CN110105632A - It is a kind of to inhibit the two-layer compound aeroge of biofilm formation, preparation method and application - Google Patents

It is a kind of to inhibit the two-layer compound aeroge of biofilm formation, preparation method and application Download PDF

Info

Publication number
CN110105632A
CN110105632A CN201910363312.1A CN201910363312A CN110105632A CN 110105632 A CN110105632 A CN 110105632A CN 201910363312 A CN201910363312 A CN 201910363312A CN 110105632 A CN110105632 A CN 110105632A
Authority
CN
China
Prior art keywords
chitosan
graphene oxide
aeroge
solution
biofilm formation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910363312.1A
Other languages
Chinese (zh)
Other versions
CN110105632B (en
Inventor
陆杨
王湘颖
薛敬哲
吴亚东
宋永红
闫旭
陈�胜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei University of Technology
Original Assignee
Hefei University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hefei University of Technology filed Critical Hefei University of Technology
Priority to CN201910363312.1A priority Critical patent/CN110105632B/en
Publication of CN110105632A publication Critical patent/CN110105632A/en
Application granted granted Critical
Publication of CN110105632B publication Critical patent/CN110105632B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • C08J9/0071Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C08J9/008Nanoparticles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22BMETHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00Methods of steam generation characterised by form of heating method
    • F22B1/006Methods of steam generation characterised by form of heating method using solar heat
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0806Silver
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/042Graphene or derivatives, e.g. graphene oxides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Cosmetics (AREA)

Abstract

The invention discloses a kind of two-layer compound aeroges for inhibiting biofilm formation, preparation method and application, cellular structure, antibacterial granule are orientated including the porous laminated structure of graphene oxide, chitosan, the porous laminated structure of the graphene oxide is located at the top of chitosan orientation cellular structure, and the antibacterial granule is evenly distributed on the duct inner wall of the chitosan orientation cellular structure;Inhibit the two-layer compound aeroge of biofilm formation in 10kW/m2Intensity of illumination under, evaporation capacity 13.5kgh‑1m‑2, evaporation efficiency 90.8%, the two-layer compound aeroge of inhibition biofilm formation of the invention is with stable structure, and good biological inhibition effect, guarantee aquaporin is unobstructed, guarantees evaporation efficiency, and recycling is good.

