CN104587918A - Silver nano-particle modified carbon ball/graphene composite aero-gel material as well as preparation method and application of material - Google Patents
Silver nano-particle modified carbon ball/graphene composite aero-gel material as well as preparation method and application of material Download PDFInfo
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Abstract
The invention provides a silver nano-particle modified carbon ball/graphene composite aero-gel material as well as a preparation method and application of the material. The material is of a three-dimensional structure, wherein silver nano-particles being 10-20nm in size are distributed on the surfaces of the carbon balls to form silver nano-particle modified carbon balls which are dispersed between graphene sheets. The preparation method comprises the following steps: firstly, preparing graphene oxide precursor dispersion liquid and then preparing a carbon ball dispersion liquid; then, preparing silver nano-particle modified carbon ball dispersion liquid; and finally, preparing a silver nano-particle modified carbon ball/graphene composite aero-gel material. The composite material can be used for adsorption of heavy metal ions and adsorption and degradation of organic pollutants in water, the material shows good adsorption effect on heavy metal ions and strong adsorption and degradation capabilities to organic pollutants due to synergistic effect of the graphene, the carbon balls and the silver nano-particles.
Description
Technical field
The invention belongs to graphene composite material field, particularly a kind of Nano silver grain modified carbon ball/Graphene aerogel composite and preparation method thereof and application.
Background technology
Graphene is by sp
2hydbridized carbon atoms bonding, and the monoatomic layer graphite with the cellular two-dimensional structure of hexagonal lattice.It causes owing to having good electric conductivity, larger theoretical specific surface area and higher mechanical stability and pays close attention to widely.But the π-π of graphene film interlayer acts on the application that agglomerated phenomenon limits Graphene significantly.The solution of the irreversible agglomeration traits of Graphene becomes the focus of technical field of material chemistry research.In recent years, Graphene and graphite oxide aerogel or the hydrosol, due to its macroscopic view and multi-functional character, receive the concern of technical field of material chemistry.Graphene aerogel maintains the superior performance of the high-specific surface area, high conductivity etc. of Graphene, and the face, face that can also overcome Graphene is to a certain extent stacking, and unique three-dimensional porous structure is conducive to its application in water treatment field simultaneously.
Aeroge, also known as xerogel, is a kind of solid material of porous foam shape, has extremely light density and very high specific area.Due to its special loose structure, aeroge is widely studied in catalysis matrix, absorbing material and conduction and insulating materials etc.The preparation of aeroge is made up of sol-gel process and supercritical drying processing procedure usually.In sol-gel process, by controlling the poly-condensation and hydrolysis condition of solution, the nanocluster of different structure is formed, inter-adhesive formation hydrogel between cluster, remaining liquid reagent be then full of chemical reaction around the solid-state skeleton of gelinite after in solution.By supercritical drying, the moisture content in hydrogel is replaced into gas, just defines aeroge.Graphene aerogel has possessed the characteristic of Graphene and aeroge simultaneously, comprises much higher porosity, ultralight density and high mechanical strength.Therefore, graphene aerogel is widely used in the fields such as absorption, catalysis, environmental protection.
Material with carbon element such as CNT, carbon nano-fiber, fullerene, carbon ball and the Graphene etc. of nanostructured are widely used in water treatment field due to higher adsorption capacity.There is various chemistry and biological pollutant in sewage, and these material with carbon elements often only there is stronger adsorption effect to part pollutant, not obvious to the adsorption effect of other pollutant, in water treatment procedure, therefore need a kind of broad-spectrum adsorbent badly.By different types of material with carbon element, as Graphene, CNT, carbon ball etc., the material with layering nanostructured of composition, because it receives concern to pollutant absorption and significantly improving of degradation effect.The various material with carbon elements forming this kind of material have different structures, scale and porosity, therefore between different material with carbon element, create special synergy.This carbon composite is stronger than single material with carbon element to absorbability that is organic and inorganic compound.
