CN1241479C - Antibacterial material of molecular sieve containing zinc and its preparing method - Google Patents
Antibacterial material of molecular sieve containing zinc and its preparing method Download PDFInfo
- Publication number
- CN1241479C CN1241479C CN 03127125 CN03127125A CN1241479C CN 1241479 C CN1241479 C CN 1241479C CN 03127125 CN03127125 CN 03127125 CN 03127125 A CN03127125 A CN 03127125A CN 1241479 C CN1241479 C CN 1241479C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zinc
- distilled water
- biotic material
- antibacterial
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to an antibacterial zinc-containing molecular sieve material and a preparing method thereof. The preparing method comprises the following steps: dissolving soluble zinc-containing salts by using distilled water; adding molecular sieves; heating the mixture to 65 to 100 DEG C; stirring the mixture at 50 to 60 rpm for 0.5 to 6 hours in a reflux mode; cooling the mixture to room temperature; carrying out vacuum filtration; flushing the mixture with distilled water for 4 to 6 times; naturally airing the mixture to obtain the antibacterial zinc-containing molecular sieve material. The mass ratio of the zinc salts to the molecular sieves to the distilled water in the antibacterial zinc-containing molecular sieve material is (1 to 10): 1:100. The antibacterial zinc-containing molecular sieve material prepared by the present invention has the characteristics of large exchange capacity, strong adsorbility, stable structure, slow ion release, etc. The prepared material has the advantages of good chemical stability and strong antibacterial effect, and is in a flexible state. Since the hole diameter of the molecular sieves is smaller than the minimum diameter length of bacteria, no bacterium invasion exists and no secondary pollution occurs. The antibacterial zinc-containing molecular sieve material can be compounded with various materials of clothes, decoration, buildings, etc., and can be extensively applied to various environments.
Description
Technical field
The present invention relates to a kind of molecular sieve antibacterial material and preparation method thereof, particularly relate to a kind of Zn molecular sieve anti-biotic material and preparation method thereof that contains.
Background technology
The bacterium that grows on trees a large amount of around us exists, although the thalli growth of some non-pathogenic bacterias is favourable with the life of breeding people.But as a rule, the malignancy of thalline and breeding bring disease and disaster for the mankind.World Health Organization's statistics in 1998 show: the death toll that nineteen ninety-five causes because of bacterial infection is 1,700 ten thousand people.In the long-term struggle of human and bacteriosis, it has been recognized that antibiotic importance.Not only at hospital, public place and dwelling house, product are applied flexibly in adhesion and the tool of production progressively adopts anti-biotic material.
The used anti-biotic material of people can be divided into three major types at present: natural antibacterial material, inorganic antibacterial material and organic anti-bacterial material.Natural antibacterial material is meant and extracts the position that animals and plants have antibacterial functions, but not scale as yet at present.The organic anti-bacterial material is meant various bacteria removers, bactericide etc., be generally the synthetic material of chemical substances such as organic acid, alcohol, ester, phenol, they have short-term bactericidal effect efficiently, but high volatility, safety and poor chemical stability, timeliness is short, easily produce the microorganism drug resistance, especially poor heat resistance (＜200 ℃), high-temperature decomposition product is poisonous, be difficult for merging, be difficult to realize the function of long acting antibiotic, can't be applied to goods such as coating, plastics, chemical fibre, pottery (warding off) porcelain, rubber with fungi-proofing object.Along with the progress of science and technology and the raising of people's living standard, the enhancing of fitness-for-all consciousness is to the also raising day by day of requirement of antibiotic quality of materials.Anti-biotic material should can be used for each details of daily production, life: arrive the factory building workshop greatly, little of fabric fibre, hard to the wall skin face of land, gentle to fit clothing, the physical state constraint that self is not existed, break away from the control of time limit of use and number of times, Here it is anti-biotic material of new generation that people expected the feature that should possess.