Description

It is a kind of to inhibit the two-layer compound aeroge of biofilm formation, preparation method and application
Technical field
The invention belongs to technical field of composite preparation more particularly to a kind of two-layer compound gas for inhibiting biofilm formation Gel, preparation method and application.
Background technique
With the rise of modern industry, the problem of being faced with increasingly severe shortage of water resources and water pollution.It is how high Effect using solar energy resources go processing seawater and industrial wastewater be one solve shortage of water resources and water pollution effective measures. Currently, can be carried out water process and sea water desalination etc. using the sun has become a popular research field.
The carbon nanotube that graphene oxide water solution, sodium alginate soln and cetyl trimethylammonium bromide are modified is mixed Close, by hydro-thermal, freezing, heat treatment and etc. prepared tri compound aeroge.Under a sunlight intensity, the airsetting The photothermal conversion efficiency of glue reaches 83%.Graphene oxide solution and a small amount of ethyl alcohol are mixed, in conjunction with hydro-thermal method, orientation freezing Technology, high-temperature calcination and plasma bombardment technology have prepared the graphene aerogel of morphology controllable, the graphene aerogel With good hydrophily, and the water evaporation rate under an Intensity of the sunlight is 1.62kgm-2h-1, while solar energy Utilization rate is up to 86.5%." advanced material " (2016, volume 28, page 9400~9407) in the U.S. describe a kind of bilayer Application of the compound nano-cellulose and graphene composite aerogel in terms of water evaporation.Nano-cellulose has big specific surface Product, open microcellular structure and has strong absorptive.Graphene can absorb sunlight.This two-layer compound aeroge exists Water evaporation rate under 10 sunlight intensities can achieve 11.8kgm-2h-1
Further graphene aerogel is extended based on absorbent properties of the graphene to sunlight, is used for sea Water desalination, the sun can induce water evaporation etc. with high scientific value and practical value.But exist in natural water body Various bacteriums and other microorganisms, their growth and breeding can affect to the structure of porous material, Such as duct deformation and closing.And then the water evaporation performance of material and being recycled for a long time are reduced by influencing Water Transport Property.Therefore, find that a kind of production method is simple, cyclicity is good and the porous material of biofilm formation can be inhibited for solar energy The fields such as induction water evaporation become a urgent problem to be solved.
Summary of the invention
Technical problem to be solved by the present invention lies in: it is currently used for the sun and can induce the material of water evaporation that it cannot be inhibited The formation of surface biological film provides two-layer compound aeroge, the preparation method and application of a kind of inhibition biofilm formation.
The present invention is to solve above-mentioned technical problem, a kind of inhibition biofilm formation of the invention by the following technical programs Two-layer compound aeroge, including the porous laminated structure of graphene oxide, chitosan be orientated cellular structure, antibacterial granule, it is described The porous laminated structure of graphene oxide be located at the top of chitosan orientation cellular structure, the antibacterial granule is distributed in described Chitosan is orientated on the duct surfaces externally and internally of cellular structure.
The antibacterial granule includes zinc oxide and/or silver.
The two-layer compound aeroge of the inhibition biofilm formation is in 10kW/m2Intensity of illumination under, evaporation capacity is 12.5~14.5kgh-1m-2, evaporation efficiency is 90.8~92.8%.
A kind of preparation method for the two-layer compound aeroge inhibiting biofilm formation, includes the following steps:
(1) preliminary redox graphene hydrogel:
(11) graphene oxide powder is add to deionized water, it is water-soluble that ultrasonic disperse is uniformly configured to graphene oxide Liquid;
(12) by graphene oxide water solution and ascorbic acid according to the mass ratio 1:1 of graphene oxide and ascorbic acid~ 3 carry out uniformly mixed, react 25~35 minutes under conditions of 85~100 DEG C, the graphene oxide water-setting tentatively restored Glue;
(2) secondary reduction graphene oxide hydrogel:
The graphene oxide hydrogel tentatively restored is cooled to room temperature, orientation freezing 25~35 minutes is thawed to room temperature It dialyses after being reacted 7~9 hours at 85~100 DEG C afterwards, obtains the graphene oxide hydrogel of secondary reduction;
(3) chitosan/anti-pollution nano particle aqueous solution is prepared:
(31) Chitosan powder is added to be configured in acetic acid solution 1~3% chitosan solution, then with 1% hydrogen Sodium hydroxide solution adjusts chitosan solution pH to neutrality;
(32) anti-pollution nano particle is add to deionized water, the anti-pollution nano particle for being configured to 1~3mg/mL is water-soluble Liquid;
(33) anti-pollution nano particle solution is added dropwise to according to anti-pollution nano particle with chitosan mass ratio for 1:50 In chitosan solution, it is uniformly mixed to obtain chitosan/anti-pollution nano particle aqueous solution;
(4) preparation inhibits the two-layer compound aeroge of biofilm formation:
