CN100500003C - Nano composite anti-bacterial agent - Google Patents
Nano composite anti-bacterial agent Download PDFInfo
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- CN100500003C CN100500003C CNB2005101174745A CN200510117474A CN100500003C CN 100500003 C CN100500003 C CN 100500003C CN B2005101174745 A CNB2005101174745 A CN B2005101174745A CN 200510117474 A CN200510117474 A CN 200510117474A CN 100500003 C CN100500003 C CN 100500003C
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- 239000003242 anti bacterial agent Substances 0.000 title abstract description 27
- 239000002114 nanocomposite Substances 0.000 title 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002131 composite material Substances 0.000 claims abstract description 55
- 239000011787 zinc oxide Substances 0.000 claims abstract description 46
- 230000002070 germicidal effect Effects 0.000 claims description 50
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 238000003756 stirring Methods 0.000 abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 9
- 238000001291 vacuum drying Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 6
- 229960001763 zinc sulfate Drugs 0.000 abstract description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- LRMILOBPOZGOSH-UHFFFAOYSA-N diazanium;carboxylato carbonate Chemical compound [NH4+].[NH4+].[O-]C(=O)OC([O-])=O LRMILOBPOZGOSH-UHFFFAOYSA-N 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 30
- 230000008569 process Effects 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 19
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 19
- 239000001099 ammonium carbonate Substances 0.000 description 19
- 230000003115 biocidal effect Effects 0.000 description 16
- 230000005540 biological transmission Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- 230000003321 amplification Effects 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 238000003199 nucleic acid amplification method Methods 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 101100310622 Mus musculus Soga1 gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000315672 SARS coronavirus Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 206010064097 avian influenza Diseases 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
A composite nano-class antibacterial agent contains nano-zinc oxide and nano-Ag, and is prepared through proportionally dissolving zinc sulfate (or nitrate) in solvent, stirring while dripping solution of ammonium dicarbonate for reaction, stirring, dripping the solution of silver nitrate and ammonium dicarbonate, stirring, washing, centrifugal separation to obtain the precursors of nano-Ag and nano-zinc oxide, vacuum drying and sintering.
Description
[technical field]
The present invention relates to a kind of antibacterial agent, especially relate to a kind of composite nano germicide.
[background technology]
Twentieth century, the countries in the world scientific and technological progress has promoted economic rapid development, the high development of science and technology civilization and material progress has entered a brand-new stage, but in the fast development in more than 100 years, people have ignored environmental pollution and healthy close relation.Worldwide ecotope and microbial environment have suffered severe contamination, bring serious disaster for human beings'health and life, make the human living space narrow and small day by day, propose grave warning to human survival simultaneously.WHO organizes statistics in 1998 to show, the whole world is annual above more than 1,600 ten thousand people because of the death toll that bacterial infection causes.Especially SARS virus in 2003, the wreaking havoc of bird flu in 2004 more allows people recognize the importance of antimicrobial product, expedited the emergence of the big market of antibiotic articles for use.Therefore, the research and development of various antibacterial agents also just become people's research focus.
Antibacterial agent can be divided into natural, organic and inorganic three major types.Natural antibacterial agent is mainly the extract of natural plants, is subjected to the restriction of resource, and application has certain difficulty.When selecting organic antibacterial agent for use, except that considering its safety (as toxic and side effect, some monomer even carcinogenesis is arranged), also there is poor heat resistance in the applicating history of organic antibacterial agent existing three more than ten years, easily decomposes and problem such as lacks service life.Compare with organic antibacterial agent, inorganic antiseptic, especially the nano inorganic antimicrobial agent that gets up of development in recent years have that broad spectrum antibacterial is good, safe, advantages such as good heat resistance, long service life, nothing volatilization and toxic and side effect, become one of current antibacterial agent hot of research and development.
