CN110214790A - A kind of magnetic bamboo charcoal/nanometer silver/titanium dioxide compound disinfectant and its preparation method and application - Google Patents
A kind of magnetic bamboo charcoal/nanometer silver/titanium dioxide compound disinfectant and its preparation method and application Download PDFInfo
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- CN110214790A CN110214790A CN201811025694.9A CN201811025694A CN110214790A CN 110214790 A CN110214790 A CN 110214790A CN 201811025694 A CN201811025694 A CN 201811025694A CN 110214790 A CN110214790 A CN 110214790A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
Abstract
The invention discloses a kind of magnetic bamboo charcoal/nanometer silver/titanium dioxide compound disinfectants and its preparation method and application, with bamboo charcoal, Fe3O4、AgNO3, butyl titanate etc. for raw material magnetic bamboo charcoal/nano silver and magnetic bamboo charcoal/nano silver/TiO are prepared for using coprecipitation method, sol-gel method, reduction method and self-assembly method2Compound disinfectant.The compound disinfectant easily recycles, characteristic with broad-spectrum sterilization, it is best to the fungistatic effect of Escherichia coli, can in the dark, the occasions sterilization such as visible light and ultraviolet light, sterilization effect is best under ultraviolet light, and the compound disinfectant shows significantly to act synergistically, can not only high-efficiency antimicrobial, and fungicide dosage can be reduced, realize the effect of save the cost.
Description
Technical field
The invention belongs to inorganic antiseptic fields, and in particular to a kind of magnetic bamboo charcoal/nanometer silver/titanium dioxide composite bactericidal
Agent and its preparation method and application.
Background technique
Since 21st century, as the development of society and people's lives level improve, people are to environmental condition
More stringent requirements are proposed with hygiene and health.Bacterium especially those many can be caused to the harmful one kind such as human body and animal
Major disease, their own have very big fertility, constantly encroach on the normal life of people, the health of people by
It seriously threatens.1998, shown by the statistics that the World Health Organization (World Healthy Ogzation, WHO) is issued
During in 1,995 one years, the whole world because bacterium infection death the total death toll of number Zhan 33%, and this ratio
There is upward increased trend every year, so it is urgent for inhibiting the growth and breeding of bacterium for the generation of this kind of disease of prevention and control
In the eyebrows and eyelashes.
The major function of anti-biotic material is exactly the growth and breeding for inhibiting or killing harmful bacteria, can be by host material not
Together, organic antibacterial agent and inorganic antiseptic two types are roughly divided into.Organic antibacterial agent sterilization speed is fast, anti-microbial property is good, but
The disadvantages of being short service life, poor heat resistance, easy decomposition, limits it and is widely used in all various aspects.Inorganic antiseptic price compared with
Height, but inorganic antiseptic with high security, heat-resisting, excellent durability, duration are strong and have the spies such as broad spectrum antibacterial
Point, these excellent features are widely used it.Titanium system, which can be divided into, by the effective component difference of antibacterial agent (has light
The TiO of catalytic action2Deng) and silver system (contain Ag+, Cu+, Zn+Equal metal ions) antibacterial agent.
Nano-titanium dioxide (TiO2) it is a kind of photocatalysis antibacterial agent, catalyst is only used as during antibacterial, theoretically
It does not consume, can permanently use.Nano-TiO2By Premeabilisation of cells effect, coacetylase destruction, it is endotoxic degradation, protein and
The denaturation decomposition and cellular oxidation of lipid are at CO2Etc. mechanism play a role, nano-TiO2Hydroxyl radical free radical is generated under illumination condition
And elemental oxygen, hydroxyl radical free radical have strong oxidizing property, are by various organic matters (including in harmful microbial body) oxygenolysis
CO2And H2O, to play antibacterial action.Silver-series antibacterial agent has large specific surface area, surface reaction activity height, Active sites
The performances such as more, high catalytic efficiency, adsorption capacity be strong.As inorganic Ag-carried antibacterial material in terms of functionality have duration,
The features such as persistence and broad spectrum activity, and have simultaneously it is heat-resist, highly-safe, be not likely to produce the advantages such as drug resistance.Nano silver
Can be formed in conjunction with germ DNA base it is cross-linked, replace it is fast cry of certain animals and pyrimidine in adjacent nitrogen key, replicate DNA can not, so that carefully
Bacterium is dead；Or in conjunction with the (- SH) group such as the intracorporal sulfydryl such as bacterium, the sulfydryl on protease is combined, protease is lost
It is devitalized, lead to bacterial death.Inorganic antiseptic passes through the antibacterial high efficiency of antimicrobial component, broad spectrum activity is intrinsic with inorganic material
Stability combine, compensate for the short slab and deficiency of organic antibacterial agent.
But in practical applications, nano silver and nano-TiO2That there are particles is small, adsorptivity is poor, be easy to reunite, there is recycling
Difficult problem, current developed carrier mainly have porous ore, glass, active carbon etc., these support materials exist mostly
Higher cost, the inefficient, defect made a low multiple use.
Summary of the invention
It is an object of the invention to provide a kind of magnetic bamboo charcoal/nano silver/dioxy in place of overcome the deficiencies in the prior art
Change titanium compound disinfectant and its preparation method and application, by nano silver, nano-TiO2It loads on magnetic bamboo charcoal simultaneously, performance is received
Meter Yin and nano-TiO2The effect of Synergistic antimicrobial, the compound disinfectant are easy to Magneto separate recycling, and the characteristic with broad-spectrum sterilization is right
The fungistatic effect of Escherichia coli is best, can in the dark, the occasions sterilization such as visible light and ultraviolet light, sterilization effect is most under ultraviolet light
It is good, can not only high-efficiency antimicrobial, and fungicide dosage can be reduced, realize the effect of save the cost, have broad application prospects.