The graphene oxide hydrogel of secondary reduction is placed in container, then pours into chitosan/anti-pollution nano into container Then container is placed in orientation freezing 25~35 minutes in liquid nitrogen by particle aqueous solution, finally inhibition biomembrane can be obtained in drying The two-layer compound aeroge of formation.
In the step (11), the concentration of graphene oxide water solution is 4~6mg/mL.
In the step (2), orientation is frozen in liquid nitrogen and carries out, and dialyzate is deionized water, dialysis time be 3 days with On.
In the step (31), the concentration of acetic acid solution is 1~2%.
In the step (33), mixing time is 3~4 hours.
In the step (4), drying carries out in freeze drier.
A kind of two-layer compound aeroge inhibiting biofilm formation can induce application on water evaporation material preparing the sun.
The two-layer compound aeroge prepared by the present invention for inhibiting biofilm formation, including the porous laminated knot of graphene oxide Structure, chitosan are orientated cellular structure, antibacterial granule, between unobvious between graphene oxide layer and chitosan/nano-particle layer Gap, the bilayer aeroge have stable structure, and graphene oxide layer is porous structure, provides channel, shell for the evaporation of moisture Glycan/Zinc oxide nanoparticle layer is the orientation cellular structure of rule, provides channel for the transmission of moisture;Inhibit biomembrane shape At two-layer compound aeroge have good compression recovery performance still be able to spring back completely under 80% contractive condition, pass through It crosses after a couple of days shaking table rocks and is still able to maintain pattern integrality, there is good inhibitory effect to the formation of biomembrane, to seawater, dirt Water etc. all has good water evaporation performance and has recyclability.
The present invention inhibits the preparation method of the two-layer compound aeroge of biofilm formation, and it is poly- that graphene hydrogel is placed in shell Among sugar/anti-pollution nano particle aqueous solution, chitosan penetrating to the inner surface in graphene hole keeps graphene oxide layer and shell poly- Sugar/nano-particle layer does not have obvious gap, improves graphene hydrogel to light by secondary reduction graphene oxide hydrogel Graphene oxide/chitosan/anti-pollution nano with double-layer structure can be obtained by the method for secondary freezing for assimilation effect Grain hydrogel, graphene oxide/chitosan/anti-pollution nano particle airsetting of double-layer structure can be obtained by Freeze Drying Technique Glue, it is simple and easy, it is easy to industrializing implementation.
The present invention has the advantage that the two-layer compound aeroge of inhibition biofilm formation of the invention compared with prior art With stable structure, good biological inhibition effect guarantees that aquaporin is unobstructed, guarantees evaporation efficiency, and recycling is good.
Detailed description of the invention
Fig. 1 is through bacterium solution treated chitosan aeroge electromicroscopic photograph;
Fig. 2 is through AM and PI dyeing treated chitosan aeroge fluorescence microscope picture;
Fig. 3 is the scanning figure of chitosan/oxidized zinc nanoparticles aeroge;
Fig. 4 is chitosan/oxidized zinc nanoparticles aeroge Mapping power spectrum;
Fig. 5 is the XRD spectrum of chitosan/oxidized zinc nanoparticles aeroge and Zinc oxide nanoparticle;
Fig. 6 is the xps energy spectrum figure of graphene oxide and chitosan/oxidized zinc;
Fig. 7 is chitosan/oxidized zinc nanoparticles through map;
Fig. 8 is the reflection map of chitosan/oxidized zinc nanoparticles;
Fig. 9 is through bacterium solution treated chitosan/oxidized zinc nanoparticles aeroge electromicroscopic photograph;
Figure 10 is through bacterium solution treated chitosan/silver nano-grain aeroge electromicroscopic photograph;
Figure 11 is photo and the cross-sectional scans photo in kind of graphite oxide aerogel;
Figure 12 is the compression cyclic curve of graphite oxide aerogel;
Figure 13 is that graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge photo in kind and longitudinal section are swept Retouch photo;
Figure 14 is graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge stability;
Figure 15 is graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge cyclicity;
Figure 16 is the ultraviolet-visible curve of methylene blue solution before and after the processing;
Figure 17 is circulating and evaporating of the graphene oxide/chitosan/oxidized zinc particle bilayer aeroge to methylene blue sewage Amount;
Figure 18 is graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge circulating and evaporating amount;
Figure 19 is graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge sodium, potassium, calcium in water before and after the processing Change with the concentration of magnesium ion.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.
Embodiment 1
The present embodiment prepares chitosan aeroge (CS aeroge), the specific steps are as follows:
(1) 2g Chitosan powder is taken, 99mL deionized water and 1mL acetic acid are added, stirs into clear solution, as 2% shell
Glycan solution;
(2) pH of chitosan solution is adjusted to neutrality with 1% sodium hydroxide solution;
It (3) is 30 points with the time that liquid nitrogen carries out orientation freezing and orientation freezing by the chitosan solution being adjusted to neutrality Clock;
(4) chitosan solution freezed is freeze-dried, chitosan aeroge can be obtained;
