CN111972435A - Preparation method of nano-silver-graphene oxide composite material - Google Patents
Preparation method of nano-silver-graphene oxide composite material Download PDFInfo
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- CN111972435A CN111972435A CN201910438873.3A CN201910438873A CN111972435A CN 111972435 A CN111972435 A CN 111972435A CN 201910438873 A CN201910438873 A CN 201910438873A CN 111972435 A CN111972435 A CN 111972435A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 5
- 239000010439 graphite Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 3
- 239000007800 oxidant agent Substances 0.000 claims abstract 2
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 238000009210 therapy by ultrasound Methods 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 230000000844 anti-bacterial effect Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 231100000331 toxic Toxicity 0.000 claims description 3
- 230000002588 toxic effect Effects 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 229960001031 glucose Drugs 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000047 product Substances 0.000 claims 1
- 239000002341 toxic gas Substances 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 13
- 230000001954 sterilising effect Effects 0.000 abstract description 9
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 238000013473 artificial intelligence Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 description 14
- 239000012065 filter cake Substances 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 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 2
- 241000233866 Fungi Species 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 210000004962 mammalian cell Anatomy 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229940083025 silver preparation Drugs 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- 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
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Inorganic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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Abstract
The invention provides a preparation method of a nano silver-graphene oxide composite material, and belongs to the technical field of new materials. The method is characterized in that an optimized auxiliary design scheme obtained by artificial intelligence design software after a series of operations is adopted. Firstly, oxidizing graphite at a certain temperature by using a concentrated H2SO4/NaNO3 system and KMNO4 as an oxidant to obtain graphene oxide. And mixing the graphene oxide dispersion liquid and the silver nitrate dispersion liquid, adding a reducing agent and a surfactant, and reacting for 2 hours at about 90 ℃ under an ultraviolet lamp to obtain the nano silver-graphene oxide composite material. The preparation method is simple and efficient, has little pollution to the environment, and the obtained nano silver-graphene oxide composite material has the advantages that the nano silver particles are uniformly adsorbed on the graphene oxide, so that the nano silver-graphene oxide composite material has lower toxicity and can keep good sterilization and mildew prevention effects for a long time.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method of a nano silver-graphene oxide composite material.
Background
Bacteria and microorganisms are seen everywhere in our life, and are the most direct and instinctive causes of human body infection and disease. In our lives, there are many antibacterial agents for sterilization, and they are classified into organic antibacterial agents, natural antibacterial agents and sterile antibacterial agents according to their structures. The organic antibacterial agent has the characteristics of wide specific antibacterial range, large antibacterial quantity, high sterilization speed and the like, but the antibacterial agent has relatively large toxic and side effects, short service life and is easy to hydrolyze. Natural antimicrobial agents are generally highly safe materials, but they are generally characterized by short life, poor heat resistance, and difficulty in reprocessing. The inorganic antibacterial agents mainly comprise silver series, copper series, zinc series and titanium series, wherein the most studied are silver series antibacterial agents, and most commercialized inorganic antibacterial agents are silver series antibacterial agents, and the inorganic antibacterial agents are characterized by good safety, heat resistance and durability, but have the defects of high price, slow antibacterial effect, incapability of quickly killing bacteria like organic antibacterial agents and almost no inhibiting effect on fungi and mold.
The nanometer technology is appeared, the sterilizing capability of the silver in the nanometer state is greatly improved, the extremely small amount of the nanometer silver can generate strong sterilizing effect, 650 kinds of bacteria can be killed within a few minutes, the broad-spectrum sterilization is realized, the drug resistance is avoided, the healing of wounds, the growth of cells and the repair of damaged cells can be promoted, the toxic reaction is avoided, and no stimulation reaction is found to the skin. As a new generation of sterilization material, the nano-silver has the advantages of super-strong sterilization, disinfection, mildew resistance and the like, good antibacterial property, biocompatibility, surface modification easiness and the like, but the nano-silver also has the problems of easy oxidation, color change, water solubility, easy volatilization and the like. How to solve these problems, the research and development of efficient, green and pollution-free nano-silver preparation technology becomes a new research subject, and needs to be solved urgently.
The graphene oxide has a large number of oxygen-containing groups on the surface, so that the graphene oxide has high dispersibility in water, is a material with antibacterial property, and has very little cytotoxicity to mammalian cells. Graphene oxide is generally obtained by oxidizing graphite with a strong acid. Currently, there are three main methods for preparing graphene oxide: the Brodie method, Staudenmier method and Hummers method. The Hummers method has relatively good timeliness and safety in the preparation process, and is the most commonly used method at present. Potassium permanganate in concentrated sulfuric acid and graphite powder are subjected to oxidation reaction to obtain brown graphite flakes, and a graphite flake layer can be peeled by ultrasonic methods and the like to form graphene oxide and can form a stable single-layer graphene oxide suspension in water.
The nano silver-graphene oxide composite material is a novel natural antibacterial agent. The graphene oxide can fix the nano-silver on the own lamellar structure by utilizing abundant functional groups of the graphene oxide, so that the nano-silver is stabilized and protected, the release speed of the nano-silver is reduced, and the antibacterial performance of the nano-silver is improved. Therefore, the nano-silver-graphene oxide composite material combines the characteristics of broad-spectrum antibacterial sterilization, strong permeability, lasting antibacterial property and no drug resistance of the nano-silver antibacterial agent, can exert the bactericidal effect of the nano-silver, can effectively inhibit the volatilization of the nano-silver, further improves the bactericidal effect, and has lower toxicity to human bodies.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and further provides a simple and efficient preparation method of a nano silver-graphene oxide composite material.
The technical scheme adopted by the invention is an optimized auxiliary design scheme obtained by a set of artificial intelligence design software which is independently developed by people after referring to a large number of existing graphene oxide preparation methods and carrying out a series of operations on the artificial intelligence design software.
The preparation method of the nano silver-graphene oxide composite material comprises the following steps.
Weighing a proper amount of graphite powder and sodium nitrate, adding the graphite powder and the sodium nitrate into a reaction bottle containing concentrated sulfuric acid at an ice water temperature, stirring by using magnetons, continuously and slowly adding potassium permanganate during the stirring, keeping the temperature at 10 ℃ or below for reaction for 1.5-3h, taking out, stirring at room temperature for 2-3d, diluting by using deionized water, adding a proper amount of 50% hydrogen peroxide, continuously stirring for 2-3h, performing centrifugal separation, washing by using 0.1mol/L dilute hydrochloric acid and distilled water for multiple times until the pH value is close to 7, and drying to obtain the graphene oxide.
2) Adding the graphene oxide prepared in the step 1) into deionized water, adjusting the graphene oxide solution to be neutral by using 0.1mol/L KOH and 0.1mol/L HCl solutions, diluting the solution to be nearly transparent by using the deionized water, adding a proper amount of Dimethylformamide (DMF), and carrying out ultrasonic treatment at room temperature for 5min to obtain a graphene oxide dispersion liquid; dissolving appropriate amount of silver nitrate in deionized water, and performing ultrasonic treatment for 5 min; adding a silver nitrate solution into a graphene oxide dispersion liquid, adding a small amount of Cetyl Trimethyl Ammonium Bromide (CTAB), performing ultrasonic treatment for 20min, then adding a reducing agent into the mixed solution, heating to 85-100 ℃, reacting for 30-180min, cooling to room temperature, performing centrifugal separation to obtain a solid product, and cleaning with absolute ethyl alcohol and distilled water to obtain the nano silver-graphene oxide composite material.
Preferably, the weight ratio of the graphite powder to the sodium nitrate in the step 1) is 1: 1.
preferably, the adding amount of the concentrated sulfuric acid in the step 1) is 10-20 times of that of the graphite powder.
Preferably, the adding amount of the potassium permanganate in the step 1) is 3 times of that of the graphite powder.
Preferably, the amount of hydrogen peroxide in step 1) is such that no bubbles are generated in the solution.
Preferably, the concentration of the graphene oxide suspension in the step 2) is 0.1-0.8 mg/mL.
Preferably, the feeding weight ratio of the silver nitrate to the graphene oxide in the step 2) is 1: 1.
Preferably, the reducing agent in step 2) is one or more of glucose, citric acid, trisodium citrate and ascorbic acid.
Preferably, the reduction reaction in step 2) is carried out under an ultraviolet lamp.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1.
60ml of concentrated sulfuric acid is poured into a 250ml reaction bottle, and the reaction bottle is placed in an ice water bath.
Adding 3g of graphite powder and 3g of sodium nitrate into a reaction bottle containing concentrated sulfuric acid, and magnetically stirring for 5 min.
9g of potassium permanganate is taken and added into a reaction bottle in small amount for many times.
After the addition, the reaction was carried out for 1.5h at a temperature not exceeding 10 ℃.
After the reaction was complete, stirring was continued at room temperature for 2 d.
The reaction solution was diluted with 70ml of deionized water, and an appropriate amount of 50% hydrogen peroxide was added until no bubbles were formed, followed by stirring for 2 hours.
And (4) performing centrifugal separation, washing a filter cake for multiple times by using 0.1mol of dilute hydrochloric acid and distilled water until the pH value is close to 7, and drying to obtain the graphene oxide.
5mg of graphene oxide is added into 50ml of deionized water, and ultrasonic treatment is carried out for 5 min.
And (3) adjusting the graphene oxide solution to be neutral by using 0.1mol of KOH and 0.1mol of HCl solution, diluting the solution to be nearly transparent by using deionized water, then adding a proper amount of dimethylformamide, and carrying out ultrasonic treatment at room temperature for 5min to obtain the graphene oxide dispersion liquid.
5mg of silver nitrate is dissolved in 5ml of deionized water, and ultrasonic treatment is carried out for 5 min.
Adding a silver nitrate solution into the graphene oxide dispersion liquid, adding a small amount of cetyl trimethyl ammonium bromide, and performing ultrasonic treatment for 20 min.
Adding 10mg citric acid into the mixed solution, performing ultrasonic treatment for 10min, heating to 100 deg.C, and reacting under ultraviolet lamp for 100 min.
Cooling to room temperature, performing centrifugal separation, respectively cleaning a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain the nano silver-graphene oxide composite material.
Example 2.
60ml of concentrated sulfuric acid is poured into a 250ml reaction bottle, and the reaction bottle is placed in an ice water bath.
Adding 3g of graphite powder and 3g of sodium nitrate into a reaction bottle containing concentrated sulfuric acid, and magnetically stirring for 5 min.
9g of potassium permanganate is taken and added into a reaction bottle in small amount for many times.
After the addition, the reaction was carried out for 3 hours at a temperature not exceeding 10 ℃.
After the reaction was complete, stirring was continued at room temperature for 3 d.
The reaction solution was diluted with 70ml of deionized water, and an appropriate amount of 50% hydrogen peroxide was added until no bubbles were formed, followed by stirring for 3 hours.
And (4) performing centrifugal separation, washing a filter cake for multiple times by using 0.1mol of dilute hydrochloric acid and distilled water until the pH value is close to 7, and drying to obtain the graphene oxide.
Adding 15mg of graphene oxide into 50ml of deionized water, and carrying out ultrasonic treatment for 5 min.
And (3) adjusting the graphene oxide solution to be neutral by using 0.1mol of KOH and 0.1mol of HCl solution, diluting the solution to be nearly transparent by using deionized water, then adding a proper amount of dimethylformamide, and carrying out ultrasonic treatment at room temperature for 5min to obtain the graphene oxide dispersion liquid.
Dissolving 15mg of silver nitrate into 10ml of deionized water, and carrying out ultrasonic treatment for 5 min.
Adding a silver nitrate solution into the graphene oxide dispersion liquid, adding a small amount of cetyl trimethyl ammonium bromide, and performing ultrasonic treatment for 20 min.
Adding 20mg sodium citrate and 20mg ascorbic acid into the mixed solution, performing ultrasonic treatment for 10min, heating to 85 deg.C, and reacting under ultraviolet lamp for 100 min.
Cooling to room temperature, performing centrifugal separation, respectively cleaning a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain the nano silver-graphene oxide composite material.
Example 3.
30ml of concentrated sulfuric acid is poured into a 150ml reaction bottle, and the reaction bottle is placed in an ice water bath.
Adding 3g of graphite powder and 3g of sodium nitrate into a reaction bottle containing concentrated sulfuric acid, and magnetically stirring for 5 min.
9g of potassium permanganate is taken and added into a reaction bottle in small amount for many times.
After the addition, the reaction was carried out for 1.5h at a temperature not exceeding 10 ℃.
After the reaction was complete, stirring was continued at room temperature for 2 d.
The reaction solution was diluted with 40ml of deionized water, and an appropriate amount of 50% hydrogen peroxide was added until no bubbles were formed, followed by stirring for 2 hours.
And (4) performing centrifugal separation, washing a filter cake for multiple times by using 0.1mol of dilute hydrochloric acid and distilled water until the pH value is close to 7, and drying to obtain the graphene oxide.
And adding 40mg of graphene oxide into 50ml of deionized water, and carrying out ultrasonic treatment for 5 min.
And (3) adjusting the graphene oxide solution to be neutral by using 0.1mol of KOH and 0.1mol of HCl solution, diluting the solution to be nearly transparent by using deionized water, then adding a proper amount of dimethylformamide, and carrying out ultrasonic treatment at room temperature for 5min to obtain the graphene oxide dispersion liquid.
40mg of silver nitrate is dissolved in 20ml of deionized water and treated by ultrasonic treatment for 5 min.
Adding a silver nitrate solution into the graphene oxide dispersion liquid, adding a small amount of cetyl trimethyl ammonium bromide, and performing ultrasonic treatment for 20 min.
Adding 80mg glucose into the mixed solution, performing ultrasonic treatment for 10min, heating to 90 deg.C, and reacting under ultraviolet lamp for 30 min.
Cooling to room temperature, performing centrifugal separation, respectively cleaning a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain the nano silver-graphene oxide composite material.
Example 4.
30ml of concentrated sulfuric acid is poured into a 150ml reaction bottle, and the reaction bottle is placed in an ice water bath.
Adding 3g of graphite powder and 3g of sodium nitrate into a reaction bottle containing concentrated sulfuric acid, and magnetically stirring for 5 min.
9g of potassium permanganate is taken and added into a reaction bottle in small amount for many times.
After the addition, the reaction was carried out for 3 hours at a temperature not exceeding 10 ℃.
After the reaction was complete, stirring was continued at room temperature for 3 d.
The reaction solution was diluted with 40ml of deionized water, and an appropriate amount of 50% hydrogen peroxide was added until no bubbles were formed, followed by stirring for 3 hours.
And (4) performing centrifugal separation, washing a filter cake for multiple times by using 0.1mol of dilute hydrochloric acid and distilled water until the pH value is close to 7, and drying to obtain the graphene oxide.
And adding 25mg of graphene oxide into 50ml of deionized water, and carrying out ultrasonic treatment for 5 min.
And (3) adjusting the graphene oxide solution to be neutral by using 0.1mol of KOH and 0.1mol of HCl solution, diluting the solution to be nearly transparent by using deionized water, then adding a proper amount of dimethylformamide, and carrying out ultrasonic treatment at room temperature for 5min to obtain the graphene oxide dispersion liquid.
Dissolving 25mg silver nitrate into 20ml deionized water, and performing ultrasonic treatment for 5 min.
Adding a silver nitrate solution into the graphene oxide dispersion liquid, adding a small amount of cetyl trimethyl ammonium bromide, and performing ultrasonic treatment for 20 min.
Adding 50mg sodium citrate into the mixed solution, performing ultrasonic treatment for 10min, heating to 95 ℃, and reacting for 180min under an ultraviolet lamp.
Cooling to room temperature, performing centrifugal separation, respectively cleaning a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain the nano silver-graphene oxide composite material.
The above examples are only partially illustrative, and the specific implementation of the present invention is not limited by the above manner, and it is within the scope of the present invention to adopt various modifications of the method concept and technical scheme of the present invention, or to apply the same to other occasions without any modification.
Claims (9)
1. A preparation method of a nano silver-graphene oxide composite material with broad-spectrum antibacterial and no toxic or side effect is characterized by comprising the following steps: the method comprises the following steps:
1) preparing graphene oxide:
weighing a proper amount of graphite powder and sodium nitrate, adding the graphite powder and the sodium nitrate into a reaction bottle containing concentrated sulfuric acid at an ice water temperature, stirring by using magnetons, continuously and slowly adding potassium permanganate during the stirring, keeping the temperature at 10 ℃ or below for reaction for 1.5-3h, taking out, stirring for 2-3d at room temperature, diluting by using deionized water, adding a proper amount of 50% hydrogen peroxide, continuously stirring for 2-3h, performing centrifugal separation, washing for multiple times by using 0.1mol/L dilute hydrochloric acid and distilled water until the pH value is close to 7, and drying to obtain graphene oxide;
2) Preparing a nano silver-graphene oxide composite material:
adding the graphene oxide prepared in the step 1) into deionized water, adjusting the graphene oxide solution to be neutral by using 0.1mol/L KOH and 0.1mol/L HCl solutions, diluting the solution to be nearly transparent by using the deionized water, adding a proper amount of Dimethylformamide (DMF), and carrying out ultrasonic treatment at room temperature for 5min to obtain a graphene oxide dispersion liquid; dissolving appropriate amount of silver nitrate in deionized water, and performing ultrasonic treatment for 5 min; adding a silver nitrate solution into a graphene oxide dispersion liquid, adding a small amount of hexadecyl trimethyl ammonium bromide, performing ultrasonic treatment for 20min, then adding a reducing agent into the mixed solution, heating to 85-100 ℃, reacting for 30-180min, cooling to room temperature, performing centrifugal separation to obtain a solid product, cleaning with absolute ethyl alcohol and deionized water, and drying to obtain the nano silver-graphene oxide composite material.
2. The method for producing graphene oxide according to claim 1, characterized in that: in the step 1), a concentrated H2SO4/NaNO3 system is adopted, KMNO4 is used as an oxidant, and graphite is oxidized at a certain temperature, SO that graphene oxide can be obtained.
3. No toxic gas is generated in the process, the oxidation time is shortened, and the product has a reasonable structure and is easy to disperse in water.
4. The method for producing graphene oxide according to claim 1, characterized in that: the weight ratio of the graphite powder, the sodium nitrate, the concentrated sulfuric acid and the potassium permanganate in the step 1) is 1: 1: 10-20:3.
5. The method for producing graphene oxide according to claim 1, characterized in that: the dosage of the hydrogen peroxide in the step 1) is until no bubbles are generated in the solution.
6. The method for preparing a nano silver-graphene oxide composite material according to claim 1, wherein: the concentration of the graphene oxide suspension in the step 2) is 0.1-0.8 mg/mL.
7. The method for preparing a nano silver-graphene oxide composite material according to claim 1, wherein: the feeding weight ratio of silver nitrate to graphene oxide in the step 2) is 1: 1.
8. The method for preparing a nano silver-graphene oxide composite material according to claim 1, wherein: the reducing agent in the step 2) is one or more of glucose, citric acid, trisodium citrate and ascorbic acid.
9. The method for preparing a nano silver-graphene oxide composite material according to claim 1, wherein: the reduction reaction in the step 2) needs to be carried out under an ultraviolet lamp.
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