaned with deionized water, is dried, and grinding obtains illite powder after flotation；
Illite powder after 15g flotation is taken, 150ml mass fractions is added and mixes 1h for 30% ammoniacal liquor, by gained
Slurries are transferred in reactor, carry out hydrothermal synthesis reaction, and reaction naturally cools to room temperature, the solidliquid mixture of gained after terminating
It is placed in supercentrifuge and centrifuges, the powder after centrifugation is cleaned with deionized water, dry, grinding obtains ammonium-bearing illite powder；
Step 2: the ammonium-bearing illite powder obtained in step one described in 10g and 3g modifying agent polyvinylpyrrolidones are taken, point
It is not scattered in 100ml distilled water, by both in being mixed at 70 DEG C after 1h, is placed in multiplex vavuum pump of circulating water type and carries out
Suction filtration, filtered filter cake is cleaned with deionized water, is dried, grinding, obtains modified ammonium-bearing illite powder；
Step 3: the modification ammonium-bearing illite powder obtained in step 2 described in 5g is added in 20ml silver nitrate solutiones,
The concentration of silver nitrate solution is 0.2mol/L~0.5mol/L, and 1h is stirred at 70 DEG C；Supernatant liquor is abandoned after static 1h, by under
Layer solidliquid mixture be placed in normal pressure microwave chemical reactor, carry out microwave reaction, obtain product be washed with deionized to
Filtrate not silver ion, is placed under uviol lamp, and with 365nm wavelength illumination 48h, grinding obtains modified ammonium-bearing illite loading nano silvery
Antibacterial material.
Flotation products therefrom is placed in multiplex vavuum pump of circulating water type in the step one carry out suction filtration 15min~
25min, filtered filter cake is cleaned 3 times~5 times with deionized water, is placed in air dry oven after drying 12h at 110 DEG C and is ground
Mill, obtains average grain diameter for 1068.3nm, and cumulative particle sizes percentile reaches the flotation that 50% corresponding particle diameter is 877.7nm
Illite powder afterwards；
Hydrothermal Synthesiss reaction temperature is 250 DEG C~300 DEG C in the step one, time of hydrothermal synthesis reaction for 0.5h~
4h, the solidliquid mixture of gained, which is placed in supercentrifuge, to be centrifuged 3 times~5 times, and the powder after centrifugation is cleaned into 3 with deionized water
It is secondary~5 times, it is placed in vacuum drying chamber at 110 DEG C of vacuum to dry and is ground after 12h, obtains average grain diameter for 884.8nm, add up grain
Degree percentile reaches the ammonium-bearing illite powder that 50% corresponding particle diameter is 630.7nm.
Modifying agent in the step 2 is also cystine.
Multiplex vavuum pump of circulating water type suction filtration 15min~25min in the step 2, by filtered filter cake deionization
Water is cleaned 3~5 times, is ground after being put into vacuum drying chamber, 110 DEG C of drying 12h of vacuum, acquisition average grain diameter is 875.7nm, is added up
Size distribution percentage reaches the modification ammonium-bearing illite powder that 50% corresponding particle diameter is 642.7nm；
In the step 3 power of normal pressure microwave chemical reactor be 200W~400W, the microwave reaction time be 5min~
30min。
The average grain diameter of the antibacterial material of modified ammonium-bearing illite loading nano silvery is 850nm~880nm in the step 3,
Cumulative particle sizes percentile reaches that 50% corresponding particle diameter is 640nm~650nm.
By above-mentioned design, the present invention can bring following beneficial effect：
Ammonium-bearing illite prepared by the present invention has good absorption property and ion-exchange capacity compared with illite raw ore.
The modification illite loading nano silvery antibacterial material finally obtained is shown well to staphylococcus aureus and Escherichia coli
Fungistatic effect, and Nano Silver is uniform in illite surface distributed, and uniform particle diameter can be widely applied to prepare various coating, modeling
The antimicrobial product such as material and cosmetics, with very wide application prospect.
Brief description of the drawings
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated：
Fig. 1 is a kind of preparation method schematic flow sheet of modified illite loading nano silvery antibacterial material in the present invention.
Fig. 2 is the XRD of Hydrothermal Synthesiss ammonium-bearing illite in the embodiment of the present invention three.
Fig. 3 is the infrared absorption spectra of Hydrothermal Synthesiss ammonium-bearing illite in the embodiment of the present invention three.
Fig. 4 is the SEM figures of Hydrothermal Synthesiss ammonium-bearing illite in the embodiment of the present invention three.
Fig. 5 is the XRD of modified illite loading nano silvery antibacterial material in the embodiment of the present invention three.
Fig. 6 is the TEM figures of modified illite loading nano silvery antibacterial material in the embodiment of the present invention three.
Fig. 7 is to the bacteriostatic test design sketch of staphylococcus aureus in the embodiment of the present invention three.
Fig. 8 is to the bacteriostatic test design sketch of Escherichia coli in the embodiment of the present invention three.
In figure, a is the X-ray diffraction curve of the former stone of illite, and b is the X-ray diffraction curve of Hydrothermal Synthesiss ammonium-bearing illite,
C is the infrared absorption curve of the former stone of illite, and d is the infrared absorption curve of Hydrothermal Synthesiss ammonium-bearing illite, and e is that modified illite is born
The X-ray diffraction curve of carrying nano silver antibacterial material.
Embodiment
A kind of modified illite loading nano silvery antibacterial material, is gone back by modified ammonium-bearing illite and silver nitrate solution mixing
Original reaction, is placed in uviol lamp natural drying in lower 48 hours, is made after grinding after the solid powder washing of acquisition.
Embodiment one：
A kind of preparation method of modified illite loading nano silvery antibacterial material, comprises the following steps, and following steps
Sequentially carry out：
Step 1: taking illite to add in deionized water, suspension, wherein illite are prepared in stirring in water bath 2h at 40 DEG C
Mass ratio with deionized water is 3:40；
After the static flotation 24h of gained suspension, supernatant liquor is abandoned, products therefrom is placed in the A types of Shanghai Yu Kang SHB- III
Suction filtration 15min is carried out in multiplex vavuum pump of circulating water type, filtered filter cake is cleaned 3 times with deionized water, until illite is former
Impurity in ore deposit is all washed off.Obtained sample is placed in the type electric heating constant temperature forced air dryings of Shanghai new talent DHG-9073BS- III
Dry after 12h and grind at 110 DEG C in case, obtain average grain diameter for 1068.3nm, D (50) is illite after 877.7nm flotation
Powder, wherein D (50) represent that the cumulative particle sizes percentile of a sample reaches particle diameter corresponding when 50%.
The illite powder after 15g flotation is taken, 150ml mass fractions is added and mixes 1h for 30% ammoniacal liquor, by institute
Obtain slurries to be transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, 0.5h is reacted at 250 DEG C, reaction terminates rear natural cooling
To room temperature.The solidliquid mixture of gained is placed in the instrument TG16-WS type table model high speed centrifuges of Hunan Hunan and centrifuged 3 times, after centrifugation
Powder is cleaned 3 times with deionized water, is finally placed in vacuum drying chamber at 110 DEG C to dry and is ground after 12h, obtaining average grain diameter is
884.8nm, D (50) are 630.7nm ammonium-bearing illite powder；
Step 2: taking 10g ammonium-bearing illites powder and 3g polyvinylpyrrolidones (PVP) to be scattered in respectively as modifying agent
In 100ml distilled water, by both in being mixed at 70 DEG C after 1h, the A types circulating water types of Shanghai Yu Kang SHB- III are placed in multi-purpose true
Suction filtration 15min is carried out in empty pump, filtered filter cake is cleaned 3 times with deionized water, and the sample of acquisition is put into vacuum drying chamber, very
Ground after empty 110 DEG C of drying 12h, obtain modified ammonium-bearing illite powder；
Step 3: the modification ammonium-bearing illite powder obtained in step 2 described in 5g is added into 20ml, 0.2mol/L nitre
In sour silver solution, 1h is stirred at 70 DEG C；Supernatant liquor is abandoned after static 1h, sample is placed in into Gongyi gives magnificent MCR-3 types normal pressure
In microwave chemical reactor, 5min is reacted under 200W, product is obtained and is washed with deionized to filtrate not silver ion, finally
It is placed under uviol lamp, with 365nm wavelength illuminations 48h, ground acquisition average grain diameter is 850~880nm, D (50) is 640~
The antibacterial material of 650nm modification ammonium-bearing illite loading nano silvery.
Modifying agent in the step 2 can also be cystine.
Because there is two kinds of modifying agent, PVP is modified ammonium-bearing illite and carries silver, and the average grain diameter for being designated as Ag-P-N is 873.2nm, D
(50) it is 649.3nm.Cystine changes ammonium-bearing illite and carries silver, and the average grain diameter for being designated as Ag-C-N is 857.8nm, and D (50) is
648.3nm。
Embodiment two：
A kind of preparation method of modified illite loading nano silvery antibacterial material, comprises the following steps, and following steps
Sequentially carry out：
Step 1: taking illite to add in deionized water, suspension, wherein illite are prepared in stirring in water bath 2h at 40 DEG C
Mass ratio with deionized water is 5:50；
After the static flotation 24h of gained suspension, supernatant liquor is abandoned, products therefrom is placed in the A types of Shanghai Yu Kang SHB- III
Suction filtration 20min is carried out in multiplex vavuum pump of circulating water type, filtered filter cake is cleaned 5 times with deionized water, until illite is former
Impurity in ore deposit is all washed off.Obtained sample is placed in the type electric heating constant temperature forced air dryings of Shanghai new talent DHG-9073BS- III
Dry after 12h and grind at 110 DEG C in case, obtain average grain diameter for 1068.3nm, D (50) is illite after 877.7nm flotation
Powder, wherein D (50) represent that the cumulative particle sizes percentile of a sample reaches particle diameter corresponding when 50%.
The illite powder after 15g flotation is taken, 150ml mass fractions is added and mixes 1h for 30% ammoniacal liquor, by institute
Obtain slurries to be transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, 4h is reacted at 300 DEG C, reaction is naturally cooled to after terminating
Room temperature.The solidliquid mixture of gained is placed in the instrument TG16-WS type table model high speed centrifuges of Hunan Hunan and centrifuged 4 times, the powder after centrifugation
End is cleaned 5 times with deionized water, is finally placed in vacuum drying chamber at 110 DEG C to dry and is ground after 12h, obtaining average grain diameter is
884.8nm, D (50) are 630.7nm ammonium-bearing illite powder；
It is scattered in respectively in 100ml distilled water Step 2: taking 10g ammonium-bearing illites powder and 3g cystines as modifying agent,
By both in being mixed at 70 DEG C after 1h, it is placed in the A type multiplex vavuum pump of circulating water type of Shanghai Yu Kang SHB- III and carries out suction filtration
20min, filtered filter cake is cleaned 5 times with deionized water, and the sample of acquisition is put into vacuum drying chamber, 110 DEG C of drying 12h of vacuum
After grind, obtain modified ammonium-bearing illite powder；
Step 3: the modification ammonium-bearing illite powder obtained in step 2 described in 5g is added into 20ml, 0.5mol/L nitre
In sour silver solution, 1h is stirred at 70 DEG C；Supernatant liquor is abandoned after static 1h, sample is placed in into Gongyi gives magnificent MCR-3 types normal pressure
In microwave chemical reactor, 30min is reacted under 400W, product is obtained and is washed with deionized to filtrate not silver ion, most
It is placed in eventually under uviol lamp, with 365nm wavelength illuminations 48h, ground acquisition average grain diameter is 850~880nm, D (50) is 640~
The antibacterial material of 650nm modification ammonium-bearing illite loading nano silvery.
Embodiment three：
A kind of preparation method of modified illite loading nano silvery antibacterial material, comprises the following steps, and following steps
Sequentially carry out：
Step 1: taking illite to add in deionized water, suspension, wherein illite are prepared in stirring in water bath 2h at 40 DEG C
Mass ratio with deionized water is 4:45；
After the static flotation 24h of gained suspension, supernatant liquor is abandoned, products therefrom is placed in the A types of Shanghai Yu Kang SHB- III
Suction filtration 25min is carried out in multiplex vavuum pump of circulating water type, filtered filter cake is cleaned 4 times with deionized water, until illite is former
Impurity in ore deposit is all washed off.Obtained sample is placed in the type electric heating constant temperature forced air dryings of Shanghai new talent DHG-9073BS- III
Dry after 12h and grind at 110 DEG C in case, obtain average grain diameter for 1068.3nm, D (50) is illite after 877.7nm flotation
Powder, wherein D (50) represent that the cumulative particle sizes percentile of a sample reaches particle diameter corresponding when 50%.
The illite powder after 15g flotation is taken, 150ml mass fractions is added and mixes 1h for 30% ammoniacal liquor, by institute
Obtain slurries to be transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, 2h is reacted at 280 DEG C, reaction is naturally cooled to after terminating
Room temperature.The solidliquid mixture of gained is placed in the instrument TG16-WS type table model high speed centrifuges of Hunan Hunan and centrifuged 5 times, the powder after centrifugation
End is cleaned 4 times with deionized water, is finally placed in vacuum drying chamber at 110 DEG C to dry and is ground after 12h, obtaining average grain diameter is
884.8nm, D (50) are 630.7nm ammonium-bearing illite powder；
Step 2: taking 10g ammonium-bearing illites powder and 3g polyvinylpyrrolidones (PVP) to be scattered in respectively as modifying agent
In 100ml distilled water, by both in being mixed at 70 DEG C after 1h, the A types circulating water types of Shanghai Yu Kang SHB- III are placed in multi-purpose true
Suction filtration 25min is carried out in empty pump, filtered filter cake is cleaned 5 times with deionized water, and the sample of acquisition is put into vacuum drying chamber, very
Ground after empty 110 DEG C of drying 12h, obtain modified ammonium-bearing illite powder；
Step 3: the modification ammonium-bearing illite powder obtained in step 2 described in 5g is added into 20ml, 0.4mol/L nitre
In sour silver solution, 1h is stirred at 70 DEG C；Supernatant liquor is abandoned after static 1h, sample is placed in into Gongyi gives magnificent MCR-3 types normal pressure
In microwave chemical reactor, 10min is reacted under 300W, product is obtained and is washed with deionized to filtrate not silver ion, most
It is placed in eventually under uviol lamp, with 365nm wavelength illuminations 48h, ground acquisition average grain diameter is 850~880nm, D (50) is 640~
The antibacterial material of 650nm modification ammonium-bearing illite loading nano silvery.
Antibacterial material to acquisition is characterized and bacteriostasis property test：
The electronegativity of itself is only relied on during common illite absorption silver ion, binding ability is weaker, and silver carrying amount is low.
Easily reunite during Nano Silver is reduced into simultaneously, cause Nano Silver particle diameter to increase, fungistatic effect reduction is unfavorable for
Carry the illitic application of silver.Therefore, illitic silver carrying amount is largely controlled by illitic adsorptivity and ion exchange energy
Power.Test result indicates that common illitic silver carrying amount is only 2.09%, to Escherichia coli and staphylococcus aureus substantially without
Fungistatic effect.Rational method is used simultaneously, and it is also to prepare modified illite that silver ion uniformly, is thoroughly reduced into Nano Silver
One key factor of loading nano silvery antibacterial material.
Carry out hydro-thermal reaction in a kettle. to synthesize ammonium-bearing illite, purpose after in an experiment mixing illite and ammoniacal liquor
It is the illitic absorption property of enhancing and ion-exchange capacity.Ammonium-bearing illite is modified by adding cystine, makes Erie
Stone is no longer single itself adsorptivity of dependence for the absorption of silver ion, also chemical coordination, improves silver ion in illite
The load capacity on surface.Silver ion is uniformly finally reduced into by Nano Silver using microwave radiation technology and the method for ultraviolet reduction.
Illite is the silicate mineral of monoclinic system, and crystal structure is similar to muscovite, belongs to the type construction unit layers of 2 ﹕ 1
Dioctahedron type.Corresponding PDF cards are No:In 2 θ it is respectively at 8.83 ° 17.65 ° and 45.18 ° in 26-0911, Fig. 2
Have three obvious diffraction maximums, diffraction maximum position is consistent with data on PDF cards, corresponding crystal face is [002], [004] and
[006].Compared simultaneously with former state it should be apparent that in the XRD spectrum of ammonium-bearing illite except diffraction maximum power not
With outside, diffraction maximum angle there occurs different degrees of skew to low-angle.According to Bragg equation 2dsin θ=n λ, its
In, d is interplanar distance, and θ is the angle between incident beam and reflecting surface, and n is diffraction progression, and λ is the wavelength of X-ray.Equation is right
Side is constant, and when θ changes are small, interplanar distance d becomes big.Understand, interatomic bond length, bond angle and bond energy of ammonium-bearing illite etc. become
Change, cause lattice structure constantly to adjust, deform, interlamellar spacing becomes big.
The isomorphous replacement of aliovalent class matter, i.e. high-valence cationic in structure cell are widely present in illite lattice can be by a low price
Cation replacement, causes charge imbalance, forms interlayer negative electrical charge, produces electrical potential difference.At this moment the chemical bond in illite crystal layer is more
It is partial to ionic bond, illite structure cell turns into one " big anion ", keeps electricity price to balance by Electrostatic Absorption low price cation,
Therefore with certain ion-exchange capacity and absorption property.Illite raw ore and ammonium-bearing illite exist as seen in Figure 3
1033cm-1And 775cm-1There is absworption peak in place, and this is respectively belonging to Si-O and Al-O stretching vibration peak, and ammonium-bearing illite exists
3330cm-1、3064cm-1、2864cm-1And 1417cm-1There is NH4+ characteristic absorption peak in place, shows NH4 in hydrothermal reaction process
+ entered in illitic interlayer.And NH4+Compared with H+、K+、Na+And Li+There is stronger exchange capacity Deng comparing, can be more preferable
The Si displaced in illite dioctahedron4+、Al3+And Ca2+Deng high-valence cationic.Particularly Ca2+With the knot of illite lattice
Conjunction ability is weaker, and aquation can be low, so being easier to be replaced away.This causes the ammonium-bearing illite of synthesis that there is stronger ion to hand over
Transducing power and absorption property.
Illite be as former state it is a kind of in pile up formula into crystal type, Close stack and spacing is narrow and small between lamella, therefore limit
Illitic ion-exchange capacity and absorption property are made.From the SEM figures of Fig. 4 ammonium-bearing illites it is observed that ammonium-bearing illite layer
Become big with the distance between layer, this rule offset with diffraction maximum position in Fig. 2 to low-angle matches.And ammonium-bearing illite table
Face there occurs warpage, and structure is more loose, and overall structure is more three-dimensional, in the similar petal-like structure of one kind.BET test results
It has been shown that, the specific surface area of former state is 5m2/ g, the specific surface area of synthesis ammonium-bearing illite reaches 20m2/ g, is 4 times of former state.
From Fig. 5 be modified illite loading nano silvery antibacterial material XRD in as can be seen that the θ of the angle of diffraction 2 38.34 °,
Occur 4 characteristic diffraction peaks at 44.22 °, 64.42 °, 77.38 ° respectively.Each peak value blocks with the accurate PDF (No 87-0597) of silver label
Upper data are consistent, and the diffraction of cubic system elemental silver [111], [200], [220] and [311] crystal face is correspond to respectively.Illustrate micro-
Nano Silver prepared by ripple auxiliary, ultraviolet reduction is the nano silver particles with face-centred cubic structure.Simultaneously in figure each diffraction maximum compared with
To be sharp, half-breadth height is small, and baseline is relatively steady in collection of illustrative plates, shows that the Nano Silver crystal property of load is good.And in XRD spectrum
In have no Ag2O characteristic diffraction peak, it is seen that silver ion reduction is more thorough into Nano Silver under this experiment condition.
The silver carrying amount of sample is tested by inductively coupled plasma (ICP), modified illite loading nano silvery suppression
The silver carrying amount of bacterium material is 27.66%, is greatly improved compared with the silver carrying amount (2.09%) of illite raw ore.On the one hand
It is that absorption property is significantly improved, therefore, it is possible to adsorb more silver because the specific surface area of the ammonium-bearing illite of Hydrothermal Synthesiss becomes big
Ion.On the other hand it is because according to Pearson hsab theory, the sulfur-containing group in cystine molecule belongs to soft base
Easily with the silver-colored coordination for belonging to soft acid, formed compared with strong bond knot so that modified illite is to the absorption of Nano Silver not merely by certainly
The adsorptivity of body also has chemical coordination.Therefore the modification illite loading nano silvery antibacterial material that prepared by the present invention has higher
Silver carrying amount.From the TEM it can be seen from the figure thats of Fig. 6 antibacterial materials, the nano-Ag particles of modified illite load are presented spherical substantially,
Particle size between 5nm~30nm, and illite surface distribution than more uniform, illustrate by uv light irradiation come also
Former Nano Silver process is gentleer, will not quickly form substantial amounts of nano-Ag particles, therefore is less likely to occur to reunite.What is obtained receives
Rice silver granuel footpath is more homogeneous, modified illite surface distribution also evenly.
Antibacterial material to preparation carries out Bactericidal test, chooses Escherichia coli and staphylococcus aureus is used as gram
The representative of negative bacterium and gram-positive bacteria.It can be seen that modification illite load nanometer prepared by the present invention from Fig. 7 and Fig. 8
Silver-colored antibacterial material shows good bacteriostasis property to both bacteriums, to the antibacterial of staphylococcus aureus and Escherichia coli
Size respectively reaches 5.68mm and 6.84mm.Because the nano-Ag particles loaded in one side illite can destroy bacterium
Cell membrane, cause seepage and the loss of intracellular organic matter, make DNA can not be randomly dispersed in the core area of cell in concentration anxiety
State, it is impossible to effectively replicated.So as to cause DNA degraded, the death of organism, it is suppressed that the growth and breeding of bacterium.Separately
One side nano silver particles discharge micro silver ion and can be combined with the thin base of the zymoprotein in bacterium, reduce bioactivity
The activity of enzyme, while the oxygen in air or water can be activated, produces active oxygen ion, is aoxidized with bacterium and gas chromatography
Reaction, causes the phosphodiester bond between the base in DNA to be broken, and destroys microbial cell DNA replication dna, plays multiple inhibiting
Or kill the effect of bacterium.Hence in so that this novel nano anti-biotic material shows good bacteriostasis property, various coating,
There is very wide application prospect in the preparation of the antimicrobial product such as plastics and cosmetics.
Claims (8)
1. a kind of modified illite loading nano silvery antibacterial material, it is characterized in that：Mixed by modified ammonium-bearing illite and silver nitrate solution
Close and carry out reduction reaction, be made after the solid powder grinding of acquisition.
2. a kind of preparation method of modified illite loading nano silvery antibacterial material, it is characterized in that：Comprise the following steps, and with
Lower step is sequentially carried out,
Step 1: taking illite to add in deionized water, suspension is prepared in stirring in water bath 2h at 40 DEG C, wherein illite is with going
The mass ratio of ionized water is (3~5):(40~50)；
After the static flotation 24h of gained suspension, supernatant liquor is abandoned, products therefrom is placed in multiplex vavuum pump of circulating water type
Row suction filtration, filtered filter cake is cleaned with deionized water, is dried, and grinding obtains illite powder after flotation；
Illite powder after 15g flotation is taken, 150ml mass fractions is added and mixes 1h for 30% ammoniacal liquor, by gained slurries
It is transferred in reactor, carries out hydrothermal synthesis reaction, reaction naturally cools to room temperature after terminating, and the solidliquid mixture of gained is placed in
Centrifuged in supercentrifuge, the powder after centrifugation is cleaned with deionized water, dried, grinding obtains ammonium-bearing illite powder；
Step 2: taking the ammonium-bearing illite powder obtained in step one described in 10g and 3g modifying agent polyvinylpyrrolidones, divide respectively
Dissipate in 100ml distilled water, by both in being mixed at 70 DEG C after 1h, be placed in multiplex vavuum pump of circulating water type and taken out
Filter, filtered filter cake is cleaned with deionized water, is dried, grinding, obtains modified ammonium-bearing illite powder；
Step 3: the modification ammonium-bearing illite powder obtained in step 2 described in 5g is added in 20ml silver nitrate solutiones, nitric acid
The concentration of silver-colored solution is 0.2mol/L~0.5mol/L, and 1h is stirred at 70 DEG C；Supernatant liquor is abandoned after static 1h, by lower floor
Solidliquid mixture is placed in normal pressure microwave chemical reactor, is carried out microwave reaction, is obtained product and be washed with deionized to filtrate
Silver ion, is not placed under uviol lamp, and with 365nm wavelength illumination 48h, grinding obtains the suppression of modified ammonium-bearing illite loading nano silvery
Bacterium material.
3. a kind of preparation method of modified illite loading nano silvery antibacterial material according to claim 2, it is characterized in that：
Flotation products therefrom is placed in multiplex vavuum pump of circulating water type in the step one and carries out suction filtration 15min~25min, by suction filtration
Filter cake afterwards is cleaned 3 times~5 times with deionized water, is placed in air dry oven at 110 DEG C to dry and is ground after 12h, is averaged
Particle diameter is 1068.3nm, and cumulative particle sizes percentile reaches illite powder after the flotation that 50% corresponding particle diameter is 877.7nm
End.
4. a kind of preparation method of modified illite loading nano silvery antibacterial material according to claim 2, it is characterized in that：
Hydrothermal Synthesiss reaction temperature is 250 DEG C~300 DEG C in the step one, and the time of hydrothermal synthesis reaction is 0.5h~4h, gained
Solidliquid mixture be placed in supercentrifuge centrifuge 3 times~5 times, the powder after centrifugation is cleaned 3 times~5 with deionized water
It is secondary, it is placed in vacuum drying chamber at 110 DEG C of vacuum to dry and is ground after 12h, obtains average grain diameter for 884.8nm, cumulative particle sizes point
Cloth percentage reaches the ammonium-bearing illite powder that 50% corresponding particle diameter is 630.7nm.
5. a kind of preparation method of modified illite loading nano silvery antibacterial material according to claim 2, it is characterized in that：
Modifying agent in the step 2 is also cystine.
6. a kind of preparation method of modified illite loading nano silvery antibacterial material according to claim 2, it is characterized in that：
Multiplex vavuum pump of circulating water type suction filtration 15min~25min in the step 2,3 are cleaned by filtered filter cake with deionized water
~5 times, ground after being put into vacuum drying chamber, 110 DEG C of drying 12h of vacuum, acquisition average grain diameter is 875.7nm, cumulative particle sizes point
Cloth percentage reaches the modification ammonium-bearing illite powder that 50% corresponding particle diameter is 642.7nm.
7. a kind of preparation method of modified illite loading nano silvery antibacterial material according to claim 2, it is characterized in that：
The power of normal pressure microwave chemical reactor is 200W~400W in the step 3, and the microwave reaction time is 5min~30min.
8. a kind of preparation method of modified illite loading nano silvery antibacterial material according to claim 2, it is characterized in that：
The average grain diameter of the antibacterial material of modified ammonium-bearing illite loading nano silvery is 850nm~880nm, cumulative particle sizes in the step 3
Percentile reaches that 50% corresponding particle diameter is 640nm~650nm.
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