Chitosan aeroge is immersed in 105In the Escherichia coli solution and staphylococcus glucose coccus solution of CFU/mL, And rocked under conditions of 37 DEG C 3 days, after a series of processes such as dehydration, fixation and freeze-drying, with scanning electron microscope to sample Product are observed, as a result such as Fig. 1.It can be seen from the figure that being grown on the duct through bacterium solution treated chitosan aeroge A large amount of Escherichia coli or staphylococcus glucose coccus, cell channels are even completely by bacterial plugging.
In order to further look at the bacterium on chitosan aeroge, also to the sample after bacterial solution culture carry out AM and PI dyeing, is observed with fluorescence microscope, as a result as shown in Fig. 2, wherein for AM by the nuclei dyeing of living cells at green, PI will The nuclei dyeing of dead cell is at red, it is found that sample has green and red appearance, illustrates there is bacterium on chitosan aeroge Growth and attachment.
Embodiment 2
The present embodiment prepares chitosan/oxidized zinc nanoparticles aeroge (CZ aeroge), the specific steps are as follows:
(1) 2g Chitosan powder is taken, 99mL deionized water and 1mL acetic acid are added, stirs into clear solution, as 2% shell Glycan solution;
(2) pH of chitosan solution is adjusted to neutrality with 1% sodium hydroxide solution;
(3) Zinc oxide nanoparticle is configured to the aqueous dispersions of 2mg/mL, be added drop-wise in chitosan solution dropwise and The mass ratio 1:50 for making Zinc oxide nanoparticle and chitosan, stirs evenly, and obtains chitosan/oxidized zinc nanoparticles mixing Liquid;
By chitosan/oxidized zinc nanoparticles mixed liquor with the time that liquid nitrogen carries out orientation freezing and is orientated freezing for 30 points Clock is then dried in freeze drier, and chitosan/oxidized zinc nanoparticles aeroge can be obtained;
Fig. 3 is the scanning figure of chitosan/oxidized zinc nanoparticles aeroge, it can be seen that chitosan/oxygen from scanning figure The aperture for changing zinc nanoparticles aeroge is 20~200 μm;
Fig. 4 is chitosan/oxidized zinc nanoparticles aeroge Mapping power spectrum, be can be seen that from Mapping power spectrum Chitosan/antimicrobial nano granular aerogel includes zinc, elements such as oxygen and carbon and zinc is evenly distributed in aeroge.
Fig. 5 is the XRD spectrum of chitosan/oxidized zinc nanoparticles aeroge and Zinc oxide nanoparticle, passes through control two The XRD spectrum of person is found, is adjusted by pH, and during freezing etc. is a series of, there is no change Zinc oxide nanoparticle in gas Existence form in gel.
Fig. 6 is the xps energy spectrum figure of graphene oxide and chitosan/oxidized zinc, it can be seen from the figure that graphene oxide The carbon and oxygen of essential element;The essential element of chitosan/oxidized zinc is carbon, oxygen, nitrogen and zinc.
Fig. 7 is the map that penetrates of chitosan/oxidized zinc nanoparticles, and Fig. 8 is the reflection of chitosan/oxidized zinc nanoparticles Map, it is known that, transmitance of the chitosan/oxidized zinc nanoparticles aeroge within the scope of 300~1200nm is about 23%, reflection Rate is about 20%.
Chitosan/oxidized zinc nanoparticles aeroge is immersed in 105The Escherichia coli solution of CFU/mL and golden yellow Portugal In grape sugar ball bacterium solution, and rocked 3 days under conditions of 37 DEG C, after a series of processes such as dehydration, fixation and freeze-drying, Sample is observed with scanning electron microscope, as a result such as Fig. 9.
It can be seen in figure 9 that by the duct of bacterium solution treated chitosan/oxidized zinc nanoparticles aeroge only There are a small amount of Escherichia coli or staphylococcus glucose coccus, by comparing with chitosan sample, passes through zinc-oxide nano Grain is added, and can significantly inhibit the breeding of Escherichia coli and staphylococcus glucose coccus to inhibit the formation of biomembrane.
Embodiment 3
The present embodiment prepares chitosan/silver nano-grain aeroge (CSS aeroge), the specific steps are as follows:
(1) 2g Chitosan powder is taken, 99mL deionized water and 1mL acetic acid are added, stirs into clear solution, as 2% shell
Glycan solution;
(2) pH of chitosan solution is adjusted to neutrality with 1% sodium hydroxide solution;
(3) silver nano-grain is configured to the aqueous dispersions of 2mg/mL, is added drop-wise in chitosan solution dropwise and makes silver Nanometer
The mass ratio of particle and chitosan is 1:50, stirs evenly, obtains chitosan/silver nano-grain mixed liquor;
It (4) is 30 points with the time that liquid nitrogen carries out orientation freezing and orientation freezing by chitosan/silver nano-grain mixed liquor Clock, with
It is dried in freeze drier afterwards, chitosan/silver nano-grain aeroge can be obtained;
Chitosan/silver nano-grain aeroge is immersed in 105The Escherichia coli solution and staphylococcus glucose of CFU/mL It in coccus solution, and is rocked 3 days under conditions of 37 DEG C, after a series of processes such as dehydration, fixation and freeze-drying, with sweeping It retouches Electronic Speculum to observe sample, as a result such as Figure 10.It can be seen from fig. 10 that by bacterium solution treated chitosan/Yin Na Substantially no Escherichia coli or staphylococcus glucose coccus on the duct of rice grain aeroge, by being carried out with chitosan sample Comparison, is added by silver nano-grain, can significantly inhibit the breeding of Escherichia coli and staphylococcus glucose coccus to inhibit The formation of biomembrane.
Embodiment 4
The present embodiment prepares graphite oxide aerogel (GO aeroge), the specific steps are as follows:
(1) graphene oxide powder is added in deionized water, ultrasound makes it be uniformly dispersed, and is configured to the oxidation of 5mg/mL Graphite