In the process meeting practical application, in the absorption improving visible ray and light-catalyzed reaction efficiency, still there is obstacle in photochemical catalyst.Many metal nanocrystals, if gold, silver etc. are under the irradiation of visible ray, have all embodied higher photocatalytic activity to whole solar spectrum scope.This kind of metal nanocrystal is as gold, silver etc., after Graphene hydrogel or aeroge are modified, it improves further to the catalytic activity of pollutant, and the composite obtained after modification has better catalytic effect than single metal nanocrystal or Graphene hydrogel, aeroge.
At present, have certain basis about the research utilizing the mode such as the 3-D solid structure material of graphene aerogel class, grapheme modified, the different nanostructured carbon material assembling of metal nanoparticle to improve water treatment efficiency, and the material phase compound of this type of difference in functionality is rarely had report in the hope of the research improving its absorption degradation efficiency in water treatment procedure.
Summary of the invention
The object of the invention is to provide a kind of Nano silver grain modified carbon ball/Graphene aerogel composite and preparation method thereof and application to overcome above the deficiencies in the prior art, the method of comparatively easy self assembly is adopted to prepare, process is simple, requires low to experimental facilities, is easy to operation.
Technical scheme of the present invention is as follows:
A kind of Nano silver grain modified carbon ball/Graphene aerogel composite, this material take graphene aerogel as carrier, the carbon ball that Nano silver grain is modified is the 3-D solid structure of active component, the Nano silver grain being wherein of a size of 10 ~ 20nm is distributed in carbon ball surface, the carbon ball that Nano silver grain is modified is dispersed between graphene film, and silver-colored carrying capacity is 6 ~ 7wt%.
The preparation method of described Nano silver grain modified carbon ball/Graphene aerogel composite, comprises the following steps:
(1) preparation of graphene oxide presoma dispersion liquid: by graphite oxide ultrasonic disperse in distilled water, obtains the graphene oxide presoma dispersion liquid of 2 ~ 3mg/ml;
(2) preparation of carbon ball dispersion liquid: the glucose solution getting 0.2 ~ 0.4mol/L puts into autoclave, hydrothermal treatment consists 4 ~ 6h at 170 ~ 180 DEG C also naturally cools to room temperature; With the glucose that ethanol, distilled water cyclic washing centrifugal segregation are unnecessary, then vacuum drying, obtains carbon ball; Carbon ball ultrasonic disperse 20min under 15000rpm, in distilled water, is formed carbon ball dispersion liquid;
(3) preparation of Nano silver grain modified carbon ball dispersion liquid: add liquor argenti nitratis ophthalmicus and obtain silver ion mixed solution in the carbon ball dispersion liquid that step (2) obtains; Also at room temperature stir 10 ~ 12h after vibration to obtain a homogeneous mixture; This mixture after centrifugation, then removes unnecessary silver ion with ethanol, distilled water cyclic washing, and then ultrasonic disperse is in distilled water, obtains the carbon ball dispersion liquid that Nano silver grain is modified;
(4) preparation of Nano silver grain modified carbon ball/Graphene aerogel composite: the carbon ball dispersion liquid adding the Nano silver grain modification that step (3) obtains in the graphene oxide presoma dispersion liquid that step (1) obtains, add cysteine after ultrasonotomography 1h, mix; Mixture is placed in 70 ~ 90 DEG C of oil bath 8 ~ 10h, carries out freeze drying after then removing unnecessary cysteine with milli-Q water, obtain Nano silver grain modified carbon ball/Graphene aerogel composite.
Further, the preparation method of described Nano silver grain modified carbon ball/Graphene aerogel composite, in step (2), the concentration of carbon ball dispersion liquid is 0.3%wt.
Further, the preparation method of described Nano silver grain modified carbon ball/Graphene aerogel composite, in the silver ion mixed solution described in step (3), concentration of silver ions is 1mol/L.