Inorganic antibacterial material with its have broad spectrum antibacterial, water-fast, acid and alkali-resistance, wash resistant, do not wear out, do not develop immunity to drugs, advantage such as antibacterial ability is lasting, more and more be subject to people's attention.Its antibiotic mode can be divided three classes: a class is to be the contact sterilization of representative with silver ion etc., and the antibiotic mechanism that contains the zinc ion material also belongs to this type of, illustrates but their detailed mechanism awaits further research; Second class is with TiO
2Deng being the photocatalysis formula sterilization of representative; The 3rd class is with Al
2O
3Deng being the far infrared radiation formula sterilization of representative.Wherein the antibacterial effect of inorganic silver series antibacterial agent is outstanding, but because silver ion is strong to the reaction sensibility of light, oxidation stain easily, this has become the major issue that limits its application, and in addition, the cost of silver-series antibacterial agent is also very high.Therefore, scientist is devoted to research and develop good anti-bacterial effect, timeliness is long, safe, serviceability is good and cheap antibacterial agent and antibacterial product thereof.
Molecular sieve is the porous polymer that silica, aluminium oxide, sodium oxide molybdena exist in varing proportions, silicon, oxygen, aluminium have constituted the electronegativity skeleton of molecular sieve, sodium ion in framework of molecular sieve can be replaced with the ion in the environment with the form of ion exchange, under the constraint of molecular sieve electronegativity skeleton, enter of the exchange capacity decline of the cation of molecular sieve with other ion in the environment with the sodium ion displacement.Characteristics such as exchange capacity is big because molecular sieve has, adsorptivity is strong, Stability Analysis of Structures, can people utilize the ion slow releasing function of molecular sieve to design a kind of novel anti-biotic material in research, makes it convenient durable and be widely used.Although the invention of the argentiferous in the existing technology, cupric antimicrobial molecule sieve has certain progressive meaning, but still has many shortcomings and discomfort:
(1) silver ion easily is reduced into silver under illumination, prolongs the antibacterial effect that is oxidized to silver oxide and then has reduced silver-colored type molecular sieve in time, is unfavorable for the long-term use of this kind antimicrobial molecule sieve.Meanwhile, silver itself involves great expense, and is difficult to generally use, and is not easy to economic operation.
(2) copper ion is as a kind of huge sum of money bits ion, when it is free on outside the molecular sieve with ionic condition, might penetrate into thalline and human body cell, include the enzyme or the protein interaction of sulfydryl with cell, cause the variation of cellular physiological activity and function, so the antibacterial agent of copper ions is subjected to certain limitation to the antimicrobial product that is applied to human epidermal directly contacts.
Zinc ion exists with ionic condition as the trace element that human body must replenish every day, and no accumulated time effect is easily absorbed by the body again, and the ion pair human body that slowly releases in the molecular sieve does not have injury.So containing Zn molecular sieve is a kind of desirable anti-biotic material.
Summary of the invention
The objective of the invention is to: propose a kind of Zn molecular sieve anti-biotic material and preparation method thereof that contains, in order to solve argentiferous molecular sieve easy oxidation discoloration, involve great expense and to contain copper zeolite has injury effect to human body problem.
Technical scheme of the present invention is to realize a kind of Zn molecular sieve anti-biotic material and preparation method thereof that contains, be characterized in: adopt the carrier of molecular sieve as anti-biotic material, utilize that molecular sieve has that exchange capacity is big, adsorptivity is strong, Stability Analysis of Structures, have characteristics such as ion slow releasing function, by the method for chemical reaction, can will have the metallic zinc ion design of sterilizing function in the micropore of molecular sieve.
Technical scheme of the present invention can further be implemented through the following steps.
One. raw material is selected
Molecular sieve mainly is divided into micro porous molecular sieve and mesopore molecular sieve.Micro porous molecular sieve is the molecule sieve of size distribution in 0.2-2nm; Mesopore molecular sieve is the another kind of molecular sieve of size distribution in 2nm-50nm, as MCM-41, SBA-15 etc. commonly used.The sodium ion of micro porous molecular sieve and mesopore molecular sieve can exchange with zinc ion and they be become contain zinc antimicrobial molecule sieve.(path length of bacterium is generally 0.5*10 to molecular sieve bore diameter less than the minimum path length of thalline
3Nm-3*10
3Nm) can not produce the intrusion of thalline, molecular sieve can not become the source of carrying of some bacterium, avoids the generation of secondary pollution; The molecular sieve granularity is less, and integral body exists with flexible state, is characterized in advancing clothing and healthy prevention articles for use next to the shin with the compound use of various materials, particularly interpolation on demand.It also can be as other anti-biotic material, joins in home decoration material, the construction material and in the household electrical appliance manufactured materials, plays antibiotic effect in most of field of people's daily life.
Used carrier material of the present invention comprises following types of molecules sieve:
A-type (3A) also is potassium A type; Chemical composition is 0.75K
2O+0.25Na
2O+Al
2O
3+ 2SiO
2Molecular sieve, aperture 0.3nm;
B-type (4A) also is sodium A type; Chemical composition is Na
2O+Al
2O
3+ 2SiO
2Molecular sieve, aperture 0.4nm;
X-type, chemical composition are Na
2O+Al
2O
3+ (2.5 ± 0.5) SiO
2Molecular sieve, aperture 1.0nm;
Y-type, chemical composition are Na
2O+Al
2O
3+ (3-6) SiO
2Molecular sieve, aperture 0.8nm;
Mesoporous MCM-41 type: Na
2O+Al
2O
3+ nSiO
2(Si/Al=4-∞, aperture 1.5-10nm);
Mesoporous SBA-15 type: Na
2O+Al
2O
3+ nSiO
2(Si/Al=4-∞, aperture 3-30nm).
Zinc-containing substance can adopt the zinc material of solubility salt such as zinc sulphate, zinc chloride, zinc nitrate etc.
Dispersant adopts inorganic pure water solvent, is generally distilled water.
Two, proportioning (mass ratio)
The ratio that contains zinc salt, molecular sieve and inorganic pure water solvent is 1-10: 1: 100.
Three, process route
Solubility is contained zinc salt with inorganic pure water dissolution with solvents, after adding molecular sieve, be heated to 65-100 ℃, after 50-60 rev/min of stirring and refluxing 0.5-6 hour, be cooled to room temperature, vacuum filtration, with distilled water flushing 4-6 time, the flush away surface ion dries naturally, promptly get and carry the Zn molecular sieve anti-biotic material, zinc ion is 50-85% to the exchange degree of sodium ion.
Optimum proportion scheme of the present invention is: the carrier of anti-biotic material is chosen as X-type molecular sieve Na
2O+Al
2O
3+ (2.5 ± 0.5) SiO
2As carrier, zinc salt is a zinc sulphate.The raw material proportioning is: the heavy 600g of zinc sulphate, molecular sieve weight 100g, water dispersant weigh 10000 grams.
The present invention compares with other correlation technique, have positive effect and advantage: that adopts the such scheme preparation contains the Zn molecular sieve anti-biotic material, it is simple to have preparation method, process route is understood, design parameter is credible, the characteristics of low cost of manufacture, prepared material have good chemical stability and very strong antibacterial effect, and exist with flexible state.
(X-Ray-Diffraction XRD) the analysis showed that the X-ray diffraction that contains zinc antimicrobial molecule sieve for preparing in above-mentioned process route and best proportioning ratio, and the characteristic peak of original X-type molecular sieve is kept.As shown in drawings, Fig. 1 is a Na type molecular sieve X-ray diffracting spectrum, and Fig. 2 is a Zn type molecular sieve X-ray diffracting spectrum, illustrates that the skeleton through molecular sieve after heating, the ion exchange does not subside, can guarantee zinc and extraneous contact area like this, improve the ability of bacteria growing inhibiting.The exchange result of zinc and sodium shows that zinc is 50%-85% to the exchange degree of sodium after reacting by above-mentioned process route, shows that zinc has entered molecular sieve.
Four, antibacterial experiment
We adopt and pave plate controlled observation counting method, are object with staphylococcus aureus (as the representative of gram-positive bacteria) and pathogenic escherichia coli (as the representative of Gram-negative bacteria), have studied the molecular sieve antibacterial effect.Concrete operations are:
Getting dilution factor is 1*10
515 milliliters of the bacterium liquid of individual thalline/milliliter, join and contain 50 milliliters of LB medium (LB medium proportioning: peptone 2.0 grams, yeast extract 1.0 grams, sodium chloride 2.0 gram, 200 milliliters of agar 3.0 grams and distilled water) and have in a certain amount of conical flask that contains Zn molecular sieve (amount ranges of anti-biotic material is 20 milligrams-100 milligrams) (control group only contains 50 milliliters of medium, and nothing contains Zn molecular sieve), 37 ℃, 50 rev/mins, shaking table was cultivated about 20 hours, stopped to cultivate.(cell concentration that is about to after the above-mentioned cultivation dilutes 10 respectively with different dilution factors
5Doubly, 10
4Doubly with 10
5Doubly) be layered on the plating medium, cultivated about 20 hours, and carried out colony counting for 37 ℃.Staphylococcus aureus and pathogenic escherichia coli antibiotic rate are all reached more than the 85%---95%.
Now (carrier of anti-biotic material is chosen as X-type molecular sieve Na with a kind of antimicrobial molecule sieve
2O+Al
2O
3+ (2.5 ± 0.5) SiO
2As carrier, zinc salt is a zinc sulphate.The raw material proportioning is: the heavy 600g of zinc sulphate, molecular sieve weight 100g, water dispersant weigh 10000 grams.The exchange degree of zinc ion and sodium ion is 85%.) addition in the antibacterial experiment system and the relation of antibacterial effect list in table 1.
Table 1: the relation of antimicrobial molecule sieve addition and antibacterial effect
| Contain Zn | 20 | 40 milligrams | 60 milligrams | 80 milligrams | 100 milligrams | Control group |
| The staphylococcus antibiotic rate | 85％ | 88％ | 95％ | 96％ | 96％ | 0 |
| The Escherichia coli antibiotic rate | 85％ | 90％ | 96％ | 96％ | 96％ | 0 |
In other embodiments, antimicrobial molecule sieve addition and antibacterial effect also have similar correlation.
Description of drawings
Fig. 1: Na type molecular sieve X-ray diffracting spectrum;
Fig. 2: Zn type molecular sieve X-ray diffracting spectrum.
Embodiment
Embodiment 1:
The carrier of anti-biotic material is chosen as X-type molecular sieve Na
2O+Al
2O
3+ (2.5 ± 0.5) SiO
2As carrier, zinc salt is a zinc sulphate.The raw material proportioning is: the heavy 600g of zinc sulphate, molecular sieve weight 100g, water dispersant weigh 10000 grams.
At normal temperatures, the 600g zinc salt with 10000 gram dissolved in distilled water, is formed colourless solution.And add the 100g molecular sieve, and being heated to 100 ℃, stirring and refluxing 6 hours is cooled to room temperature, suction filtration, with distillation washing 6 times, the flush away surface ion dries.Promptly obtain containing the Zn molecular sieve anti-biotic material, wherein the exchange degree of zinc ion and sodium ion is 85%.Staphylococcus aureus and pathogenic escherichia coli antibiotic rate are all reached 95%.
Embodiment 2:
The carrier of anti-biotic material is chosen as X-type molecular sieve Na
2O+Al
2O
3+ (2.5 ± 0.5) SiO
2As carrier, zinc salt is a zinc sulphate.The raw material proportioning is: the heavy 300g of zinc sulphate, molecular sieve weight 100g, distilled water dispersant weigh 10000 grams.
At normal temperatures, the 300g zinc salt with 10000 gram dissolved in distilled water, is formed colourless solution.And add the 100g molecular sieve, and be heated to 95 ℃, stirring and refluxing 3 hours, cooling, suction filtration, with distillation washing 6 times, the flush away surface ion dries.Promptly obtain containing the Zn molecular sieve anti-biotic material, wherein the exchange degree of zinc ion and sodium ion is 75%, and staphylococcus aureus and pathogenic escherichia coli antibiotic rate are all reached 85%.
Embodiment 3:
The carrier of anti-biotic material is chosen as B-type (4A), also is sodium A type; Chemical composition is Na
2O+Al
2O
3+ 2SiO
2Molecular sieve, aperture 0.4nm.
Zinc sulphate: molecular sieve: the ratio of distilled water is 3: 1: 100.
At normal temperatures, the 300g zinc salt with 10000 gram dissolved in distilled water, is formed colourless solution.And add the 100g molecular sieve, and be heated to 90 ℃, stirring and refluxing 4 hours, cooling, suction filtration, with distillation washing 6 times, the flush away surface ion dries, and promptly obtains containing the Zn molecular sieve anti-biotic material, and wherein the exchange degree of zinc ion and sodium ion is 80%.Staphylococcus aureus and pathogenic escherichia coli antibiotic rate are all reached 90%.
Embodiment 4:
The carrier of anti-biotic material is chosen as mesoporous MCM-41 type: Na
2O+Al
2O
3+ nSiO
2(Si/Al=4-∞, aperture 1.5-10nm);
Zinc nitrate: molecular sieve: the ratio of distilled water is 6: 1: 100.
At normal temperatures, 600g is sold sour zinc with 10000 gram dissolved in distilled water, form colourless solution.And add the 100g molecular sieve, and be heated to 95 ℃, stirring and refluxing 3 hours, cooling, suction filtration, with distillation washing 6 times, the flush away surface ion dries, and promptly obtains containing the Zn molecular sieve anti-biotic material, and wherein the exchange degree of zinc ion and sodium ion is 80%.Staphylococcus aureus and pathogenic escherichia coli antibiotic rate are all reached 90%.
Claims (5)
1, a kind of preparation contains the method for Zn molecular sieve anti-biotic material, its step is as follows: solubility is contained zinc salt add molecular sieve after with dissolved in distilled water, be heated to 65-100 ℃, with 50-60 rev/min of stirring and refluxing 0.5--6 hour, be cooled to room temperature again, vacuum filtration, with distilled water flushing 4-6 time, naturally dry, promptly get and carry the Zn molecular sieve anti-biotic material, the mass ratio that wherein contains zinc salt, molecular sieve and distilled water is 1-10: 1: 100.
2, preparation as claimed in claim 1 contains the method for Zn molecular sieve anti-biotic material, it is characterized in that: it is a kind of in zinc sulphate, zinc chloride or the zinc nitrate that described solubility contains zinc salt.
3, preparation as claimed in claim 1 contains the method for Zn molecular sieve anti-biotic material, it is characterized in that: described molecular sieve can be a kind of in the molecular sieve as described below:
(1) A-type molecular sieve also is potassium A type, and chemical composition is 0.75K
2O+0.25Na
2O+Al
2O
3+ 2SiO
2, aperture 0.3nm;
(2) B-type molecular sieve also is sodium A type, and chemical composition is Na
2O+Al
2O
3+ 2SiO
2, aperture 0.4nm;
(3) X-type molecular sieve, chemical composition are Na
2O+Al
2O
3+ (2.5 ± 0.5) SiO
2, aperture 1.0nm;
(4) Y-shaped molecular sieve, chemical composition are Na
2O+Al
2O
3+ (3-6) SiO
2, aperture 0.8nm;
(5) mesoporous MCM-41 type molecular sieve, chemical composition is Na
2O+Al
2O
3+ nSiO
2, Si/Al=4-∞, aperture 1.5-10nm;
(6) mesoporous SBA-15 type molecular sieve, chemical composition is Na
2O+Al
2O
3+ nSiO
2, Si/Al=4-∞, aperture 3-30nm.
4, contain the Zn molecular sieve anti-biotic material, it is characterized in that by the preparation of following method: solubility is contained zinc salt add molecular sieve after with dissolved in distilled water, be heated to 65-100 ℃, with 50-60 rev/min of stirring and refluxing 0.5--6 hour, be cooled to room temperature again, vacuum filtration, with distilled water flushing 4-6 time, naturally dry, promptly get and carry the Zn molecular sieve anti-biotic material, the mass ratio that wherein contains zinc salt, molecular sieve and distilled water is 1-10: 1: 100, the metallic zinc ion distribution was in the micropore of molecular sieve, and zinc ion is 50-85% to the exchange degree of sodium ion.
