CN1459474A - Micro-mesoporous silica heterocomplex and preparation method and application thereof - Google Patents

Micro-mesoporous silica heterocomplex and preparation method and application thereof Download PDF

Info

Publication number
CN1459474A
CN1459474A CN 02117491 CN02117491A CN1459474A CN 1459474 A CN1459474 A CN 1459474A CN 02117491 CN02117491 CN 02117491 CN 02117491 A CN02117491 A CN 02117491A CN 1459474 A CN1459474 A CN 1459474A
Authority
CN
China
Prior art keywords
mesoporous silica
dioxide
silica particles
preparation
little mesoporous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 02117491
Other languages
Chinese (zh)
Other versions
CN1228395C (en
Inventor
唐芳琼
孟宪伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technical Institute of Physics and Chemistry of CAS
Original Assignee
Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Technical Institute of Physics and Chemistry of CAS filed Critical Technical Institute of Physics and Chemistry of CAS
Priority to CN 02117491 priority Critical patent/CN1228395C/en
Publication of CN1459474A publication Critical patent/CN1459474A/en
Application granted granted Critical
Publication of CN1228395C publication Critical patent/CN1228395C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicinal Preparation (AREA)

Abstract

The invention belongs to the field of micro-mesoporous silica carrier antibacterial materials and application thereof in antibacterial products, and particularly relates to a silica composite silver and/or titanium dioxide complex with micropores and mesopores, a preparation method and application thereof. Nanometer or submicron micro-mesoporous silica particles are used as carriers, and a thin layer of silver phosphate and/or titanium dioxide is compounded in the micro-mesoporous silica particles and on the shallow surface of the micro-mesoporous silica particles. The structure of the micro-mesoporous silica is a loose porous structure, the particle size is 50 nm-20000 nm, the thickness of a composite layer of silver phosphate and/or titanium dioxide on the shallow surface is 5-100 nm, and the thickness of an internal composite layer is 1-5 nm. The complex has antibacterial effect, and can be used as antibacterial material in paint, ceramic, rubber, plastic, paper or chemical fiber. The mesoporous silicon dioxide which is relatively cheap and has good hydrophilicity is used as a carrier to compound the titanium dioxide, so that the super-hydrophilicity in the photocatalysis process of the titanium dioxide can be well maintained.

Description

Micromesohole silicon dioxide heterocompound and its production and use
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.
CN 02117491 2002-05-20 2002-05-20 Micro-mesoporous silica heterocomplex and preparation method and application thereof Expired - Fee Related CN1228395C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 02117491 CN1228395C (en) 2002-05-20 2002-05-20 Micro-mesoporous silica heterocomplex and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 02117491 CN1228395C (en) 2002-05-20 2002-05-20 Micro-mesoporous silica heterocomplex and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN1459474A true CN1459474A (en) 2003-12-03
CN1228395C CN1228395C (en) 2005-11-23

Family

ID=29426604

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 02117491 Expired - Fee Related CN1228395C (en) 2002-05-20 2002-05-20 Micro-mesoporous silica heterocomplex and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN1228395C (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101983569A (en) * 2010-11-25 2011-03-09 中国地质大学(武汉) Titanium dioxide nano antibacterial agent taking halloysite as carrier and preparation method thereof
CN101984008A (en) * 2010-10-29 2011-03-09 沈阳化工大学 Organic nano anti-corrosion coating and preparation method thereof
CN102151577A (en) * 2011-01-28 2011-08-17 东华大学 Ag3PO4/Mg-Al LDO (Layered Double Oxide) visible light composite photo catalyst, preparation and application thereof
CN102872889A (en) * 2012-10-10 2013-01-16 江苏大学 Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same
CN103039521A (en) * 2011-10-11 2013-04-17 国家纳米科学中心 Method for preparing antibacterial powder loaded with monodisperse silver nanometer mesoporous silica
CN103271048A (en) * 2006-03-14 2013-09-04 印可得株式会社 Antibacterial composition containing organic silver complexes, antibacterial treatment methods using the same and antibacterial formed article
CN104488966A (en) * 2014-12-10 2015-04-08 陕西科技大学 Antimicrobial agent for quartz-carried nano silver phosphate ceramic and preparation method thereof
CN106633152A (en) * 2016-12-29 2017-05-10 浙江大学常州工业技术研究院 Preparation method and application of antibacterial packaging film based on mesoporous silicon
CN107051187A (en) * 2016-12-29 2017-08-18 王重庆 Performances of Novel Nano-Porous meter level air catalyst mixture solution and preparation method thereof
CN108003794A (en) * 2017-12-11 2018-05-08 合众(佛山)化工有限公司 A kind of ceramic polished liquid of photocatalyst type
CN108641449A (en) * 2018-05-29 2018-10-12 中建河图建设有限公司 A kind of environmental protection coating material and preparation method thereof with antibacterial and deodorization functions
CN109310355A (en) * 2016-06-30 2019-02-05 拓自达电线株式会社 Electrode material
WO2019153229A1 (en) * 2018-02-09 2019-08-15 纳琦环保科技有限公司 Method for synthesizing composite photocatalytic material having photothermal synergistic effect
CN111574871A (en) * 2020-04-23 2020-08-25 武汉中科先进技术研究院有限公司 Modified fluorosilane composite sol, preparation method thereof, coating containing modified fluorosilane composite sol, and preparation method and application of coating
CN111621989A (en) * 2020-06-05 2020-09-04 漳州华飞体育用品有限公司 Antibacterial wear-resistant ball leather and manufacturing method thereof
CN111644146A (en) * 2020-06-16 2020-09-11 福建远翔新材料股份有限公司 Preparation method of nano silicon dioxide silver-loaded antibacterial material
CN111804284A (en) * 2020-07-06 2020-10-23 中国人民解放军联勤保障部队第九〇〇医院 Adsorbent, preparation method thereof and mask containing adsorbent
CN113201960A (en) * 2021-04-30 2021-08-03 北京依依星科技有限公司 Photocatalytic paper and preparation method thereof
CN113337064A (en) * 2021-06-17 2021-09-03 广东川奥高新科技有限公司 Antibacterial wear-resistant runway floor composite material and preparation method thereof
CN114836070A (en) * 2022-07-01 2022-08-02 广东卡百利新材料科技有限公司 Self-cleaning antibacterial coating and preparation method thereof
US11490846B2 (en) 2016-06-30 2022-11-08 Tatsuta Electric Wire & Cable Co., Ltd. Bioelectrode and method for producing bioelectrode
CN116138268A (en) * 2022-11-17 2023-05-23 浙江枫翎控股集团有限公司 Silica porous antibacterial material, preparation method thereof and silica-titania mesoporous capsule structure antibacterial material