Further, the preparation method of described Nano silver grain modified carbon ball/Graphene aerogel composite, described in step (4), semicystinol concentration is 0.11 ~ 0.13mol/L.
Further, the preparation method of described Nano silver grain modified carbon ball/Graphene aerogel composite, in step (4), the volume ratio of graphite oxide quality and cysteine is 1:2 ~ 1:3, and the volume ratio of the carbon ball dispersion liquid that described graphene oxide presoma dispersion liquid and Nano silver grain are modified is 8:9 ~ 8:10.
Further, the preparation method of described Nano silver grain modified carbon ball/Graphene aerogel composite, in step (4), freeze drying temperature is-50 DEG C, and the time is 24h.
The application of described Nano silver grain modified carbon ball/Graphene aerogel composite absorption degradation organic pollution in water treatment procedure.
The application of described Nano silver grain modified carbon ball/Graphene aerogel composite Adsorption of Heavy Metal Ions in water treatment procedure.
Nano silver grain modified carbon ball/Graphene aerogel composite provided by the invention, due to the compound action of Nano silver grain, carbon ball, Graphene in material, and as the three-dimensional porous structure of aeroge, this material can be repeatedly used and is easy to transfer and be reclaimed, meanwhile, this material has the stronger adsorption capacity of heavy metal ion and the absorption degradation efficiency higher to organic pollution.
The preparation method of Nano silver grain modified carbon ball/Graphene aerogel composite provided by the invention is a kind of method of comparatively easy self assembly, and preparation process is simple, requires low to experimental facilities, is easy to operation.
Accompanying drawing explanation
Fig. 1 is field emission scanning electron microscope (SEM) picture of different aeroge in the embodiment of the present invention 1, wherein (a) field emission scanning electron microscope (SEM) picture that is graphene aerogel; B field emission scanning electron microscope (SEM) picture that () is carbon ball/Graphene aerogel composite; C field emission scanning electron microscope (SEM) picture that () is Nano silver grain modified carbon ball/Graphene aerogel composite.
Fig. 2 is projection Electronic Speculum (TEM) picture of Nano silver grain modified carbon ball/Graphene composite aerogel in the embodiment of the present invention 2, graphene aerogel, carbon ball/Graphene composite aerogel.
Fig. 3 is the infrared spectrum of Nano silver grain modified carbon ball/Graphene composite aerogel in the embodiment of the present invention 1, graphene aerogel, carbon ball/Graphene composite aerogel.
Fig. 4 is the effect time history plot of Nano silver grain modified carbon ball/Graphene aerogel composite of obtaining of embodiment 3 and graphene aerogel material degradation p-nitrophenol.
Detailed description of the invention
Embodiment 1
A preparation method for Nano silver grain modified carbon ball/Graphene aerogel composite, concrete steps are as follows:
(1) preparation of graphite oxide: by purity be 99.5% graphite 1g add 90ml mass fraction be 98% the concentrated sulfuric acid and 25ml mass fraction be 65% red fuming nitric acid (RFNA) composition mixed solution in, frozen water mixing bath (temperature controls less than 4 DEG C) in stirring 20min.Add 6g potassium permanganate at leisure afterwards, stir 1h.Then mixed solution is heated to 85 DEG C and keeps 30min, then the hydrogen peroxide that 10ml mass fraction is 30% is added, stir 10min, suction filtration is carried out to mixture, finally by 100ml watery hydrochloric acid and 150ml deionized water, cyclic washing is carried out to solids, after three washings, solid matter is placed in 60 DEG C of dry 12h of vacuum drying chamber and obtains graphite oxide.
(2) preparation of graphene oxide presoma dispersion liquid: by graphite oxide ultrasonic disperse obtained in step (1) in distilled water, obtain the graphene oxide presoma dispersion liquid of 2.5mg/ml.
