CN100489040C - Composite nano antiseptic titania/silica powder and its preparation - Google Patents

Composite nano antiseptic titania/silica powder and its preparation Download PDF

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CN100489040C
CN100489040C CNB021115699A CN02111569A CN100489040C CN 100489040 C CN100489040 C CN 100489040C CN B021115699 A CNB021115699 A CN B021115699A CN 02111569 A CN02111569 A CN 02111569A CN 100489040 C CN100489040 C CN 100489040C
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CN1384150A (en
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高濂
张汝冰
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Shanghai Institute of Ceramics of CAS
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Abstract

The present invention belongs to the field of ceramic nano-powder. Through the reaction of titanium sulfate with sodium silicate, dispersing the reaction produced precipitate into the solution of silver nitrate, adding Na3PO4 solution for mixing reaction producing Ag3PO4 precipitate, drying and calcining, composite TiO2/SiO2 nano-powder with excellent dispersivity is produced. Because TiO2 particle is coated with one layer of SiO2 film, the TiO2/SiO2 nano-particle has reduced surface energy and is hardly aggregated and the composite TiO2/SiO2 nano-powder has excellent disperse state and narrow size distribution of 40-50 nm. The composite TiO2/siO2 nano-powder has high bactericidal effect to coliform bacteria, candida albicans and staphylococcus aureus.

