CN105233794A - Preparation method for prussian blue/graphene/carbon fiber composite material - Google Patents
Preparation method for prussian blue/graphene/carbon fiber composite material Download PDFInfo
- Publication number
- CN105233794A CN105233794A CN201510703334.XA CN201510703334A CN105233794A CN 105233794 A CN105233794 A CN 105233794A CN 201510703334 A CN201510703334 A CN 201510703334A CN 105233794 A CN105233794 A CN 105233794A
- Authority
- CN
- China
- Prior art keywords
- cfs
- graphene
- carbon fiber
- preparation
- gns
- 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
Links
Abstract
The invention discloses a preparation method for a prussian blue/graphene/carbon fiber composite material. The preparation method comprises firstly preparing a carbon fiber/graphene composite carrier, and then depositing Prussian blue on the composite carrier. The prepared CFs/GNs/PB composite material possesses excellent selective adsorption capability on metal caesium in a water solution and is easy for operation and separation.
Description
One, technical field
The present invention relates to a kind of Prussian blue/preparation method of graphene/carbon fiber composite, this material can be used for the enrichment of caesium in the aqueous solution.
Two, background technology
Heavy rare alkaline metal caesium has stronger chemism and excellent photoelectric properties, is widely used in traditional applications such as electronics industry, glass ceramics, biochemistry, medicine.Carry out the enrichment of aqueous solution caesium and there is important economic implications.On the other hand, the waste water containing caesium may have radiation, harm water resource environment.Cube ferric ferrocyanide (Prussian blue, PB) is face-centered lattice structure, moisture molecule in structure cell; Hydration Cs
+ size conforms to its lattice cage size, reacted by proton matter solution, selectively be adsorbed on the hydrophilic defects position (X.Liu of PB, etal.BioresourceTechnology, 2014,160:142-149), thus having good selective adsorption capacity to caesium, is a kind of excellent adsorbent.For improving absorption property, researcher has prepared the PB and derivant composite materials thereof that silica (T.Sangvanichetal.JournalofHazardousMaterials, 2010,182:225-231) is carrier.Because PB class adsorbent is Powdered, the actual difficulty that uses is separated, and for this reason, researcher has developed magnetic Fe
3o
4the PB composite (T.Sasaki.etal.ChemistryLetters, 2012,41,1,32-34) of carrier core shell structure.But containing the caesium aqueous solution often complicated component, practical operation is difficult to carry out, and easily forms secondary pollution.
Conducting polypropylene nitrile carbon fiber and Graphene are two kinds of unique carbon support material.This carbon fiber is except absorption and eluting rate is high, physics and chemical stability well except, goes back convenient operation and be separated, but its surface inertness is large, lack and have chemically active functional group.Graphene is a kind of micron order carbonaceous material of carbon atom tightly packed one-tenth individual layer bi-dimensional cellular shape lattice structure, has excellent photoelectricity and absorption property.The present invention in conjunction with the feature of associated materials, design and synthesis is easy to operate, be separated Prussian blue/graphene/carbon fiber composite (CFs/GNs/PB), this material can be used for the enrichment of caesium in the aqueous solution.
Three, summary of the invention
The present invention aim to provide a kind of Prussian blue/preparation method of graphene/carbon fiber composite, first prepare carbon fiber/graphite alkene complex carrier, then deposit Prussian blue thereon, referred to as CFs/GNs/PB.CFs/GNs/PB composite prepared by the present invention has excellent selective adsorption capacity to the metal caesium in the aqueous solution, convenient operation be separated.
The preparation method of the graphene oxide that the present invention uses is conventional method, bibliography W.S.Hummers, etal.JournaloftheAmericanChemicalSociety, 1958,80 (6), 1339-1339, and concrete set-up procedure is as follows:
(1) cold stage: add 1g crystalline flake graphite and 0.75gNaNO in flask
3, in ice-water bath, slowly add 75mL98wt%H
2sO
4solution and 4.5gKMnO
4, reaction 2h.
(2) thermophase in: flask is taken out from ice-water bath, continue reaction 3 ~ 96h at 35 DEG C.