(3) preparation of carbon ball dispersion liquid: getting concentration is that to be placed on volume be in the autoclave of 200ml for the glucose solution 100ml of 0.2mol/L, and hydrothermal treatment consists 4h at 170 DEG C also naturally cools to room temperature; With ethanol washing and under 15000rpm centrifugation 20min, then with distilled water washing and under 15000rpm centrifugation 20min, so repeatedly remove unnecessary glucose, after centrifugation terminates, by product vacuum drying 12h at 60 DEG C, obtain carbon ball; Carbon ball ultrasonic disperse 20min under 15000rpm, in 10ml distilled water, is formed the carbon ball dispersion liquid that concentration is 0.3%wt.
(4) preparation of Nano silver grain modified carbon ball dispersion liquid: slowly add liquor argenti nitratis ophthalmicus to control in mixed solution concentration of silver ions for 1mol/L in the carbon ball dispersion liquid of preparation in step (3); Thermal agitation 15min also at room temperature stirs 11h in 200rpm and obtains a homogeneous mixture; This mixture is centrifugation 15min at 3,000 rpm, then removes unnecessary silver ion four times with ethanol, distilled water cyclic washing, and ultrasonic disperse, in 10ml distilled water, obtains the homogeneous solution of Nano silver grain modified carbon ball.
(5) preparation of Nano silver grain modified carbon ball/Graphene aerogel composite: get graphene oxide presoma dispersion liquid 8ml obtained in step (2), add the carbon ball dispersion liquid that Nano silver grain obtained in 9ml step (4) is modified wherein, add the cysteine that 3ml concentration is 0.11mol/L after ultrasonotomography 1h, fully mix; Then mixture is placed in 90 DEG C of oil bath 8h, with milli-Q water to remove unnecessary cysteine, at-50 DEG C after freeze drying 24h, obtain the aerogel material of Nano silver grain modified carbon ball/Graphene compound, this material SEM picture is as shown in (c) in Fig. 1, as can be seen from (c), Nano silver grain is distributed in carbon ball surface, and the carbon ball that Nano silver grain is modified is entrained in graphene aerogel material.
Graphene oxide presoma dispersion liquid obtained in step (2) is placed in 90 DEG C of oil bath 8h, at-50 DEG C after freeze drying 24h, graphene aerogel material can be obtained, field emission scanning electron microscope (SEM) picture that Fig. 1 (a) is graphene aerogel, as can be seen from (a), graphene aerogel presents the structure of porous three-dimensional.Get graphene oxide presoma dispersion liquid 8ml obtained in step (2), add carbon ball dispersion liquid obtained in 9ml step (3) wherein, add the cysteine that 3ml concentration is 0.11mol/L after ultrasonotomography 1h, fully mix, then mixture is placed in 90 DEG C of oil bath 8h, with milli-Q water to remove unnecessary cysteine, at-50 DEG C after freeze drying 24h, obtain the aerogel material of carbon ball/Graphene compound, field emission scanning electron microscope (SEM) picture that Fig. 1 (b) is carbon ball/Graphene aerogel composite, as can be seen from (b), carbon ball is the comparatively uniform bead of size, carbon ball/Graphene aerogel composite entirety is in 3-D solid structure, be embodied in the graphene aerogel material of porous three-dimensional and be mingled with carbon ball, carbon ball hinders the reunion of Graphene wherein effectively.
Contrasted as can be seen from the SEM picture of the aerogel material of graphene aerogel material, carbon ball/Graphene aerogel composite and Nano silver grain modified carbon ball/Graphene compound, the aerogel material of Nano silver grain modified carbon ball/Graphene compound is 3-D solid structure, the Nano silver grain being of a size of 10 ~ 20nm is distributed in carbon ball surface, and the carbon ball that the Nano silver grain of formation is modified is dispersed between graphene film; Described material take graphene aerogel as carrier, and the carbon ball that Nano silver grain is modified is active component, and silver-colored carrying capacity is 6 ~ 7wt%.Its infrared spectrum as shown in Figure 3, along with the removal of oxygen-containing functional group in its respective composite aquogel, define new composite aerogel, in conjunction with the infrared spectrum of carbon ball/Graphene composite aerogel, find effective compound of Graphene and carbon ball in carbon ball/Graphene aerogel composite.