Description

Nano-titanium oxide/silicon oxide composite antibiosis powder and preparation method
Technical field
The present invention relates to nano-titanium oxide/silicon oxide (TiO 2/ SiO 2) composite antibiosis powder, preparation method.Belong to the ceramic nano-powder body field.
Background technology
Current, nano-TiO 2Powder with its excellence anti-microbial property become one of focus of anti-biotic material development research (S.Kayano, Y.Kikuchi, K.Hashzmoto, et al.Environ.Sci.Tech.1998,32 (5): 726; M.J.Domck, M.W.Lechevallier et al.Appl.Environ.Micro, 1984; 48 (2): 289).Nano-TiO 2Be widely used in antibacterial water treatment unit, food product pack, commodity of sanitation, makeup, textiles, germ resistance tableware and the durable consumer's goods such as table trencher, antibacterial carpet, medical dressing and medical equipment.Antiseptic-germicide of a great variety, performance is different.And nano-TiO 2Also have following characteristics: the one, the antimicrobial efficiency height take place about about 24h as the effect of silver-series antibacterial agent, and titanium oxide only needs about 1h; The 2nd, TiO 2Be a kind of semipermanent antiseptic-germicide of keeping antibacterial effect, can effect descend gradually along with the stripping of antiseptic-germicide unlike other antiseptic-germicide; The 3rd, good security is arranged, can be used for foodstuff additive etc., have no adverse effects with skin contact.(referring to Ma Chengyin, Yang Cuichun. New Chemical Materials, 1994 (4): 41-42; Fan An, Zu Yong. the titanium industrial progress, 1998 (3): 33-34) but pure nano-TiO 2Germicidal action uviolizing (comprising the ultraviolet ray in the sunlight) must be arranged, lower to the utilization ratio of visible light; And different bacteriums is had different germicidal actions, and this is its advantage, is again its shortcoming, and the cell walls that has is to the light-catalyzed reaction sensitivity, and some bacterium then has protective effect to this reaction; Nano-TiO 2Powder is easily reunited, thereby the contact area of minimizing and bacterium has influenced sterilization effect.In order to overcome single nano-TiO 2Whether the limitation of antiseptic-germicide can TiO 2Be carrier core,, coat one deck nano silicon, on certain degree, have the effect of control antimicrobial component slowly-releasing, can prolong the antibiotic validity period of powder on its surface by suitable precipitation reaction, and because at TiO 2Particle surface has coated one deck SiO 2Film has reduced nano-TiO 2The surface energy of particle makes the particle after compound be not easy to reunite, and has improved sterilization effect.Because the fermi level of silver is less than TiO 2Fermi level, promptly in the electron density of silver ions less than TiO 2The electron density of conduction band.This can not only influence the recombination rate of electron-hole pair, improves the surface hydroxyl position, improves antibacterial effect, can also make TiO 2The absorbing wavelength range extension to the visible region, improve antimicrobial efficiency.This design of the present invention just.
Summary of the invention
According to above-mentioned design, the object of the present invention is to provide a kind of nano-TiO 2/ SiO 2Composite antibiosis powder and preparation method wish that it can overcome the problem that simple nano-antibacterial powder exists, and makes anti-microbial property be better than pure nano-TiO 2Antibiotic powder.
Nano-TiO 2/ SiO 2The composite antibiosis powder is to adopt to add Ti (SO in water glass solution 4) 2, the re-adjustment solution parameter makes TiO 2The method preparation that particle precipitation comes out, and at TiO 2/ SiO 2The micro-Trisilver phosphate of absorption in the carrier.The porous nano TiO of preparation 2/ SiO 2Intestinal bacteria, Candida albicans and three kinds of mushrooms the most representative of streptococcus aureus are all had good killing action, act on 60 minutes, killing rate all can reach 98%.
Preparation feature of the present invention is to adopt titanium sulfate and water glass reaction, will react the gained throw out and be dispersed in the silver nitrate solution, and add Na 3PO 4The solution hybrid reaction generates Ag 3PO 4Precipitation, the drying roasting obtains finely disseminated nano-TiO then 2/ SiO 3Matrix material.
The main processes that the present invention relates to comprises: at first under vigorous stirring, with 0.2-0.5mol/lTi (SO 4) 2Splash in the 0.4-1.0mol/l sodium silicate solution, regulate pH=8-10 with alkali lye again, keep this pH value and stir, wear out 2-5h; With 2500-4500 rev/min speed centrifugal settling, throw out is used distilled water wash earlier, use (the NH of 10%-50% concentration again 4) 2CO 3Solution washing; The gained throw out is well dispersed in the silver nitrate solution of 0.1-0.8%, adds Na again 3PO 4The solution hybrid reaction generates Ag 3PO 4Precipitation, frozen centrifugation sedimentation under the ultra-sonic dispersion effect then; At 60-80 ℃ of following vacuum-drying 8h, be warming up to 100-250 ℃ again and carry out drying earlier, roasting obtains dispersed good nano combined micro mist in 200-300 ℃ at last.The nanometer composite Ti O that makes with the inventive method 2/ SiO 2Powder presents good dispersiveness, and particle size distribution is narrow, and particle size range is 40-50nm.Composite particles shows good dispersion state, mainly is because at TiO 2Particle surface has coated one deck SiO 2Film has reduced nano-TiO 2The surface energy of particle makes the particle after compound be not easy to reunite.In addition, the dispersion state that composite particles is good also has substantial connection with the processes such as preparation, washing and drying of particulate.Nanometer SiO 2Help to improve TiO 2Photo-catalyst function (detailed with embodiment 2 and table 4).With (NH 4) 2CO 3Solution washs precipitation, can replace the Na in the disgorging +And SO 4 2-If contain Na in the composite particles +, in reaction process, will cause acid sites to poison, reactive behavior is descended.Facts have proved, with (NH 4) 2CO 3Solution is more infused the end than using distilled water wash better effects if, ion to remove merely, and NH 4 -And CO 3 2-Can in thermal treatment, be removed.
The described NaPO that mixes 4And AgNO 3Mole ratio be 3:1, the concentration that generates Trisilver phosphate is between 0.02-0.80%, but 0.1% to be the best, to intestinal bacteria, golden yellow grape ball, Candida albicans all demonstrate the highest bacteriostasis rate (seeing embodiment 3 for details).