Aqueous solution;
(2) mass ratio of the graphene oxide water solution of 5mg/mL and ascorbic acid is mixed according to 1:2, is being vibrated It is mixed on device uniformly;
(3) uniformly mixed graphene oxide water solution is placed in the container of capping, reacts 30 under conditions of 95 DEG C Minute, the graphene oxide hydrogel tentatively restored;
(4) the graphene oxide hydrogel of acquisition tentatively restored is cooled to room temperature, it will using the method for orientation freezing It is used liquid nitrogen frozen 30 minutes;
(5) it will be thawed at room temperature with the graphene oxide after liquid nitrogen frozen, then continued under conditions of 95 DEG C Reaction 8 hours, obtains the graphene oxide hydrogel of secondary reduction;
(6) obtained graphene oxide hydrogel is dialysed three days or more in deionized water;
(7) the graphene oxide hydrogel after dialysing carries out orientation freezing 30 minutes with liquid nitrogen, is then freeze-dried The graphite oxide aerogel with compression recovery performance can be obtained.
Photo and the cross-sectional scans photo in kind of Figure 11 graphite oxide aerogel.It can from cross-sectional scans photo Out, graphite oxide aerogel has porous structure, and duct size is about 40~60 μm, these cellular structures are the steaming of moisture content Hair provides channel.
Figure 12 is the compression cyclic curve of graphite oxide aerogel, and under 80% contractive condition, graphene oxide is still It can be restored to original height, this compressibility is that the property of can be recycled of device provides the foundation.
In addition, the analysis of light absorption is also carried out to graphite oxide aerogel, in the wave-length coverage of 300~1200nm Interior, graphite oxide aerogel is essentially 0 to the reflection of light and transmitance, illustrates that graphite oxide aerogel has good light Absorbent properties, this provides theoretical basis for the preparation that the sun can induce water evaporating apparatus.
Embodiment 5
The present embodiment prepares double-deck graphene oxide/chitosan aeroge (GC aeroge), the specific steps are as follows:
(1) 2g Chitosan powder is taken, 99mL deionized water and 1mL acetic acid are added, stirs into clear solution, as 2% shell Glycan solution;
(2) pH of chitosan solution is adjusted to neutrality with 1% sodium hydroxide solution;
Graphene oxide powder is added in deionized water, ultrasound makes it be uniformly dispersed, and is configured to the oxidation stone of 5mg/mL Black aqueous solution;
(3) mass ratio of the graphene oxide water solution of 5mg/mL and ascorbic acid is mixed according to 1:2, is being vibrated It is mixed on device uniformly;
(4) uniformly mixed graphene oxide water solution is placed in the container of capping, reacts 30 under conditions of 95 DEG C Minute, the graphene oxide hydrogel tentatively restored;
(5) the graphene oxide hydrogel of acquisition tentatively restored is cooled to room temperature, it will using the method for orientation freezing It is used liquid nitrogen frozen 30 minutes;
(6) it will be thawed at room temperature with the graphene oxide after liquid nitrogen frozen, then continued under conditions of 95 DEG C Reaction 8 hours, obtains the graphene oxide hydrogel of secondary reduction;
(7) obtained graphene oxide hydrogel is dialysed three days or more in deionized water;
(8) the graphene oxide hydrogel after dialysis is placed in a beaker center and pours into suitable chitosan solution, used Liquid nitrogen carries out orientation freezing 30 minutes, is then freeze-dried in freeze drier, and it is poly- that graphene oxide/shell can be obtained Sugared bilayer aeroge.
It, will be double-deck in order to which the formation of further quantitative analysis bacterial biof iotalm can induce the influence of water evaporating apparatus to the sun Graphene oxide/chitosan aeroge is 1053 are cultivated in the Escherichia coli of CFU/mL and the bacterium solution of staphylococcus glucose coccus It, cultivation temperature is 37 DEG C.Then, by the sample after culture in 10kWm-2Intensity of illumination under carry out the sun can induce water evaporation Experiment.By multiple parallel laboratory test, it can be deduced that, it is double after Escherichia coli and staphylococcus glucose coccus bacterium solution culture Layer graphene oxide/chitosan aeroge evaporation capacity and evaporation efficiency under the intensity of illumination of 10 sun are respectively 9.1kgh- 1m-2, 61% (Escherichia coli) and 8.4kgh-1m-2, 56.8% (staphylococcus glucose coccus).
Embodiment 6
The present embodiment preparation inhibits the double-deck graphene oxide/chitosan/oxidized zinc nanoparticles airsetting of biofilm formation Glue (GCZ aeroge), the specific steps are as follows:
(1) 2g Chitosan powder is taken, 99mL deionized water and 1mL acetic acid are added, stirs into clear solution, as 2% shell Glycan solution;
(2) pH of chitosan solution is adjusted to neutrality with 1% sodium hydroxide solution;
(3) Zinc oxide nanoparticle is configured to the aqueous dispersions of 2mg/mL, be added drop-wise in chitosan solution dropwise and The mass ratio 1:50 for making Zinc oxide nanoparticle and chitosan, stirs evenly, and obtains chitosan/oxidized zinc nanoparticles mixing Liquid;
(4) graphene oxide powder is added in deionized water, ultrasound makes it be uniformly dispersed, and is configured to the oxidation of 5mg/mL Graphene aqueous solution;
(5) mass ratio of the graphene oxide water solution of 5mg/mL and ascorbic acid is mixed according to 1:2, is being vibrated It is mixed on device uniformly;