Embodiment 2
A preparation method for Nano silver grain modified carbon ball/Graphene aerogel composite, concrete steps are as follows:
(1) preparation of graphite oxide: by purity be 99.5% graphite 1g add 90ml mass fraction be 98% the concentrated sulfuric acid and 25ml mass fraction be 65% red fuming nitric acid (RFNA) composition mixed solution in, frozen water mixing bath (temperature controls less than 4 DEG C) in stirring 20min.Add 6g potassium permanganate at leisure afterwards, stir 1h.Then mixed solution is heated to 85 DEG C and keeps 30min, then the hydrogen peroxide that 10ml mass fraction is 30% is added, stir 10min, suction filtration is carried out to mixture, finally by 100ml watery hydrochloric acid and 150ml deionized water, cyclic washing is carried out to solids, after three washings, solid matter is placed in 60 DEG C of dry 12h of vacuum drying chamber and obtains graphite oxide.
(2) preparation of graphene oxide presoma dispersion liquid: by graphite oxide ultrasonic disperse obtained in step (1) in distilled water, obtain the graphene oxide presoma dispersion liquid of 2mg/ml.
(3) preparation of carbon ball dispersion liquid: getting concentration is that to be placed on volume be in the autoclave of 200ml for the glucose solution 100ml of 0.35mol/L, and hydrothermal treatment consists 5h at 175 DEG C also naturally cools to room temperature; With ethanol washing and under 15000rpm centrifugation 20min, then with distilled water washing and under 15000rpm centrifugation 20min, so repeatedly remove unnecessary glucose, after centrifugation terminates, by product vacuum drying 12h at 60 DEG C, obtain carbon ball; Carbon ball ultrasonic disperse 20min under 15000rpm, in 10ml distilled water, is formed the carbon ball dispersion liquid that concentration is 0.3%wt.
(4) preparation of Nano silver grain modified carbon ball: slowly add liquor argenti nitratis ophthalmicus to control in mixed solution concentration of silver ions for 1mol/L in the carbon ball dispersion liquid of preparation in step (3); Thermal agitation 15min also at room temperature stirs 10h in 200rpm and obtains a homogeneous mixture; This mixture is centrifugation 15min at 3,000 rpm, then removes unnecessary silver ion three times with ethanol, distilled water cyclic washing, and ultrasonic disperse, in 10ml distilled water, obtains the homogeneous solution of Nano silver grain modified carbon ball.The TEM picture of this Nano silver grain modified carbon ball as shown in Figure 2, can clearly be found out, Nano silver grain is 10 ~ 20nm, is distributed in carbon ball surface.
(5) preparation of Nano silver grain modified carbon ball/Graphene aerogel composite: get graphene oxide presoma dispersion liquid 8ml obtained in step (2), add the carbon ball dispersion liquid that Nano silver grain obtained in 10ml step (4) is modified wherein, add the cysteine that 3ml concentration is 0.12mol/L after ultrasonotomography 1h, fully mix; Then mixture is placed in 80 DEG C of oil bath 9h, with milli-Q water to remove unnecessary cysteine, and at-50 DEG C after freeze drying 24h, obtains the aerogel material of Nano silver grain modified carbon ball/Graphene compound.
Graphene oxide presoma dispersion liquid obtained in step (2) is placed in 80 DEG C of oil bath 9h, and at-50 DEG C after freeze drying 24h, can obtain graphene aerogel material, this material presents the structure of porous three-dimensional.Get graphene oxide presoma dispersion liquid 8ml obtained in step (2), add carbon ball dispersion liquid obtained in 10ml step (3) wherein, add the cysteine that 3ml concentration is 0.12mol/L after ultrasonotomography 1h, fully mix; Then mixture is placed in 80 DEG C of oil bath 9h, with milli-Q water to remove unnecessary cysteine, at-50 DEG C after freeze drying 24h, obtain the aerogel material of carbon ball/Graphene compound, in this material, carbon ball is the comparatively uniform bead of size, and carbon ball/Graphene aerogel composite entirety, in 3-D solid structure, is embodied in the graphene aerogel material of porous three-dimensional and is mingled with carbon ball.
As can be seen from the Structure Comparison of the aerogel material of graphene aerogel material, carbon ball/Graphene aerogel composite and Nano silver grain modified carbon ball/Graphene compound, the aerogel material of Nano silver grain modified carbon ball/Graphene compound is 3-D solid structure, the Nano silver grain being of a size of 10 ~ 20nm is distributed in carbon ball surface, and the carbon ball that the Nano silver grain of formation is modified is dispersed between graphene film; Described material take graphene aerogel as carrier, and the carbon ball that Nano silver grain is modified is active component, and silver-colored carrying capacity is 6 ~ 7wt%.
Embodiment 3
A preparation method for Nano silver grain modified carbon ball/Graphene aerogel composite, concrete steps are as follows:
(1) preparation of graphite oxide: by purity be 99.5% graphite 1g add 90ml mass fraction be 98% the concentrated sulfuric acid and 25ml mass fraction be 65% red fuming nitric acid (RFNA) composition mixed solution in, frozen water mixing bath (temperature controls less than 4 DEG C) in stirring 20min.Add 6g potassium permanganate at leisure afterwards, stir 1h.Then mixed solution is heated to 85 DEG C and keeps 30min, then the hydrogen peroxide that 10ml mass fraction is 30% is added, stir 10min, suction filtration is carried out to mixture, finally by 100ml watery hydrochloric acid and 150ml deionized water, cyclic washing is carried out to solids, after three washings, solid matter is placed in 60 DEG C of dry 12h of vacuum drying chamber and obtains graphite oxide.
(2) preparation of graphene oxide presoma dispersion liquid: by graphite oxide ultrasonic disperse obtained in step (1) in distilled water, obtain the graphene oxide presoma dispersion liquid of 3mg/ml.
(3) preparation of carbon ball dispersion liquid: getting concentration is that to be placed on volume be in the autoclave of 200ml for the glucose solution 100ml of 0.4mol/L, and hydrothermal treatment consists 6h at 180 DEG C also naturally cools to room temperature; With ethanol washing and under 15000rpm centrifugation 20min, then with distilled water washing and under 15000rpm centrifugation 20min, so repeatedly remove unnecessary glucose, after centrifugation terminates, by product vacuum drying 12h at 60 DEG C, obtain carbon ball; Carbon ball ultrasonic disperse 20min under 15000rpm, in 10ml distilled water, is formed the carbon ball dispersion liquid that concentration is 0.3%wt.
(4) preparation of Nano silver grain modified carbon ball: slowly add liquor argenti nitratis ophthalmicus to control in mixed solution concentration of silver ions for 1mol/L in the carbon ball dispersion liquid of preparation in step (3); Thermal agitation 15min also at room temperature stirs 12h in 200rpm and obtains a homogeneous mixture; This mixture is centrifugation 15min at 3,000 rpm, then removes unnecessary silver ion five times with ethanol, distilled water cyclic washing, and ultrasonic disperse, in 10ml distilled water, obtains the homogeneous solution of Nano silver grain modified carbon ball.
(5) preparation of Nano silver grain modified carbon ball/Graphene aerogel composite: get graphene oxide presoma dispersion liquid 8ml obtained in step (2), add the carbon ball dispersion liquid that Nano silver grain obtained in 10ml step (4) is modified wherein, add the cysteine that 2ml concentration is 0.12mol/L after ultrasonotomography 1h, fully mix; Then mixture is placed in 90 DEG C of oil bath 10h, with milli-Q water to remove unnecessary cysteine, and at-50 DEG C after freeze drying 24h, obtains the aerogel material of Nano silver grain modified carbon ball/Graphene compound.
