CN111185170A - Preparation method of nano-silver antibacterial composite material wrapped by nano-zinc oxide - Google Patents
Preparation method of nano-silver antibacterial composite material wrapped by nano-zinc oxide Download PDFInfo
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- CN111185170A CN111185170A CN202010057292.8A CN202010057292A CN111185170A CN 111185170 A CN111185170 A CN 111185170A CN 202010057292 A CN202010057292 A CN 202010057292A CN 111185170 A CN111185170 A CN 111185170A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 326
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 181
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims description 115
- 239000002244 precipitate Substances 0.000 claims description 98
- 239000000243 solution Substances 0.000 claims description 94
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 57
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 46
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000001914 filtration Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 31
- 238000010992 reflux Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- 150000003751 zinc Chemical class 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical group CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 claims description 5
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 23
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 34
- 238000005406 washing Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000011259 mixed solution Substances 0.000 description 25
- 238000001291 vacuum drying Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910052709 silver Inorganic materials 0.000 description 15
- 239000004332 silver Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000011049 filling Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- -1 rare earth metal ion Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/39—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
Abstract
The invention relates to the technical field of nano zinc oxide composite materials, in particular to a preparation method of a nano silver antibacterial composite material wrapped by nano zinc oxide. According to the invention, the porous nano zinc oxide is synthesized by the aid of the auxiliary agent, the porous nano zinc oxide with porous surface, large specific surface area and strong adsorption force is synthesized, the porous nano zinc oxide is subjected to surface modification treatment, the modified nano zinc oxide is not easy to agglomerate, and the surface modified nano silver can smoothly enter pores of the surface modified nano zinc oxide to prepare the composite material with the surface modified nano silver coated by the surface modified nano zinc oxide.
Description
Technical Field
The invention relates to the technical field of nano zinc oxide composite materials, in particular to a preparation method of a nano silver antibacterial composite material wrapped by nano zinc oxide.
Background
In recent years, with the rapid development of society and the increasing living standard of materials, people have increasingly raised requirements for their living environment, and therefore, antibacterial materials have also been receiving wide attention. Among them, nano zinc oxide is one of the green antibacterial agents which are actively researched at present.
The nano zinc oxide is a wide forbidden band II and VI compound semiconductor material, has a regular hexagonal wurtzite structure, is small in size and large in specific surface area, and shows very high chemical activity. Because of its excellent photocatalytic activity under the irradiation of ultraviolet light, it can decompose organic substance, and has the action of resisting bacteria and deodorizing, and at the same time, because of its low cost and rich resource, it has important application value in the fields of ceramics, chemical industry, electronics, optics, biology and medicine, etc.
In recent years, how to improve the photocatalytic activity of nano zinc oxide, particularly the catalytic activity of visible light, is one of the research hotspots in the scientific community, the antibacterial performance of nano zinc oxide depends on the strength of the photocatalytic activity, so that the modification of nano zinc oxide material is of great significance, and the deposition of noble metal on the surface of zinc oxide semiconductor and the metal ion doping of zinc oxide are the most common methods. Noble metal deposition is typically deposition of Ag or Pd on the surface of zinc oxide. Chinese patent document CN107376905A discloses a method for preparing Ag/ZnO composite material capable of degrading formaldehyde, which disperses Ag nanoparticles on the surface of ZnO by physical vapor deposition. The metal ion-doped zinc oxide can be classified into transition metal ion doping, alkali metal doping, alkaline earth metal doping, rare earth metal ion doping, and the like according to the doping type. The silver ions have antibacterial property, and can change the surface property of zinc oxide after being doped with zinc oxide, so that the photocatalytic efficiency of the zinc oxide can be greatly improved, and the silver ions are widely applied. However, the improved method by Ag deposition has high requirements for gas pressure, temperature, and equipment, which directly results in high production cost and is uneconomical. The radius of the silver ions is far larger than that of the zinc ions, so that the silver ions are difficult to enter crystal lattices of the zinc oxide, and most of the silver ions are diffused on the surfaces of zinc oxide particles. The method limits the addition amount of silver and simultaneously weakens the synergistic antibacterial effect of the silver.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the nano-silver antibacterial catalytic composite material which has good photocatalytic effect and antibacterial effect and has the photocatalytic effect in the visible light region, and the preparation method is simple and easy to implement.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide comprises the following steps:
preparing porous nano zinc oxide: adding a sodium hydroxide solution and a dispersion liquid of an auxiliary agent into a zinc salt solution while stirring the zinc salt solution, stirring the mixture for 3-5h, standing, filtering and collecting a precipitate, and performing heat treatment on the precipitate at the temperature of 400-800 ℃ for 4-6h to obtain porous nano zinc oxide; the amount of the sodium hydroxide is 0.9-1.1 times of that of the zinc salt, and the mass of the auxiliary agent is 1-5% of that of the zinc salt.
Preferably, the zinc salt is zinc nitrate, zinc acetate, zinc chloride or zinc sulfate.
Preferably, the dispersant is at least one selected from cetyl trimethyl ammonium bromide, SBA-15 molecular sieve, MCM-41, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and polyethylene glycol 400 (PEG-400).
Preferably, the solvents of the zinc salt solution, the sodium hydroxide solution and the dispersion liquid of the auxiliary agent are all water.
Preparing surface modified nano zinc oxide: dispersing a silane coupling agent and porous nano zinc oxide in a solvent, refluxing for 4-6h at 75-80 ℃ under the environment of pH value of 4-10, collecting precipitates and drying to obtain surface modified nano zinc oxide; the mass ratio of the silane coupling agent to the nano zinc oxide is 1-3: 10.
Preferably, the silane coupling agent for preparing the surface modified nano zinc oxide is gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, phenylaminopropyl trimethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-methacryloxypropyl triethoxysilane, vinyltrimethylsilane or vinyltriethoxysilane.
Preferably, the silane coupling agent and the porous nano zinc oxide are dispersed in absolute ethyl alcohol.
Preparing surface modified nano silver powder: adding nano silver powder into a silane coupling agent solution with the pH value of 3-4, dispersing the mixture at 40-50 ℃, collecting precipitates and drying to obtain surface modified nano silver powder; the mass ratio of the silane coupling agent in the silane coupling agent solution to the nano silver powder is 2-4: 10.
Preferably, the silane coupling agent used for preparing the surface-modified silver nanopowder is dodecyl trimethoxysilane, vinyl triethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane.
Preferably, the solvent of the silane coupling agent solution is absolute ethyl alcohol.
Preparing composite powder: and (3) dropwise adding the dispersion liquid of the surface-modified nano silver powder into the dispersion liquid of the surface-modified nano zinc oxide, refluxing the mixture for 3-5h at 70-80 ℃ after dropwise adding, collecting the precipitate, and carrying out heat treatment on the precipitate to obtain the composite powder.
Preferably, when the composite powder is prepared, the precipitate is subjected to heat treatment at the temperature of 300-500 ℃ for 3-5 h.
Preferably, the mass ratio of the surface modified nano silver powder to the surface modified nano zinc oxide is 1-3: 10.
Preferably, in the dispersion liquid of the surface-modified silver nanopowder, the volume ratio of the mass of the surface-modified silver nanopowder to the solvent is less than or equal to 50 g/L.
Preferably, the solvent of the dispersion liquid of the surface-modified silver nanopowder is absolute ethyl alcohol.
Preferably, when the volume of the dispersion liquid of the surface-modified nano zinc oxide is less than or equal to 1L, the dropping speed of the dispersion liquid of the surface-modified nano silver powder is 0.1 mL/2-6S.
Preferably, the solvent of the dispersion liquid of the surface modified nano silver powder is absolute ethyl alcohol
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the porous nano zinc oxide is synthesized by the aid of the auxiliary agent, the porous nano zinc oxide with porous surface, large specific surface area and strong adsorption force is synthesized, the surface modification treatment is carried out on the porous nano zinc oxide, the modified nano zinc oxide is not easy to agglomerate, when the modified nano zinc oxide reacts with the surface modified nano silver modified by the silane coupling agent, the surface modified nano silver can smoothly enter pores of the surface modified nano zinc oxide due to the characteristics of the porous surface and the large specific surface area, the surface modified nano silver and the surface modified nano zinc oxide are subjected to a grafting reaction, and finally the composite material of the surface modified nano silver wrapped by the surface modified nano zinc oxide is prepared.
In the aspect of photocatalysis, the photo-generated electrons generated by the surface modified nano zinc oxide prepared by the invention continuously migrate to the precious metal conduction band, and the holes are remained on the valence band of the semiconductor zinc oxide, so that the recombination probability of the photo-generated electrons and the holes is reduced, and the range of absorption wavelength is expanded, thereby greatly improving the photocatalysis efficiency, having the effects of sterilization and formaldehyde removal under visible light without ultraviolet irradiation.
The nano zinc oxide-coated silver composite material prepared by the invention has strong adsorption capacity, can effectively adsorb and decompose pollutant gases such as formaldehyde and the like to achieve the aim of removing formaldehyde, and simultaneously, after the zinc oxide on the surface of the composite material adsorbs bacteria for sterilization, the silver coated in the composite material further kills the bacteria, thereby improving the antibacterial and bactericidal capacity of the composite material.
According to the invention, the nano-silver composite material wrapped by the nano-zinc oxide is synthesized by reacting the surface modified nano-zinc oxide with the surface modified nano-silver, so that the problem of high production cost of precious metal deposited nano-zinc oxide is solved, the problem of difficulty in doping the zinc oxide with silver ions is also solved, the preparation method is simple and easy to produce, and the prepared composite material has high photocatalytic activity and good antibacterial and sterilization effects.
Detailed Description
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to the following specific embodiments.
Example 1
The embodiment provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, which specifically comprises the following steps:
(1) dissolving zinc nitrate in water to form a uniform solution, adding a dispersion liquid of hexadecyl trimethyl ammonium bromide (water is used as a solvent), wherein the addition amount of the hexadecyl trimethyl ammonium bromide is 3% of the mass of the zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 3 hours at room temperature (25-30 ℃), standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times with water, and then placing the precipitates at 400 ℃ for heat treatment for 4 hours to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is in the range of 100-160nm, the pore diameter is in the range of 15-30nm, and the particle size distribution is uniform.
(2) Dispersing 1g of silane coupling agent gamma-aminopropyltriethoxysilane in 100ml of absolute ethanol, adding 10g of porous nano-zinc oxide after uniform dispersion, then putting the mixed solution into a 250ml round-bottom flask, adjusting the pH to 4 with hydrochloric acid, heating in an oil bath, refluxing for 4h at 75 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times with absolute ethanol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified nano-zinc oxide.
Dispersing 10g of the surface modified nano zinc oxide in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃ for 1 week, wherein the precipitation amount in the dispersion liquid is not more than 10% of the mass of the surface modified nano zinc oxide, and the dispersion liquid has good stability, so that the surface modified nano zinc oxide is not easy to agglomerate.