(6) uniformly mixed graphene oxide water solution is placed in the container of capping, reacts 30 under conditions of 95 DEG C Minute, the graphene oxide hydrogel tentatively restored;
(7) the graphene oxide hydrogel of acquisition tentatively restored is cooled to room temperature, it will using the method for orientation freezing It is used liquid nitrogen frozen 30 minutes;
(8) it will be thawed at room temperature with the graphene oxide after liquid nitrogen frozen, then continued under conditions of 95 DEG C Reaction 8 hours, obtains the graphene oxide hydrogel of secondary reduction;
(9) obtained graphene oxide hydrogel is dialysed three days or more in deionized water;
(10) the graphene oxide hydrogel after dialysis is placed in a beaker center and pours into suitable chitosan/oxidized zinc Nanoparticles solution carries out orientation freezing 30 minutes with liquid nitrogen, is then freeze-dried, be can be obtained in freeze drier Graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge.
Figure 13 is that graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge photo in kind and longitudinal section are swept Retouch photo.In figure, a is photo in kind, and b is longitudinal section scanned photograph, and c, d are partial sweep photo.
It can be seen that, the outer layer of graphene oxide is wrapped up by chitosan/oxidized zinc nanoparticles layer from photo in kind.
Do not have between graphene oxide layer and chitosan/oxidized zinc nanoparticles layer from can be seen that in the scanning figure of longitudinal section There is obvious gap, illustrates that the bilayer aeroge has structured stability.
As can be seen that graphene oxide layer is porous structure from partial sweep photo, channel is provided for the evaporation of moisture, Chitosan/oxidized zinc nanoparticles layer is the orientation cellular structure of rule, provides channel for the transmission of moisture.
It, will be double-deck in order to which the formation of further quantitative analysis bacterial biof iotalm can induce the influence of water evaporation performance to the sun Graphene oxide/chitosan aeroge is 1053 are cultivated in the Escherichia coli of CFU/mL and the bacterium solution of staphylococcus glucose coccus It, cultivation temperature is 37 DEG C.
By the sample after culture in 10kWm-2Intensity of illumination under carry out the sun and can induce the experiment of water evaporation.By multiple Parallel laboratory test, the double-deck graphene oxide after Escherichia coli and staphylococcus glucose coccus bacterium solution culture/chitosan/oxidized Zinc nanoparticles aeroge evaporation capacity and evaporation efficiency under the intensity of illumination of 10 sun are respectively 13.3kgh-1m-2, 89.4% (Escherichia coli) and 13.4kgh-1m-2, 89.7% (staphylococcus glucose coccus).
Compared to no aeroge that antimicrobial nano particle is added, graphene oxide/chitosan/oxidized zinc nanoparticles airsetting Glue still shows fabulous volatility after bacterium solution processing.The double-deck aeroge containing Zinc oxide nanoparticle is in Escherichia coli 1.46 and 1.59 times of the double-deck aeroge of Zinc oxide nanoparticle are respectively free of with the evaporation rate of staphylococcus glucose coccus.
To graphene oxide/chitosan/antimicrobial nano granular aerogel in tap water, the intensity of illumination of 10 sun Under, graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge evaporation capacity and evaporation efficiency are respectively 13.5kgh- 1m-2With 90.8%.This and in two kinds of bacterium solutions cultivate after the evaporation of graphene oxide/chitosan/antimicrobial nano granular aerogel Amount and evaporation efficiency are very nearly the same.Therefore, the formation that can effectively inhibit biomembrane by the addition of antimicrobial nano particle, from And the sun for avoiding the duct of porous support from occurring to block and then influence device can induce water evaporation efficiency.
Graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge stability is probed into, such as Figure 14 institute Show.Sample is placed in the centrifuge tube for adding water, is rocked in the shaking table of 100rpm 7 days, the macro morphology of the sample does not occur Change.
Graphene oxide/chitosan/oxidized zinc nanoparticles bilayer aeroge cyclicity is probed into, also to same Sample has carried out 20 vaporization cycles, and after 20 circulations, which is still able to maintain well stable volatility, Evaporation capacity is maintained at 13.5kgh-1m-2Left and right, as shown in figure 15.
Other than being evaporated to normal water body and more bacterium water bodys, the evaporation experiment of sewage also has been carried out to sample.
Under conditions of a sunlight, graphene oxide/chitosan/oxidized zinc particle bilayer aeroge can be to 50mg/L Methylene blue solution be evaporated, and by 10 circulation after, aeroge is still able to maintain stable evaporation capacity, by processing Afterwards, methylene blue is removed, uv-visible absorption spectra such as Figure 16, to circulating and evaporating amount such as Figure 17 institute of methylene blue sewage Show.
It can induce the application range of water evaporating apparatus to expand the sun, manually illumination of the seawater in 1 sunlight Evaporation experiment has been carried out under intensity.As can be seen from Figure 18, in 10 circulations, which maintains stable evaporation capacity. Carry out the measurement of ICP-AES by the liquid before evaporating and after evaporation, such as Figure 19, sodium, potassium, calcium and magnesium ion in water it is dense Degree has the decline of conspicuousness.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (10)