(3) hot stage: this flask is proceeded in thermostat water bath, slowly adds 150mL5wt%H
2sO
4solution, reacts 2h at 98 DEG C.After reaction terminates, system temperature is down to 60 DEG C, adds 10mL30wt%H
2o
2, stir 2 hours, then that mixture is centrifugal, remove supernatant liquor, add 500mL3wt%H to lower floor's solids
2sO
4and 0.5wt%H
2o
2mixed solution, ultrasonic 60min under 140W.After reprocessing reaction after mixture 3-5 time, in lower floor's solid, add 3wt%HCl solution 500mL, ultrasonic 60min under 140W, the solid after centrifugal is placed in deionized water for ultrasonic distributed and saved for subsequent use.
The preparation method of CFs/GNs/PB composite of the present invention comprises the steps:
1, the preparation (CFs/GNs) of carbon fiber/graphite alkene complex carrier
1. the preparation of aminated Graphene: added by graphene oxide in dispersion solvent, be fully mixed and made into graphene oxide suspension, adds catalyst and diamines subsequently, react 1-5 hour at 20-120 DEG C, filter, absolute ethanol washing, aminated Graphene is obtained, referred to as GN after drying.Described dispersion solvent is DMF, absolute ethyl alcohol, acetone or acetonitrile.Wherein the mass ratio of catalyst, graphene oxide suspension and diamines is 1:100:50 ~ 3:500:500; Containing graphene oxide 0.1-2g in 1L graphene oxide suspension;
2. the preparation of carboxylated carbon fiber: with conducting polypropylene nitrile carbon fiber for working electrode, immersed in the sulfuric acid solution of 9.8g/L, 1.8V anodic oxygenization 30 minutes, generates carboxylated carbon fiber, referred to as CFs;
3. immersed by CFs in aminated graphene suspension, adjustment solution ph is 2-6, adds catalyst, reacts 1-5 hour at 20-120 DEG C, generates the carbon fiber that single-layer graphene is modified, referred to as CFs/GN.The solvent of described aminated graphene suspension is the one in DMF, absolute ethyl alcohol, acetone, acetonitrile, and proportioning is the aminated Graphene/L of 0.1-2g.Wherein the mass ratio of carboxylated carbon fiber, catalyst and aminated graphene suspension is 1:1:100 ~ 1:3:500;
4. CFs/GN is immersed in graphene oxide suspension, add catalyst, at 20-120 DEG C, react 1-5 hour, generate the carbon fiber that bilayer graphene is modified.The solvent of described graphene oxide suspension is the one in DMF, absolute ethyl alcohol, acetone, acetonitrile, and proportioning is 0.1-2g graphene oxide/L.The wherein carbon fiber (CFs/GN) of single-layer graphene modification: catalyst: the mass ratio of graphene oxide suspension is 1:1:100-1:3:500;
5. the carbon fiber that obtained bilayer graphene is modified is repeated step 3. with step reaction 4. 2-7 time, finally generate multi-layer graphene/carbon fiber complex carrier, referred to as CFs/GNs.
Described catalyst is the one in 1-ethyl-(3-dimethyl aminopropyl) carbodiimide, N-hydroxy-succinamide, dicyclohexylcarbodiimide.
Described diamines is the one in dimethyl-ethylenediamine, Udmh ethylenediamine, ethylenediamine.
2, the preparation of CFs/GNs/PB composite
1. regulate the pH value of potassium ferrocyanide solution to be 2-7, CFs/GNs complex carrier is immersed in potassium ferrocyanide solution, at 20-110 DEG C, soaks 10-50 minute, dried for standby;
2. the pH value regulating iron chloride mixed solution is 1-5, is immersed in iron chloride mixed solution by the CFs/GNs adsorbing potassium ferrocyanide, at 10-100 DEG C, soaks 10-50 minute, dry;
3. step 1. immersion process 2. 3-7 time is repeated, the Prussian blue/graphene/carbon fiber composite of final acquisition (CFs/GNs/PB).
The concentration of described potassium ferrocyanide is 4.2-63.2g/L.