Described different drying temperature is to nano-TiO 2/ SiO 2Fig. 2 is listed in the infrared property influence of matrix material.Fig. 2 is TiO 2/ SiO 2The infrared spectrogram of composite granule after heat preservation hot under 100 ℃, 150 ℃, 200 ℃, 250 ℃ four kinds of differing tempss is handled.3000-3500cm among the figure -1The absorption peak in zone is-stretching vibration of OH group causes, is the stack at various-OH (as Si-O-OH, Ti-O-OH) peak, and is relevant with water of constitution.1610cm -1The absorption peak at place is the flexural vibration of the O-H key of physical absorption water, is positioned at 1000-1250cm -1Asymmetric acromion is caused by Si-O-asymmetrical stretching vibration of Si key in the scope; Symmetry vibration 855cm -1And 640cm -1The peak come from the contribution of Si-O-Si key and Ti-O-Ti key respectively, and at 1023cm -1The peak then be that Si-O-Ti and Si-OH cause. as seen from the figure, TiO 2/ SiO 2Gel after heat treatment, the vibration peak of organic group weakens gradually, to 250 ℃, the organic group completely dissolve. it can also be seen that from figure, along with thermal treatment temp raises gradually, TiO 2/ SiO 2Surface adsorption water in the gel and chemically-bonded water not only do not disappear, and the trend of increase is arranged on the contrary. and its reason may be TiO 2Or SiO 2Organic group in the molecular network is decomposed by charing gradually, SiO 2Ability with very strong hydrophilic and planar water when these samples are placed in the air, has been adsorbed a large amount of water, and has been had portion water to change chemically-bonded water into.
The composite antibiosis powder of the present invention's preparation has following characteristics:
(1) at described nano-TiO 2/ SiO 2In the complex antimicrobials, by titanium sulfate and water glass reaction and treated, at TiO 2Particle surface coats one deck SiO 2Film, Ag +Mode with chemical bonding is combined in the host crystal lattice.This bonding mode can not be transformed into Ag 2O and variable color, ability high temperature more than 800 ℃, and character is unaffected; Described Ag +Exist with the Trisilver phosphate form.
(2) TiO 2/ SiO 2The complex antimicrobials weather resistance is better, even does not also detect the Ag that drop goes out in water +TiO 2/ SiO 2The particle diameter of composite antibiosis powder is 40-50nm.
(3) high-efficiency broad spectrum germ resistance can prevent bacterium, mould and algal grown in the environment, and consumption is 1/10th of other inorganic antiseptic.The special construction of nanometer is applied to not influence in the transparent article transparency;
(4) owing to Trisilver phosphate content in the complex antimicrobials has only thousandth, so it is cheap;
(5) TiO 2/ SiO 2The complex antimicrobials Application Areas is wide, can be used for makeup, medical facilities and need through the high material of the security requirements such as hot packing of steam sterilizing.
Therefore, TiO of the present invention 2/ SiO 2Composite nanoparticle is considered to a kind of very promising novel antibacterial material.
Description of drawings
Fig. 1 is the nano-TiO of preparation method's preparation provided by the invention 2/ SiO 2Transmission electron microscope photo.
Fig. 2 is a nano-TiO under the different drying temperatures 2/ SiO 2The infrared spectrum of matrix material; X-coordinate is the wave number (cm of absorption peak -1), ordinate zou is an intensity in transmission.
Embodiment
Embodiment 1 nano-TiO 2/ SiO 2The preparation of composite antibiosis powder
With 0.2mol/l Ti (SO 4) 2Splash in the 0.5mol/l water glass solution, regulate pH=9 with alkali lye again, keep this acidity value and stir, wear out 2h; 4500 rev/mins speed centrifugal settling is used distilled water wash earlier with throw out, uses (NH again 4) 2CO 3Solution washing; Gained precipitation is well dispersed in 0.1% the silver nitrate solution, adds Na again 3PO 4The solution hybrid reaction generates Ag 3PO 4Precipitation, freezing for some time under the ultra-sonic dispersion effect then, frozen centrifugation sedimentation again; At 80 ℃ of following vacuum-drying 8h, be warming up to 120 ℃ again and carry out drying earlier, last roasting obtains dispersed good nano combined micro mist.Fig. 1 is transmission electron microscope (TEM) photo of composite particles.Particle diameter among the figure distributes very even, all about 50nm.
Embodiment 2 TiO 2/ SiO 2Fungistatic effect to intestinal bacteria, Candida albicans and streptococcus aureus
TiO with preparation among the embodiment 1 2/ SiO 2Composite granule is mixed with 2% antimicrobial fluid; Bacterial classification inoculation to be measured in the liquid shaking bottle substratum of 50ml, is cultivated 18h-24h, bacterium liquid 1ml is joined in the 100ml damping fluid, promptly make tranquillization suspension, standby.The bacterial classification of antibiotic detection is: intestinal bacteria, gold-coloured staphylococci, Candida albicans.Getting 0.5ml bacterium liquid then joins 4.5ml and contains in 0.5% antimicrobial, with suction pipe bacterium liquid 0.25ml is moved on to watch-glass respectively, and liquid level is paved into the circle of the about 2cm of diameter, after the illumination, after washing with 10M 0.85% physiological saline, the bacterium liquid of each watch-glass is inoculated in the substratum, cultivated 24 hours for 35 ℃, insulation 90min, measure the diameter of antibacterial ring at last, its result all has good killing action to its surperficial intestinal bacteria, Candida albicans and streptococcus aureus shown in table 1, table 2, table 3.With pure nano-TiO 2Sterilant is compared (table 4), at TiO 2/ SiO 2Antimicrobial fluid in the streptococcus aureus survival rate very little, TiO 2/ SiO 2Sterilizing rate will be higher than pure TiO 2, this shows nanometer SiO 2Help to improve TiO 2The photo-catalyst function.
Table 1TiO 2/ SiO 2Fungistatic effect to intestinal bacteria (8099)
Figure C02111569D00071
Table 2 TiO 2/ SiO 2Fungistatic effect to streptococcus aureus (ATCC6536)
Figure C02111569D00081
Table 3 TiO 2/ SiO 2Ceramic membrane is to the fungistatic effect of Candida albicans (ATCC10231)
Table 4 TiO 2/ SiO 2The bacteriostatic experiment result
Laboratory sample A B C
The bacterium contrast 1.0*10 6 1.0*10 6 1.0*10 6
Actual bacterial growth number (individual) 3.62*10 5 3.62*10 5 3.62*10 5
Viable count (individual) 1.28*10 4 5.2*10 4 1.23*10 5
A:TiO 2/ SiO 2, B: pure TiO 2, C: control sample
Embodiment 3 is at TiO 2/ SiO 2Middle doping different concns Trisilver phosphate is to the influence of sterilizing rate
At TiO 2/ SiO 2In doping phosphoric acid silver, can not only influence the recombination rate of electron-hole pair, improve the surface hydroxyl position, improve antimicrobial efficiency, also may make TiO 2The absorbing wavelength range extension to the visible region, increase sun transformation of energy and utilization.Ion doping is relevant with ions dosage to the influence of the recombination rate of the mobility of interface electronics, electric charge carrier and photocatalytic activity, and table 5 is at TiO 2/ SiO 2In doping different concns Trisilver phosphate to the influence (acting on 60 minutes) of sterilizing rate, as seen from table, be 0.1% to be optimum doping concentration when the concentration of Trisilver phosphate.Adulterated Ag 3PO 4Be by AgNO 3With Na 3PO 4Reaction and generate.
Table 5 is at TiO 2/ SiO 2Middle doping different concns Trisilver phosphate is to the influence of sterilizing rate
Trisilver phosphate concentration (%) Intestinal bacteria bacteriostasis rate (%) Golden yellow grape ball bacteriostasis rate (%) Candida albicans bacteriostasis rate (%)
0.02 32.31 29.54 25.47
0.04 35.14 30.34 30.77
0.06 54.86 57.41 59.78
0.08 74.10 81.45 78.54
0.10 98.91 98.21 98.84
0.50 97.55 98.49 98.11
0.80 98.88 98.27 97.60

Claims (7)

1. nano-TiO 2/ SiO 2The composite antibiosis powder is characterized in that titanium sulfate and water glass reaction and treated, at TiO 2Particle surface cladding one deck SiO 2Film, Ag +Mode with chemical bonding is combined in the host crystal lattice.
2. by the described nano-TiO of claim 1 2/ SiO 2The composite antibiosis powder is characterized in that described Ag+ exists with the Trisilver phosphate form; TiO 2/ SiO 2The particle diameter of composite granule is 40-50nm.
3. by the described nano-TiO of claim 1 2/ SiO 2The preparation method of composite antibiosis powder is characterized in that adopting the reaction of titanium sulfate and water glass, will react the gained precipitation again and be dispersed in the silver nitrate solution, and add Na 3PO 4The solution hybrid reaction generates Ag 3PO 4Precipitation, drying, roasting form then.
4. by the described nano-TiO of claim 3 2/ SiO 2The preparation method of composite antibiosis powder is characterized in that concrete processing parameter and step are:
(1) with 0.2-0.5mol/l Ti (SO 4) 2Splash in the 0.4-1.0mol/l sodium silicate solution; PH is adjusted to 8-10;
(2) keep pH value, stir, wore out 2-5 hour;
(3) with 2500-4500 rev/min speed centrifugal settling, use distilled water wash earlier, use (NH again 4) 2CO 3Solution washing;
(4) throw out is dispersed in the silver nitrate solution of 0.1-0.8%, and adds Na 3PO 4Solution, reaction generates Ag 3PO 4The precipitation of 0.02-0.80%;
(5) at 60-80 ℃ of vacuum-drying 8h, be warming up to 100-250 ℃ of drying again, make 200-300 ℃ of roasting at last.
5. by claim 3 or 4 described nano-TiOs 2/ SiO 2Each method of the system of composite antibiosis powder is characterized in that Na 3PO 4And Ag 3PO 4By 3: mole ratio is reacted.
6. by the described nano-TiO of claim 4 2/ SiO 2The preparation method of composite antibiosis powder is characterized in that washing with (NH4) 2CO 3, concentration is 10%-50%.
7. by claim 1 or 2 described nano-TiOs 2/ SiO 2The composite antibiosis powder is used as antibacterials, it is characterized in that being configured to 2% antimicrobial fluid, and he has in Trisilver phosphate concentration to large intestine mandarin orange bacterium, candida albicans and golden yellow staphylococcus is 0.1% o'clock, acts on 60 minutes, and sterilization rate reaches 98%.
CNB021115699A 2002-04-29 2002-04-29 Composite nano antiseptic titania/silica powder and its preparation Expired - Fee Related CN100489040C (en)

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CN102210324B (en) * 2010-04-09 2013-06-19 中国科学院海洋研究所 Selective bactericide with composite nanoparticles as well as preparation and application thereof
CN102872889B (en) * 2012-10-10 2014-08-20 江苏大学 Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same
CN103355349A (en) * 2013-06-27 2013-10-23 南京市荣达树脂有限公司 Preparation method of antibacterial powders for antibacterial coating
CN104488966B (en) * 2014-12-10 2017-11-17 陕西科技大学 A kind of quartz load nano silver ceramics antiseptic and preparation method thereof
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