1. a kind of two-layer compound aeroge for inhibiting biofilm formation, which is characterized in that including the porous laminated knot of graphene oxide Structure, chitosan are orientated cellular structure, antibacterial granule, and the porous laminated structure of the graphene oxide is located at chitosan orientation duct The top of structure, the antibacterial granule are distributed on the duct surfaces externally and internally of the chitosan orientation cellular structure.
2. a kind of two-layer compound aeroge for inhibiting biofilm formation according to claim 1, which is characterized in that described Antibacterial granule includes zinc oxide and/or silver.
3. a kind of two-layer compound aeroge for inhibiting biofilm formation according to claim 1, which is characterized in that described Inhibit the two-layer compound aeroge of biofilm formation in 10kW/m2Intensity of illumination under, evaporation capacity be 12.5~14.5kgh-1m-2, Evaporation efficiency is 90.8~92.8%.
4. a kind of preparation method of the two-layer compound aeroge as claimed in any one of claims 1 to 3 for inhibiting biofilm formation, It is characterized by comprising the following steps:
(1) preliminary redox graphene hydrogel:
(11) graphene oxide powder is add to deionized water, ultrasonic disperse is uniformly configured to graphene oxide water solution;
(12) by graphene oxide water solution and ascorbic acid according to mass ratio 1:1~3 of graphene oxide and ascorbic acid into Row is uniformly mixed, and is reacted 25~35 minutes under conditions of 85~100 DEG C, the graphene oxide hydrogel tentatively restored;
(2) secondary reduction graphene oxide hydrogel:
The graphene oxide hydrogel tentatively restored is cooled to room temperature, orientation freezing 25~35 minutes, thaw to after room temperature It dialyses after being reacted 7~9 hours at 85~100 DEG C, obtains the graphene oxide hydrogel of secondary reduction;
(3) chitosan/anti-pollution nano particle aqueous solution is prepared:
(31) Chitosan powder is added to be configured in acetic acid solution 1~3% chitosan solution, then with 1% hydroxide Sodium solution adjusts chitosan solution pH to neutrality;
(32) anti-pollution nano particle is add to deionized water, is configured to the anti-pollution nano particle aqueous solution of 1~3mg/mL;
(33) anti-pollution nano particle solution shell is added dropwise to chitosan mass ratio according to anti-pollution nano particle for 1:50 to gather In sugar juice, it is uniformly mixed to obtain chitosan/anti-pollution nano particle aqueous solution;
(4) preparation inhibits the two-layer compound aeroge of biofilm formation:
The graphene oxide hydrogel of secondary reduction is placed in container, then pours into chitosan/anti-pollution nano particle into container Then container is placed in orientation freezing 25~35 minutes in liquid nitrogen by aqueous solution, finally inhibition biofilm formation can be obtained in drying Two-layer compound aeroge.
5. the preparation method according to claim 4, which is characterized in that in the step (11), graphene oxide water solution Concentration be 4~6mg/mL.
6. the preparation method according to claim 4, which is characterized in that in the step (2), orientation be frozen in liquid nitrogen into Row, dialyzate are deionized water, and dialysis time is 3 days or more.
7. the preparation method according to claim 4, which is characterized in that in the step (31), the concentration of acetic acid solution is 1 ~2%.
8. the preparation method according to claim 4, which is characterized in that in the step (33), mixing time is 3~4 small When.
9. the preparation method according to claim 4, which is characterized in that dry in freeze drier in the step (4) It carries out.
10. a kind of two-layer compound aeroge as claimed in any one of claims 1 to 3 for inhibiting biofilm formation is preparing the sun It can induce the application on water evaporation material.
CN201910363312.1A 2019-04-30 2019-04-30 Double-layer composite aerogel for inhibiting biofilm formation, preparation method and application Active CN110105632B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910363312.1A CN110105632B (en) 2019-04-30 2019-04-30 Double-layer composite aerogel for inhibiting biofilm formation, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910363312.1A CN110105632B (en) 2019-04-30 2019-04-30 Double-layer composite aerogel for inhibiting biofilm formation, preparation method and application

