A kind of preparation method of graphene/nano silver composite antibacterial material
Technical field
The invention belongs to field of new materials, and in particular to a kind of preparation method of graphene/nano silver composite antibacterial material.
Background technology
Health is the topic that today's society people pay close attention to the most, however, in the environment that we live, there is a large amount of
The growth and breeding of bacterium, these bacteriums seriously threatens the health of the mankind.Suitable antiseptic is selected to inhibit harmful bacteria
Growth and breeding can effective guarantee people health.
Antiseptic can be divided into organic antibacterial agent, natural antibacterial agent, inorganic antiseptic according to structure difference.These three antibacterials are each
The characteristics of having oneself, organic antibacterial agent bactericidal effect is good, price is low, but safety is poor, environmental pollution is serious.Natural antibacterial agent comes
It is safe, environmental pollution is small from natural, but heat resistance, persistence are poor.Inorganic antiseptic have persistence it is high, it is heat-resist,
The good characteristics such as drug resistance, safety height are not likely to produce, in biological medicine, air purification, building coating, clothes, ceramics, health
There are wide development space and application potential in the fields such as kitchen tools.In inorganic antiseptic field, the silver system that surely belongs to of most study resists
Microbial inoculum, the inorganic antiseptic being commercialized at present are silver-series antibacterial agent mostly.Silver-series antibacterial agent include silver ion, metallic silver and
Silver nano-grain.Compared with silver ion, metallic silver, nano-Ag particles due to the quantum effect of nano-particle, small-size effect with
And great specific surface area so that the anti-microbial property of nano-Ag particles is far longer than traditional silver-series antibacterial agent.However, nano silver
The deficiencies of particle antiseptic is slow there are onset time, stability is poor, easy to change, therefore, how to solve these problems, research and development height
Effect, nontoxic (low toxicity) and the lasting silver-series antibacterial agent of effect are the research hotspots of current Material Field.
Graphene is a kind of individual layer laminated structure two-dimensional material being made of carbon atom, its carbon atom is with sp2Hydridization rail
Road, which is formed, has the cellular planar structure of hexangle type, has high-specific surface area, mechanical property outstanding, heat conductivility and efficient
The excellent specific properties such as electron transmission.Recent research indicate that:The layer structure of graphene can directly pierce through the cell membrane of bacterium, cause
The leakage of bacterium content simultaneously causes its death, and graphene is smaller to the cytotoxicity of mammal.In addition, graphene can be used as
The excellent carrier of inorganic nano-particle makes nano-particle stability improve.Therefore, suitable mode is selected, graphene/nano is prepared
The stability of Nano silver grain not only can be improved in the silver-colored composite antibacterial material of rice, improves its water solubility, and the two has collaboration anti-
Bacterium acts on.
It is original that the preparation method of existing graphene/nano silver composite material, which is typically with graphene oxide and silver nitrate,
Material, is made, hydrazine, sodium borohydride and hydroquinone are the most common reducing agents of redox graphene by chemical reduction method.
These reducing agents all have very high toxicity, this brings prodigious risk to environment and human health.Therefore, find green,
Efficiently, the preparation method of nontoxic new reducing agent and its suitable industrial production graphene is urgently to be resolved hurrily.
Invention content
The purpose of the present invention is to provide a kind of preparation method of graphene/nano silver composite antibacterial material, this method choosings
It is restored with environment-friendly type reducing agent, avoids injury of the toxic reducing agent such as hydrazine, sodium borohydride, hydroquinone to environment.
A kind of preparation method of graphene/nano silver composite antibacterial material provided by the invention, carries out as steps described below:
(1) by 2-4gNaNO3It is added in 500mL four-hole boiling flasks, addition 98% concentrated sulfuric acids of 100-150mL, under condition of ice bath
Cooling, when temperature of reaction system is less than 5 DEG C, the graphite powder that 5g dryings are added under stirring condition is vigorously stirred after mixing
Under, it is slowly added to 10-20g potassium permanganate, the temperature of control reaction mixture is no more than 20 DEG C during charging, and charging terminates
Afterwards, reacting liquid temperature is risen to 35 ± 3 DEG C, reacts 100-180min;After reaction, reacting liquid temperature is risen to 98 DEG C, play
Under strong stirring, 200-250mL distilled water is slowly added dropwise, after adding, control reacting liquid temperature continues to stir 10- at 98 DEG C or so
Then the deionized water of 600-800mL is added by reaction terminating in 20min;It is not anti-that the removing of 30-50mL30% hydrogen peroxide is added simultaneously
The potassium permanganate answered, at this moment solution become vivid yellow from brownish black;It filters while hot, 5% hydrochloric acid is used in combination to wash away metal ion
Afterwards, it is washed with deionized into filtrate without SO4 2-(BaCl2Solution detects);Then dry in 50-70 DEG C of baking oven, it obtains
Graphite oxide powder;
(2) the above-mentioned graphite oxides of 1g are added in 100-200mL deionized waters, under the ultrasonic power of 300-500W
30-45min is managed, under the speed of 8000-10000rpm, after centrifuging 5-8min, sediment is removed, obtains graphene oxide dispersion
Liquid;
(3) into the graphene oxide dispersion obtained by step (2), silver nitrate is added, obtains mixed solution;In 60-100
DEG C evaporation mixed solution 10-18h, obtain absorption silver ion graphene oxide;
(4) graphene oxide of above-mentioned absorption silver ion is put into the solution containing reducing agent and carries out reduction treatment, obtained
To graphene/nano silver composite antibacterial material.