Graphene oxide presoma dispersion liquid obtained in step (2) is placed in 90 DEG C of oil bath 10h, and at-50 DEG C after freeze drying 24h, can obtain graphene aerogel material, this material presents the structure of porous three-dimensional.Get graphene oxide presoma dispersion liquid 8ml obtained in step (2), add carbon ball dispersion liquid obtained in 10ml step (3) wherein, add the cysteine that 2ml concentration is 0.12mol/L after ultrasonotomography 1h, fully mix; Then mixture is placed in 90 DEG C of oil bath 10h, with milli-Q water to remove unnecessary cysteine, at-50 DEG C after freeze drying 24h, obtain the aerogel material of carbon ball/Graphene compound, in this material, carbon ball is the comparatively uniform bead of size, and carbon ball/Graphene aerogel composite entirety, in 3-D solid structure, is embodied in the graphene aerogel material of porous three-dimensional and is mingled with carbon ball.
As can be seen from the Structure Comparison of the aerogel material of graphene aerogel material, carbon ball/Graphene aerogel composite and Nano silver grain modified carbon ball/Graphene compound, the aerogel material of Nano silver grain modified carbon ball/Graphene compound is 3-D solid structure, the Nano silver grain being of a size of 10 ~ 20nm is distributed in carbon ball surface, and the carbon ball that the Nano silver grain of formation is modified is dispersed between graphene film; Described material take graphene aerogel as carrier, and the carbon ball that Nano silver grain is modified is active component, and silver-colored carrying capacity is 6 ~ 7wt%.
Embodiment 4: the application of Nano silver grain modified carbon ball/Graphene aerogel composite Adsorption of Heavy Metal Ions provided by the invention and organic pollution
Get Nano silver grain modified carbon ball/Graphene aerogel composite obtained in 10mg embodiment 2 to put into containing 15mg/L methylene blue, 10mg/L Cr VI and 5mg/L hexavalent uranium solution, and stir 18h.According to the concentration value change of pollutant before and after absorption, as calculated, obtaining Nano silver grain modified carbon ball/Graphene aerogel composite to chromic adsorption efficiency is 83.96%, is 84.5% to uranic adsorption efficiency, is 100% to the adsorption efficiency of methylene blue.
The adsorption efficiency of material can be obtained by following formulae discovery:
Q = （C
0- Ce）/C
0，
Wherein Q represents the adsorption efficiency of Nano silver grain modified carbon ball/Graphene aerogel composite, C
0initial concentration and the equilibrium concentration of pollutant is represented respectively with Ce.
As can be seen here, Nano silver grain modified carbon ball/Graphene aerogel composite all has higher adsorption capacity for the heavy metal ion such as Cr VI, hexavalent uranium and methylene blue class dyestuff and organic pollution.
Embodiment 5: the application of Nano silver grain modified carbon ball provided by the invention/Graphene aerogel composite degradable organic pollutant
Be the sodium borohydride solution adding 30mmol/L in the p-nitrophenyl phenol solution of 0.1mmol/L in 20ml concentration, regulate pH value of solution to 10.5, then add 30mg Nano silver grain modified carbon ball/Graphene aerogel composite; Meanwhile, be add 30mg graphene aerogel material in 10.5 isopyknic p-nitrophenols, sodium borohydride mixed solution to test as a comparison to above-mentioned pH.
To record in bi-material degradation process p-nitrophenol concentration respectively over time (as Fig. 4), and thus the degradation efficiency of Nano silver grain modified carbon ball/Graphene aerogel composite and graphene aerogel is contrasted.Result shows, and the efficiency of Nano silver grain modified carbon ball/Graphene aerogel composite degraded p-nitrophenol is apparently higher than Graphene gel.As can be seen here, Nano silver grain modified carbon ball/Graphene aerogel composite has higher degradation efficiency to organic pollution.