5, the described Zn molecular sieve anti-biotic material that contains of claim 4 is in the application aspect anti-biotic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03127125 CN1241479C (en) | 2003-09-02 | 2003-09-02 | Antibacterial material of molecular sieve containing zinc and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03127125 CN1241479C (en) | 2003-09-02 | 2003-09-02 | Antibacterial material of molecular sieve containing zinc and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1518877A CN1518877A (en) | 2004-08-11 |
| CN1241479C true CN1241479C (en) | 2006-02-15 |
Family
ID=34285973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03127125 Expired - Fee Related CN1241479C (en) | 2003-09-02 | 2003-09-02 | Antibacterial material of molecular sieve containing zinc and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1241479C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011027892A1 (en) * | 2009-09-07 | 2011-03-10 | ライオン株式会社 | Disinfectant composition and disinfecting method |
| CN102391573B (en) * | 2011-09-19 | 2014-04-23 | 中山大学 | Modified polypropylene plastic and preparation method and use thereof |
| CN106719818A (en) * | 2016-11-18 | 2017-05-31 | 宁夏大学 | The preparation method of one metal ion species/oxide composite antibacterial material |
| CN107810974A (en) * | 2017-11-14 | 2018-03-20 | 江苏师范大学 | A kind of efficient compound air purifying preparation |
| CN108849980A (en) * | 2018-07-20 | 2018-11-23 | 山东理工大学 | A method of efficient carrying silver antimicrobials are prepared by carrier of Zn hydridization NaA molecular sieve |
| CN111296483B (en) * | 2020-03-05 | 2021-06-08 | 浙江大学 | Preparation method of zinc-containing molecular sieve antibacterial material |
| CN112741111A (en) * | 2020-12-31 | 2021-05-04 | 江苏万源新材料股份有限公司 | Antibacterial molecular sieve and preparation method thereof |
-
2003
- 2003-09-02 CN CN 03127125 patent/CN1241479C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1518877A (en) | 2004-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100574615C (en) | A kind of Zeolite base composite antibiotic material and preparation method thereof | |
| US5714430A (en) | Mixtures containing fine metallic silver particles on a neutral to basic non-zeolite carrier oxide | |
| CN101142919B (en) | Sepiolite broad-spectrum inorganic antibiotic agent containing composite metal ion and its preparation method | |
| CN103891776B (en) | Rare earth-copper/zinc-containing inorganic-organic montmorillonite nano composite antimicrobial agent and preparation method thereof | |
| CN102138569A (en) | Rare-earth composite antibacterial agent and application thereof | |
| CN100508757C (en) | Kernel-shell structured rare-earth nanometer antibiotic agent, prepn. method and application thereof | |
| CN1241479C (en) | Antibacterial material of molecular sieve containing zinc and its preparing method | |
| CN105061632B (en) | The preparation method and bacteriostasis property of a kind of curdlan quaternary ammonium salt | |
| CN104631115A (en) | Antibacterial anti-odor finishing application technology for textiles | |
| CN101589727A (en) | A kind of preparation method of silver-carrying nano-antimicrobial organic montmorillonite | |
| CN1568704A (en) | Composite nanometer antibiotic material, preparation method and products thereof | |
| CN101049279A (en) | Antibacterial shampoo of Nano silver, and preparation method | |
| CN101347127A (en) | Novel surrounding purifying material as well as preparation and use thereof | |
| CN1310589C (en) | Method for preparing superfine composite inorganic antimicrobial agent | |
| US20220331746A1 (en) | Light-driven filtration antibacterial composite membrane and preparation method and use thereof | |
| CN102405932A (en) | Silver-bearing copper silicon nano mesoporous inorganic antimicrobial agent and preparation method thereof | |
| CN101397401A (en) | Water polyurethane base flower cluster-shaped zinc oxide nanometer whisker antibiotic composite material, preparation method and use thereof | |
| CN113040169B (en) | Carbon doped MoS2/CoP/C composite antibacterial material and preparation method and application thereof | |
| CN100341411C (en) | Inorganic compound antibacterial agent, and its preparing method and use | |
| CN1615700A (en) | Inorganic mesoporous antiseptic material and its preparing method | |
| CN108849980A (en) | A method of efficient carrying silver antimicrobials are prepared by carrier of Zn hydridization NaA molecular sieve | |
| CN104855419A (en) | Nano-grade mesoporous zinc hydroxystannate-modified graphene oxide hybrid antibacterial agent and preparation method thereof | |
| CN111296483B (en) | Preparation method of zinc-containing molecular sieve antibacterial material | |
| CN1274595C (en) | Process for preparing silicon gel carrying silver ion | |
| CN1358441A (en) | Copper-carried montmorillonite solid and liquid disinfectant and preparation process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |