CN115137669A - Preparation method of silicon dioxide loaded nano-silver composite material - Google Patents
Preparation method of silicon dioxide loaded nano-silver composite material Download PDFInfo
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- CN115137669A CN115137669A CN202210724405.4A CN202210724405A CN115137669A CN 115137669 A CN115137669 A CN 115137669A CN 202210724405 A CN202210724405 A CN 202210724405A CN 115137669 A CN115137669 A CN 115137669A
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- silver
- silicon dioxide
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- sodium silicate
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 74
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920001690 polydopamine Polymers 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 45
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 45
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 45
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 37
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 27
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 27
- 235000011152 sodium sulphate Nutrition 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 20
- 229960003638 dopamine Drugs 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
- -1 silver ions Chemical class 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229940034610 toothpaste Drugs 0.000 claims description 10
- 239000000606 toothpaste Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000003385 bacteriostatic effect Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 abstract description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 6
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 104
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 42
- 238000003756 stirring Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 26
- 229910001961 silver nitrate Inorganic materials 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000001509 sodium citrate Substances 0.000 description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 241000228245 Aspergillus niger Species 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000022 bacteriostatic agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 208000025157 Oral disease Diseases 0.000 description 2
- 208000014151 Stomatognathic disease Diseases 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 208000030194 mouth disease Diseases 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000008223 sterile water Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241001360526 Escherichia coli ATCC 25922 Species 0.000 description 1
- 208000003445 Mouth Neoplasms Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000010641 Tooth disease Diseases 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000037123 dental health Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- CAEFTTNJCFXOSS-UHFFFAOYSA-N dioxosilane;silver Chemical compound [Ag].O=[Si]=O CAEFTTNJCFXOSS-UHFFFAOYSA-N 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 208000012987 lip and oral cavity carcinoma Diseases 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0279—Porous; Hollow
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/02—Local antiseptics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/614—By macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/621—Coated by inorganic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Oncology (AREA)
- Communicable Diseases (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of a silicon dioxide loaded nano-silver composite material. According to the method, dopamine hydrochloride is added in the process of preparing silicon dioxide by a precipitation method, so that polydopamine is generated, has reducibility and can be reduced to generate nano silver, other reducing agents are added to improve the load rate of the nano silver, the silver content in the residual reaction solution is reduced, then the regenerated silicon dioxide is coated outside the nano silver, the polydopamine has adhesiveness, the nano silver and the outer-layer silicon dioxide can be prevented from falling off, the load rate of the nano silver is improved, and the silver residue in the reaction solution is reduced; and the obtained silicon dioxide loaded nano-silver composite material has proper friction cleaning capability.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of a silicon dioxide loaded nano-silver composite material.
Background
The incidence rate of oral diseases is high, the number of the affected groups is large, the dental diseases seriously affect daily life and even possibly cause oral cancer, so that the care of the dental health and the establishment of a good oral environment are very important. The selection and use of toothpaste is an important link in preventing dental diseases. The tooth disease is mainly caused by harmful flora in oral cavity, the antibacterial agent added in the toothpaste can inhibit the growth of bacteria, the common antibacterial agent triclosan can generate chloroform with chlorine in tap water, so that carcinogenicity exists, and the common antibacterial agent can influence the secretion of hormone of human body to make bacteria generate drug resistance. Fluorine in the fluorine-containing toothpaste has potential toxicity to human bodies while inhibiting and killing bacteria. The silver is used as a broad-spectrum antibacterial agent, is safe, non-toxic and non-irritant, can prevent oral diseases caused by various harmful microorganisms, and has a lasting drug effect.
The abrasive is used as an essential component in toothpaste and can help to remove tartar on the surface of teeth. Silica has chemical inertness, toothpaste system compatibility and suitable attrition values, and is well suited as an abrasive. But the porous and large inner surface area of the film is easy to absorb moisture in the air, and bacteria are easy to breed in the storage process.
The silica-loaded silver is prepared into the composite material, so that the problem of bacteria breeding during storage can be solved, and the use of a bacteriostatic agent in a toothpaste system can be omitted. At present, the silicon dioxide loaded nano silver is mainly prepared by a method of physically adsorbing nano silver on synthetic silicon dioxide, the nano silver has low loading rate, easy shedding and poor stability, the preparation method is complex, the reaction time is long, the cost is high, the silver content in the residual reaction liquid is higher, and the environmental pollution is great. Meanwhile, in the prior art, the sodium silicate solution and the silver ion solution are uniformly mixed, and then the loading of the nano silver is finished in the process of separating out the silicon dioxide by adopting an acid-dropping alkali mode, however, the obtained material has low nano silver loading, easy shedding and high silver residue, and can cause the reduction of the yield and purity of the silicon dioxide. In addition, the silicon dioxide product is dried, ground, surface-modified and loaded with nano silver after being prepared by the related technology, but the method has the advantages of less treatment capacity, long surface modification time (up to 18-30 h) and high production cost.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the first aspect of the invention provides a preparation method of a silicon dioxide loaded nano-silver composite material, dopamine or salt thereof is added in the process of preparing silicon dioxide by a precipitation method, the generated poly-dopamine has reducibility and can be reduced to generate nano-silver, other reducing agents are added to improve the load rate of the nano-silver, the silver content in the residual reaction solution is reduced, then the silicon dioxide is generated to be coated outside the nano-silver, the poly-dopamine has adhesiveness, the nano-silver and the outer layer silicon dioxide can be prevented from falling off, the load rate of the nano-silver is improved, and the silver residue in the reaction solution is reduced; and the obtained silicon dioxide loaded nano-silver composite material has proper friction cleaning capability.
The second aspect of the invention provides a silica-supported nano-silver composite material obtained by the preparation method.
The third aspect of the invention is to provide the application of the silica-supported nano silver composite material.
Specifically, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a silicon dioxide loaded nano-silver composite material, which comprises the following steps:
s1, adding acid into a mixed solution of sodium sulfate and sodium silicate to react to obtain a silicon dioxide inner core;
s2, reacting the silicon dioxide kernel with dopamine or salt thereof and silver ions to obtain an intermediate material which is used for modifying polydopamine and loading nano silver on the surface of the silicon dioxide kernel;
and S3, simultaneously adding sodium silicate and acid into the intermediate material for reaction to obtain the silicon dioxide loaded nano-silver composite material with the surface of the intermediate material coated with the silicon dioxide shell.
According to the preparation method, firstly, a sodium sulfate solution and a sodium silicate solution are mixed, silicon dioxide can be rapidly precipitated under the action of sodium sulfate in an acid-drop alkali mode to prepare a core with a compact structure, then dopamine or salt thereof is added, dopamine can be rapidly polymerized to generate polydopamine under the condition of high temperature, the polymerization speed of the dopamine is increased by the strong oxidizing property of silver ions, and then polydopamine and nano-silver are subjected to surface modification on the silicon dioxide core by utilizing the strong adhesion capacity of the polydopamine to silicon dioxide and the strong reducibility of the polydopamine to the silver ions. And then, continuously depositing silicon dioxide on the surface modified poly-dopamine and nano-silver loaded silicon dioxide inner core in an acid-base co-dripping mode to form a shell, wherein the core and the shell of the silicon dioxide are better wrapped and combined in the presence of poly-dopamine, the nano-silver is not easy to run off, and the silicon dioxide shell generated by acid-base co-dripping is loose and porous and has proper friction cleaning capability.
Therefore, according to the preparation method provided by the invention, the loading rate of the nano-silver can be effectively improved, the nano-silver is prevented from falling off, the composite material has a good antibacterial effect, and the obtained silicon dioxide loaded nano-silver composite material has proper friction cleaning capability.
In some embodiments of the invention, in step S1, the pH is controlled during the reaction to be in the range of 9 to 11, preferably 9.5 to 10.5, e.g. 9,9.5, 10, 10.5, 11, etc.
In some examples of the present invention, in step S1, the addition of the acid is stopped when the reaction is carried out to a pH of not less than 8.5, preferably when the pH reaches 8.5.
In some examples of the invention, in step S1, the acid comprises sulfuric acid at a concentration of 2-10M, preferably 4-6M, for example 2M,3M,4M,5M,6M,7M,8M,9M,10M, etc.
In some embodiments of the invention, the acid is added at a rate of 3 to 10m in step S1 3 H, preferably from 4.5 to 7.5m 3 H, e.g. 3m 3 /h，3.5m 3 /h，4m 3 /h，4.5m 3 /h，5m 3 /h，5.5m 3 /h，6m 3 /h，6.5m 3 /h，7m 3 /h，7.5m 3 /h，8m 3 /h，8.5m 3 /h，9m 3 /h，9.5m 3 /h，10m 3 H/h and so on.
In some embodiments of the invention, the temperature of the reaction in step S1 is 50 to 99 ℃, preferably 60 to 90 ℃, more preferably 65 to 85 ℃, such as 50 ℃,55 ℃,60 ℃,65 ℃,70 ℃,75 ℃,80 ℃,85 ℃,90 ℃,95 ℃,99 ℃ and the like.
In some embodiments of the present invention, in the mixed solution of sodium sulfate and sodium silicate, the ratio of sodium sulfate to sodium silicate is 4-40g:1mol, for example 4g:1mol,6g:1mol,8g:1mol,10g:1mol,12g:1mol,14g:1mol, 1lg: 1mol,18g:1mol,20g:1mol,22g:1mol,24g:1mol,26g:1mol,28g:1mol,30g:1mol,32g:1mol,34g:1mol,36g:1mol,38g:1mol,40g:1mol, and the like.
In some examples of the present invention, the mixed solution of sodium sulfate and sodium silicate has a mass concentration of sodium sulfate of 0.1% to 2.5%, for example, 0.1%,0.2%,0.3%,0.4%,0.5%,0.6%,0.7%,0.8%,0.9%,1%,1.2%,1.4%,1.6%,1.8%,2%,2.2%,2.4%,2.5%, etc.; the concentration of sodium silicate is 0.5 to 1.5M, for example, 0.5M,0.6M,0.7M,0.8M,0.9M,1M,1.1M,1.2M,1.3M,1.4M,1.5M, and the like.
In some examples of the present invention, the mixed solution of sodium sulfate and sodium silicate may be obtained by mixing a sodium sulfate solution with a sodium silicate solution, considering the difference in solubility of sodium sulfate and sodium silicate. The sodium sulfate solution has a mass concentration of 0.5% to 5%, preferably 1% to 3%, for example 0.5%,1%,1.5%,2%,2.5%,3%,3.5%,4%,4.5%,5%, etc. The sodium silicate solution has a concentration of 1 to 5M, preferably 2 to 3M, for example, 1M,1.5M,2M,2.5M,3M,3.5M,4M,4.5M,5M, etc. The sodium silicate solution can be prepared by liquefying solid sodium silicate at high temperature and adding water, wherein the modulus of the solid sodium silicate is 2-4, preferably 3-3.5. The volume ratio of the sodium sulfate solution to the sodium silicate solution is preferably 1-5:1, preferably 1.4 to 2.4:1, e.g. 1:1,1.2:1,1.4:1,1.6:1,1.8:1,2:1,2.2:1,2.4:1,2.6:1,2.8:1,3:1,3.2:1,3.4:1,3.6:1,3.8:1,4:1,4.2:1,4.4:1,4.6:1,4.8:1,5:1, etc.
In some embodiments of the invention, the ratio of dopamine or salt thereof in step S2 to sodium silicate in step S1 is 0.5-3g:1mol, preferably 0.7 to 2g:1mol, for example 0.5g:1mol,0.7g:1mol,1g: 1.2g, 1 mol: 1mol,1.4g:1mol,1.6g:1mol,1.8g:1mol,2g:1mol,2.2g:1mol,2.4g:1mol,2.6g:1mol,2.8g:1mol,3g:1mol, etc.
In some embodiments of the invention, the molar ratio of silver ions in step S2 to sodium silicate in step S1 is from 0.05 to 1:1, preferably 0.09-0.6:1, e.g. 0.05:1,0.05:1,0.09:1,0.1:1,0.12:1,0.14:1,0.16:1,0.18:1,0.2:1,0.25:1,0.3:1,0.35:1,0.4:1,0.45:1,0.5:1,0.55:1,0.6:1,0.65:1,0.7:1,0.75:1,0.8:1,0.85:1,0.9:1,0.95:1,1:1. preferably, the silver ions are reacted with the silica core in the form of a silver ion solution having a concentration of 0.5 to 5M, preferably 1 to 2M, such as 0.5M,1M,1.5M,2M,2.5M,3M,3.5M,4M,4.5M,5M, and the like. In practical operation, the mixed solution containing the silicon dioxide inner core is obtained in the step S1, and the silver ion solution is 2-5m 3 H, preferably from 2.5 to 3.5m 3 The reaction mixture was added at a rate of/h. Preferably, the silver ion solution comprises a silver nitrate solution.
In some embodiments of the present invention, during or after the reaction between the silica core and dopamine or its salt and silver ion, a step of reducing the silver ion by adding a reducing agent is further included. Preferably, the reducing agent comprises at least one of sodium citrate, vitamin C, ascorbic acid, sodium ascorbate, preferably sodium citrate. By adding the reducing agent, silver ions in the solution can be fully reduced into nano silver, the silver content in the residual reaction liquid is reduced, the nano silver loading rate is improved, and the guarantee is provided for green production.
In some examples of the invention, the mass ratio of the reducing agent to dopamine or salt thereof is 1:1.5-8, preferably 1:1.8-6.7, e.g. 1:1.5,1:1.8,1:2,1:2.2,1:2.4,1:2.6,1:2.8,1:3,1:3.5,1:4,1:4.5,1:5,1:5.5,1:6,1:6.5,1:6.7,1:7,1:7.5,1:8, and the like. Preferably, the dopamine salt comprises dopamine hydrochloride.
In some examples of the present invention, the reaction in steps S1 and S2 is carried out under stirring at a rate of 10 to 50Hz, preferably 20 to 40Hz, such as 10Hz,15Hz,20Hz,25Hz,30Hz,33Hz,35Hz,40Hz,45Hz,50Hz, etc., independently.
In some examples of the present invention, in step S3, the pH of the system is controlled to 8 to 9 during the reaction, and the addition of the acid is stopped until the pH reaches 4 to 5. In step S3, the acid comprises sulfuric acid at a concentration of 2-10M, preferably 4-6M, for example, 2M,3M,4M,5M,6M,7M,8M,9M,10M, etc. The concentration of the sulfuric acid may be the same as that in step S1, or may be different from that in step S1. The adding speed of the sulfuric acid is 3-10m 3 H, preferably from 4.5 to 7.5m 3 H, e.g. 3m 3 /h，3.5m 3 /h，4m 3 /h，4.5m 3 /h，5m 3 /h，5.5m 3 /h，6m 3 /h，6.5m 3 /h，7m 3 /h，7.5m 3 /h，8m 3 /h，8.5m 3 /h，9m 3 /h，9.5m 3 /h，10m 3 H, etc.
In some examples of the invention, the molar ratio (or mass ratio) of the sodium silicate in step S3 to the sodium silicate in step S1 is 1:0.5-5, preferably 1:1-2.3, e.g. 1:0.5,1:1,1:1.5,1:2,1:2.3,1:2.5,1:3,1:3.5,1:4,1:4.5,1:5, and the like. Preferably, the sodium silicate in step S3 is added to the mixed solution containing the intermediate material obtained in step S2 in the form of a solution having a concentration of 1 to 5M, preferably 2 to 3M, for example, 1m,1.5m,2m,2.5m,3m,3.5m,4m,4.5m,5m, etc., and the concentration of the sodium silicate solution in step S3 may be the same as or different from that in step S1. The silicic acidThe addition speed of sodium solution is 5-20m 3 H, preferably from 10 to 14m 3 H, e.g. 5m 3 /h，6m 3 /h，7m 3 /h，8m 3 /h，9m 3 /h，10m 3 /h，11m 3 /h，12m 3 /h，13m 3 /h，14m 3 /h，15m 3 /h，16m 3 /h，17m 3 /h，18m 3 /h，19m 3 /h，20m 3 H, etc.
In some examples of the invention, in step S3, the reaction is kept under stirring at a rate of 10 to 50Hz, preferably 20 to 40Hz, such as 10Hz,15Hz,20Hz,25Hz,30Hz,33Hz,35Hz,40Hz,45Hz,50Hz, and the like. The stirring speed in step S3 may be the same as that in step S1 or S2, or may be different. Preferably, in step S3, after the addition of sulfuric acid is stopped, the stirring speed may be reduced, and the stirring may be continued to complete the reaction.
In some examples of the present invention, step S3 further includes a post-treatment process after the reaction is completed. The post-treatment may be carried out by filtration, washing, drying and the like, which are techniques commonly used in the art.
In some embodiments of the present invention, after steps S1 and S2 are completed, no post-processing is required, and the next step can be performed directly.
In some embodiments of the present invention, the solution involved in the preparation method of the present invention is an aqueous solution, a small molecule alcohol (e.g., methanol, ethanol) solution, or a small molecule alcohol-water solution, preferably an aqueous solution.
In some more preferred embodiments of the present invention, the method for preparing the silica-supported nano-silver composite material comprises the steps of:
step one, preparing a sodium sulfate solution: dissolving sodium sulfate in water to obtain 1.0-3.0% solution;
step two, preparing a sodium silicate solution: liquefying solid sodium silicate with modulus of 3.0-3.5 at high temperature, adding water to adjust the concentration to 2.0-3.0M solution;
step three, preparing a sulfuric acid solution: preparing 4.0-6.0M sulfuric acid solution;
fourthly, dissolving silver nitrate in water to prepare a solution with the concentration of 1.0-2.0M;
fifthly, adding the sodium sulfate solution of the first step into a reaction tank, wherein the sodium sulfate solution is 10-12m in volume 3 Sodium silicate solution 5-7m 3 Heating to 65-85 deg.C, stirring at 10-50Hz and 4.5-7.5m 3 Dropwise adding a sulfuric acid solution at the flow rate of/h, controlling the pH value in the reaction process to be 9.5-10.5, and stopping adding acid when the pH value of the solution reaches 8.5;
sixthly, continuously adding 15-20kg of dopamine or salt thereof into the reaction kettle by 2.5-3.5m 3 Dropping at a flow rate of 2-3m 3 Adding 3-8kg of sodium citrate into the silver nitrate solution after the dropwise addition of the silver nitrate solution is finished, and stirring for 1-3h;
seventhly, continuing to move to the reaction tank by 10-14m 3 Dripping 3-5m of sodium silicate solution at the flow rate of/h 3 At a height of 4.5-7.5m 3 Dropwise adding a sulfuric acid solution at a flow rate of/h, controlling the pH value of the reaction process to be 8.0-9.0, and stopping adding acid at a stirring speed of 5-20Hz for 0.5-2h when the pH value of the solution reaches 4.0-5.0;
and eighthly, carrying out filter pressing, washing and drying on the materials to obtain the silicon dioxide loaded nano silver composite material.
The second aspect of the invention provides the silica-supported nano silver composite material obtained by the preparation method.
In some examples of the invention, the silica-supported nanosilver composite has any one or more of the following technical parameters: (1) the water absorption capacity is 15-20mL/20g; (2) oil absorption value of 100-150mL/100g; (3) the copper loss value is 5.0-7.0mg; (4) The bacteriostasis rate to any one or more of colibacillus, staphylococcus aureus, pseudomonas aeruginosa and aspergillus niger is more than 99 percent.
The third aspect of the invention provides application of the silicon dioxide loaded nano-silver composite material in preparing an abrasive, a bacteriostatic agent or toothpaste.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel preparation method of a silicon dioxide composite material for loading and preventing nano silver from falling off, dopamine hydrochloride is added in the process of preparing silicon dioxide by a precipitation method to generate poly-dopamine which has reducibility and can be reduced to generate nano silver, sodium citrate or other reducing agents are added to further improve the loading rate of the nano silver, the silver content in the residual reaction liquid is reduced, then the silicon dioxide is generated to be coated outside the nano silver, and the poly-dopamine which has adhesiveness can prevent the nano silver and the outer layer silicon dioxide from falling off.
Meanwhile, the silver ion solution is added after the silicon dioxide core is formed, so that the influence on the precipitation of the silicon dioxide is small, and the yield and the purity of the silicon dioxide are improved. Compared with the prior art of carrying out post-treatment on a silicon dioxide product and then carrying out nano silver loading, the method has the advantages of short modification time, preparation in a reaction process, simple preparation method, high yield and cost reduction.
In addition, the invention controls the precipitation condition of the silicon dioxide, so that the inner core of the silicon dioxide is a compact structure, and the outer shell of the silicon dioxide on the outer surface is loose and porous, has proper friction cleaning capability, and can be applied to toothpaste as an abrasive and a bacteriostatic agent.
In short, the preparation process of the silica-loaded nano silver is simple, the conditions can be controlled, the adsorption efficiency of the nano silver is improved, the content of residual silver in a reaction solution can be reduced, meanwhile, the nano silver loading rate of the silica is high, the antibacterial rate of the silica on escherichia coli, staphylococcus aureus, pseudomonas aeruginosa and aspergillus niger is more than 99%, the nano silver is not easy to fall off, the silica composite material has the functions of antibiosis and cleaning friction, and the formula of the toothpaste can be simplified.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are those conventional in the art.
Example 1
The embodiment provides a preparation method of a silica-supported nano-silver composite material, which comprises the following steps:
firstly, dissolving sodium sulfate in water to prepare a solution with the mass concentration of 1.0%, and stirring for 30 minutes for later use.
And step two, after the solid sodium silicate with the modulus of 3.0 is liquefied at high temperature, adding water to prepare a solution with the concentration of 2.0M, and stirring for 30 minutes for later use.
Thirdly, preparing 4.0M sulfuric acid solution and stirring for 30 minutes for later use.
And fourthly, dissolving silver nitrate in water to prepare a solution with the concentration of 1.2M, and stirring for 30 minutes for later use.
Step five, adding the sodium sulfate solution 10m prepared in the step one into a reaction tank 3 7m sodium silicate solution prepared in the second step 3 Heating to 65 ℃, the stirring speed was 33Hz at 4.0m 3 Dropwise adding the sulfuric acid solution prepared in the step S3 at the flow rate of/h, controlling the pH value in the reaction process to be 9.5-10.5, and stopping adding acid when the pH value of the solution reaches 8.5.
Sixthly, continuously adding 15kg of dopamine hydrochloride with the volume of 2.5m into the reaction kettle 3 Dripping silver nitrate solution with the flow rate of 2.5 m/h 3 After the silver nitrate solution is dripped, 3kg of sodium citrate is added, and the mixture is stirred for 2 hours.
Seventh step, continue to 10m to the reaction tank 3 Dropping sodium silicate solution 5m at a flow rate of/h 3 At 5.0m 3 Dropwise adding sulfuric acid solution at a flow rate of/h, controlling the pH value of the solution to be 8.0-9.0 in the reaction process, stopping adding acid when the pH value of the solution reaches 4.0-5.0, and stirring for 1h at a stirring speed of 15 Hz.
And eighthly, carrying out filter pressing, washing and drying on the material prepared in the seventh step to obtain the silicon dioxide loaded nano silver composite material.
Example 2
The embodiment provides a preparation method of a silica-supported nano-silver composite material, which comprises the following steps:
first, sodium sulfate was dissolved in water to prepare a 2.0% solution, and the solution was stirred for 30 minutes.
And step two, after the solid sodium silicate with the modulus of 3.2 is liquefied at high temperature, adding water to prepare a solution with the concentration of 2.5M, and stirring for 30 minutes for later use.
Thirdly, preparing 5.0M sulfuric acid solution and stirring for 30 minutes for later use.
And fourthly, dissolving silver nitrate in water to prepare a solution with the concentration of 1.8M, and stirring for 30 minutes for later use.
Step five, adding 11m of the sodium sulfate solution prepared in the step one into a reaction tank 3 6m of sodium silicate solution prepared in the second step 3 Heating to 75 deg.C, stirring at 33Hz and 5.0m 3 Dropwise adding the sulfuric acid solution prepared in the step S3 at the flow rate of/h, controlling the pH value in the reaction process to be 9.5-10.5, and stopping adding acid when the pH value of the solution reaches 8.5.
Sixthly, continuously adding 15kg of dopamine hydrochloride with the volume of 3.0m into the reaction kettle 3 Dripping silver nitrate solution 2m at the flow rate of/h 3 After the dropwise addition of the silver nitrate solution is finished, 5kg of sodium citrate is added, and the mixture is stirred for 2 hours.
Seventh step, continue with 12m to the reaction tank 3 Dropping sodium silicate solution 4m at a flow rate of/h 3 At 6.0m 3 Dropwise adding sulfuric acid solution at a flow rate of/h, controlling the pH value of the solution to be 8.0-9.0 in the reaction process, and stopping adding acid at a stirring speed of 15Hz for 1h when the pH value of the solution reaches 4.0-5.0.
And eighthly, carrying out filter pressing, washing and drying on the material prepared in the seventh step to obtain the silicon dioxide loaded nano silver composite material.
Example 3
The embodiment provides a preparation method of a silica-supported nano-silver composite material, which comprises the following steps:
first, sodium sulfate was dissolved in water to prepare a 3.0% solution, and the solution was stirred for 30 minutes.
And step two, after the solid sodium silicate with the modulus of 3.5 is liquefied at high temperature, adding water to prepare a solution with the concentration of 3.0M, and stirring for 30 minutes for later use.
Thirdly, preparing 6.0M sulfuric acid solution and stirring for 30 minutes for later use.
Fourthly, dissolving silver nitrate in water to prepare a solution with the concentration of 2.0M, and stirring for 30 minutes for later use.
Fifthly, adding the sodium sulfate solution 12m prepared in the first step into a reaction tank 3 5m sodium silicate solution prepared in the second step 3 Am, lThe temperature is raised to 85 ℃, the stirring speed is 33Hz, and the stirring speed is 6.0m 3 Dropwise adding the sulfuric acid solution prepared in the step S3 at the flow rate of/h, controlling the pH value in the reaction process to be 9.5-10.5, and stopping adding acid when the pH value of the solution reaches 8.5.
Sixthly, continuously adding 15kg of dopamine hydrochloride into the reaction kettle by 3.5m 3 Dropping silver nitrate solution at a flow rate of 2 m/h 3 After the dropwise addition of the silver nitrate solution is finished, 8kg of sodium citrate is added, and the mixture is stirred for 2 hours.
Seventh, continue to the reaction tank for 10m 3 Dropping sodium silicate solution at the flow rate of 3m 3 At 7.0m 3 Dropwise adding sulfuric acid solution at the flow rate of/h, controlling the pH value of the reaction process to be 8.0-9.0, and stopping adding acid at the stirring speed of 15Hz for 1h when the pH value of the solution reaches 4.0-5.0.
And eighthly, carrying out filter pressing, washing and drying on the material prepared in the seventh step to obtain the silicon dioxide silver-loaded composite material.
Comparative example 1
This comparative example was prepared similarly to example 2 except that 3.5m was used after the sodium silicate solution was added in the fifth step 3 Dripping silver nitrate solution 2m at the flow rate of/h 3 And after the fifth step of reaction is finished, implementing the seventh step without adding dopamine and sodium citrate.
Comparative example 2
This comparative example was prepared similarly to example 2, except that 3.5m was added after the sodium silicate solution was added in the fifth step 3 Dropping silver nitrate solution at a flow rate of 2 m/h 3 And sixthly, adding no silver nitrate solution.
Comparative example 3
The comparative example was prepared similarly to example 2, except that dopamine hydrochloride was not added in the sixth step, as in example 2.
Comparative example 4
The comparative example was prepared similarly to example 2, except that sodium citrate was not added in the sixth step, as in example 2.
Comparative example 5
The comparative example was prepared similarly to example 2, except that sulfuric acid was added in the fifth stepAfter the sodium solution, the sodium silicate solution and the sulfuric acid solution are simultaneously dripped into a reaction tank at the dripping speed of 12m 3 The total adding amount of the sodium silicate solution and the sulfuric acid solution is 12m 3 。
Comparative example 6
The comparative example was prepared similarly to example 2, except that in the fifth step, an equal amount of water was used instead of the sodium sulfate solution.
Comparative example 7
The comparative example was prepared in a manner similar to that of example 2.
The difference between the comparative example and the example 2 is that the seventh step is directly carried out after the fifth step reaction, the material obtained in the seventh step is subjected to pressure filtration, washing and drying to obtain silicon dioxide, then 2g of the silicon dioxide is added into 400mL of Tris-HCl buffer solution (pH = 8.5) containing 15mg of dopamine hydrochloride, the mixture is stirred at 200rpm for 2h at room temperature for dopamine modification, and after washing and drying, the mixture is added into 200mL0.1M silver nitrate solution, stirred at 200rpm for 2h at room temperature (20 ℃) and then dried after washing.
Comparative example 8
The preparation method is similar to that of example 2.
The difference between the comparative example and the example 2 is that the seventh step is directly implemented after the fifth step reaction, the material obtained in the seventh step is subjected to filter pressing, washing and drying to obtain silicon dioxide, then 2g of the silicon dioxide is added into 400mL of Tris-HCl buffer solution (pH = 8.5) containing 15mg of dopamine hydrochloride, the mixture is stirred at the stirring speed of 200rpm at 75 ℃ for 2h for dopamine modification, and after washing and drying, the mixture is added into 200mL0.1M silver nitrate solution, stirred at the stirring speed of 200rpm at 75 ℃ for 2h, and after washing and drying, the mixture is dried.
<xnotran> </xnotran>
Test samples: the silica-supported nano silver composite materials prepared in examples 1 to 3 and comparative examples 1 to 8;
the test method comprises the following steps:
and (3) determining the water absorption capacity, the oil absorption value and the copper consumption: reference is made to QB/T2346-2015;
residual silver content (residual silver content) of the reaction solution: the ICP method uses an AG-1 silver ion analyzer, shanghai war electron technology, inc.
Silver content of the composite material: concentrated nitric acid digestion, ICP method, using AG-1 silver ion tester, shanghai war electron technology, inc.
Antibacterial property: standard strains (supplied by Kyork, guangdong, inc.) were used: escherichia coli ATCC25922, pseudomonas aeruginosa ATCC27853, staphylococcus aureus ATCC25923, aspergillus niger ATCC16404.
(1) Quantitative test of bacteriostatic properties (no impregnation): quantitatively measuring the sterilization performance by using a plate counting method, putting 1g of sample into the bacterial suspension containing the strain, uniformly oscillating, taking 1mL of bacterial liquid, and diluting in a test tube containing sterile water to obtain the bacterial liquid before bacteriostasis. And (4) taking 1mL of bacterial liquid from the bacterial suspension subjected to oscillation sterilization for 24h, and diluting the bacterial liquid in a test tube filled with sterile water to obtain the bacterial liquid subjected to bacteriostasis. And respectively taking 1mL of the two treated bacterial liquids, transferring the two bacterial liquids into a culture dish, injecting culture solution at about 45 ℃, culturing at 37 ℃ for 24 hours at constant temperature, taking out the plate, counting, repeating the test for 3 times, and averaging the values.
(2) And (3) testing the stability of antibacterial performance (after soaking): and (3) putting 10g of sample into 400mL of deionized water, soaking for 48h, stirring for 15min every 12h, filtering out the sample, adding 400mL of deionized water, soaking for 24h, taking out the sample, drying, carrying out quantitative inspection according to the step (1), and evaluating the antibacterial stability and durability of the sample.
And (3) test results:
table 1 results of performance testing
TABLE 2 results of the bacteriostatic properties
From the above tables 1 and 2, it can be seen that:
(1) The water absorption capacity of the silica-loaded nano-silver composite material of the embodiments 1 to 3 is 15 to 20mL/20g, the oil absorption value is 100 to 150mL/100g, the copper consumption value is 5.0 to 7.0mg, the standard requirements of the silica abradant are met, the silver content in the composite material is high, the silver content in the reaction residual liquid is lower than 5mg/L, the bacteriostasis rate to escherichia coli, pseudomonas aeruginosa, staphylococcus aureus and aspergillus niger is more than 99.9%, the bacteriostasis effect is durable, the bacteriostasis rate is still more than 99.9% after the impregnation, and the silica-loaded nano-silver is shown to be slowly released in the reaction process.
(2) Compared with the example 2, the comparative example 1 is that silver nitrate is added before the reaction starts, dopamine hydrochloride and sodium citrate are not added in the midway, silver in the silver nitrate is not reduced and is adsorbed in silicon dioxide in the form of silver ions, the silver content is low, the residual silver content of the reaction liquid is high, and the bacteriostatic effect is unstable; comparative example 2 silver nitrate is added before the reaction starts, silver ions are reduced into nano silver through polydopamine and sodium citrate, the content of the silver is improved due to the dopamine, but the precipitation of silicon dioxide is influenced in the reaction process, the silver ions are adsorbed into the silicon dioxide in advance, the storage process is unstable, and the bacteriostatic effect is reduced; comparative example 3 no dopamine hydrochloride was added, the silica and silver particles lacked adhesion, silver nitrate was reduced only by sodium citrate, the silver content in the composite was reduced, and the residual silver content in the reaction solution was high; comparative example 4 no sodium citrate was added, the polydopamine failed to completely reduce the silver nitrate, and the residual silver content in the reaction solution increased; comparative example 5 acid and alkali were used in the first step to replace acid and alkali drop, and comparative example 6 water was used to replace sodium sulfate, with the result that the copper loss value of silica was reduced; comparative example 7 by treating silica with dopamine at room temperature, as a result, the antibacterial performance is reduced before impregnation, and the performance is obviously reduced after impregnation; comparative example 8 by treating silica with dopamine at 75 ℃, the bacteriostatic performance before impregnation was still below 99% and the bacteriostatic effect was not durable.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a silicon dioxide loaded nano-silver composite material is characterized by comprising the following steps: the method comprises the following steps:
s1, adding acid into a mixed solution of sodium sulfate and sodium silicate to react to obtain a silicon dioxide inner core;
s2, reacting the silicon dioxide inner core with dopamine or salt thereof and silver ions to obtain an intermediate material for modifying polydopamine and loading nano silver on the surface of the silicon dioxide inner core;
and S3, simultaneously adding sodium silicate and acid into the intermediate material for reaction to obtain the silicon dioxide loaded nano-silver composite material with the surface of the intermediate material coated with the silicon dioxide shell.
2. The method of claim 1, wherein: in the step S1, the pH is controlled to be 9-11 in the reaction process.
3. The method of claim 2, wherein: in step S1, the addition of the acid is stopped when the reaction is carried out until the pH is not less than 8.5.
4. The method of claim 1, wherein: in step S1, the reaction temperature is 50-99 ℃.
5. The method of claim 1, wherein: in the mixed solution of sodium sulfate and sodium silicate, the ratio of sodium sulfate to sodium silicate is 4-40g:1mol.
6. The method of claim 1, wherein: the ratio of the dopamine or the salt thereof in the step S2 to the sodium silicate in the step S1 is 0.5-3g:1mol.
7. The method according to claim 6, wherein: the molar ratio of the silver ions in the step S2 to the sodium silicate in the step S1 is 0.05-1:1.
8. the production method according to any one of claims 1 to 7, characterized in that: the method also comprises the step of adding a reducing agent to reduce silver ions during or after the reaction of the silicon dioxide inner core, dopamine or salt thereof and silver ions.
9. The silica-supported nano-silver composite material obtained by the preparation method of any one of claims 1 to 8.
10. Use of the silica-loaded nanosilver composite of claim 9 in the manufacture of an abrasive, a bacteriostatic or a toothpaste.
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|---|---|---|---|---|
| CN115970669A (en) * | 2022-12-30 | 2023-04-18 | 广东工业大学 | Modified titanium dioxide particles and preparation method and application thereof |
| CN116426282A (en) * | 2023-03-09 | 2023-07-14 | 深圳市光与生物科技有限公司 | Biotin modified rare earth doped inorganic material and preparation method thereof |
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|---|---|---|---|---|
| CN115970669A (en) * | 2022-12-30 | 2023-04-18 | 广东工业大学 | Modified titanium dioxide particles and preparation method and application thereof |
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| CN116426282A (en) * | 2023-03-09 | 2023-07-14 | 深圳市光与生物科技有限公司 | Biotin modified rare earth doped inorganic material and preparation method thereof |
| CN116426282B (en) * | 2023-03-09 | 2024-04-12 | 深圳市光与生物科技有限公司 | Biotin modified rare earth doped inorganic material and preparation method thereof |
| CN117244414A (en) * | 2023-09-21 | 2023-12-19 | 苏州苏瑞膜纳米科技有限公司 | Preparation method for preparing separation membrane by utilizing radiation curing to realize rapid drying |
| CN117244414B (en) * | 2023-09-21 | 2024-05-17 | 苏州苏瑞膜纳米科技有限公司 | Preparation method for preparing separation membrane by utilizing radiation curing to realize rapid drying |
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