Claims (9)
1. Nano silver grain modified carbon ball/Graphene aerogel composite, it is characterized in that, this material take graphene aerogel as carrier, the carbon ball that Nano silver grain is modified is the 3-D solid structure of active component, the Nano silver grain being wherein of a size of 10 ~ 20nm is distributed in carbon ball surface, the carbon ball that Nano silver grain is modified is dispersed between graphene film, and silver-colored carrying capacity is 6 ~ 7wt%.
2. the preparation method of Nano silver grain modified carbon ball/Graphene aerogel composite according to claim 1, is characterized in that, comprise the following steps:
(1) preparation of graphene oxide presoma dispersion liquid: by graphite oxide ultrasonic disperse in distilled water, obtains the graphene oxide presoma dispersion liquid of 2 ~ 3mg/ml;
(2) preparation of carbon ball dispersion liquid: the glucose solution getting 0.2 ~ 0.4mol/L puts into autoclave, hydrothermal treatment consists 4 ~ 6h at 170 ~ 180 DEG C also naturally cools to room temperature; With the glucose that ethanol, distilled water cyclic washing centrifugal segregation are unnecessary, then vacuum drying, obtains carbon ball; Carbon ball ultrasonic disperse 20min under 15000rpm, in distilled water, is formed carbon ball dispersion liquid;
(3) preparation of Nano silver grain modified carbon ball dispersion liquid: add liquor argenti nitratis ophthalmicus and obtain silver ion mixed solution in the carbon ball dispersion liquid that step (2) obtains; Also at room temperature stir 10 ~ 12h after vibration to obtain a homogeneous mixture; This mixture after centrifugation, then removes unnecessary silver ion with ethanol, distilled water cyclic washing, and then ultrasonic disperse is in distilled water, obtains the carbon ball dispersion liquid that Nano silver grain is modified;
(4) preparation of Nano silver grain modified carbon ball/Graphene aerogel composite: the carbon ball dispersion liquid adding the Nano silver grain modification that step (3) obtains in the graphene oxide presoma dispersion liquid that step (1) obtains, add cysteine after ultrasonotomography 1h, mix; Mixture is placed in 70 ~ 90 DEG C of oil bath 8 ~ 10h, carries out freeze drying after then removing unnecessary cysteine with milli-Q water, obtain Nano silver grain modified carbon ball/Graphene aerogel composite.
3. the preparation method of Nano silver grain modified carbon ball/Graphene aerogel composite according to claim 2, is characterized in that, in step (2), the concentration of carbon ball dispersion liquid is 0.3%wt.
4. the preparation method of Nano silver grain modified carbon ball/Graphene aerogel composite according to claim 2, is characterized in that, in the silver ion mixed solution described in step (3), concentration of silver ions is 1mol/L.
5. the preparation method of Nano silver grain modified carbon ball/Graphene aerogel composite according to claim 2, is characterized in that, described in step (4), semicystinol concentration is 0.11 ~ 0.13mol/L.
6. the preparation method of Nano silver grain modified carbon ball/Graphene aerogel composite according to claim 2, it is characterized in that, in step (4), the volume ratio of graphite oxide quality and cysteine is 1:2 ~ 1:3, and the volume ratio of the carbon ball dispersion liquid that described graphene oxide presoma dispersion liquid and Nano silver grain are modified is 8:9 ~ 8:10.
7. the preparation method of Nano silver grain modified carbon ball/Graphene aerogel composite according to claim 2, is characterized in that, in step (4), freeze drying temperature is-50 DEG C, and the time is 24h.
8. the application of Nano silver grain modified carbon ball according to claim 1/Graphene aerogel composite absorption degradation organic pollution in water treatment procedure.
9. the application of Nano silver grain modified carbon ball according to claim 1/Graphene aerogel composite Adsorption of Heavy Metal Ions in water treatment procedure.
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