CN1459474A - Micromesohole silicon dioxide heterocompound and its preparation method and use - Google Patents
Micromesohole silicon dioxide heterocompound and its preparation method and use Download PDFInfo
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Abstract
An antibacterial composition for paint, ceramics, rubber, plastics, etc. is composed of microporous or mesoporous SiO2 particles as carrier and silver phosphate and/or TiO2 as active components which are compounded on the surface of the said SiO2 particle. Its advantages are high antibacterial effect, high hydrophilicity and low cost.
Description
Technical field
The invention belongs to little mesoporous silicon oxide carrier antibacterial material and the Application Areas in antimicrobial prod thereof, what particularly relate to tens nanometers to tens micron has micropore, the mesoporous compound silver of silicon-dioxide and/or complex body of titanium dioxide and its production and use.
Background technology
Bacterium and invasive organism are one of main killers of human health, and the development and application of anti-biotic material reduces disease to the protection human health, has crucial meaning.The nucleus of anti-biotic material is an antiseptic-germicide, and antiseptic-germicide is the extremely sensitive chemical ingredientss of microorganism such as a kind of bacterium, mould.Can be divided into silver system according to the effective constituent difference of antiseptic-germicide and (contain Ag
+, Cu
2+, Zn
2+Deng metal ion) and titanium system (having the titanium dioxide of photocatalysis etc.) antiseptic-germicide.
" chemistry world ", 2000, the 7 phases, 339-342, point out in " inorganic antiseptic general introduction " literary composition: the anti-microbial property of silver-series antibacterial agent is caused by the metal stripping, promptly by slowly-releasing Ag
+, Cu
2+And Zn
2+Ion stops the breeding of microorganism and plays germicidal action.The metal ion of stripping, particularly silver ions combine with cytolemma and membrane protein, make three-dimensional arrangement damage (Denaturation), produce dysfunction at short notice.And arrive inner metal ion, enzyme is produced obstacle and produces dysfunction with the DNA reaction.The antibacterial ability of silver is the strongest in the silver-series antibacterial agent, and zinc, copper etc. use separately generally all can not satisfy antibiotic requirement, therefore usually mixes use with silver.TiO
2Anti-biotic material has nontoxic, tasteless, nonirritant, thermostability and good heat resistance, and certainly as characteristics such as whites.TiO
2Be non-stripping property antiseptic-germicide, thereby be a kind of semi-permanent mould antiseptic-germicide, can effect descend gradually along with the stripping of antiseptic-germicide unlike other antiseptic-germicide.So TiO
2Anti-biotic material has become one of focus of development research.
But, TiO
2Be subjected to uviolizing, oxygen can break away from reduction, and causes the following TiO of variation, particularly 100nm of self tone
2Particle, because surface-area is big, photocatalytic activity height, the easier degraded that causes other organic supplementary component.Calendar year 2001 " Chinese first anti-biotic material industry development conference collection of thesis " P49-55 also points out general TiO simultaneously in " the antibacterial and mouldproof application performance research of nano titanium oxide "
2Thick product powder is assembled serious, and the coacervate granularity reaches submicron and micron order, is subjected to light activated electronics and hole from TiO
2Moving to the surface in the body often needs the time of millisecond to the microsecond level, and this moment is at TiO
2Recombination probability is very big in the body, is difficult for forming electron-hole pair on the surface and comes activated surface absorption water and air etc., promptly is difficult for producing active group, can not bring into play due anti-microbial property.Therefore developed nano-TiO then
2The surface coats treatment technology, its main method is to handle coating and nano grain surface generation chemistry and physical reaction by kinds of surface, carry out surface inorganic and organic nano coating layer and handle, change the particle surface state, thereby improve the dispersiveness and the base material consistency of powder; The modifier that also requires simultaneously to add can make the photochemical activity of titanium dioxide improve.
" material nova---nanometer material science " P46-50 in 1998 points out that mesoporous Heterogeneous Composite body is the brand-new research object that just has been born in recent years, and it is the artificial compound system that is assembled by mesoporous solid and heterogeneous nano particle or cluster.Mesic hole compound outstanding feature structurally is, the mesoporous solid that has a meso-scale hole provides a three-dimensional space for heterogeneous assembling and filling.Because quantum size effect, small size confinement effect and interface coupling, make it have the property that nano particle and mesoporous solid do not possess, some effect of nano particle will become more remarkable in assembly system.For example, photoelectric enhancing is a critical nature of mesic hole compound.Therefore be carrier with little mesoporous silicon oxide, compound phosphoric acid silver and/or titania nanoparticles are formed mesoporous Heterogeneous Composite body, are a kind of novel anti-biotic material preparing methods.
Summary of the invention
One of purpose of the present invention provides a kind of micromesohole silicon dioxide heterocompound, this complex body purity height, good dispersity, narrow diameter distribution, uniform particles; This species complex is compound one deck Trisilver phosphate and/or a titania nanoparticles on little mesoporous silica particles inside and shallow surface, makes little mesoporous silica particles have antibacterial properties.
Two of purpose of the present invention provides a kind of preparation method of micromesohole silicon dioxide heterocompound.
Three of purpose of the present invention provides a kind of purposes of micromesohole silicon dioxide heterocompound.
The objective of the invention is to realize by following technical scheme:
Micromesohole silicon dioxide heterocompound with antibacterial of the present invention is as carrier with nanometer or the little mesoporous silica particles of submicron, on little mesoporous silica particles inside and shallow surface, be compounded with Trisilver phosphate and/or titanium dioxide layer, make it give full play to the high-efficiency antimicrobial effect of titanium dioxide photochemical activity and/or silver ions.
The structure of little mesoporous silicon oxide is a kind of loose and porous structure, particle diameter is between 50nm-20000nm, described on the shallow surface of little mesoporous silica particles the thickness of compound Trisilver phosphate and/or titanium dioxide be 5～100nm, be about 1-5nm at the thickness of inner compound Trisilver phosphate of little mesoporous silica particles and/or titanium dioxide.The size of micromesohole silicon dioxide heterocompound of the present invention is between 55nm-22000nm.This micromesohole silicon dioxide heterocompound has anti-microbial effect.
Preparation method's step of the micromesohole silicon dioxide heterocompound with antibacterial of the present invention is as follows:
(1). in water, the weight percent concentration of silica dioxide granule in water is 10～50%, is preferably 20～35% with nanometer or the little mesoporous silica particles dispersed with stirring of submicron.
(2). the aqueous solution of preparation Sodium phosphate dibasic, its volumetric molar concentration is 0.01～1mol/L, is preferably 0.01～0.3mol/L.
(3). the preparation silver complex aqueous solution, its volumetric molar concentration is 0.01～1mol/L, is preferably 0.01～0.3mol/L.
(4). the disodium phosphate soln of step (2) preparation is slowly joined in the nanometer or the little mesoporous silica particles solution of submicron of step (1) preparation, wherein, the consumption of disodium phosphate soln is determined silicon-dioxide in the mixed solution according to the thickness requirement of required Trisilver phosphate composite bed: the mol ratio of Sodium phosphate dibasic is 1: 0.02～1: 0.5.
(5). with the silver complex solution of step (3) preparation, slowly join in the mixed solution of step (4) preparation, the consumption of silver complex solution is determined according to the consumption of Sodium phosphate dibasic, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver ions is 1: 1～1: 4.
(6). the mixed solution of step (5) is separated, the throw out distilled water wash, drying finally obtains the silicon-dioxide Heterogeneous Composite particle of compound skim Trisilver phosphate on little mesoporous silica particles inside and shallow surface.
(7). with the little mesoporous silicon oxide-Trisilver phosphate composite particles of step (6) preparation; or directly little mesoporous silica particles is distributed in the dehydrated alcohol; making little mesoporous silicon oxide-Trisilver phosphate composite particles or the weight percent concentration of little mesoporous silica particles in dehydrated alcohol is 1～40%, is preferably 10～35%.
(8). preparation titanium tetrachloride ethanolic soln, titanium tetrachloride and alcoholic acid volume ratio are 1: 0.2-1: 5, be preferably 1: 0.5-1: 2.
(9). slowly in the mixed solution of step (7), add the titanium tetrachloride ethanolic soln of step (8) preparation, stir.The add-on of titanium tetrachloride is determined silicon-dioxide in the mixed solution according to the thickness requirement of the composite bed of required titanium dioxide granule: the titanium tetrachloride initial molar ratio is 1: 0.02～1: 3.
(10). with the mixed solution ageing of step (9) 24 hours, constantly adding a certain amount of water under the condition of stirring, the add-on of water according to adding titanium tetrachloride determine water in the mixed solution: the initial molar ratio of titanium tetrachloride is 1: 0.05～1: 0.5.
(11). with the mixed solution ageing of step (10) after 24 hours, separate, drying precipitate is 300 ℃ of-900 ℃ of roastings in temperature, pulverize, finally obtain at little mesoporous silica particles the micromesohole silicon dioxide heterocompound of compound skim Trisilver phosphate and titanium dioxide on the inner and shallow surface; Or obtain at little mesoporous silica particles the micromesohole silicon dioxide heterocompound of compound skim titanium dioxide on the inner and shallow surface.
Described silver complex can be silver-ammonia complex or silver thiosulfate complex etc., is preferably silver-ammonia complex.
The product purity height that method of the present invention is prepared, good dispersity, and the particulate size can be controlled by reaction conditions.
The anti-microbial property that uses inhibition zone method to carry out anti-biotic material detects.
What the present invention was significantly different with other anti-biotic material technology of preparing is in the present invention, to be evenly to coat certain thickness Trisilver phosphate and/or titanium dioxide on the loose porous little mesoporous preparing spherical SiO 2 particle, making particle have very strong antibacterial properties.
Micromesohole silicon dioxide heterocompound with antibacterial of the present invention can also have other to coat kind, as first dioxide composite titanium layer on and the shallow surface inner at little mesoporous silica particles, and then the compound phosphoric acid silver layer.
Micromesohole silicon dioxide heterocompound with strong antibacterial of the present invention is of many uses, be a kind of novel high function fine inorganic material, this complex body can be entrained in coating, pottery, rubber, plastics, paper or the fibers material and use as anti-biotic material.Micromesohole silicon dioxide heterocompound purity height with antibacterial of the present invention, good dispersity, and the particulate size is controlled.So can be used for the product of high platform, as: high-grade paint, self-cleaning material etc.
Of the present invention have strong antibacterial micromesohole silicon dioxide heterocompound and have:
1. prepare simplely, be easy to apply.
2. with comparatively inexpensive, the mesoporous silicon oxide of good hydrophilic property is made the carrier composite titanium dioxide, can well keep the Superhydrophilic in the optically catalytic TiO 2 process.
3. mesoporous silicon oxide is made the compound silver of carrier, and the method that preparation has very strong anti-microbial effect material is a very economical and superior.
4. by the size of selecting the silicon-dioxide kernel and the composite bed thickness of controlling Trisilver phosphate and/or titanium dioxide, be easy to make the product of different field purposes desired size.
5. mesoporous silicon oxide is made the anti-biotic material that carrier composite titanium dioxide and silvery are equipped with, and just has very strong anti-microbial effect under very weak visible light effect.
6. because TiO
2Be non-stripping property antiseptic-germicide, thereby be a kind of semi-permanent mould antiseptic-germicide, can effect descend gradually along with the stripping of antiseptic-germicide unlike other antiseptic-germicide.
Embodiment
Embodiment 1
The self-control micropore SiO that particle diameter is about 170 nanometers
2The particle ultra-sonic dispersion is in dehydrated alcohol, and its volumetric concentration is 2%.At this mixed solution and dripping volumetric concentration ratio is 1: 2 titanium tetrachloride and ethanolic soln, and the mol ratio that makes silicon-dioxide and titanium tetrachloride is 1: 1.3, and its dropping time is 20 minutes, ageing 24 hours.Slowly add a certain amount of water, the mol ratio of water and titanium tetrachloride is 2: 1.Obtain white opacity solution, centrifugation, the centrifugal product drying of gained, 500 ℃ of following roastings, obtain having particle diameter in 175 nanometers, the micromesohole silicon dioxide heterocompound of compound about 5 nano titanium oxides on inner compound about 2 nanometers of little mesoporous silica particles and shallow surface.Use intestinal bacteria to carry out bacteriostasis property and detect, inhibition zone is 12mm.
Embodiment 2
The mesoporous SiO of self-control that particle diameter is about 2000 nanometers
2The particle ultra-sonic dispersion is in water, and volumetric concentration is 15%.Slowly add disodium phosphate soln, silicon-dioxide in the mixed solution: the mol ratio of disodium phosphate soln is 1: 0.05.Add silver-ammonia complex (specifically) solution then, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver ions is 1: 1.Resultant mixed solution is separated, the throw out distilled water wash, drying, pulverizing, 500 ℃ of following roastings, obtain having particle diameter in 2005 nanometers, the mesoporous silica Heterogeneous Composite body of compound about 5 nanometer Trisilver phosphates on inner compound about 1 nanometer of little mesoporous silica particles and shallow surface.Use intestinal bacteria to carry out bacteriostasis property and detect, inhibition zone is 11mm.
Embodiment 3
The mesoporous SiO of self-control that particle diameter is about 2000 nanometers
2The particle ultra-sonic dispersion is in dehydrated alcohol, and volumetric concentration is 20%.At this mixed solution and dripping volumetric concentration ratio is 1: 1 titanium tetrachloride and ethanolic soln, and the mol ratio that makes silicon-dioxide-titanium tetrachloride is 1: 0.3, and its dropping time is 20 minutes, ageing 24.0 hours.Slowly add a certain amount of water, the mol ratio of water and titanium tetrachloride is 5: 1.Obtain white opacity solution, centrifugation, the centrifugal product drying of gained, 500 ℃ of following roastings, obtain having particle diameter in 20005 nanometers, the mesoporous silica Heterogeneous Composite body of compound about 5 nano titanium oxides on inner compound about 2 nanometers of little mesoporous silica particles and shallow surface.Use intestinal bacteria to carry out bacteriostasis property and detect, inhibition zone is 9mm.
Embodiment 4
The mesoporous SiO of self-control that particle diameter is about 2000 nanometers
2The particle ultra-sonic dispersion is in water, and volumetric concentration is 30%.Slowly add disodium phosphate soln, silicon-dioxide in the mixed solution: the mol ratio of disodium phosphate soln is 1: 0.05.Add in silver-ammonia complex Sodium phosphate dibasic then: the mol ratio of silver ions is 1: 1.Resultant mixed solution is separated, the throw out distilled water wash, drying is pulverized, and just obtains little mesoporous silicon oxide-Trisilver phosphate composite particles.In dehydrated alcohol, volumetric concentration is 15% with this composite particles ultra-sonic dispersion.At this mixed solution and dripping volumetric concentration ratio is 1: 2 titanium tetrachloride and ethanolic soln, and the mol ratio that makes silicon-dioxide-titanium tetrachloride is 10: 1, and its dropping time is 20 minutes, ageing 24.0 hours.Slowly add a certain amount of water, the mol ratio of water and titanium tetrachloride is 3: 1.Obtain white opacity solution, centrifugation, the centrifugal product drying of gained, 600 ℃ of following roastings obtain little mesoporous SiO
2-AgpPO
4-TiO
2The Heterogeneous Composite body.Particle diameter is in 2010 nanometers, the Trisilver phosphate of compound about 10 nanometers and the micromesohole silicon dioxide heterocompound of titanium dioxide on inner compound about 2 nanometer Trisilver phosphates of little mesoporous silica particles and shallow surface.Use intestinal bacteria to carry out bacteriostasis property and detect, inhibition zone is 16mm.
Embodiment 5
The mesoporous SiO of self-control that particle diameter is about 5000 nanometer rice
2The particle ultra-sonic dispersion is in water, and its volumetric concentration is 25%.Slowly add disodium phosphate soln, silicon-dioxide in the mixed solution: the mol ratio of disodium phosphate soln is 10: 1.Add in silver-ammonia complex Sodium phosphate dibasic then: the mol ratio of silver ions is 1: 0.75.Resultant mixed solution is separated, the throw out distilled water wash, drying is pulverized, and just obtains mesoporous silicon oxide-Trisilver phosphate composite particles.In dehydrated alcohol, its volumetric concentration is 15% with this composite particles ultra-sonic dispersion.At this mixed solution and dripping volumetric concentration ratio is 1: 1 titanium tetrachloride and ethanolic soln, and the mol ratio that makes silicon-dioxide-titanium tetrachloride is 1: 0.3, and its dropping time is 20 minutes, ageing 24.0 hours.Slowly add a certain amount of water, the mol ratio of water and titanium tetrachloride is 1: 0.2.Obtain white opacity solution, centrifugation, the centrifugal product drying of gained, 600 ℃ of following roastings obtain mesoporous Heterogeneous Composite body anti-biotic material.Use intestinal bacteria to carry out bacteriostasis property and detect, inhibition zone is 12mm.
Claims (10)
1. micromesohole silicon dioxide heterocompound is characterized in that: described complex body be with nanometer or the little mesoporous silica particles of submicron as carrier, be compounded with Trisilver phosphate and/or titanium dioxide layer at little mesoporous silica particles on the inner and shallow surface;
The structure of described little mesoporous silicon oxide is a kind of loose and porous structure, particle diameter is between 50nm-20000nm, described on the shallow surface of little mesoporous silica particles the thickness of compound Trisilver phosphate and/or titanium dioxide be 5～100nm, be 1-5nm at the thickness of inner compound Trisilver phosphate of little mesoporous silica particles and/or titanium dioxide;
The size of described micromesohole silicon dioxide heterocompound is between 55nm-22000nm.
2. complex body as claimed in claim 1 is characterized in that: the little mesoporous silica particles of described nanometer or submicron is the preparing spherical SiO 2 particle.
3. preparation method as any described micromesohole silicon dioxide heterocompound of claim 1-2, it is characterized in that: preparation method's step of described micromesohole silicon dioxide heterocompound is:
(1). in water, the weight percent concentration of silica dioxide granule in water is 10～50% with nanometer or the little mesoporous silica particles dispersed with stirring of submicron;
(2). the aqueous solution of preparation Sodium phosphate dibasic;
(3). the preparation silver complex aqueous solution;
(4). the disodium phosphate soln of step (2) preparation is slowly joined in the nanometer or the little mesoporous silica particles solution of submicron of step (1) preparation, and wherein, silicon-dioxide: the mol ratio of Sodium phosphate dibasic is 1: 0.02～1: 0.5;
(5). with the silver complex solution of step (3) preparation, slowly join in the mixed solution of step (4) preparation, wherein, Sodium phosphate dibasic: the mol ratio of silver ions is 1: 1～1: 4;
(6). the mixed solution of step (5) is separated, and to the throw out washing, drying finally obtains at little mesoporous silica particles the silicon-dioxide Heterogeneous Composite particle of compound one deck Trisilver phosphate on the inner and shallow surface;
(7). with the little mesoporous silicon oxide-Trisilver phosphate composite particles of step (6) preparation, or directly little mesoporous silica particles is distributed in the dehydrated alcohol;
(8). preparation titanium tetrachloride ethanolic soln, titanium tetrachloride and alcoholic acid volume ratio are 1: 0.2-1: 5;
(9). slowly in the mixed solution of step (7), add the titanium tetrachloride ethanolic soln of step (8) preparation, stir; Wherein, silicon-dioxide: the titanium tetrachloride initial molar ratio is 1: 0.02～1: 3;
(10). the mixed solution ageing with step (9), under agitation add entry, wherein, water: the initial molar ratio of titanium tetrachloride is 1: 0.05～1: 5;
(11). with the mixed solution ageing of step (10), separate, drying precipitate is 300 ℃ of-900 ℃ of roastings in temperature, pulverize, finally obtain at little mesoporous silica particles the micromesohole silicon dioxide heterocompound of compound one deck Trisilver phosphate and titanium dioxide on the inner and shallow surface; Or obtain at little mesoporous silica particles the micromesohole silicon dioxide heterocompound of compound layer of titanium dioxide on the inner and shallow surface.
4. method as claimed in claim 3 is characterized in that: described silver complex is silver-ammonia complex or silver thiosulfate complex.
5. method as claimed in claim 3 is characterized in that: the weight percent concentration of described step (1) silica dioxide granule in water is 20～35%.
6. method as claimed in claim 3 is characterized in that: the aqueous solution volumetric molar concentration of described step (2) Sodium phosphate dibasic is 0.01～1mol/L.
7. method as claimed in claim 3 is characterized in that: the volumetric molar concentration of described step (3) the silver complex aqueous solution is 0.01～1mol/L.
8. method as claimed in claim 3 is characterized in that: the little mesoporous silicon oxide of described step (7)-Trisilver phosphate composite particles or the weight percent concentration of little mesoporous silica particles in dehydrated alcohol are 10～40%.
9. method as claimed in claim 3 is characterized in that: described step (8) titanium tetrachloride and alcoholic acid volume ratio are 1: 0.5-1: 2.
10. purposes as any described micromesohole silicon dioxide heterocompound of claim 1-2, it is characterized in that: described complex body has very strong antibacterial, this complex body is entrained in coating, pottery, rubber, plastics, paper or the fibers material uses as anti-biotic material.
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