Wherein, the silver nitrate described in step (3) is with graphite oxide mass ratio:0.01-0.5:1-2.
Wherein, the reducing agent described in step (4) be glyoxalic acid, a concentration of 100-200g/L of reducing agent, reducing agent with
Graphite oxide mass ratio is 10-20:1.
Wherein, 30-80 DEG C of reduction temperature described in step (4), recovery time 4-8h.
The present invention prepares graphite oxide using chemical method, uses environmental-friendly glyoxalic acid for reducing agent, prepare graphene/
Nano silver composite antibacterial material, preparation method is simple, reaction condition is mild, controllable, is suitable for mass producing.
Description of the drawings
The TEM figures of graphene/nano silver anti-biotic material prepared by Fig. 1 embodiments 1
XRD diagram ((a) graphene oxide of graphene/nano silver anti-biotic material prepared by Fig. 2 embodiments 1;(b) graphene/
Silver composite material)
Raman spectrogram ((a) graphene oxide of graphene/nano silver anti-biotic material prepared by Fig. 3 embodiments 1;(b) stone
Black alkene/silver composite material)
Specific implementation mode
With reference to specific embodiment, description is of the invention in further detail.It should be understood that these embodiments are intended merely to
It illustrates the present invention, rather than limits the scope of the invention in any way.
Embodiment 1
(1) by 2gNaNO3It is added in 500mL four-hole boiling flasks, addition 98% concentrated sulfuric acids of 100mL, it is cooling under condition of ice bath,
When temperature of reaction system is less than 5 DEG C, the graphite powder that 5g dryings are added under stirring condition is vigorously stirred down after mixing, is delayed
Slow that 10g potassium permanganate is added, the temperature of control reaction mixture is no more than 20 DEG C during charging, after charging, will react
Liquid temperature rises to 35 DEG C, reacts 100min.After reaction, reacting liquid temperature is risen to 98 DEG C, be vigorously stirred down, is slowly added dropwise
200mL distilled water, after adding, control reacting liquid temperature at 98 DEG C or so, continue stir 10min, then be added 600mL go from
Sub- water is by reaction terminating;30mL30% hydrogen peroxide is added simultaneously and removes unreacted potassium permanganate, at this moment solution is from dark brown discoloration
For vivid yellow.It filters, after being used in combination 5% hydrochloric acid to wash away metal ion, is washed with deionized into filtrate without SO while hot4 2-
(BaCl2Solution detects);Then dry in 50 DEG C of baking oven, the graphite oxide powder of acquisition;
(2) the above-mentioned graphite oxides of 1g are added in 100mL deionized waters, 30min are handled under the ultrasonic power of 300W,
Under the speed of 8000rpm, after centrifuging 8min, sediment is removed, graphene oxide dispersion is obtained;
(3) into the graphene oxide dispersion obtained by step (2), silver nitrate, silver nitrate and graphite oxide quality is added
The ratio between be:0.01:2;After mixing, mixed solution 18h is evaporated at 60 DEG C, obtains the graphene oxide of absorption silver ion;
(4) it is in 100g/L glyoxylic acid solutions the graphene oxide of above-mentioned absorption silver ion to be put into 100mL mass concentrations
Reduction treatment is carried out, recovery time 8h at 30 DEG C obtains graphene/nano silver composite antibacterial material.
Embodiment 2
(1) by 4gNaNO3It is added in 500mL four-hole boiling flasks, addition 98% concentrated sulfuric acids of 150mL, it is cooling under condition of ice bath,
When temperature of reaction system is less than 5 DEG C, the graphite powder that 5g dryings are added under stirring condition is vigorously stirred down after mixing, is delayed
Slow that 20g potassium permanganate is added, the temperature of control reaction mixture is no more than 20 DEG C during charging, after charging, will react
Liquid temperature rises to 32 DEG C, reacts 180min.After reaction, reacting liquid temperature is risen to 98 DEG C, be vigorously stirred down, is slowly added dropwise
250mL distilled water, after adding, control reacting liquid temperature at 98 DEG C or so, continue stir 20min, then be added 800mL go from
Sub- water is by reaction terminating;50mL30% hydrogen peroxide is added simultaneously and removes unreacted potassium permanganate, at this moment solution is from dark brown discoloration
For vivid yellow.It filters, after being used in combination 5% hydrochloric acid to wash away metal ion, is washed with deionized into filtrate without SO while hot4 2-
(BaCl2Solution detects);Then dry in 70 DEG C of baking oven, the graphite oxide powder of acquisition;
(2) the above-mentioned graphite oxides of 1g are added in 200mL deionized waters, 45min are handled under the ultrasonic power of 500W,
Under the speed of 10000rpm, after centrifuging 5min, sediment is removed, graphene oxide dispersion is obtained;
(3) into the graphene oxide dispersion obtained by step (2), silver nitrate, silver nitrate and graphite oxide quality is added
The ratio between be:0.5:1;After mixing, mixed solution 10h is evaporated at 100 DEG C, obtains the graphene oxide of absorption silver ion;
(4) it is in 200g/L glyoxylic acid solutions the graphene oxide of above-mentioned absorption silver ion to be put into 100mL mass concentrations
Reduction treatment is carried out, recovery time 4h at 80 DEG C obtains graphene/nano silver composite antibacterial material.
Embodiment 3
(1) by 3gNaNO3It is added in 500mL four-hole boiling flasks, addition 98% concentrated sulfuric acids of 120mL, it is cooling under condition of ice bath,
When temperature of reaction system is less than 5 DEG C, the graphite powder that 5g dryings are added under stirring condition is vigorously stirred down after mixing, is delayed
Slow that 15g potassium permanganate is added, the temperature of control reaction mixture is no more than 20 DEG C during charging, after charging, will react
Liquid temperature rises to 38 DEG C, reacts 120min.After reaction, reacting liquid temperature is risen to 98 DEG C, be vigorously stirred down, is slowly added dropwise
220mL distilled water, after adding, control reacting liquid temperature at 98 DEG C or so, continue stir 15min, then be added 700mL go from
Sub- water is by reaction terminating;40mL30% hydrogen peroxide is added simultaneously and removes unreacted potassium permanganate, at this moment solution is from dark brown discoloration
For vivid yellow.It filters, after being used in combination 5% hydrochloric acid to wash away metal ion, is washed with deionized into filtrate without SO while hot4 2-
(BaCl2Solution detects);Then dry in 60 DEG C of baking oven, the graphite oxide powder of acquisition;
(2) the above-mentioned graphite oxides of 1g are added in 150mL deionized waters, 40min are handled under the ultrasonic power of 400W,
Under the speed of 9000rpm, after centrifuging 7min, sediment is removed, graphene oxide dispersion is obtained;
(3) into the graphene oxide dispersion obtained by step (2), silver nitrate, silver nitrate and graphite oxide quality is added
The ratio between be:0.2:1.5, after mixing, mixed solution 12h is evaporated at 80 DEG C, obtain the graphene oxide of absorption silver ion;
(4) it is in 150g/L glyoxylic acid solutions the graphene oxide of above-mentioned absorption silver ion to be put into 100mL mass concentrations
Reduction treatment is carried out, recovery time 6h at 60 DEG C obtains graphene/nano silver composite antibacterial material.
Embodiment 4
(1) by 2.5gNaNO3It is added in 500mL four-hole boiling flasks, addition 98% concentrated sulfuric acids of 130mL, it is cold under condition of ice bath
But, when temperature of reaction system is less than 5 DEG C, the graphite powder that 5g dryings are added under stirring condition is vigorously stirred after mixing
Under, it is slowly added to 12g potassium permanganate, the temperature of control reaction mixture is no more than 20 DEG C, after charging during charging, will
Reacting liquid temperature rises to 34 DEG C, reacts 160min.After reaction, reacting liquid temperature is risen to 98 DEG C, be vigorously stirred down, slowly
240mL distilled water is added dropwise, after adding, control reacting liquid temperature continues to stir 12min at 98 DEG C or so, is then added 750mL's
Deionized water is by reaction terminating;35mL30% hydrogen peroxide is added simultaneously and removes unreacted potassium permanganate, at this moment solution is from dark brown
Discoloration is vivid yellow.It filters while hot, after being used in combination 5% hydrochloric acid to wash away metal ion, nothing is washed with deionized into filtrate
SO4 2-(BaCl2Solution detects);Then dry in 55 DEG C of baking oven, the graphite oxide powder of acquisition;
(2) the above-mentioned graphite oxides of 1g are added in 180mL deionized waters, 35min are handled under the ultrasonic power of 450W,
Under the speed of 8500rpm, after centrifuging 6min, sediment is removed, graphene oxide dispersion is obtained;
(3) into the graphene oxide dispersion obtained by step (2), silver nitrate, silver nitrate and graphite oxide quality is added
The ratio between be:0.1:1.5, mixed solution 16h is evaporated at 70 DEG C, obtains the graphene oxide of absorption silver ion;
(4) it is in 120g/L glyoxylic acid solutions the graphene oxide of above-mentioned absorption silver ion to be put into 100mL mass concentrations
Reduction treatment is carried out, recovery time 7h at 50 DEG C obtains graphene/nano silver composite antibacterial material.
Embodiment 5
Sample antibiotic property test according to《GB/T 21510-2008 nano inorganic material anti-microbial property detection methods》, bacterium
Kind selects Escherichia coli and staphylococcus aureus.Test result is as shown in table 1:
1 resulting materials bacteriostasis rate of table