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103271048A (en) * 2006-03-14 2013-09-04 印可得株式会社 Antibacterial composition containing organic silver complexes, antibacterial treatment methods using the same and antibacterial formed article
CN103271048B (en) * 2006-03-14 2014-07-30 印可得株式会社 Antibacterial composition containing organic silver complexes, antibacterial treatment methods using the same and antibacterial formed article
CN101984008A (en) * 2010-10-29 2011-03-09 沈阳化工大学 Organic nano anti-corrosion coating and preparation method thereof
CN101983569A (en) * 2010-11-25 2011-03-09 中国地质大学(武汉) Titanium dioxide nano antibacterial agent taking halloysite as carrier and preparation method thereof
CN101983569B (en) * 2010-11-25 2014-01-01 中国地质大学(武汉) Titanium dioxide nano antibacterial agent taking halloysite as carrier and preparation method thereof
CN102151577B (en) * 2011-01-28 2013-03-06 东华大学 Ag3PO4/Mg-Al LDO (Layered Double Oxide) visible light composite photo catalyst, preparation and application thereof
CN102151577A (en) * 2011-01-28 2011-08-17 东华大学 Ag3PO4/Mg-Al LDO (Layered Double Oxide) visible light composite photo catalyst, preparation and application thereof
CN103039521B (en) * 2011-10-11 2014-11-05 国家纳米科学中心 Method for preparing antibacterial powder loaded with monodisperse silver nanometer mesoporous silica
CN103039521A (en) * 2011-10-11 2013-04-17 国家纳米科学中心 Method for preparing antibacterial powder loaded with monodisperse silver nanometer mesoporous silica
CN102872889A (en) * 2012-10-10 2013-01-16 江苏大学 Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same
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
CN104488966A (en) * 2014-12-10 2015-04-08 陕西科技大学 Antimicrobial agent for quartz-carried nano silver phosphate ceramic and preparation method thereof
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
US11490846B2 (en) 2016-06-30 2022-11-08 Tatsuta Electric Wire & Cable Co., Ltd. Bioelectrode and method for producing bioelectrode
CN109310355A (en) * 2016-06-30 2019-02-05 拓自达电线株式会社 Electrode material
CN106633152A (en) * 2016-12-29 2017-05-10 浙江大学常州工业技术研究院 Preparation method and application of antibacterial packaging film based on mesoporous silicon
CN107051187A (en) * 2016-12-29 2017-08-18 王重庆 Performances of Novel Nano-Porous meter level air catalyst mixture solution and preparation method thereof
CN108003794A (en) * 2017-12-11 2018-05-08 合众(佛山)化工有限公司 A kind of ceramic polished liquid of photocatalyst type
WO2019153229A1 (en) * 2018-02-09 2019-08-15 纳琦环保科技有限公司 Method for synthesizing composite photocatalytic material having photothermal synergistic effect
CN108641449A (en) * 2018-05-29 2018-10-12 中建河图建设有限公司 A kind of environmental protection coating material and preparation method thereof with antibacterial and deodorization functions
CN111574871B (en) * 2020-04-23 2021-07-23 武汉中科先进技术研究院有限公司 Modified fluorosilane composite sol, preparation method thereof, coating containing modified fluorosilane composite sol, and preparation method and application of coating
CN111574871A (en) * 2020-04-23 2020-08-25 武汉中科先进技术研究院有限公司 Modified fluorosilane composite sol, preparation method thereof, coating containing modified fluorosilane composite sol, and preparation method and application of coating
CN111621989A (en) * 2020-06-05 2020-09-04 漳州华飞体育用品有限公司 Antibacterial wear-resistant ball leather and manufacturing method thereof
CN111621989B (en) * 2020-06-05 2023-07-11 漳州华飞体育用品有限公司 Antibacterial wear-resistant ball leather and manufacturing method thereof
CN111644146A (en) * 2020-06-16 2020-09-11 福建远翔新材料股份有限公司 Preparation method of nano silicon dioxide silver-loaded antibacterial material
CN111804284A (en) * 2020-07-06 2020-10-23 中国人民解放军联勤保障部队第九〇〇医院 Adsorbent, preparation method thereof and mask containing adsorbent
CN113201960A (en) * 2021-04-30 2021-08-03 北京依依星科技有限公司 Photocatalytic paper and preparation method thereof
CN113337064A (en) * 2021-06-17 2021-09-03 广东川奥高新科技有限公司 Antibacterial wear-resistant runway floor composite material and preparation method thereof
CN113337064B (en) * 2021-06-17 2022-06-10 广东川奥高新科技有限公司 Antibacterial wear-resistant runway floor composite material and preparation method thereof
CN114836070A (en) * 2022-07-01 2022-08-02 广东卡百利新材料科技有限公司 Self-cleaning antibacterial coating and preparation method thereof
CN114836070B (en) * 2022-07-01 2022-09-06 广东卡百利新材料科技有限公司 Self-cleaning antibacterial coating and preparation method thereof
CN116138268A (en) * 2022-11-17 2023-05-23 浙江枫翎控股集团有限公司 Silica porous antibacterial material, preparation method thereof and silica-titania mesoporous capsule structure antibacterial material

Also Published As

Publication number Publication date
CN1228395C (en) 2005-11-23

Similar Documents

Publication Publication Date Title
CN1228395C (en) Micro-mesoporous silica heterocomplex and preparation method and application thereof
Pandimurugan et al. UV protection and antibacterial properties of seaweed capped ZnO nanoparticles coated cotton fabrics
Huang et al. Optical properties of biomass-derived nanomaterials for sensing, catalytic, biomedical and environmental applications
CN1082529C (en) Method for preparing hollow silica particles
CN1083866C (en) Method for preparing particles comprising a core and a silica shell
CN1844289A (en) Nano functional anion materials and use thereof
CN1459476A (en) Silver phosphate antibacterial modified titanium dioxide composite particle and preparation method and application thereof
CN1064285A (en) When containing the titanium dioxide of micro-pigment, preparation adds the colloid tindioxide
CN1169874C (en) Bioactive nano composite PVA-hydroxyapatite aquagel and its prepn.
CN1517394A (en) Water-solubility natural film and its proparation method
CN101816302A (en) Nuclear shell structure intelligent disinfectant containing silver
Chen et al. Construction of selenium-embedded mesoporous silica with improved antibacterial activity
Beiranvand et al. Graphene Oxide/Hydroxyapatite/Silver (rGO/HAP/Ag) nanocomposite: Synthesis, characterization, catalytic and antibacterial activity
CN112795098A (en) Antibacterial plastic and preparation method thereof
CN1784974A (en) Composite photocatalitic germicide
CN1302997C (en) Nanometer titanium dioxide powder dispersion method
CN1147543C (en) Titania nano-paint for photocatalytic decomposition of organic matter and its prepn
CN1709062A (en) Medical stone inorganic antibacterial agent and its preparing method
CN1299576C (en) Silicon dioxide coated tourmaline and titanium dioxide particle composite antibacterial material and preparation method and application thereof
CN100489040C (en) Composite nano antiseptic titania/silica powder and its preparation
CN1299577C (en) Tourmaline and titanium dioxide particle composite coated with micro mesoporous silicon dioxide on surface and preparation method and application thereof
CN111100553B (en) Slow-release/self-cleaning bifunctional alcohol-soluble protein-based hybrid microcapsule coating material and preparation method thereof
CN1557728A (en) Antimicrobial compound for anion water purifying and activating, its pelletized product and preparation method
Patil et al. Green synthesis of graphene based silver nanocomposite for enhanced antibacterial activity against dental pathogens
CN1264407C (en) Process for preparing compound inorganic germicide

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20051123

Termination date: 20140520