(3) Dispersing 2g of silane coupling agent gamma-glycidoxypropyltrimethoxysilane in 100ml of absolute ethyl alcohol, dropwise adding a hydrochloric acid solution to adjust the pH value to 4 after uniform dispersion, then adding 6g of nano silver powder with the particle size of 15-25nm, mixing uniformly, ultrasonically dispersing the mixed solution in a constant-temperature oil bath at 40 ℃, simultaneously mechanically stirring for 3 hours, filtering, washing the precipitate with toluene, and then placing in a vacuum drying box to obtain the surface modified nano silver powder.
(4) Dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion solution, then filling the first dispersion solution into a 500mL round-bottom flask, then dispersing 1g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion solution, adding the second dispersion solution into the first dispersion solution in a dropwise manner, wherein the dropwise adding speed of the second dispersion solution is 0.1mL/2s, refluxing the mixed solution at 70 ℃ for 3h after the dropwise adding is finished, then filtering and collecting a precipitate, washing the precipitate for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 300 ℃ for 3h after the drying is finished to obtain the composite material.
Tests show that the sterilization rate of the composite material formed after the precipitate is subjected to heat treatment at 300 ℃ for 3 hours is 98%, so that silver in the mixture is not oxidized into oxide in the heat treatment process, the silver is kept in a simple substance state, and the silver is wrapped by the surface modified nano zinc oxide and is not oxidized.
Example 2
The embodiment provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, which specifically comprises the following steps:
(1) dissolving zinc chloride in water to form a uniform solution, then adding a dispersion solution (water is used as a solvent) of cetyl trimethyl ammonium bromide and an SBA-15 molecular sieve, wherein the addition amounts of the cetyl trimethyl ammonium bromide and the SBA-15 molecular sieve are respectively 1.5% of the mass of zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 5 hours at room temperature (25-30 ℃), then standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times, and then placing the precipitates at 600 ℃ for heat treatment for 5 hours to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is in the range of 90-160nm, the pore diameter is in the range of 20-40nm, and the particle size distribution is uniform.
(2) Dispersing 1g of silane coupling agent gamma-methacryloxypropyltrimethoxysilane in 100mL of absolute ethyl alcohol, adding 6g of porous nano-zinc oxide after uniform dispersion, then putting the mixed solution into a 250mL round-bottom flask, adjusting the pH to 5 with hydrochloric acid, heating in an oil bath, refluxing for 5h at 75 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times with absolute ethyl alcohol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified nano-zinc oxide.
Dispersing 10g of the surface modified nano zinc oxide in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃ for 1 week, wherein the precipitation amount in the dispersion liquid is not more than 10% of the mass of the surface modified nano zinc oxide, and the dispersion liquid has good stability, so that the surface modified nano zinc oxide is not easy to agglomerate.
(3) Dispersing 2g of silane coupling agent vinyl triethoxysilane in 100mL of absolute ethanol, dropwise adding hydrochloric acid solution to adjust the pH value to 4 after uniform dispersion, then adding 10g of nano silver powder with the particle size of 15-25nm, mixing uniformly, ultrasonically dispersing the mixed solution in a constant-temperature oil bath at 45 ℃, simultaneously mechanically stirring for 4h, filtering, washing the precipitate with toluene, and placing in a vacuum drying oven to obtain the surface modified nano silver powder.
(4) Dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion, then filling the first dispersion into a 500mL round-bottom flask, then dispersing 1.5g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion, adding the second dispersion into the first dispersion in a dropwise manner, wherein the dropwise adding speed of the second dispersion is 0.1mL/3s, refluxing the mixed solution at 75 ℃ for 3h after the dropwise adding is finished, then filtering and collecting precipitates, washing the precipitates for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 400 ℃ for 4h after the drying is finished to obtain the composite material.
Example 3
The embodiment provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, which specifically comprises the following steps:
(1) dissolving zinc sulfate in water to form a uniform solution, adding a dispersion solution (water is used as a solvent) of polyvinylpyrrolidone and sodium dodecyl benzene sulfonate, wherein the addition amounts of the polyvinylpyrrolidone and the sodium dodecyl benzene sulfonate are respectively 1.5% of the mass of zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 5 hours at room temperature (25-30 ℃), standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates with excessive water, and then, carrying out heat treatment for 5 hours at 650 ℃ to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is within the range of 120-180nm, the pore diameter is within the range of 25-35nm, and the particle size distribution is uniform.
(2) Dispersing 1g of silane coupling agent phenylaminopropyl trimethoxy silane in 100mL of absolute ethyl alcohol, adding 10g of porous nano zinc oxide after uniform dispersion, then putting the mixed solution into a 250mL round-bottom flask, adjusting the pH to 10 with hydrochloric acid, heating in an oil bath, refluxing for 5h at 80 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times with absolute ethyl alcohol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified nano zinc oxide.
Dispersing 10g of the surface modified nano zinc oxide in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃ for 1 week, wherein the precipitation amount in the dispersion liquid is not more than 10% of the mass of the surface modified nano zinc oxide, and the dispersion liquid has good stability, so that the surface modified nano zinc oxide is not easy to agglomerate.
(3) Dispersing 2g of silane coupling agent dodecyl trimethoxy silane in 100mL of absolute ethyl alcohol, dropwise adding a hydrochloric acid solution to adjust the pH value to 4 after uniform dispersion, then adding 8g of nano silver powder with the particle size of 15-25nm, mixing uniformly, ultrasonically dispersing the mixed solution in a constant-temperature oil bath at 45 ℃, simultaneously mechanically stirring for 3h, filtering, washing the precipitate with toluene, and then placing in a vacuum drying oven to obtain the surface modified nano silver powder.
(4) Dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion, then filling the first dispersion into a 500mL round-bottom flask, then dispersing 2.5g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion, adding the second dispersion into the first dispersion in a dropwise manner, wherein the dropwise adding speed of the second dispersion is 0.1mL/4s, refluxing the mixed solution at 80 ℃ for 3h after the dropwise adding is finished, then filtering and collecting precipitates, washing the precipitates for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 450 ℃ for 5h after the drying is finished to obtain the composite material.
Example 4
The embodiment provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, which specifically comprises the following steps:
(1) dissolving zinc acetate in water to form a uniform solution, then adding a dispersion solution (water is used as a solvent) of cetyl trimethyl ammonium bromide and an SBA-15 molecular sieve, wherein the addition amounts of the cetyl trimethyl ammonium bromide and the SBA-15 molecular sieve are respectively 1.5% of the mass of zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 5 hours at room temperature (25-30 ℃), then standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times, and then placing the precipitates at 600 ℃ for heat treatment for 5 hours to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is in the range of 90-150nm, the pore diameter is in the range of 25-45nm, and the particle size distribution is uniform.
(2) Dispersing 1g of silane coupling agent gamma-methacryloxypropyltriethoxysilane in 100mL of absolute ethanol, adding 8g of porous nano-zinc oxide after uniform dispersion, then putting the mixed solution into a 250mL round-bottom flask, adjusting the pH to 10 with hydrochloric acid, heating in an oil bath, refluxing for 4h at 80 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times with absolute ethanol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified nano-zinc oxide.
Dispersing 10g of the surface modified nano zinc oxide in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃ for 1 week, wherein the precipitation amount in the dispersion liquid is not more than 10% of the mass of the surface modified nano zinc oxide, and the dispersion liquid has good stability, so that the surface modified nano zinc oxide is not easy to agglomerate.
(3) Dispersing 2g of silane coupling agent vinyl trimethoxy silane in 100mL of absolute ethyl alcohol, dropwise adding a hydrochloric acid solution to adjust the pH value to 3.5 after uniform dispersion, then adding 10g of nano silver powder with the particle size of 15-25nm, mixing uniformly, ultrasonically dispersing the mixed solution in a constant-temperature oil bath at 50 ℃, simultaneously mechanically stirring for 5h, filtering, washing the precipitate with toluene, and then placing in a vacuum drying oven to obtain the surface modified nano silver powder.
(4) Dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion solution, then filling the first dispersion solution into a 500mL round-bottom flask, then dispersing 2g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion solution, adding the second dispersion solution into the first dispersion solution in a dropwise manner, wherein the dropwise adding speed of the second dispersion solution is 0.1mL/2s, refluxing the mixed solution at 75 ℃ for 3h after the dropwise adding is finished, then filtering and collecting a precipitate, washing the precipitate for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 500 ℃ for 5h after the drying is finished to obtain the composite material.
Example 5
The embodiment provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, which specifically comprises the following steps:
(1) dissolving zinc nitrate in water to form a uniform solution, adding a dispersion liquid of sodium dodecyl benzene sulfonate (water is used as a solvent) into the uniform solution, wherein the addition amount of the sodium dodecyl benzene sulfonate is 1 percent of the mass of the zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 4 hours at room temperature (25-30 ℃), standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times with water, and then, placing the precipitates at 500 ℃ for heat treatment for 5 hours to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is within the range of 100-170nm, the pore diameter is within the range of 20-30nm, and the particle size distribution is uniform.
(2) Dispersing 1g of silane coupling agent gamma-aminopropyltrimethoxysilane in 100mL of absolute ethyl alcohol, adding 5g of porous nano zinc oxide after uniform dispersion, then putting the mixed solution into a 250mL round-bottom flask, adjusting the pH to 6 by using hydrochloric acid, heating by using an oil bath, refluxing for 4h at 75 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times by using absolute ethyl alcohol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified nano zinc oxide.
Dispersing 10g of the surface modified nano zinc oxide in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃ for 1 week, wherein the precipitation amount in the dispersion liquid is not more than 10% of the mass of the surface modified nano zinc oxide, and the dispersion liquid has good stability, so that the surface modified nano zinc oxide is not easy to agglomerate.
(3) Dispersing 2g of silane coupling agent gamma-methacryloxypropyltrimethoxysilane into 100mL of absolute ethyl alcohol, dropwise adding a hydrochloric acid solution to adjust the pH value to 4 after uniform dispersion, then adding 8g of nano silver powder with the particle size of 15-25nm, after uniform mixing, ultrasonically dispersing the mixed solution in a constant-temperature oil bath at 45 ℃, simultaneously mechanically stirring for 4 hours, filtering, washing the precipitate with toluene, and then placing in a vacuum drying oven to obtain the surface modified nano silver powder.
(4) Dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion solution, then filling the first dispersion solution into a 500mL round-bottom flask, then dispersing 2g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion solution, adding the second dispersion solution into the first dispersion solution in a dropwise manner, wherein the dropwise adding speed of the second dispersion solution is 0.1mL/4s, refluxing the mixed solution at 70 ℃ for 3h after the dropwise adding is finished, then filtering and collecting a precipitate, washing the precipitate for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 400 ℃ for 4h after the drying is finished to obtain the composite material.
Example 6
The embodiment provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, which specifically comprises the following steps:
(1) dissolving zinc sulfate in water to form a uniform solution, adding a dispersion solution (water is used as a solvent) of MCM-41 and polyvinylpyrrolidone, wherein the addition amounts of the MCM-41 and the polyvinylpyrrolidone are respectively 1.5% of the mass of zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 5 hours at room temperature (25-30 ℃), standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates with excessive water, and then, carrying out heat treatment for 6 hours at 500 ℃ to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is within the range of 120-180nm, the pore diameter is within the range of 25-45nm, and the particle size distribution is uniform.
(2) Dispersing 1g of silane coupling agent gamma-glycidoxypropyltriethoxysilane in 100mL of absolute ethanol, adding 8g of porous nano-zinc oxide after uniform dispersion, then putting the mixed solution into a 250mL round-bottom flask, adjusting the pH to 4 with hydrochloric acid, heating in an oil bath, refluxing for 4h at 75 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times with absolute ethanol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified nano-zinc oxide.
Dispersing 10g of the surface modified nano zinc oxide in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃ for 1 week, wherein the precipitation amount in the dispersion liquid is not more than 10% of the mass of the surface modified nano zinc oxide, and the dispersion liquid has good stability, so that the surface modified nano zinc oxide is not easy to agglomerate.
(3) Dispersing 2g of silane coupling agent gamma-methacryloxypropyltrimethoxysilane into 100mL of absolute ethyl alcohol, dropwise adding a hydrochloric acid solution to adjust the pH value to 4 after uniform dispersion, then adding 8g of nano silver powder with the particle size of 15-25nm, after uniform mixing, ultrasonically dispersing the mixed solution in a constant-temperature oil bath at 45 ℃, simultaneously mechanically stirring for 4 hours, filtering, washing the precipitate with toluene, and then placing in a vacuum drying oven to obtain the surface modified nano silver powder.
(4) Dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion solution, then filling the first dispersion solution into a 500mL round-bottom flask, then dispersing 3g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion solution, adding the second dispersion solution into the first dispersion solution in a dropwise manner, wherein the dropwise adding speed of the second dispersion solution is 0.1mL/4s, refluxing the mixed solution at 70 ℃ for 3h after the dropwise adding is finished, then filtering and collecting a precipitate, washing the precipitate for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 500 ℃ for 5h after the drying is finished to obtain the composite material.
Example 7
The embodiment provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, which specifically comprises the following steps:
(1) dissolving zinc nitrate in water to form a uniform solution, adding a dispersion liquid of hexadecyl trimethyl ammonium bromide (water is used as a solvent), wherein the addition amount of the hexadecyl trimethyl ammonium bromide is 5% of the mass of the zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 3 hours at room temperature (25-30 ℃), standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times with water, and then placing the precipitates at 800 ℃ for heat treatment for 4 hours to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is within the range of 100-170nm, the pore diameter is within the range of 15-30nm, and the particle size distribution is uniform.
(2) Dispersing 3g of silane coupling agent vinyl trimethyl silane in 100ml of absolute ethyl alcohol, adding 10g of porous nano zinc oxide after uniform dispersion, then putting the mixed solution into a 250ml round-bottom flask, adjusting the pH to 4 by using hydrochloric acid, heating by using an oil bath, refluxing for 6h at 75 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times by using absolute ethyl alcohol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified nano zinc oxide.
Dispersing 10g of the surface modified nano zinc oxide in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃ for 1 week, wherein the precipitation amount in the dispersion liquid is not more than 10% of the mass of the surface modified nano zinc oxide, and the dispersion liquid has good stability, so that the surface modified nano zinc oxide is not easy to agglomerate.
(3) Dispersing 2g of silane coupling agent gamma-glycidoxypropyltrimethoxysilane in 100ml of absolute ethyl alcohol, dropwise adding a hydrochloric acid solution to adjust the pH value to 3 after uniform dispersion, then adding 5g of nano silver powder with the particle size of 15-25nm, mixing uniformly, ultrasonically dispersing the mixed solution in a constant-temperature oil bath at 40 ℃, simultaneously mechanically stirring for 3 hours, filtering, washing the precipitate with toluene, and then placing in a vacuum drying box to obtain the surface modified nano silver powder.
(4) Dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion solution, then filling the first dispersion solution into a 500mL round-bottom flask, then dispersing 1g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion solution, adding the second dispersion solution into the first dispersion solution in a dropwise manner, wherein the dropwise adding speed of the second dispersion solution is 0.1mL/2s, refluxing the mixed solution at 70 ℃ for 3h after the dropwise adding is finished, then filtering and collecting a precipitate, washing the precipitate for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 300 ℃ for 3h after the drying is finished to obtain the composite material.
Comparative example 1
The comparative example provides a preparation method of a composite material of nano zinc oxide and nano silver, which specifically comprises the following steps:
(1) dissolving zinc nitrate in water to form a uniform solution, quickly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 3 hours at room temperature (25-30 ℃), then standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times, and then placing the precipitates at 400 ℃ for heat treatment for 4 hours to obtain zinc oxide powder. The particle size of the obtained zinc oxide powder is observed by a particle sizer, the particle size is in the range of 0.1-1 mu m, the particle size distribution is wide, and a porous structure is not seen.
The steps (2), (3) and (4) are the same as those of the example 1, only the porous nano zinc oxide powder is replaced by the zinc oxide powder instead of the porous nano zinc oxide, which is prepared in the step (1), and the surface modified nano zinc oxide is replaced by the surface modified zinc oxide powder in the example 1.
And (3) dispersing 10g of the surface modified nano zinc oxide prepared in the step (2) in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃, wherein after 8h, a precipitate can be obviously seen in a dispersion liquid, the stability of the dispersion liquid is relatively poor, and the surface modified nano zinc oxide in the solution is easy to agglomerate.
Comparative example 2
The comparative example provides a preparation method of a composite material of nano zinc oxide and nano silver, which specifically comprises the steps (1), (2) and (3) as described in example 1, and is consistent with the step (4) except that in the step (4), the step (4) of the comparative example is as follows:
dispersing 10g of surface modified nano zinc oxide in 100mL of absolute ethyl alcohol to form a first dispersion solution, then filling the first dispersion solution into a 500mL round-bottom flask, then dispersing 4g of surface modified nano silver powder in 200mL of absolute ethyl alcohol to form a second dispersion solution, adding the second dispersion solution into the first dispersion solution in a dropwise manner, wherein the dropwise adding speed of the second dispersion solution is 1mL/1s, refluxing the mixed solution at 70 ℃ for 3h after the dropwise adding is finished, then filtering and collecting precipitates, washing the precipitates for multiple times by using toluene, drying in a vacuum drying oven, and carrying out heat treatment at 300 ℃ for 3h after the drying is finished to obtain the composite material.
Comparative example 3
The comparative example provides a method for preparing a nano-silver antibacterial composite material coated with nano-zinc oxide, the specific steps are basically the same as those of example 1, except that the silane coupling agent used in step (2) of the comparative example is dodecyl trimethoxy silane, i.e. the dodecyl trimethoxy silane is used to replace gamma-aminopropyl triethoxy silane in step (2) of example 1, and the other steps are the same as those of example 1.
And (3) dispersing 10g of the surface modified nano zinc oxide prepared in the step (2) in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃, obviously seeing precipitate in the dispersion liquid after 12h, ensuring that the stability of the dispersion liquid is relatively poor, and easily agglomerating the surface modified nano zinc oxide in the solution.
Comparative example 4
The comparative example provides a preparation method of nano-silver antibacterial composite material coated with nano-zinc oxide, the specific steps are basically the same as those of example 1, except that the silane coupling agent used in step (3) of the comparative example is phenylaminopropyl trimethoxy silane, i.e. phenylaminopropyl trimethoxy silane is used to replace gamma-glycidoxypropyl trimethoxy silane in step (3) of example 1, and the other steps are the same as those of example 1.
Comparative example 5
The comparative example provides a method for preparing nano-silver antibacterial composite material coated with nano-zinc oxide, the specific steps are basically the same as those of example 1, except that the silane coupling agent used in step (3) of the comparative example is gamma-aminopropyltrimethoxysilane, namely, the gamma-aminopropyltrimethoxysilane is used to replace the gamma-glycidoxypropyltrimethoxysilane in step (3) of example 1, and the other steps are the same as those of example 1.
Comparative example 6
The comparative example provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, the specific steps are basically the same as those of the example 1, except that the silane coupling agent used in the step (3) of the comparative example is gamma-glycidoxypropyltriethoxysilane, namely the gamma-glycidoxypropyltriethoxysilane replaces the gamma-glycidoxypropyltrimethoxysilane in the step (3) of the example 1, and the other steps are the same as those of the example 1.
Comparative example 7
The comparative example provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, the specific steps are basically the same as those of the example 1, except that the silane coupling agent used in the step (3) of the comparative example is gamma-methacryloxypropyltriethoxysilane, namely, the gamma-glycidoxypropyltrimethoxysilane in the step (3) of the example 1 is replaced by the gamma-methacryloxypropyltriethoxysilane, and other steps are the same as those of the example 1.
Comparative example 8
The comparative example provides a preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide, the specific steps are basically the same as those of the example 1, except that the silane coupling agent used in the step (3) of the comparative example is vinyl trimethylsilane, namely, the vinyl trimethylsilane is used for replacing the gamma-glycidyl ether oxypropyl trimethoxysilane in the step (3) of the example 1, and the other steps are the same as those of the example 1.
Comparative example 9
The comparative example provides a preparation method of a composite material of nano zinc oxide and nano silver, which specifically comprises the following steps:
(1) dissolving zinc nitrate in water to form a uniform solution, adding a dispersion liquid of hexadecyl trimethyl ammonium bromide (water is used as a solvent), wherein the addition amount of the hexadecyl trimethyl ammonium bromide is 3% of the mass of the zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 3 hours at room temperature (25-30 ℃), standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times with water, and then placing the precipitates at 400 ℃ for heat treatment for 4 hours to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is in the range of 350-1500nm, the pore diameter is in the range of 15-30nm, and the particle size distribution is wide.
(2) Dispersing 1g of silane coupling agent gamma-aminopropyltriethoxysilane in 100ml of absolute ethanol, adding 10g of porous nano zinc oxide after uniform dispersion, then putting the mixed solution into a 250ml round-bottom flask, adjusting the pH to 4 by hydrochloric acid, heating in an oil bath, refluxing for 4h at 75 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times by absolute ethanol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified zinc oxide.
Steps (3) and (4) were the same as those of example 1.
And (3) dispersing 10g of the surface modified nano zinc oxide prepared in the step (2) in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃, and after 24 hours, generating a small amount of precipitate in the dispersion liquid, wherein the stability of the dispersion liquid is relatively poor, and the surface modified nano zinc oxide in the solution is easy to agglomerate.
Comparative example 10
The comparative example provides a preparation method of a composite material of nano zinc oxide and nano silver, which specifically comprises the following steps:
(1) dissolving zinc nitrate in water to form a uniform solution, adding a dispersion liquid of hexadecyl trimethyl ammonium bromide (water is used as a solvent), wherein the addition amount of the hexadecyl trimethyl ammonium bromide is 3% of the mass of the zinc nitrate, rapidly pouring a sodium hydroxide solution with the same mole as the zinc nitrate under the condition of stirring, stirring for 3 hours at room temperature (25-30 ℃), standing the reaction solution, filtering and collecting precipitates within 24 hours, washing the precipitates for many times with water, and then placing the precipitates at 400 ℃ for heat treatment for 4 hours to obtain the porous nano zinc oxide. The particle size and the pore diameter of the obtained porous nano zinc oxide are observed by a particle sizer, the particle size is in the range of 300-1100nm, the pore diameter is in the range of 15-30nm, and the particle size distribution is wide.
(2) Dispersing 4g of silane coupling agent gamma-aminopropyltriethoxysilane in 100ml of absolute ethanol, adding 10g of porous nano zinc oxide after uniform dispersion, then putting the mixed solution into a 250ml round-bottom flask, adjusting the pH to 4 by hydrochloric acid, heating in an oil bath, refluxing for 4h at 75 ℃, filtering after the reaction is finished to obtain a precipitate, washing the precipitate for multiple times by absolute ethanol, and placing the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain the surface modified zinc oxide.
Steps (3) and (4) were the same as those of example 1.
And (3) dispersing 10g of the surface modified nano zinc oxide prepared in the step (2) in 100mL of absolute ethyl alcohol, standing at the room temperature of 25-30 ℃, wherein after 8h, a precipitate can be obviously seen in a dispersion liquid, the stability of the dispersion liquid is relatively poor, and the surface modified nano zinc oxide in the solution is easy to agglomerate.
Comparative example 11
The comparative example provides a preparation method of a composite material of nano zinc oxide and nano silver, which specifically comprises the steps (1), (2) and (4) as described in example 1, and is consistent with the step (3) except that in the step (3), the step (3) of the comparative example is as follows:
3g of silane coupling agent gamma-glycidoxypropyltrimethoxysilane is dispersed in 100ml of absolute ethyl alcohol, hydrochloric acid solution is dropwise added after uniform dispersion to adjust the pH value to 5, 7g of nano silver powder with the particle size of 15-25nm is added, after uniform mixing, the mixed solution is ultrasonically dispersed in a constant temperature oil bath at 60 ℃, and is mechanically stirred for 3 hours at the same time, then filtration is carried out, and precipitates are washed by toluene and then placed in a vacuum drying box to obtain the surface modified nano silver powder.
And (3) testing: the composite materials prepared in the above examples and comparative examples were tested for their bactericidal and formaldehyde-removing properties
Testing one: the composite materials prepared in the above examples and comparative examples were tested for bactericidal properties
The detection method comprises the following steps: the composite materials prepared in the examples and the comparative examples are respectively used for preparing dispersion liquid with water, the mass fraction of the composite material is 1.5%, and sample liquid corresponding to the composite materials prepared in the examples and the comparative examples is prepared by ultrasonic dispersion.
Uniformly mixing the sample solution and the staphylococcus aureus solution in equal volume, oscillating the mixture on an oscillator for 30min, then uniformly coating 50mL of the solution on a plate for experiment, putting the plate for experiment and a control plate without the composite material into a thermostatic chamber, standing the plate for 24h, taking out the plate and the control plate, counting the colony number of the plate respectively, and then calculating the sterilization rate.
The bactericidal ratio (number of colonies in control experiment-number of colonies in sample experiment)/number of colonies in control experiment X100%
And (2) testing: the formaldehyde removing performance of the composite materials prepared in the above examples and comparative examples was examined
The detection method comprises the following steps: the composite material is sprayed on a clean glass plate, and after air drying, detection is carried out according to JC/1074 plus 2008 'indoor air purification function coating material purification performance'.
The results of the tests one and two are shown in the following table.
Comparative example 1 the nano zinc oxide having a porous structure could not be formed because the assistant was added during the preparation of the porous nano zinc oxide, and the prepared zinc oxide powder had no porous structure and was a non-nano material having a particle size in the range of 0.1 to 1 μm. Although the composite material was subsequently prepared in the same manner as in example 1, the antibacterial ability of the prepared composite material was significantly reduced, and the antibacterial ratio was only 52%. Therefore, the particle size distribution and the surface of the zinc oxide have no pores, so that the structure of the composite material is changed, the recombination probability of electrons and holes is influenced, and the antibacterial capability of the composite material is influenced.
Comparative example 2 because the surface-modified nano zinc oxide and the surface-modified nano silver powder are not properly matched, the addition amount of the surface-modified nano silver powder is large, and the speed of dripping the dispersion liquid in which the surface-modified nano silver powder is dispersed into the dispersion liquid of the surface-modified nano zinc oxide is too high, the structure of the silver coated by the nano zinc oxide is changed, the recombination probability of electrons and holes cannot be effectively reduced, so that the antibacterial capacity of the formed composite material is remarkably reduced, and the antibacterial rate is only 72%.
In comparative example 3, when the surface-modified nano-zinc oxide is prepared, the structure of the prepared surface-modified nano-zinc oxide is affected, so that the antibacterial rate of the finally prepared composite material is obviously reduced, and the antibacterial rate is 76%. In comparative examples 4 to 8, since the surface-modified nano silver was used as the silane coupling agent during the preparation of the surface-modified nano silver, the structure of the prepared surface-modified nano silver was also affected, so that the antibacterial rate of the finally prepared composite material was also significantly reduced, and the antibacterial rate was between 65% and 70%.
In comparative example 9, because more additives are added during the preparation of the porous nano zinc oxide, the prepared porous nano zinc oxide has relatively large particle size and relatively small pore size, and the distribution range of the particle size is relatively wide, the antibacterial rate of the finally prepared composite material is obviously reduced, and thus, the particle size, the pore size and the particle size distribution of the porous nano zinc oxide all influence the antibacterial ability of the finally formed composite material. In comparative example 10, since a large amount of silane coupling agent was added during the preparation of surface-modified nano zinc oxide, the addition amount of silane coupling agent also affected the structure of surface-modified nano zinc oxide, and finally affected the antibacterial ability of the formed composite material.
In comparative example 11, the structure of the formed surface-modified nano silver was affected and the antibacterial ability of the formed composite material was finally affected due to the addition of a large amount of silane coupling agent during the preparation of the surface-modified nano silver and the interaction of the silane coupling agent and the nano silver powder in the environment of pH 5 and 60 ℃.
The technical contents of the present invention are further illustrated by the examples, so as to facilitate the understanding of the reader, but the embodiments of the present invention are not limited thereto, and any technical extension or re-creation based on the present invention is protected by the present invention.
Claims (10)
1. A preparation method of a nano-silver antibacterial composite material wrapped by nano-zinc oxide is characterized by comprising the following steps:
preparing porous nano zinc oxide: adding a sodium hydroxide solution and a dispersion liquid of an auxiliary agent into a zinc salt solution while stirring the zinc salt solution, stirring the mixture for 3-5h, standing, filtering and collecting a precipitate, and performing heat treatment on the precipitate at the temperature of 400-800 ℃ for 4-6h to obtain porous nano zinc oxide; the amount of the sodium hydroxide is 0.9-1.1 times of that of the zinc salt, and the mass of the auxiliary agent is 1-5% of that of the zinc salt:
preparing surface modified nano zinc oxide: dispersing a silane coupling agent and porous nano zinc oxide in a solvent, refluxing for 4-6h at 75-80 ℃ under the environment of pH value of 4-10, collecting precipitates and drying to obtain surface modified nano zinc oxide; the mass ratio of the silane coupling agent to the nano zinc oxide is 1-3: 10;
preparing surface modified nano silver powder: adding nano silver powder into a silane coupling agent solution with the pH value of 3-4, dispersing the mixture at 40-50 ℃, collecting precipitates and drying to obtain surface modified nano silver powder; the mass ratio of the silane coupling agent in the silane coupling agent solution to the nano silver powder is 2-4: 10;
preparing composite powder: and (3) dropwise adding the dispersion liquid of the surface-modified nano silver powder into the dispersion liquid of the surface-modified nano zinc oxide, refluxing the mixture for 3-5h at 70-80 ℃ after dropwise adding, collecting the precipitate, and carrying out heat treatment on the precipitate to obtain the composite powder.
2. The method for preparing nano-zinc oxide coated nano-silver antibacterial composite material according to claim 1, wherein the zinc salt is zinc nitrate, zinc acetate, zinc chloride or zinc sulfate.
3. The method for preparing nano-zinc oxide coated nano-silver antibacterial composite material according to claim 1, wherein the dispersing agent is at least one selected from cetyl trimethyl ammonium bromide, SBA-15 molecular sieve, MCM-41, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and polyethylene glycol 400(PEG 400).
4. The method for preparing nano-silver antibacterial composite material coated with nano-zinc oxide according to claim 1, wherein the silane coupling agent for preparing surface modified nano-zinc oxide is gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, phenylaminopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-methacryloxypropyltriethoxysilane, vinyltrimethylsilane or vinyltriethoxysilane.
5. The method for preparing nano-silver antibacterial composite material coated with nano-zinc oxide according to claim 1, wherein the silane coupling agent for preparing the surface-modified nano-silver powder is dodecyl trimethoxy silane, vinyl triethoxy silane, gamma-aminopropyl triethoxy silane, gamma-glycidyl ether oxypropyl trimethoxy silane or gamma-methacryloxypropyl trimethoxy silane.
6. The method for preparing nano-silver antibacterial composite material wrapped with nano-zinc oxide as claimed in claim 1, wherein the precipitate is heat treated at 500 ℃ for 3-5h at 300 ℃ when preparing the composite powder.
7. The method for preparing nano-silver antibacterial composite material coated with nano-zinc oxide according to claim 1, wherein the mass ratio of the surface modified nano-silver powder to the surface modified nano-zinc oxide is 1-3: 10 when preparing the composite powder.
8. The method for preparing nano-silver antibacterial composite material coated with nano-zinc oxide according to claim 1, wherein the mass-to-solvent volume ratio of the surface-modified nano-silver powder in the dispersion of the surface-modified nano-silver powder is less than or equal to 50g/L when preparing the composite powder.
9. The method for preparing the nano-silver antibacterial composite material coated with nano-zinc oxide according to claim 8, wherein when the volume of the dispersion liquid of the surface-modified nano-zinc oxide is less than or equal to 1L in preparing the composite powder, the dropping speed of the dispersion liquid of the surface-modified nano-silver powder is 0.1 mL/2-6S.
10. The method for preparing nano-silver antibacterial composite material coated with nano-zinc oxide according to claim 8, wherein the solvent of the dispersion liquid of the surface-modified nano-silver powder is absolute ethyl alcohol when preparing the composite powder.
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