Inorganic antiseptic mainly comprises two big classes, and a class is the metal ion that will have a sterilization idiocratic as Ag
+, Cu
+, Zn
+Even load is on inorganic carrier, and that its carrier mainly contains is phosphate-based, silicate and active carbon, glass etc., and this class antibacterial agent is more (special permission No. 3448530 as Japan of research at present; No. the 3176054th, Japan's special permission; Chinese patent ZL01125125.5 number; Chinese patent discloses CN1286915A number etc.), and sell at the market existing procucts.Do not have antibiotic property but the shortcoming of this class antibacterial agent is a carrier material, the antibacterial metal ions load capacity is limited and can not control arbitrarily, and antibiotic effective ingredient is few, antibiotic limited time.And only have antibiotic property and do not have the self-cleaning effect of degradation of organic substances; Another kind of is with TiO
2With ZnO be the photocatalysis antibacterial agent of representative, mainly be nano-scale n type semiconductor powder, under photocatalysis, will be adsorbed on the OH-and the H on surface
2The O molecular oxygen changes into hydroxyl radical free radical with strong oxidability (OH) etc., to have the microorganism in the environment and suppresses and killing action.People pass through at TiO in recent years
2The various rare earths of last load, Ag
+, Cu
+And doping N, Fe wait and improve its photocatalytic activity and widen the excitation wavelength scope, and obtained preferably that effect (discloses CN 1559226A number as Chinese patent; Soga et al.J.Surf.Anal., 1999,5 (2): P326; No. 99126362.6, Chinese patent ZL; No. 03117960.6, Chinese patent ZL; BeataKosowska, Sylwia Mozia, Antoni W.Morawski et al.Solar Energy Materials ﹠amp; SolarCells, 2005,88:P269-280 etc.).But this class antibacterial agent must particularly just have the ability of sterilization, degradation of organic substances and auto purification under the UV-irradiation under light conditions.Therefore developing that a kind of illumination is arranged still be all to have microbe killing properties under the unglazed photograph condition, and have the antibacterial agent applicable to multiple occasion of photocatalysis to degrade organic matter and auto purification ability under illumination, will be a up-and-coming developing direction.Chinese patent disclose CN1586202A number by behind the coated porous calcium hydroxy phosphate in nano titanium oxide surface again the method for load silver ion obtained TiO
2And Ag
+Compound antibacterial agent, but this product cost is higher.
[summary of the invention]
Technical problem to be solved by this invention is: a kind of composite nano germicide is provided, and this antibacterial agent has high antibiotic and biocidal efficacies, can also degradable organic pollutant, deodorizing and auto purification, and cost is lower.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: the invention provides a kind of composite nano germicide, it comprises nano zine oxide and Nano Silver, the particle diameter of described nano zine oxide and Nano Silver is 10～30nm, Nano Silver is 1～50 to 99～50 with the mass ratio of nano zine oxide, and nano zine oxide and Nano Silver exist with following form: zinc oxide is attached to the nano-Ag particles form, argent is attached to the nano granular of zinc oxide form, independently nano-Ag particles, nano granular of zinc oxide independently.
The invention has the beneficial effects as follows: self-existent nanometer Ag and ZnO particle can play sterilization and photocatalysis respectively, can promote its photocatalytic activity attached to the Ag on the ZnO nano grain surface, can improve the bactericidal property of nanometer Ag attached to the ZnO on the nanometer Ag particle surface, this composite nano germicide has high antibiotic and biocidal efficacies, can also degradable organic pollutant, deodorizing and auto purification, and cost is lower.
Below in conjunction with the drawings and the specific embodiments the present invention is further described:
[description of drawings]
Figure 1A is the transmission electron microscope photo of the composite nano germicide that obtains under the first embodiment process conditions.
Figure 1B is the transmission electron microscope photo of another different amplification of the composite nano germicide of Figure 1A.
Fig. 2 is the size distribution of the composite nano germicide that obtains figure as a result under the first embodiment process conditions.
Fig. 3 is the X-ray diffraction of the composite nano germicide that obtains figure as a result under the first embodiment process conditions.
Fig. 4 A is the transmission electron microscope photo of the composite nano germicide that obtains under the second embodiment process conditions.
Fig. 4 B is the transmission electron microscope photo of another different amplification of the composite nano germicide of Fig. 4 A.
Fig. 5 is the size distribution of the composite nano germicide that obtains figure as a result under the second embodiment process conditions.
Fig. 6 A is the transmission electron microscope photo of the composite nano germicide that obtains under the 3rd embodiment process conditions.
Fig. 6 B is the transmission electron microscope photo of another different amplification of the composite nano germicide of Fig. 6 A.
Fig. 7 is the size distribution of the composite nano germicide that obtains figure as a result under the 3rd embodiment process conditions.
Fig. 8 A is the transmission electron microscope photo of the composite nano germicide that obtains under the 4th embodiment process conditions.
Fig. 8 B is the transmission electron microscope photo of another different amplification of the composite nano germicide of Fig. 8 A.
Fig. 9 is the size distribution of the composite nano germicide that obtains figure as a result under the 4th embodiment process conditions.
Figure 10 is the X-ray diffraction of the composite nano germicide that obtains figure as a result under the 4th embodiment process conditions.
Figure 11 A is the transmission electron microscope photo of the composite nano germicide that obtains under the 5th embodiment process conditions.
Figure 11 B is the transmission electron microscope photo of another different amplification of the composite nano germicide of Figure 11 A.
Figure 12 is the size distribution of the composite nano germicide that obtains figure as a result under the 5th embodiment process conditions.
[embodiment]
Composite nano germicide of the present invention is by the ZnO of different proportion and the molecular serial nano complex antimicrobials of Ag nanoparticle.In antibacterial agent of the present invention, part ZnO, Ag adhere to mutually, part is self-existent nano-ZnO, Ag particle, therefore this antibacterial agent had both had antibiotic, the biocidal efficacies of nanometer Ag, ZnO and metal ion, have the photocatalyst effect again, and two kinds of nano materials mutually promote, make it not only have high antibiotic property, can also degradable organic pollutant, deodorizing, auto purification, be applicable to illumination and unglazed according to the various products that use under the condition.And can make it have different antibiotic and photocatalysis performances, to adapt to the requirement of various different occasions by adjusting ZnO and the ratio of Ag nano particle in antibacterial agent.This composite nano antibacterial agent cost is lower than like product such as TiO in addition
2And Ag or nanometer Ag antibacterial agent.
Chinese patent disclose disclose for CN1341358A number a kind of by water capacity acidic amino acid silver and amino-acid zinc and catabolite is silver-colored and zinc oxide is the antibacterial agent of material of main part.The present invention is with its difference: 1. synthetic process and principle are different, the present invention at first obtains mixed uniformly presoma by simple inorganic chemistry reaction, promptly reacts the carbonate precursor that generates mixed uniformly Zn and Ag by sulfuric acid or nitrate and the carbonic hydroammonium etc. that contain Ag and Zn; Under conditions such as air, ammonia and vacuum, add thermolysis then and obtain ZnO and Ag composite nano antibacterial agent.Whole process of preparation expects that from former method all belongs to the inorganic chemistry category, pollution-free and sewage etc.This method technology is simple, raw material sources are wide, cost is low, equipment is simple, be convenient to large-scale production.2. raw materials used difference, it is raw material that the present invention selects the sulfuric acid of cheap conventional Zn or nitrate and carbonic hydroammonium and silver nitrate for use, and cost is reduced greatly.3. obtained product form difference, the present invention at first obtains forerunner's homogeneous mixture with simple chemical reaction, in heating process subsequently, generate ZnO and Ag nano particle that particle diameter is 10～30nm simultaneously, the product that obtains is neither complete cladded type, neither complete self-existent ZnO and Ag nano particle, but partly adhere to mutually, part independently exists with form of nanoparticles.Self-existent like this nanometer Ag and ZnO particle can play bactericidal action, and the Ag that is attached on the ZnO nano grain surface can promote its photo-catalysis capability, are attached to ZnO on the Ag nano grain surface and can improve its surface-active and promote its antibiotic property.In addition, can be by in various atmosphere such as ammonia, adding thermolysis to composite nano antibacterial agent mix N and other element, thus widened its light-catalysed light wave scope.So the composite nano antibacterial agent that the present invention obtains had both had high antibiotic, biocidal efficacies, had the photocatalysis effect again, and adjusting process and composition reach different performance as required, and pollution-free and sewage the like waste product.This series antibacterial agent application is wide, safe, lasting, high temperature resistant, have no drug resistance and non-secondary pollution.
The concrete preparation method of above-mentioned composite nano germicide is as follows:
(1) preparation of presoma
Prepare certain density zinc sulphate or zinc nitrate, silver nitrate and ammonium bicarbonate aqueous solution at first on request.The concentration of getting a parts by volume is that 0.5～5mol/L zinc sulphate or zinc nitrate solution place container, under 10～90 ℃ temperature, constantly stir, and drip 0.5～5mol/L ammonium bicarbonate solution of equal volume with the liquid droping speed of 2～15ml/s, after ammonium hydrogencarbonate dropwises, continue to stir after 0.5～3 hour, while is the silver nitrate and the ammonium hydrogencarbonate of Ag:ZnO=1～50:50～99 with liquid droping speed dropping equal volume and the concentration of 2～15ml/s by mass ratio again, and solution dropwises back continuation stirring to be stopped after 0.5～3 hour reacting.Clean with redistilled water and/or absolute ethyl alcohol then and centrifugation goes out precursor mixture, vacuum drying subsequently, presoma preparation so far finishes.
(2) sintering of presoma
The presoma sample that drying is good is placed in vacuum controlled atmosphere furnace or the chamber type electric resistance furnace, under any one atmospheric condition in air, nitrogen containing atmosphere such as ammonia or the vacuum condition, be warming up to 380～600 ℃ with certain speed, and under this temperature, be incubated 2～5 hours, by the time after sufficient reacting carries out, with the stove cooling, can obtain zinc oxide/silver-colored composite nano germicide.
Below will simply enumerate several embodiments and come detailed in addition explanation:
The preparation method's of composite nano germicide of the present invention first embodiment is as follows:
Getting 200ml concentration is that 1～2mol/L solution of zinc sulfate is in there-necked flask, under 20～50 ℃ temperature, constantly stir, and drip 1～2mol/L ammonium bicarbonate solution of 200ml with the liquid droping speed of 3～8ml/s, after ammonium hydrogencarbonate dropwises, continue to stir after 0.5 hour, dripping by mass ratio with the liquid droping speed of 2～6ml/s simultaneously is that the concentration of Ag:ZnO=10:90 is 0 again.The silver nitrate of 1～1mol/L and 0.Each 100ml of 1～1mol/L ammonium hydrogencarbonate.Solution dropwises back continuation stirring and stops reaction after 0.5～1 hour.Go out presoma, vacuum drying subsequently with redistilled water and absolute ethyl alcohol washing and precipitating thing and centrifugation then.Dried presoma is placed chamber type electric resistance furnace, under air, be warming up to 430～460 ℃, and under this temperature, be incubated 3～5 hours,, can obtain zinc oxide/silver-colored composite nano germicide with the stove cooling with certain speed.Figure 1A and Figure 1B are the transmission electron microscope photo of zinc oxide/silver-colored composite nano germicide different amplification of obtaining under these process conditions.Fig. 2 is the size distribution result of zinc oxide/silver-colored composite nano germicide of obtaining under these process conditions.Fig. 3 is the X-ray diffraction result (XRD) of zinc oxide/silver-colored composite nano germicide of obtaining under these process conditions.This sample is 0.0075% (75PPm) in unglazed minimum inhibitory concentration of shining under the condition; The 365nm ultra violet lamp can be degraded to colourless solution with methyl orange solution.
The preparation method's of composite nano germicide of the present invention second embodiment is as follows:
Getting 200ml concentration is that 0.5～1.5mol/L solution of zinc sulfate is in there-necked flask, under 20～50 ℃ temperature, constantly stir, and drip 0.5～1.5mol/L ammonium bicarbonate solution of 200ml with the liquid droping speed of 3～8ml/s, after ammonium hydrogencarbonate dropwises, continue to stir after 1 hour, dripping by mass ratio with the liquid droping speed of 2～6ml/s simultaneously is that the concentration of Ag:ZnO=10:90 is silver nitrate and each 100ml of 0.1～1mol/L ammonium hydrogencarbonate of 0.1～1mol/L again.Solution dropwises back continuation stirring and stops reaction after 0.5～1.5 hour.Go out presoma, vacuum drying subsequently with redistilled water and/or absolute ethyl alcohol washing and precipitating thing and centrifugation then.Dried presoma is placed vacuum drying oven, under vacuum condition, be warming up to 400～430 ℃, and under this temperature, be incubated 2～4 hours,, can obtain zinc oxide/silver-colored composite nano germicide with the stove cooling with certain speed.Fig. 4 A and Fig. 4 B are the transmission electron microscope photo of zinc oxide/silver-colored composite nano germicide different amplification of obtaining under these process conditions.Fig. 5 is the size distribution result of zinc oxide/silver-colored composite nano germicide of obtaining under these process conditions.This sample is 0.0175% (175PPm) in unglazed minimum inhibitory concentration of shining under the condition; The 365nm ultra violet lamp can be degraded to colourless solution with methyl orange solution.
The preparation method's of composite nano germicide of the present invention the 3rd embodiment is as follows:
Getting 100ml concentration is that 0.5～1.5mol/L solution of zinc sulfate is in there-necked flask, under 20～40 ℃ temperature, constantly stir, and drip 0.5～1.5mol/L ammonium bicarbonate solution of 100ml with the liquid droping speed of 3～5ml/s, after ammonium hydrogencarbonate dropwises, continue to stir after 1～1.5 hour, the while is silver nitrate and each 50ml of 0.05～0.1mol/L ammonium hydrogencarbonate of 0.05～0.1mol/L with the liquid droping speed dropping concentration of 3～5ml/s again, is Ag:ZnO=5:95 by mass ratio.Solution dropwises back continuation stirring and stops reaction after 0.5～1 hour.Go out presoma, vacuum drying subsequently with redistilled water or absolute ethyl alcohol washing and precipitating thing and centrifugation then.Dried presoma is placed chamber type electric resistance furnace, under air, be warming up to 440～500 ℃, and under this temperature, be incubated 2～4 hours,, can obtain zinc oxide/silver-colored composite nano germicide with the stove cooling with certain speed.Fig. 6 A and Fig. 6 B are the transmission electron microscope photo of zinc oxide/silver-colored composite nano germicide different amplification of obtaining under these process conditions.Fig. 7 is the size distribution result of zinc oxide/silver-colored composite nano germicide of obtaining under these process conditions.This sample is 0.0250% (250PPm) in unglazed minimum inhibitory concentration of shining under the condition; The 365nm ultra violet lamp can be degraded to colourless solution with methyl orange solution.
The preparation method's of composite nano germicide of the present invention the 4th embodiment is as follows:
Getting 200ml concentration is 0.5～1.5mol/L zinc nitrate [Zn (NO
3)
2] solution is in there-necked flask, under 20～30 ℃ temperature, constantly stir, and drip 0.5～1.5mol/L ammonium bicarbonate solution of 200ml with the liquid droping speed of 4～6ml/s, after ammonium hydrogencarbonate dropwises, continue to stir after 0.5～1 hour, the while is silver nitrate and each 100ml of 0.1～0.5mol/L ammonium hydrogencarbonate of 0.1～0.5mol/L with the liquid droping speed dropping concentration of 2～5ml/s again, is Ag:ZnO=10:90 by mass ratio.Solution dropwises back continuation stirring and stops reaction after 0.5～1 hour.Go out presoma, vacuum drying subsequently with redistilled water and absolute ethyl alcohol washing and precipitating thing and centrifugation then.Dried presoma is placed chamber type electric resistance furnace, under air, be warming up to 450～500 ℃, and under this temperature, be incubated 2～4 hours,, can obtain zinc oxide/silver-colored composite nano germicide with the stove cooling with certain speed.Fig. 8 A and Fig. 8 B are the transmission electron microscope photo of zinc oxide/silver-colored composite nano germicide different amplification of obtaining under these process conditions.Fig. 9 is the size distribution result of zinc oxide/silver-colored composite nano germicide of obtaining under these process conditions.Figure 10 is the X-ray diffraction result (XRD) of zinc oxide/silver-colored composite nano germicide of obtaining under these process conditions.This sample is 0.0175% (175PPm) in unglazed minimum inhibitory concentration of shining under the condition; The 365nm ultra violet lamp can be degraded to colourless solution with methyl orange solution.
The preparation method's of composite nano germicide of the present invention the 5th embodiment is as follows:
Getting 200ml concentration is that 0.5～1.5mol/L zinc nitrate [Zn (NO3) 2] solution is in there-necked flask, under 20～30 ℃ temperature, constantly stir, and drip 0.5～1.5mol/L ammonium bicarbonate solution of 200ml with the liquid droping speed of 4～6ml/s, after ammonium hydrogencarbonate dropwises, continue to stir after 0.5～1 hour, while is silver nitrate and each 100ml of 0.1～0.5mol/L ammonium hydrogencarbonate of 0.1～0.5mol/L with the liquid droping speed dropping concentration of 2～5ml/s again, is Ag:ZnO=10:90 by mass ratio.Solution dropwises back continuation stirring and stops reaction after 0.5～1 hour.Go out presoma, vacuum drying subsequently with redistilled water and absolute ethyl alcohol washing and precipitating thing and centrifugation then.Dried presoma is placed vacuum drying oven, under vacuum condition, be warming up to 380～440 ℃, and under this temperature, be incubated 2～5 hours,, can obtain zinc oxide/silver-colored composite nano germicide with the stove cooling with certain speed.Figure 11 A and Figure 11 B are the transmission electron microscope photo of zinc oxide/silver-colored composite nano germicide different amplification of obtaining under these process conditions.Figure 12 is the size distribution result of zinc oxide/silver-colored composite nano germicide of obtaining under these process conditions.This sample is 0.02% (200PPm) in unglazed minimum inhibitory concentration of shining under the condition; The 365nm ultra violet lamp can be degraded to colourless solution with methyl orange solution.
Claims (2)
1. composite nano germicide, it comprises nano zine oxide and Nano Silver, it is characterized in that: the particle diameter of described nano zine oxide and Nano Silver is 10～30nm, Nano Silver is 1～50 to 99～50 with the mass ratio of nano zine oxide, and nano zine oxide and Nano Silver exist with following form: zinc oxide is attached to the nano-Ag particles form, argent is attached to the nano granular of zinc oxide form, independently nano-Ag particles, nano granular of zinc oxide independently.
2. composite nano germicide as claimed in claim 1 is characterized in that: described composite nano germicide also is doped with nitrogen.
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| CN102502779A (en) * | 2011-09-28 | 2012-06-20 | 苏州苏纳特科技有限公司 | Quick preparation method for silver-loaded zinc oxide nanometer composite powder |
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| CN111501361A (en) * | 2020-04-30 | 2020-08-07 | 浙江乔治白服饰股份有限公司 | Western-style clothes based on anti-stain antibacterial fabric |
| CN112175369B (en) * | 2020-10-13 | 2022-09-30 | 广东国立科技股份有限公司 | High-fluidity medical antibacterial degradable composite material and preparation method thereof |
| CN113583344B (en) * | 2021-08-10 | 2022-12-23 | 仙桃市鼎业劳保用品有限公司 | Antibacterial wear-resistant polypropylene plastic and application thereof |
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