The technical solution adopted by the present invention to solve the technical problems first is that:
A kind of preparation method of magnetic bamboo charcoal/nanometer silver/titanium dioxide compound disinfectant, comprising:
1) by the Fe of 0.05~0.15mol/L2+The Fe of solution and 0.15~0.25mol/L3+Solution is stirred at 45~55 DEG C
It mixes uniformly；Then under stiring thereto be added dropwise 1.5~2.5mol/L NaOH solution, until solution ph be 10.8~
11.2；At 75~85 DEG C, the sodium citrate solution of 0.05~0.15mol/L is added dropwise thereto, continues 0.5~1.5h of stirring, i.e.,
Obtain Fe3O4Suspension；It is separated by solid-liquid separation, washs, it is dry, obtain Fe3O4；According to the ratio of mass ratio 1:3~5, to Fe3O4Middle investment
Bamboo charcoal stirs 0.5~1.5h；2000~4000r/min is centrifuged 10~20min, the bamboo charcoal washing after centrifugation, 65~75 DEG C of dryings
4~6h is ground up, sieved, and magnet sorting obtains magnetic bamboo charcoal；
2) butyl titanate is mixed at 25~35 DEG C with dehydrated alcohol, after 500~700rpm stirs 25~35min, is added
Glacial acetic acid continues 25~35min of stirring；Separately take HNO3、C2H5OH and water mix, and mixed liquor are obtained, with 1min at 25~35 DEG C
The speed of 25~35 drops instills the mixed liquor to the mixture of 900~1100rpm butyl titanate that stirred and dehydrated alcohol
In system, after being stirred to react 1.5~2.5h, 2~4d, 95~105 DEG C of dry 1~3h, 250~350 DEG C of heat treatments 25 are spontaneously dried
It is warming up to 500~600 DEG C after~35min and keeps the temperature 1.5~2.5h and grinds in air after taking out cooling, obtains nano-TiO2
Powder；
3) 125~135 DEG C are warming up in stirring, under counterflow condition, polyvinylpyrrolidone is dissolved in ethylene glycol, then
AgNO is added3, 0.5~1.5h of insulation reaction obtains nano silver colloidal sol；Nano silver colloidal sol acetone, dehydrated alcohol wash, 45~
55 DEG C of dry 5~7h, obtain nano-Ag particles；
4) nano-TiO prepared by step 2) is added in the nano-Ag particles prepared to step 3)2Powder, 45~55 DEG C of stirrings
25~35min is reacted, the magnetic bamboo charcoal of step 1) preparation is added, is warming up to 75~85 DEG C, continues to be stirred to react 1~3h, it will
Obtained solution is separated by solid-liquid separation, and 75~85 DEG C of dry 3~5h are to get the magnetic bamboo charcoal/nano silver/TiO2Compound disinfectant.
In one embodiment: in the step 1), bamboo charcoal wash it is not muddy to supernatant, in 90~110 DEG C of dryings after washing
At least 10h is crushed, and is crossed 200 meshes, is then put into the Fe again3O4In.
In one embodiment: in the step 2), butyl titanate, dehydrated alcohol, glacial acetic acid, HNO3、C2H5The volume of OH and water
Than for 15~16:14.5~15.5:1~2:0.5~1.5:7~8:4~5.
In one embodiment: in the step 3), polyvinylpyrrolidone and AgNO3Mass ratio be 5~7:1.
In one embodiment: in the step 4), nano-Ag particles, nano-TiO2The mass ratio of powder and magnetic bamboo charcoal is 1:
9~11:18~22.
The technical solution adopted by the present invention to solve the technical problems second is that:
A kind of magnetic bamboo charcoal according to prepared by above-mentioned preparation method/nanometer silver/titanium dioxide compound disinfectant.
The technical solution adopted by the present invention to solve the technical problems third is that:
Above-mentioned magnetic bamboo charcoal/application of the nanometer silver/titanium dioxide compound disinfectant as fungicide.
In one embodiment: the bacterium bag includes Gram-negative bacteria, gram-positive bacteria, lower fungus, higher fungus, yeast
Bacterium.
In one embodiment: the bacterium bag includes Escherichia coli Escherichia coli, proteus vulgaris Proteus
Vulgaris, bacillus subtilis Bacillus subtilis, staphylococcus aureus Staphylococcus aureus, rice
Head mold Mucor sp., aspergillus niger Aspergillus niger, Penicillium citrinum Penicillium sp., saccharomyces cerevisiae
Saccharomyces cerevisiae。
The technical program compared with the background art, it has the following advantages:
The method comprises the steps of firstly, preparing magnetic Fes out3O4, tax magnetic is carried out to bamboo charcoal, it is then more using sol-gel method and liquid phase again
First alcohol reduction method prepares nano-TiO respectively2Powder and nano-Ag particles, finally by self-assembly method prepare magnetic bamboo charcoal/
Nano silver/TiO2Compound disinfectant.Nano-TiO2With photocatalysis antibacterial effect, and silver and silver ion also have stronger sterilization
Effect, two kinds of antibacterial agents are in the defect for being applied alone Shi Douyou certain, and one side silver-series antibacterial agent is in slow release silver ion, silver content
Do not cause toxicity damage to human body and can reach antibacterial purpose etc. is more difficult to control.Another aspect TiO2It can only be in ultraviolet light
Photocatalysis antibacterial could be generated according to lower, and light utilization efficiency is very low, the small part light source of UV light region can only be utilized.The present invention
By nano silver, nano-TiO2It loads on magnetic bamboo charcoal simultaneously, the defect and deficiency of both sides each other can be made up, it is anti-to play collaboration
The effect of bacterium.Meanwhile bamboo charcoal is a kind of porous plastid, specific area is up to 300m2/ g or more, also have fabulous adsorption-decomposition function,
The characteristics such as hygroscopic desiccation, deodorizing antibiotic, utilize magnetic Fe3O4Particle carries out after tax magnetic loading nano silvery, nanometer again to bamboo charcoal
TiO2, the fungicide of acquisition can be recycled by magnetic separation partition method, so that material recovery becomes simple and fast, be had more
Add wide application prospect.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is magnetic ferroferric oxide FT-IR map.
Fig. 2 is nanometer Fe3O4XRD diffracting spectrum.
Fig. 3 is magnetic ferroferric oxide, bamboo charcoal, magnetic bamboo charcoal FT-IR map (a- magnetic bamboo charcoal, b- bamboo charcoal, c- magnetism four
Fe 3 O).
Fig. 4 is bamboo charcoal, magnetic ferroferric oxide, (a- magnetic bamboo charcoal, b- magnetism four aoxidize magnetic bamboo charcoal XRD comparison map
Three-iron, c- are ground up, sieved bamboo charcoal).
Fig. 5 is nano-TiO2FT-IR map.
Fig. 6 is nano-TiO2XRD diffracting spectrum.
Fig. 7 attaches most importance to the ultra-violet absorption spectrum of nano silver that retrial is tested (a, b, c, d respectively represent four repetitions and test).
Fig. 8 is using PVP as protective agent, and reduction of ethylene glycol silver nitrate prepares the FT-IR spectrogram of nano silver.
Fig. 9 is nano-TiO2XRD diffracting spectrum.
Figure 10 is FT-IR spectrum (a- magnetic bamboo charcoal/nano silver, the b- magnetic bamboo charcoal/nanometer of three kinds of different fungicide
TiO2, c- magnetic bamboo charcoal/nano silver/TiO2)。
Figure 11 is XRD diffracting spectrum (the a- magnetic bamboo charcoal/nano silver/TiO of three kinds of different fungicide2, b- magnetic bamboo charcoal/
Nano-TiO2, c- magnetic bamboo charcoal/nano silver).
Figure 12 is compound disinfectant recovering effect schematic diagram in air.
Figure 13 is compound disinfectant recovering effect schematic diagram in water.
Figure 14 is nano silver to Escherichia coli killing effect (a, b- nano silver；C, d- magnetic bamboo charcoal).
Figure 15 is magnetic bamboo charcoal/nano silver to Escherichia coli killing effect (a, b- magnetic bamboo charcoal/nano silver；C, d- are magnetic
Bamboo charcoal).
Figure 16 is nano-TiO2To Escherichia coli killing effect (a, b- nano-TiO2；C, d- magnetic bamboo charcoal).
Figure 17 is magnetic bamboo charcoal/nano-TiO2To Escherichia coli killing effect (a, b- magnetic bamboo charcoal/nano-TiO2；C, d- magnetic
Property bamboo charcoal).
Figure 18 is magnetic bamboo charcoal/nano silver/TiO2To Escherichia coli killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO2；
C, d- magnetic bamboo charcoal).
Figure 19 is compound disinfectant to Escherichia coli killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO2；C- magnetic bamboo
Charcoal).
Figure 20 is killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO of the compound disinfectant to proteus vulgaris2；C,
D- magnetic bamboo charcoal).
Figure 21 is compound disinfectant to bacillus subtilis killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO2；C, d-
Magnetic bamboo charcoal).
Figure 22 is killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO of the compound disinfectant to staphylococcus aureus2；
C, d- magnetic bamboo charcoal).
Figure 23 is killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO of the compound disinfectant to saccharomycete2；C, d- are magnetic
Bamboo charcoal).
Figure 24 is killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO of the compound disinfectant to aspergillus niger2；C, d- are magnetic
Bamboo charcoal).
Figure 25 is killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO of the compound disinfectant to Rhizopus oryzae2；C, d- are magnetic
Bamboo charcoal).
Figure 26 is killing effect (a, b- magnetic bamboo charcoal/nano silver/TiO of the compound disinfectant to Penicillium citrinum2；C, d- are magnetic
Bamboo charcoal).
Figure 27 is that (a- is dark, b- visible light, and c- is incandescent to Escherichia coli killing effect for compound disinfectant under different light sources
Lamp, d- ultraviolet light).
Specific embodiment
The contents of the present invention are illustrated below by embodiment:
Embodiment
1) one, 500mL beaker is taken, weighs 8.34g FeSO respectively4·7H2O and 16.22g FeCl3·6H2O is dissolved in
In 300mL deionized water, it is configured to the Fe of 0.1mol/L2+With the Fe of 0.2mol/L3+Solution, while weighing 40g NaOH preparation
The NaOH solution 500mL of 2.0mol/L, spare tune pH value weigh the lemon that 1.4705g sodium citrate prepares 50mL 0.1mol/L
Acid sodium solution.The FeSO that will be prepared4Solution and FeCl3Solution is transferred in 500mL flask, is put into and is warming up to 50 DEG C in advance
Thermostat water bath in, with accurate reinforcement electric mixer with 1000rpm revolving speed stir 30min, at the same time, open heat collecting type
Constant temperature blender with magnetic force, setting temperature are 80 DEG C, and stirring while is slowly added dropwise the NaOH solution of 2.0mol/L, solution colour from
Brown color becomes sepia, finally becomes black completely, shows that for alkalinity, it is molten to then proceed to dropwise addition NaOH for solution ph at this time
Liquid, until solution ph becomes 11.Flask is transferred in 80 DEG C of constant temperature blender with magnetic force, is put into rotor, is added few drops
The sodium citrate solution of 0.1mol/L continues to stir 1h to get the Fe of black3O4Suspension sample.By Fe obtained3O4It is suspended
Liquid is stood, and natural subsidence discards supernatant liquid, is repeatedly washed with deionized, measured until alkalescent with wide pH value test paper.It takes out
It is put into 70 DEG C of electric drying oven with forced convection after filter until being dried to loose powder, the nano ferriferrous oxide of preparation is carried out
X-ray diffractometer (XRD) and fourier transform infrared spectroscopy analyzer (FT-IR) phenetic analysis.
Fe2+And Fe3+ Fe is prepared under alkaline condition3O4Reaction principle are as follows:
Fe2++2Fe3++8OH-→Fe3O4+4H2O
The nanometer Fe prepared according to the method described above3O4, theoretical yield 6.96g, according to mass ratio 1:4's after the completion of preparation
Relationship is to Fe3O427.84g bamboo charcoal is put into suspension, quickly stirs 1h with electric mixer.3000r/min is centrifuged 15min, from
Bamboo charcoal after the heart is repeatedly washed with deionized water, to remove SO4 2-And Cl-, then 70 DEG C of dryings in electric drying oven with forced convection
5h is ground up, sieved, and is sub-elected with magnet by the bamboo charcoal of tax magnetic to get magnetic bamboo charcoal carrier.
2) constant temperature blender with magnetic force is opened, setting temperature is 30 DEG C, with pipette accurate measuring 15.5mL metatitanic acid fourth first
Transesterify continues to measure 15.1mL dehydrated alcohol in flask, is put into constant temperature blender with magnetic force into 100mL single-necked flask,
It is fixed with iron stand, 600rpm stirs the stabilizer glacial acetic acid of accurate measuring 1.5mL after 30min, continues to stir 30min；It is stirring
Accurate measuring 0.9mL HNO while mixing3、7.6mL C2H5The deionized water of OH and 4.0mL vibrates back and forth in separatory funnel
It mixes；The revolving speed of magnetic stirring apparatus is increased to 1000rpm, temperature continues to remain 30 DEG C, and the speed dripped with 1min 30 will divide
Mixed liquor in liquid funnel instills in flask, after being stirred to react 2h, observes flask edge solution, discovery just stops when having colloidal sol formation
It only stirs, spontaneously dries 3d, 100 DEG C of dry 2h at room temperature, turn yellow the xerogel crystal with black mixing, grinding becomes brilliant
Body powder is put into and is warming up to 550 DEG C after the heat treatment of 300 DEG C of 30min of progress in Muffle furnace and keeps the temperature 2h, is after taking out cooling
Pale yellow powder, grinding contact a period of time with air up to white nano-TiO2Powder.By the nano-TiO of preparation2Powder carries out
XRD and FT-IR characterization.
3) it measures 7.5mL ethylene glycol to be placed in the three-necked flask of clean dried, be condensed back, under conditions of magnetic agitation,
It is added 0.750g polyvinylpyrrolidone (PVP), until being completely dissolved, is increased to 130 DEG C to temperature, adds 0.125g
AgNO3, solution colour slowly turns yellow from colourless, and insulation reaction 1h obtains nano silver colloidal sol.It is pipetted with 0.1mL pipette
4.95mL dehydrated alcohol is added in the product 0.05mL of preparation, and oscillation shakes up, then with 1mL pipette from diluting 100 just now
1mL is measured in solution again, 4mL dehydrated alcohol is added, obtains the product solution of 500 times of dilution, until solution dilution becomes light
Yellow, it is clear and transparent, until spectrophotometer measurement being used.It is reference liquid with dehydrated alcohol, is carried out with ultraviolet specrophotometer
Spectrum analysis.
By the nano silver colloidal sol of preparation, acetone washing is first used, 12000r/min is centrifuged 15min until supernatant is transparent,
Supernatant is removed, directly adds acetone into centrifuge tube, with glass bar stirring and dissolving, continuation is centrifuged according to above-mentioned condition, connects down
It is washed twice with same method with dehydrated alcohol, the nano-Ag particles medication spoon of centrifuge tube bottom precipitation is gently plucked out,
It is transferred in beaker, with a small amount of dehydrated alcohol washing centrifuge tube, remaining nano-Ag particles is dissolved in dehydrated alcohol, then
Be transferred in beaker together, product is ground up, sieved, nano-Ag particles is made by 50 DEG C of vacuum drying 6h, then carry out FT-IR and
XRD characterization.
4)AgNO3It is reduced into nano silver, it is assumed that AgNO3It is completely reduced into nano silver, calculating theoretical resulting yield is
0.079g also known as takes 0.75g nano-TiO according to the relation that mass ratio is 1:10:202Powder and 1.50g magnetic bamboo charcoal.It will system
Standby nano-Ag particles pour into 250mL flask, and nano-TiO is added2Powder is warming up to 50 DEG C, is stirred to react 30min, then plus
Enter magnetic bamboo charcoal, be warming up to 80 DEG C, continue to be stirred to react 2h, obtained solution is depressurized and is filtered, 80 DEG C of dry 4h, grinding obtains
Magnetic bamboo charcoal/nano silver/TiO2Compound disinfectant.
The present invention is further illustrated below in conjunction with experimental example:
Material to be tested:
It is bamboo charcoal, potato (commercially available), Oxford cup (8 × 6 × 10mm), Escherichia coli (Escherichia coli), common
Proteus (Proteus vulgaris), bacillus subtilis (Bacillus subtilis), staphylococcus aureus
(Staphylococcus aureus), aspergillus niger (Aspergillus niger), Penicillium citrinum (Penicillium sp.), rice
Head mold (Mucor sp.), saccharomyces cerevisiae (Saccharomyces cerevisiae).
1 phenetic analysis of experimental example
The XRD-6100X x ray diffractometer x produced using Shimadzu, Japan, sample test target are Cu target, graphite list
Color device, CuK alpha ray, λ=0.15418nm, power 2.0kW, work press 40.0kV, operating current 30.0mA, scanning angle
Range is 10 °~80 °, and sampling interval is 0.0200 (deg), and sweep speed is 4 °/min.
Fourier transform infrared spectroscopy analyzer (TENSOR-27, German Bruker company), analyzes the infrared signature of product.
2550 ultraviolet-uisible spectrophotometer of UV (Shimadzu, Japan).Sample after taking a certain amount of 500 times of dilution
Solution is placed in quartz colorimetric utensil (1cm light path), setting wavelength be 800nm~200nm, be put into after baseline correction reference liquid without
Water-ethanol, prepare liquid start to measure after automatic zero set, characterize the resonance absorbing peak of nano-Ag particles.
1) phenetic analysis of nano ferriferrous oxide
The product infrared absorption pattern of preparation is as shown in Figure 1, in shortwave area 553cm-1And 410cm-1There are two magnetism
Fe3O4Characteristic absorption peak, be tetrahedron and octahedral Fe-O key stretching vibration respectively.Four iron oxide are prepared, solution is controlled
PH value be it is crucial, on the other hand to completely cut off air, not so can generate Fe2O3, due to Fe2O3Fe-O key stretching vibration peak be
630cm-1And 430cm-1, which there are not the two absorption peaks, illustrates to prepare purer magnetism
Fe3O4。
From the Fe of Fig. 23O4Found on the X-ray diffraction spectrogram of particle, the diffraction spectral peak of magnetic particle appear in 2 θ=
At 15.86 °, 30.06 °, 35.76 °, 43.32 °, 53.56 °, 57.10 °, 62.68 °, Fe is respectively corresponded3O4Cube crystal face
(11), the position of (220), (311), (400), (422), (511), (440).In conjunction with the analysis of infrared spectroscopy, explanation is prepared
Magnetic Fe3O4。
2) powder of bamboo charcoal and magnetic bamboo charcoal characterizes
Essential element is tri- kinds of elements of C, H, O in bamboo charcoal, main in infrared spectrum in addition to this there are also a small amount of N and metal
The chemical bond oscillations gained to be formed with tri- kinds of elements of C, H, O, such as 2109cm in Fig. 3-1Place is the stretching vibration peak of R-C ≡ C-H,
878cm-1For the wagging vibration peak of C-H group in aromatic ring structure, the two characteristic peaks go out in bamboo charcoal and magnetic bamboo charcoal
It is existing, and magnetic Fe is had also appeared in magnetic bamboo charcoal3O4(553cm-1) characteristic peak, this illustrate bamboo charcoal assign magnetic success, and
No change has taken place for structure after assigning magnetic.
As shown in figure 4, all there is diffraction maximum in 2 θ=16.46 °, 35.52 °, 43.26 ° of threes, in 2 θ=16.46 °,
The diffraction peak intensity of magnetic bamboo charcoal compared with magnetization three-iron diffraction peak intensity, it is roughly the same with the diffraction peak intensity of raw material bamboo charcoal；
And at 2 θ=35.52 °, the diffraction peak intensity of magnetic bamboo charcoal is consistent with the diffraction peak intensity of magnetization three-iron, and than bamboo charcoal
Diffraction peak intensity；Three's peak intensity is in the same size at 2 θ=43.26 °.It also found in magnetic bamboo charcoal spectrogram, raw material bamboo charcoal
2 θ=26.84 ° of characteristic peak, 29.48 ° and other 2 θ=39.44 ° of peak, 47.5 °, 48.48 ° of all disappearances, illustrate that bamboo charcoal is assigning magnetic
In the process, part crystal form is changed；But occur 2 θ=16.46 °, 30.06 °, 35.52 °, 43.26 °, 53.56 °,
57.10 °, 62.68 ° of magnetic Fes3O4Characteristic absorption peak, illustrate bamboo charcoal assign magnetic success.
3) phenetic analysis of nano-titanium dioxide
As shown in figure 5, in 1090cm-1There is the strong characteristic absorption peak of Ti-O key, nano-TiO2Characteristic absorption
Peak is generally between 500~700nm, therefore red shift has occurred in absorption peak, it can thus be appreciated that nano-TiO manufactured in the present embodiment2Grain
Diameter is bigger than normal.Infrared vibration absorbs map to be occurred without other miscellaneous peaks, illustrates that the product purity of preparation is higher.
If Fig. 6 is nano-TiO2The diffracting spectrum of XRD, it can be seen that 2 θ be 25.38 °, 37.88 °, 48.08 °,
53.92 °, 55.08 °, 62.72 °, 75.06 ° there is stronger characteristic absorption peak, consult corresponding known to JCPDS card
Absorption peak is Anatase (101), (004), (200), (105), (211).The photocatalysis effect of Anatase is than golden red
Good, the TiO manufactured in the present embodiment of stone phase2Mainly based on Anatase, and crystal form is preferable.
4) phenetic analysis of nano-Ag particles
As shown in Figure 7, the ultra-violet absorption spectrum for four nano silvers that respectively not prepared by same date, it can be seen that nanometer
Argent grain has a very strong absorption peak at 440nm, this is the characteristic absorption peak of nano-Ag particles, and prepared by the present embodiment
Nano silver particles pattern be spherical shape.The absorption peak position at plasmon absorption peak, absorb peak width and peak strength with
Particle size, particle diameter distribution and the particle concentration of nano silver particles are at corresponding relationship.Partial size is smaller, and it is blue to absorb peak-to-peak value
It moves, that is, more close toward shortwave；It is wider to absorb peak width, particle diameter distribution is more extensive；Peak strength is bigger, particle concentration
It is higher.Nano silver particles partial size is smaller, and specific surface area is bigger, therefore releases more Ag+, fungistatic effect will be more preferable,
So the nano silver particles partial size of preparation is the smaller the better.This repeats the nanometer that experiment shows the preparation of liquid phase polyol reduction method
Silver is spherical shape, and particle diameter is smaller, and partial size is more concentrated, since peak strength is big, so the product yield of preparation is higher,
It is a feasible experimental program.
Using PVP as protective agent dispersing agent, the nano silver of ethylene glycol weak reductant preparation, N or the O generation of Argent grain and PVP
Coordination combines, therefore forms a clad on nano-Ag particles surface, the reunion of particle is hindered, to obtain smaller particle, more
The nano silver particles of dispersion.1645cm-1For the characteristic peak of C=O in PVP, this absorption peak does not change a lot,
1273cm-1The vibration absorption peak of body is complexed for N-OH, the obvious blue shift of this absorption peak weakens, and 1041cm-1For the vibration peak of C-N
Red shift enhancing, this illustrates that PVP is mainly that N and Ag is coordinated to the protective effect of nano silver particles, O hardly with Ag be coordinated or
Seldom.
The X ray diffracting spectrum result of nano silver is shown in Fig. 9, in figure nano silver particles 2 θ be 38.24 °, 48.14 °,
There are 4 apparent absorption peaks at 62.78 °, 75.08 °, it is corresponding with (111) of elemental silver, (200), (220), (311), it removes
Except this, Ag is had also appeared2The absorption peak of O, (a111), (a200) and (a220).Illustrate that nano silver manufactured in the present embodiment is molten
Glue, when washing drying becomes Argent grain, some has been oxidized to Ag2O.It can using Scherere formula using XRD diagram
Calculate the crystallite dimension of each crystal face.
D=R λ/β cos θ
In formula, D- particle diameter, R- constant (0.89), λ-incident X-rays wavelength (0.15418nm), the θ-angle of diffraction
It spends (°), β-diffraction maximum peak width at half height (rad).The average grain diameter that nano silver is obtained by calculation is 43.2nm, with ultraviolet suction
The analysis for receiving spectrogram matches.
5) characterization of compound disinfectant
From in the infrared spectrogram of three kinds of fungicide it can be found that all there is magnetic Fe in three kinds of fungicide3O4Feature
Vibration peak, the Fe-O absorption peak in magnetic bamboo charcoal/bactericidal nano-silver agent is in 553cm-1Place, magnetic bamboo charcoal/nano-TiO2And magnetism
Bamboo charcoal/nano silver/TiO2Fe-O absorption peak in fungicide is in 437cm-1Place, with magnetic Fe manufactured in the present embodiment3O4Spectral peak phase
Compare and blue shift has occurred, hexagonal hole is presented in the bamboo charcoal after charing, thus it is speculated that possible magnetic bamboo charcoal is in load nano-TiO2When, by
In nano-TiO2Partial size is larger, the biggish magnetic Fe of partial size when load3O4It goes out, is left compared with small particle to having squeezed
Magnetic Fe3O4Particle is in the hex hole of bamboo charcoal, therefore blue shift has occurred in peak value, and nano silver partial size is smaller, can be in magnetism
Fe3O4Together by bamboo Charcoal Adsorption in the gap of particle, therefore peak value does not change.Nano-TiO2In Ti-O key characteristic peak
1090cm-1In magnetic bamboo charcoal/nano-TiO2With magnetic bamboo charcoal/nano silver/TiO2There is embodiment in fungicide spectrogram, illustrates TiO2
It is successfully supported on bamboo charcoal, and spectrogram shows that three kinds of fungicide are all magnetic Fe3O4Eigen vibration peak, illustrate that fungicide exists
It is loaded successfully on magnetic bamboo charcoal.