Publications (2)

Publication Number Publication Date
CN110105632A true CN110105632A (en) 2019-08-09
CN110105632B CN110105632B (en) 2021-04-02

Family

ID=67487999

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910363312.1A Active CN110105632B (en) 2019-04-30 2019-04-30 Double-layer composite aerogel for inhibiting biofilm formation, preparation method and application

Country Status (1)

Country Link
CN (1) CN110105632B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110528268A (en) * 2019-08-19 2019-12-03 成都良品家饰工程有限公司 A kind of nanometer of light purification fabric and its manufacturing method
CN112876594A (en) * 2021-01-21 2021-06-01 中南大学 Hydrogel material and preparation method thereof
CN112915935A (en) * 2021-01-25 2021-06-08 合肥工业大学 Bionic magnetic fibroin-based composite aerogel, and preparation method and application thereof
CN112961246A (en) * 2021-02-07 2021-06-15 西南大学 Nano microsphere anti-biofilm peptide CRAMP and preparation method and application thereof
CN113908780A (en) * 2021-11-01 2022-01-11 山东第一医科大学(山东省医学科学院) Graphene-attapulgite composite elastic aerogel and application thereof in seawater desalination
CN114682178A (en) * 2022-04-07 2022-07-01 合肥工业大学 Shape memory type composite aerogel for inhibiting biofouling, preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103043654A (en) * 2011-10-12 2013-04-17 国家纳米科学中心 Film containing graphene and/or graphene oxide, and preparation method thereof
CN105771915A (en) * 2016-03-30 2016-07-20 安徽大学 Preparation method for circulation adsorbent graphene/molybdenum disulfide/chitosan compound aquogel
CN106076272A (en) * 2016-06-24 2016-11-09 四川大学 A kind of preparation method of adsorbent for heavy metal
WO2016161123A8 (en) * 2015-03-31 2018-02-01 Aerogel Technologies, Llc Aerogel materials and methods for their production
WO2018087542A1 (en) * 2016-11-09 2018-05-17 University Of York Cyrene and ternary mixtures of cyrene for the enhanced use of dispersion and solvation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103043654A (en) * 2011-10-12 2013-04-17 国家纳米科学中心 Film containing graphene and/or graphene oxide, and preparation method thereof
WO2016161123A8 (en) * 2015-03-31 2018-02-01 Aerogel Technologies, Llc Aerogel materials and methods for their production
CN105771915A (en) * 2016-03-30 2016-07-20 安徽大学 Preparation method for circulation adsorbent graphene/molybdenum disulfide/chitosan compound aquogel
CN106076272A (en) * 2016-06-24 2016-11-09 四川大学 A kind of preparation method of adsorbent for heavy metal
WO2018087542A1 (en) * 2016-11-09 2018-05-17 University Of York Cyrene and ternary mixtures of cyrene for the enhanced use of dispersion and solvation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
XIANGYING WANG 等: "Anti-biofouling double-layered unidirectional scaffold for long-term solar-driven water evaporation", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
杜敏芝: "石墨烯基功能纺织品制备及其性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *
王湘颖: "基于壳聚糖的多维仿生纳米材料的制备及应用", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110528268A (en) * 2019-08-19 2019-12-03 成都良品家饰工程有限公司 A kind of nanometer of light purification fabric and its manufacturing method
CN112876594A (en) * 2021-01-21 2021-06-01 中南大学 Hydrogel material and preparation method thereof
CN112915935A (en) * 2021-01-25 2021-06-08 合肥工业大学 Bionic magnetic fibroin-based composite aerogel, and preparation method and application thereof
CN112961246A (en) * 2021-02-07 2021-06-15 西南大学 Nano microsphere anti-biofilm peptide CRAMP and preparation method and application thereof
CN113908780A (en) * 2021-11-01 2022-01-11 山东第一医科大学(山东省医学科学院) Graphene-attapulgite composite elastic aerogel and application thereof in seawater desalination
CN114682178A (en) * 2022-04-07 2022-07-01 合肥工业大学 Shape memory type composite aerogel for inhibiting biofouling, preparation method and application thereof
CN114682178B (en) * 2022-04-07 2023-02-10 合肥工业大学 Shape memory type composite aerogel for inhibiting biofouling, preparation method and application thereof

Also Published As

Publication number Publication date
CN110105632B (en) 2021-04-02

Similar Documents

Publication Publication Date Title
CN110105632A (en) It is a kind of to inhibit the two-layer compound aeroge of biofilm formation, preparation method and application
Tekin et al. Thermal, photocatalytic, and antibacterial properties of calcinated nano-TiO2/polymer composites
Zhang et al. Scalable, self-cleaning and self-floating bi-layered bacterial cellulose biofoam for efficient solar evaporator with photocatalytic purification
CN113005765B (en) Hydrophilic-hydrophobic 'Shuangshen' structure composite photothermal conversion material, preparation method and application thereof
CN105594739B (en) A kind of visible light catalytic composite antibacterial material and preparation method thereof
CN104119164B (en) The production method of zeolite compression Nutrition Soil
CN113815072B (en) Wood-based composite material for photo-thermal sewage purification and preparation method and application thereof
CN104119172B (en) The production method of Kaolin Tailings compression Nutrition Soil
CN113042077B (en) Photo-thermal-photochemical synergistic conversion hydrogel material and preparation method and application thereof
CN110075923A (en) A kind of g-C3N4The bionical construction method and application thereof of/BiOI-pDA@PVDF photocatalysis membrana
CN109433153A (en) A kind of lignin porous charcoal and its preparation method and application that Nano-lanthanum hydroxide is modified
CN105148894A (en) Preparation method of hydroxylation titanium oxide/graphene visible light catalysis material
CN105727895A (en) Shaddock peel activated carbon-chitosan adsorbent and preparation method and application thereof
US20210113992A1 (en) Biological morph-genetic wo3 photocatalyst and preparation method and application thereof
CN109896722A (en) A kind of spherical nanometer calper calcium peroxide preparation method for deeply dehydrating sludge
CN104119189B (en) The production method of attapulgite clay mine tailing compression Nutrition Soil
CN108128800B (en) Preparation method of zinc oxide nanocrystal
CN108855033B (en) Method for preparing porous nanosheet three-dimensional zinc oxide photocatalytic material by taking shaddock endothelium as template
CN109942880A (en) A kind of preparation method of nano-cellulose base porous compound material
CN113786782A (en) Preparation method and application of self-blackening quinoa cellulose/graphene oxide aerogel
CN110433789B (en) Method for preparing photocatalytic biochar composite material by utilizing eichhornia crassipes accumulated nano zinc oxide
Fan et al. Architecting a bifunctional solar evaporator of perovskite La0. 5Sr0. 5CoO3 for solar evaporation and degradation
CN113321255B (en) Preparation method and application of manganese oxide-biochar composite solar interface evaporation material
CN109810697A (en) A kind of dictyophora phalloidea cap carbon quantum dot and preparation method thereof
CN114570402A (en) Preparation method of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material and application of carbon-defect-containing and oxygen-doped carbon nitride photocatalytic material in removal of tetracycline in water body

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant