CN114425055B - 一种二氧化硅负载多金属纳米颗粒及其制备方法及其抗菌应用 - Google Patents
一种二氧化硅负载多金属纳米颗粒及其制备方法及其抗菌应用 Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000000443 aerosol Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000000084 colloidal system Substances 0.000 claims abstract description 3
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 3
- 239000011858 nanopowder Substances 0.000 claims abstract description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 241000588724 Escherichia coli Species 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001580 bacterial effect Effects 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 241000894007 species Species 0.000 claims 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 5
- 238000001856 aerosol method Methods 0.000 abstract description 4
- 241000894006 Bacteria Species 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 14
- 238000011068 loading method Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 11
- 229910017944 Ag—Cu Inorganic materials 0.000 description 8
- 229910017518 Cu Zn Inorganic materials 0.000 description 8
- 229910017752 Cu-Zn Inorganic materials 0.000 description 8
- 229910017943 Cu—Zn Inorganic materials 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 238000001994 activation Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 244000157072 Hylocereus undatus Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000018481 Hylocereus undatus Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NZWXMOTXTNDNLK-UHFFFAOYSA-N [Cu].[Zn].[Ag] Chemical compound [Cu].[Zn].[Ag] NZWXMOTXTNDNLK-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- 241000304886 Bacilli Species 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 235000010837 Echinocereus enneacanthus subsp brevispinus Nutrition 0.000 description 1
- 235000006850 Echinocereus enneacanthus var dubius Nutrition 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 241000194017 Streptococcus Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 229940065181 bacillus anthracis Drugs 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009690 centrifugal atomisation Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/38—Silver; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/30—Zinc; Compounds thereof
-
- A—HUMAN NECESSITIES
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- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/24—Heavy metals; Compounds thereof
- A61K33/34—Copper; Compounds thereof
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
- A61K47/6921—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit the form being a particulate, a powder, an adsorbate, a bead or a sphere
- A61K47/6923—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit the form being a particulate, a powder, an adsorbate, a bead or a sphere the form being an inorganic particle, e.g. ceramic particles, silica particles, ferrite or synsorb
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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Abstract
本发明公开了一种二氧化硅负载多金属纳米颗粒的制备方法，包括如下步骤：1)将复合金属盐、硅源和酸溶于水中混合，引入挥发性有机溶剂，混合均匀形成胶体溶液或均相溶液，得前驱体溶液；2)将所得前驱体溶液经过雾化器形成气溶胶液滴；3)将形成的气溶胶液滴导入高温管式炉中进行煅烧，形成纳米粉体颗粒，即二氧化硅负载多金属纳米颗粒。本发明首次提出采用气溶胶法制备二氧化硅包覆银铜双纳米合金纳米颗粒，可有效解决现有制备二氧化硅包覆银铜双纳米颗粒的技术难题，所得复合材料可对多种细菌表现出良好的抑制和消杀作用；且涉及的制备方法简单、操作方便，适合推广应用。
Description
技术领域
本发明属于功能材料制备技术领域，具体涉及一种二氧化硅负载多金属纳米颗粒及其制备方法及其抗菌应用。
背景技术
随着纳米技术的快速发展，纳米材料已经融入到了人们日常生活的方方面面。纳米材料的独特性质在抗菌领域也发挥着极为重要的作用。其中，银纳米粒子就是一种常见的广谱抗菌性。它具有良好的生物相容性，对多种细菌产生抑制作用而不产生耐药性。另外，氧化铜、氧化亚铜、纳米铜等也均有抗菌作用。研究表明，银铜双金属纳米颗粒之间的协同作用，会极大的提升其抗菌性能。
目前制备双金属纳米颗粒的方法包括共还原法、连续还原法等化学还原方法，以及多元醇还原法、置换反应法微波辅助加热法等方式，但均因操作方式复杂，不利于大规模工业化生产。另外，在制备过程中，颗粒的粒径可控性较差，金属纳米颗粒容易发生团聚等不利因素，还会降低载体的负载强度。
发明内容
本发明的主要目的在于针对现有制备技术存在的不足，提供一种基于气溶胶法制备二氧化硅包覆银铜双纳米合金纳米颗粒的方法，解决现有制备二氧化硅包覆银铜双纳米颗粒的技术难题，并可对多种细菌表现出良好的抑制和消杀作用；且涉及的制备方法简单、操作方便，适合推广应用。
为实现上述目的，本发明采用的技术方案为：
一种二氧化硅负载多金属纳米颗粒的制备方法，包括如下步骤：
1)将复合金属盐、硅源和酸溶于水中混合，引入挥发性有机溶剂，混合均匀形成胶体溶液或均相溶液，得前驱体溶液；
2)将所得前驱体溶液经过雾化器形成气溶胶液滴；
3)将形成的气溶胶液滴导入高温管式炉中进行煅烧，形成纳米粉体颗粒，即二氧化硅负载多金属纳米颗粒。
上述方案中，所述复合金属盐为银盐、铜盐和锌盐中的两种以上。
上述方案中，所述银盐选自硝酸银、氟化银，高氯酸银等可溶性银盐中的一种或几种；铜盐选自硝酸铜、硫酸铜、氯化铜等可溶性铜盐中的一种或几种；锌盐选自氢氧化锌、氯化锌、硫化锌、硝酸锌等可溶性锌盐中的一种或几种。
上述方案中，所述硅源选自正硅酸乙酯、甲基三乙氧基硅烷、甲基三甲氧基硅烷、3-氨丙基三乙氧基硅烷等中的一种或几种。
上述方案中，所述酸源为盐酸、硫酸、硝酸或氯酸；所得前驱体溶液的pH值为1～7。
上述方案中，所述前驱体溶液中复合金属盐引入的金属单质与硅源的质量比为1:100～10:1。
上述方案中，所述复合金属盐引入的金属单质两两之间的质量比为1:(0.1～10):(0.1～10)。
上述方案中，所述挥发性有机溶剂为甲醇、乙醇、异丙醇、二甲基甲酰胺、乙酸、乙腈中的一种或几种；挥发性有机溶剂与复合金属盐的液固比为(1～50):1ml:g。
上述方案中，所述气溶胶液滴的粒径为0.01-200μm。
上述方案中，步骤2)中形成气溶胶液滴的雾化方式可选用超声波雾化器、空气压缩式雾化器、离心雾化等雾化方式。
上述方案中，步骤3)中所述煅烧温度为100～1600℃，煅烧时间为0.1～60s。
上述方案中，步骤3)中采用的煅烧气氛为空气、N2、Ar、CO2、O2、He或其他混合气体。
优选的，所述二氧化硅负载多金属纳米颗粒进一步进行高温活化，采用的温度为100～1600℃，时间为1～72h，活化气氛包括Air、N2、Ar、H2、He、O2、CO、CO2等气体及其混合气体。
根据上述方案制备的二氧化硅负载多金属纳米颗粒，其中多金属纳米颗粒包括银纳米颗粒、铜纳米颗粒和锌纳米颗粒中的两种以上，且被包覆在多孔二氧化硅微球中。
上述方案中，所述二氧化硅负载多金属纳米颗粒的粒径为100～600nm；其中包覆的金属纳米颗粒粒径为1～20nm。
将上述方案所得二氧化硅负载多金属纳米颗粒进行抗菌应用，适用的菌种包括双球菌、链球菌、葡萄球菌等球菌，枯草芽孢杆菌、炭疽芽孢杆菌等杆菌；具有广谱抗菌性。
本发明所述气溶胶法利用雾化装置，使前驱体溶液分散为单分散性较高的液滴进入反应阶段，达到了化学过程中的平衡统一，保证了所获得纳米材料的粒径可控和较好的单分散性；同时本发明采取一步法制备工艺，可有效避免后续处理过程中金属颗粒的二次烧结团聚，进一步保证所得金属负载颗粒的单分散性和良好的活性，具有很好的应用前景。
与现有技术相比，本发明的有益效果为：
1)本发明首次提出采用气溶胶法制备二氧化硅负载多金属纳米颗粒，通过液滴的蒸发自组装一步实现金属纳米粒子在多孔二氧化硅中的合成及原位负载；同时，通过对前驱体溶液配比和温度的调节，可制备出不同负载尺寸的金属纳米颗粒；在活化过程中通过对温度和时间的调节，可以控制金属粒子生长，达到最佳抗菌效果。
2)本发明所得产物中多金属纳米颗粒包括银纳米颗粒、铜纳米颗粒和锌纳米颗粒中的两种以上，且被包覆在多孔二氧化硅微球中形成高负载量“火龙果”型双金属/三金属纳米颗粒，二氧化硅微球的孔道结构可对金属粒子发挥限位生长作用，并有效防止金属纳米粒子的团聚问题；所得金属粒子颗粒较小，在“火龙果”的特殊结构下材料抗菌性能时效较长，可达到缓慢释放的效果。
3)发明所述的二氧化硅负载银铜锌多金属纳米颗粒的制备方法，生产周期短、条件可控、操作便捷、清洁无污染，且整体制备条件可控，可根据生产需求和产品需求变更制备条件，从而达到不同粒径、不同尺寸、不同负载量、不同比例的多金属包覆SiO2纳米颗粒，具有巨大的应用潜力。
4)本发明所述制备方法对其他具有抗菌性能的金属合金普遍适用，可为高性能氧化硅保护纳米粒子的制备提供一条全新思路。
附图说明
图1为实施例1所得Ag-Cu@SiO2颗粒的XRD图；
图2为实施例1所得Ag-Cu@SiO2颗粒的TEM图；
图3为实施例2所得Cu-Zn@SiO2颗粒的TEM图；
图4为实施例3所得Ag-Zn@SiO2颗粒的TEM图；
图5为实施例4所得Ag-Cu-Zn@SiO2颗粒的TEM图。
图6为应用例1中检测不同银铜比例Ag-Cu@SiO2双金属纳米颗粒对E.coli杀菌性能图。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
一种二氧化硅负载银铜多金属纳米颗粒，其制备方法包括如下步骤：
1)分别称取0.0185g三水合硝酸铜、0.0130g硝酸银、25g去离子水、4.8578g APTES和0.09g硝酸，混合搅拌均匀，得前驱溶液；
2)以N2为载气，并控制载气压力为0.2Mpa，通过雾化器使前驱体溶液雾化成微小的气溶胶液滴，然后并送入600℃管式炉中反应1-2s；收集热处理所得样品粉末，即得Ag-Cu@SiO2纳米颗粒。
本实施例所得产物的XRD结果如图1，结果表明，所得产物为无定性二氧化硅与金属银和铜的复合材料；本实施例所得产物的TEM图见图2，结果表明，所得产物由二氧化硅负载纳米颗粒而成，其中多孔二氧化硅微球中形成高负载量的“火龙果”型双金属纳米颗粒。
经测试，本实施例所得产物中金属(Ag-Cu)负载量为1％(1％Ag-Cu@SiO2)。
实施例2
一种二氧化硅负载铜锌多金属纳米颗粒，其制备方法包括如下步骤：
1)分别称取0.0384g三水合硝酸铜、0.0609g硝酸锌、25g去离子水、4.8578gAPTES、12.66mL乙醇和1.0g硝酸，混合搅拌均匀，得前驱溶液；
2)以H2/N2为载气(H2的体积分数为7％)，并控制载气压力为0.3Mpa，通过雾化器使前驱体溶液雾化成微小的气溶胶液滴，然后并送入600℃管式炉中，反应0.9-1s；收集热处理所得样品粉末，即得Cu-Zn@SiO2纳米颗粒。
本实施例所得产物的TEM图见图3。
经测试，本实施例所得产物中金属(Cu-Zn)负载量为2％(2％Cu-Zn@SiO2)。
实施例3
一种二氧化硅负载银锌多金属纳米颗粒，其制备方法包括如下步骤：
1)分别称取1.3201g硝酸锌、0.7617g硝酸银、25g去离子水、4.8578g APTES、0.090g硝酸，混合搅拌均匀，得前驱溶液；
2)以N2为载气，并控制载气压力为0.1Mpa，通过雾化器使前驱体溶液雾化成微小的气溶胶液滴，然后并送入800℃管式炉中，反应3-4s；收集热处理所得样品粉末，重新置于管式炉中在N2氛围下活化6h，得到活化后的Ag-Zn@SiO2纳米颗粒。
本实施例所得产物的TEM图见图4。
经测试，本实施例所得产物中金属(Ag-Zn)负载量为30％(30％Ag-Zn@SiO2)。
实施例4
一种二氧化硅负载银铜锌多金属纳米颗粒，其制备方法包括如下步骤：
1)分别称取0.0185g三水合硝酸铜、0.0130g硝酸银、0.0225g硝酸锌、25g去离子水、6.7964g APTES和0.18g硝酸，混合搅拌均匀，得前驱溶液；
2)以N2为载气，并控制载气压力为0.2Mpa，通过雾化器使得前驱体溶液雾化成微小的气溶胶液滴，然后并送入500℃管式炉中反应1-2s；收集热处理所得样品粉末，重新置于管式炉中在H2氛围下活化5h，即得Ag-Cu-Zn@SiO2纳米颗粒。
本实施例所得产物的TEM图见图5。
经测试，本实施例所得产物中金属(Ag-Cu-Zn)负载量为3％(3％Ag-Cu-Zn@SiO2)。
应用例1
为进一步验证根据上述方案所得二氧化硅负载Ag-Cu@SiO2双金属纳米颗粒的效果，检测不同银铜比例Ag-Cu@SiO2双金属纳米颗粒对E.coli杀菌性能，结果如图6所示。
结果表明，Cu@SiO2纳米颗粒(粉色圆形)与空白对照组(黑色正方形)中细菌生长趋势大体相同，均在24h内持续生长，只展现微弱的抗菌活性；随着银-铜比例(摩尔比)的不断增加，在加入Ag-Cu@SiO2(Ag 75％)纳米颗粒的细菌悬浮液，在24h内可以达到完全杀菌的效果。
上述结果表明，对E.coli而言，本发明所述银铜摩尔比例的双金属Ag-Cu@SiO2纳米颗粒对细菌的杀菌效果强于单金属Ag@SiO2和Cu@SiO2纳米颗粒，进一步说明了双金属之间的协同抗菌效应。
应用例2
参照制备工艺分别制备活化处理前后金属负载量分别为1％、4％、8％的Ag-Zn@SiO2双金属纳米颗粒，具体制备方法的主要区别在于：
针对1％Ag-Zn@SiO2，步骤1)采用的原料用量为0.1123g硝酸锌、0.0648g硝酸银、25g去离子水、4.8578g APTES、0.090g硝酸；
针对4％Ag-Zn@SiO2，步骤1)采用的原料用量为0.3928g硝酸锌、0.2256g硝酸银、25g去离子水、4.8578g APTES、0.090g硝酸；
针对8％Ag-Zn@SiO2，步骤1)采用的原料用量为0.6764g硝酸锌、0.3890g硝酸银、25g去离子水、4.8578g APTES、0.090g硝酸。
将上述活化处理前后的不同金属负载量的Ag-Zn@SiO2纳米颗粒分别进行E.coli杀菌性能测试，结果见表1。
表1不同Ag-Zn@SiO2双金属纳米颗粒活化后前后对E.coli的最低抑菌浓度(μg/mL)
结果表明，本发明采用的活化处理工艺，可进一步有效提升所得复合纳米材料的抗菌性能。
显然，上述实施例仅仅是为清楚地说明所作的实例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。
Claims (5)
1.一种二氧化硅负载多金属纳米颗粒的制备方法，其特征在于，包括如下步骤：
1）将复合金属盐、硅源和酸源溶于水中混合，引入挥发性有机溶剂，混合均匀形成胶体溶液或均相溶液，得前驱体溶液；
2）将所得前驱体溶液经过雾化器形成气溶胶液滴；
3）将形成的气溶胶液滴导入高温管式炉中进行煅烧，形成纳米粉体颗粒，即二氧化硅负载多金属纳米颗粒；
所述复合金属盐为银盐和铜盐，或银盐和锌盐；
所述硅源为3-氨丙基三乙氧基硅烷；
所述酸源为硝酸；所得前驱体溶液的pH值为1~7；
步骤3）中所述煅烧温度为600-800℃，煅烧时间为0.1~60s；
所述二氧化硅负载多金属纳米颗粒进一步进行高温活化，采用的温度为100~1600℃，时间为1~72h，活化气氛为N2，或N2和H2；
所得多金属纳米颗粒包括银纳米颗粒和铜纳米颗粒，或银纳米颗粒和锌纳米颗粒，且被包覆在多孔二氧化硅微球中；所述二氧化硅负载多金属纳米颗粒的粒径为100~600nm；其中包覆的金属纳米颗粒粒径为1~20 nm。
2.根据权利要求1所述的制备方法，其特征在于，所述前驱体溶液中复合金属盐引入的金属元素和与硅源的质量比为1:100~10:1。
3.根据权利要求1所述的制备方法，其特征在于，所述挥发性有机溶剂为甲醇、乙醇、异丙醇中的一种或几种；挥发性有机溶剂与复合金属盐的液固比为（1~50):1 ml:g。
4.根据权利要求1~3任一项所述制备方法制备的二氧化硅负载多金属纳米颗粒。
5.权利要求4所述二氧化硅负载多金属纳米颗粒在制备抗菌产品领域中的应用，其特征在于，适用菌种为大肠杆菌E.coli。
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