The magnetic Fe that three kinds of different fungicide all occur3O4Cube crystal face (11) diffraction maximum, illustrate that fungicide has been born
It carries successfully, by observing spectrogram peak, it can be clearly seen that magnetic bamboo charcoal/nano silver/TiO2Peak value and magnetic bamboo charcoal/nanometer
TiO2It is roughly the same, there is fine distinction with magnetic bamboo charcoal/nano silver, illustrates nano silver, nano-TiO2It loads in magnetic bamboo charcoal
It is not change product characteristics since hexagonal hole special in bamboo charcoal structure is completed by physical absorption.
The test of 2 compound disinfectant recyclability of experimental example
One, 500mL beaker is taken, a certain amount of deionized water is added, the compound disinfectant of 2g is added toward beaker, is stirred
Uniformly, alnico magnets are fastened with a rope, puts into beaker, the recyclability of compound disinfectant is measured, by what is recycled
Compound disinfectant is put into 100 DEG C of electric drying oven with forced convections, is weighed after being completely dried, and the rate of recovery is calculated.
Figure 12 and Figure 13 be compound disinfectant in air with the recovering effect figure in water, the results showed that, in air, magnetic
Iron can reach 100% to the rate of recovery of compound disinfectant substantially；Recovering effect in water is poor, but it is dry to pass through repeatedly recycling
After dry, the compound disinfectant of 2.000g can recycle 1.732g, and the rate of recovery can reach 86.6%, this illustrates four oxygen of nanometer of preparation
Changing three-iron is that tool is magnetic, and illustrates that bamboo charcoal has good suction-operated, is a kind of good support materials, Er Qietong
The compound disinfectant for crossing the preparation of this experimental method can repeat recycling and use.
Test of the different fungicide of experimental example 3 to Escherichia coli sterilization ability
Nano silver, nano-TiO are inquired into using inhibition zone method2, magnetic bamboo charcoal/nano silver, magnetic bamboo charcoal/nano-TiO2, it is magnetic
Bamboo charcoal/nano silver/TiO2Bactericidal effect of five kinds of different fungicide to Escherichia coli.Measuring method with above-mentioned Bactericidal test,
It is a difference in that the strain antibacterial agent different with addition only with Escherichia coli, is equally every group and does two parallel tests, it is ultraviolet
It is cultivated under illumination condition for 24 hours, observes and measures antibacterial circle diameter size.
Table 1 is different fungicide to Escherichia coli killing effect antibacterial circle diameter correlation data.As shown in Table 1, nano silver,
Magnetic bamboo charcoal/nano silver, nano-TiO2, magnetic bamboo charcoal/nano-TiO2, magnetic bamboo charcoal/nano silver/TiO2Suppression to Escherichia coli
Bacterium effect is incremented by successively.When due to production plate, the culture medium content that each plate is added is consistent (20mL), and Oxford cup
Diameter is identical, it is possible to thinks to be identical toward the amount of the fungicide of Kong Lijia every time, although magnetropism bamboo charcoal/nano silver,
Magnetic bamboo charcoal/TiO2, magnetic bamboo charcoal/nano silver/TiO2Magnetic bamboo charcoal is added in these three antibacterial agents, effective bacteriostatic agent is caused (to be received
Meter Yin or TiO2) content is reduced, but the bactericidal effect of above-mentioned 3 kinds of fungicide has improvement, shows that magnetic bamboo charcoal can not only be made
For the carrier of fungicide, reduce the dosage of fungicide, and the bactericidal effect of fungicide can be improved, i.e., to fungicide nano silver or
TiO2There is synergistic effect in terms of sterilization.It can be seen that the compound disinfectant of preparation can not only play the role of high-efficiency antimicrobial, and can be with
Its dosage is reduced, has the function that reduce cost.
The different fungicide of table 1 are to Escherichia coli killing effect
The fungicidal spectrum of 4 compound disinfectant of experimental example is studied
1) configuration of culture medium and actication of culture
Configure beef-protein medium (culture bacterium), potato dextrose medium (PDA, culture mould and ferment
Female bacterium), adjust pH to dispense after 7, natural ph respectively, every bottle substantially 150mL or so, while 16 test tubes are taken, eight additions
Suitable beef-protein medium, eight addition PDA culture mediums.At the same time, 9mL deionized water is measured, is added to eight
Only in clean test tube, sterile water is prepared.Culture dish is wrapped with brown paper, is put into high-pressure sterilizing pot together, 121 DEG C go out
16 test tubes after sterilizing are shelved plate, after cooling, with inclined-plane method of scoring respectively by Escherichia coli, golden yellow by bacterium 30min
Staphylococcus, bacillus subtilis, proteus vulgaris, aspergillus niger, Penicillium citrinum, Rhizopus oryzae and saccharomyces cerevisiae are inoculated into test tube
In, every group inoculation two, for 24 hours, the strain after activation is transferred in 4 DEG C of refrigerators, spare for 37 DEG C (28 DEG C of saccharomycete) cultures.
2) Bactericidal test
By three kinds of culture medium heating and meltings, sterile water, culture dish, liquid relief liquid rifle, Oxford cup etc. are put into aseptic operating platform,
Ultraviolet lamp sterilization 15min is opened, alcolhol burner is lighted, clamps Oxford cup in alcolhol burner flame envelope 5~10s of calcination with tweezers, then put
Enter in culture dish, each symmetrically placed four Oxford cups of culture dish.Then it is measured in four times with the liquid-transfering gun of 5mL after having melted
Three kinds of culture medium 20mL in culture dish, stand natural cooling ten minutes.At the same time, after fetching activation in advance in refrigerator
Strain, be well dispersed in sterile water with the strain that sterile working method fetches oese, with liquid-transfering gun measure 0.3mL bacterium
Liquid is transferred in culture dish, and bacterium solution is dispersed in media surface using spread plate method, is continued to repeat to be coated with once, is
Guarantee that plate covers with bacterium, continue that coating is primary, and bacterium flame calcination spreader is completed in every coating, is coated with after completion
With flame calcination tweezers, Oxford cup is taken out one by one from culture medium, it is complete to will appear four diameters in each culture dish at this time
Exactly the same hole, it is contemplated that magnetic bamboo charcoal has been also possible to bacteriostasis, so in two holes be added magnetic bamboo charcoal powder as
Compound disinfectant is added in control group, other two apertures, and the amount added is that hole is filled up, and every group is done two parallel tests, and 37 DEG C of bacterium
Ultraviolet lighting culture for 24 hours, measures antibacterial circle diameter under (27 DEG C of mould, saccharomycete and actinomyces) after the completion of culture.
Antibacterial circle diameter is bigger, illustrates that compound disinfectant is stronger to the bacterium inhibitory effect, is pressed by the antibacterial circle diameter that is averaged of table 2
According to arranging from big to small are as follows: Escherichia coli > proteus vulgaris > bacillus subtilis > staphylococcus aureus > Rhizopus oryzae > black
Aspergillus > Penicillium citrinum > saccharomyces cerevisiae, this shows magnetic bamboo charcoal/nano silver/TiO2Compound disinfectant has broad spectrum antibacterial.
The fungicidal spectrum of 2 compound disinfectant of table
Gram-positive bacteria (G+) cell wall the characteristics of be that chemical constituent is simple, thickness is big, substantially by peptide glycan and
Teichoic acid composition.Gram-negative bacteria (G-) cell wall level is more, ingredient is more complex, and thickness is compared with G+Bacterium is thin, therefore mechanical strength
Compared with G+Bacterium is weak.Yeast cell wall outer layer is mannosan, and centre is protein, and internal layer is glucan, and " sandwich is presented
The structure of shape ".The internal layer of higher fungus (aspergillus, mould) cell wall is chitin, and outer layer is protein；And lower fungus (root
It is mould) cell wall constituent based on cellulose.Therefore it can be seen that the cell wall of bacterium forms relatively simple, the cell wall knot of fungi
Structure is complicated, single to analyze from cell wall this aspect, and compound disinfectant is greater than fungi (mould and ferment to the killing effect of bacterium
It is female), and for G in bacterium-The killing effect of bacterium is greater than G+Bacterium.In fungi, lower fungus (head mold) is killed
Effect of going out is greater than higher fungus (aspergillus, mould), due to " sandwich " structure of yeast cell wall, so that compound disinfectant pair
Killing effect in it is most weak.
Influence of 5 light source of experimental example to compound disinfectant performance
Measuring method is Escherichia coli for examination bacterium referring to above-mentioned Bactericidal test, and the plate point of compound disinfectant will be added
It is not placed under dark, incandescent lamp, natural light, ultraviolet light and is cultivated for 24 hours, paired observation inhibition zone size.
Anatase type nano TiO2Forbidden bandwidth be 3.2eV, Semiconductor absorption threshold values λ g and forbidden bandwidth Eg have with
Lower relational expression: λ g (nm)=1240/Eg (eV).Thus formula is it is found that TiO2The maximum wavelength of photocatalysis irradiation is 387.5nm.Therefore
Under dark condition, nano-TiO2Without fungistatic effect, only nano silver plays bacteriostasis, by chart above it is found that incandescent lamp
Under illumination condition, nano-TiO2Photo-catalyst agent only shows faint bacteriostasis, and sunlight is a continuous spectrum,
It wherein just include ultraviolet light, so culture has preferable fungistatic effect under the conditions of solar irradiation, ultraviolet wavelength range is
10nm~400nm, therefore the fungistatic effect under ultraviolet lighting is best.Show TiO2Photo-catalyst agent must with 387.5nm with
Under short wavelength light irradiate competence exertion bacteriostasis, wavelength beyond ultraviolet light range except, almost without fungistatic effect.
The measurement of 6 minimal inhibitory concentration of experimental example
LB liquid medium 50mL is taken, is inoculated with Escherichia coli with sterile working method, 150r/min culture 12h is prepared into greatly
Enterobacteria bacteria suspension, is diluted to 1 × 105~1 × 106cfu/mL.0.2g compound disinfectant is weighed, with LB liquid medium constant volume
To 100mL, it is configured to the solution of 2000 μ g/mL, pipettes sample solution 10mL in conical flask with liquid-transfering gun, 10mL is added
LB culture medium is configured to 1000 μ g/mL suspensions, dilutes a series of solution of concentration using double dilution method: 500 μ g/mL,
250 μ g/mL, 125 μ g/mL, 62.5 μ g/mL, 31.25 μ g/mL, 15.625 μ g/mL, while a conical flask is taken, 10mL LB is added
Culture medium is as positive control.10mL LB liquid is separately added into the solution and positive controls of a series of concentration with liquid-transfering gun
Culture medium measures OD 600nm respectively, and then 37 DEG C of shaking table cultures for 24 hours, use light splitting light photometer measurement OD 600nm value again,
If the OD 600nm absorption value of solution does not become larger under a certain concentration and the solution O D 600nm lower than it with a concentration absorbs
Value increases, and illustrates that the concentration is minimal inhibitory concentration (MIC).
Escherichia coli bacteria suspension after culture for 24 hours is measured into OD600nm value, is compared with the light absorption value before culture,
It was found that concentration of sterilant is the hydroponics front and back of 1000 μ g/mL, 500 μ g/mL, 250 μ g/mL, 125 μ g/mL and 62.5 μ g/mL
Light absorption value is constant, this shows that the fungicide of this 5 kinds of concentration can inhibit Escherichia coli Growth completely, and in the bacterium of 31.25 μ g/mL
Light absorption value becomes larger after suspension culture, illustrates that the minimal inhibitory concentration of compound disinfectant manufactured in the present embodiment is 62.5 μ g/mL, kills
Microbial inoculum bactericidal property is excellent.
OD600nm light absorption value before and after 3 Escherichia coli bacteria suspension culture of table
Present invention employs chemical coprecipitation, sol-gel method and liquid phase polyol reduction methods to be prepared for magnetism respectively
Fe3O4Particle, nano-TiO2Powder and nano-Ag particles, and loaded by self-assembly method and magnetic bamboo charcoal/receive is made into magnetic bamboo charcoal
Meter Yin/TiO2Then compound disinfectant carries out phenetic analysis to compound disinfectant, studies its fungicidal spectrum, and investigate it to large intestine
The killing performance of bacillus, obtains following result:
1) magnetic bamboo charcoal/nano silver/TiO2Fungicide has permanent magnetism, can carry out recycling and reusing with magnet.
2) nano silver, nano-TiO2It is to be loaded on magnetic bamboo charcoal by physisorption, does not influence fungicide
Anti-microbial property.
3) nano silver prepared by the present invention is ball-type, and average particle size 43.2nm, particle diameter distribution more concentrates, yield
It is higher, and the nano silver prepared has high-efficiency antimicrobial.
4) nano-TiO prepared by the present invention2, product purity it is higher, crystal form is preferable, mainly based on Anatase.
5) compound disinfectant, which has, preferably recycles and reuses performance, and the aerial rate of recovery can achieve 100%,
Also it can reach 86.6% in water.
6) present invention is prepared for magnetic bamboo charcoal/nano silver/TiO2Compound disinfectant, in ultraviolet lighting and 37 DEG C of condition of culture
Under, successively successively decrease to the killing effect of Gram-negative bacteria, gram-positive bacteria, lower fungus, higher fungus, saccharomycete, has
There is the characteristic of broad-spectrum sterilization.
7) compound disinfectant under ultraviolet light under the conditions of have preferable sterilization effect, the illumination condition except 387.5nm
Under, sterilization effect is poor.
It 8) is 1 × 10 in the bacterial concentration of Escherichia coli5~1 × 106In the case where cfu/mL, the minimum of compound disinfectant
Mlc is 62.5 μ g/mL.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (9)
1. a kind of magnetic bamboo charcoal/nanometer silver/titanium dioxide compound disinfectant preparation method, it is characterised in that: include:
1) by the Fe of 0.05~0.15mol/L2+The Fe of solution and 0.15~0.25mol/L3+Solution, it is equal in 45~55 DEG C of stirrings
It is even；Then the NaOH solution of 1.5~2.5mol/L is added dropwise thereto under stiring, until solution ph is 10.8~11.2；75
At~85 DEG C, the sodium citrate solution of 0.05~0.15mol/L is added dropwise thereto, continues 0.5~1.5h of stirring to get Fe3O4It is outstanding
Turbid；It is separated by solid-liquid separation, washs, it is dry, obtain Fe3O4；According to the ratio of mass ratio 1:3~5, to Fe3O4Middle investment bamboo charcoal, is stirred
Mix 0.5~1.5h；2000~4000r/min is centrifuged 10~20min, the bamboo charcoal washing after centrifugation, 65~75 DEG C of dry 4~6h,
It is ground up, sieved, magnet sorting obtains magnetic bamboo charcoal；
2) butyl titanate is mixed at 25~35 DEG C with dehydrated alcohol, after 500~700rpm stirs 25~35min, ice second is added
Acid continues 25~35min of stirring；Separately take HNO3、C2H5OH and water mix, and mixed liquor are obtained, with 1min 25 at 25~35 DEG C
The speed of~35 drops instills the mixed liquor to the mixed system of 900~1100rpm butyl titanate that stirred and dehydrated alcohol
In, after being stirred to react 1.5~2.5h, natural drying 2~4d, 95~105 DEG C of dry 1~3h, 250~350 DEG C of heat treatments 25~
It is warming up to 500~600 DEG C after 35min and keeps the temperature 1.5~2.5h and grinds in air after taking out cooling, obtains nano-TiO2Powder
Body；
3) under stirring, counterflow condition, polyvinylpyrrolidone is dissolved in ethylene glycol, 125~135 DEG C is warming up to, adds
AgNO3, 0.5~1.5h of insulation reaction obtains nano silver colloidal sol；Nano silver colloidal sol acetone, dehydrated alcohol wash, and 45~55 DEG C
Dry 5~7h, obtains nano-Ag particles；
4) nano-TiO prepared by step 2) is added in the nano-Ag particles prepared to step 3)2Powder, 45~55 DEG C are stirred to react
25~35min adds the magnetic bamboo charcoal of step 1) preparation, is warming up to 75~85 DEG C, continues to be stirred to react 1~3h, will obtain
Solution be separated by solid-liquid separation, 75~85 DEG C of dry 3~5h are to get the magnetic bamboo charcoal/nano silver/TiO2Compound disinfectant.
2. magnetic bamboo charcoal according to claim 1/nanometer silver/titanium dioxide compound disinfectant preparation method, feature
Be: in the step 1), bamboo charcoal washs not muddy to supernatant, in 90~110 DEG C of dry at least 10h after washing, crushes, mistake
Then 200 meshes put into the Fe again3O4In.
3. magnetic bamboo charcoal according to claim 1/nanometer silver/titanium dioxide compound disinfectant preparation method, feature
It is: in the step 2), butyl titanate, dehydrated alcohol, glacial acetic acid, HNO3、C2H5The volume ratio of OH and water is 15~16:
14.5~15.5:1~2:0.5~1.5:7~8:4~5.
4. magnetic bamboo charcoal according to claim 1/nanometer silver/titanium dioxide compound disinfectant preparation method, feature
It is: in the step 3), polyvinylpyrrolidone and AgNO3Mass ratio be 5~7:1.
5. magnetic bamboo charcoal according to claim 1/nanometer silver/titanium dioxide compound disinfectant preparation method, feature
It is: in the step 4), nano-Ag particles, nano-TiO2The mass ratio of powder and magnetic bamboo charcoal is 1:9~11:18~22.
6. magnetic bamboo charcoal/nano silver/dioxy prepared by a kind of preparation method according to any one of claim 1 to 5
Change titanium compound disinfectant.
7. a kind of magnetic bamboo charcoal as claimed in claim 6/application of the nanometer silver/titanium dioxide compound disinfectant as fungicide.
8. application according to claim 7, it is characterised in that: the bacterium bag include Gram-negative bacteria, gram-positive bacteria,
Lower fungus, higher fungus, saccharomycete.
9. application according to claim 7, it is characterised in that: the bacterium bag include Escherichia coli Escherichia coli,
Proteus vulgaris Proteus vulgaris, bacillus subtilis Bacillus subtilis, staphylococcus aureus
Staphylococcus aureus, Rhizopus oryzae Mucor sp., aspergillus niger Aspergillus niger, Penicillium citrinum
Penicillium sp., Saccharomyces Cerevisiae in S accharomyces cerevisiae.
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