The mixed solution that described iron chloride mixed solution is made up of iron chloride and surfactant, described surfactant is the one in dodecyl sodium sulfate, lauryl alcohol polyethenoxy ether sodium sulfate, sldium lauryl sulfate, methyl sodiosul foaliphatate, polyvinylpyrrolidone; In described iron chloride mixed solution, the concentration of iron chloride is 2.7-40.5g/L, and in iron chloride mixed solution, the addition of surfactant is the 0.1%-1% of iron chloride mixed solution quality.
Potassium ferrocyanide used during synthetic material and the mass ratio of iron chloride are 1:1-1:6.
The mass ratio of CFs/GNs complex carrier and potassium ferrocyanide solution is the mass ratio of 1:150-1:300, CFs/GNs complex carrier and iron chloride mixed solution is 1:150-1:300.
KOH or the HCl aqueous solution that the pH value regulator used during adjust ph is 0.1mol/L.
[CFs/GNs/PB composite is tested the absorption property of caesium in the aqueous solution]
The cesium chloride aqueous solution of configuration 20mg/L and 80mg/L.CFs/GNs/PB composite the present invention prepared is directly used in the enrichment of caesium in the aqueous solution.At 25 DEG C, enrichment is after 2 hours, adopts atomic absorption spectrography (AAS) to detect the change of cesium ion concentration before and after absorption, investigates material of the present invention to the concentration effect of caesium.
Aas determination cesium ion concentration:
Calibration curve method is adopted to measure cesium ion concentration.Standard liquid is prepared: cesium ion standard aqueous solution: take 0.005g cesium chloride and be dissolved in redistilled water, be diluted to scale in 250mL volumetric flask.Now cesium ion solution concentration is 20mg/L.Potassium chloride solution: take 6.25g potassium chloride and be dissolved in 250mL volumetric flask.Now potassium ion solution concentration is 25g/L.
Calibration curve: the standard liquid 0,0.0625,0.625,1.25,2.50,3.75,5.00 and the 6.25mL that pipette 20mg/L caesium, be placed in 25mL volumetric flask respectively, adding 2.5mL concentration is 25g/L Klorvess Liquid, adding 0.5mL volume ratio is 1:1 red fuming nitric acid (RFNA), shakes up rear redistilled water and is diluted to scale.Atomic Absorption Spectrometer measures its absorbance, drawing standard curve.
Sample determination: pipette the solution after 2.5mL absorption cesium ion in 25mL volumetric flask, adding 2.5mL concentration is 25g/L Klorvess Liquid, adding 0.5mL volume ratio is 1:1 red fuming nitric acid (RFNA), shakes up rear redistilled water and is diluted to scale, Atomic Absorption Spectrometer measures its absorbance.Cesium ion concentration is found by calibration curve.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention aminated Graphene and graphene oxide are hocketed on carbon fiber acid amides reaction, prepare carbon fiber and graphite alkene complex carrier (CFs/GNs), increase carbon fiber specific area, the method is simply controlled, and the CFs/GNs made has good conduction and absorption property.
2, the upper contained graphene oxide of CFs/GNs and aminated Graphene, to iron ion, ferrous cyanide ion, there is good electrostatic attraction respectively, make the CFs/GNs/PB composite stability that obtains strong, Prussian blue (PB) difficult drop-off on it.
3, the present invention is by alternately immersing CFs/GNs in potassium ferrocyanide and ferric chloride solution, CFs/GNs generates ferric ferrocyanide (Prussian blue), thus obtains CFs/GNs/PB.This material has concentrated carbon fiber, Graphene and Prussian blue advantage, has excellent selective absorption performance, convenient operation to cesium ion in the aqueous solution, is easy to be separated.
Four, accompanying drawing explanation
Figure 1A is that (illustration a) and the scanning electron microscope (SEM) photograph of GN (illustration b) for CFs/GNs, CFs.Naked CFs surface be smooth (a), Graphene is sheet (illustration b) to illustration, when CFs modifies after multi-layer graphene, the lamellar graphite alkene of the visible superposition in CFs/GNs surface.Figure 1B is the scanning electron microscope (SEM) photograph of the CFs/GNs/PB for preparing of the present invention and its upper PB (illustration) deposited.As seen from the figure, on it, the PB of deposition is cube structure.
Fig. 2 is the X-crystallogram of CFs/GNs/PB prepared by the present invention.24.0 °, naked carbon fiber is the diffraction maximum (Q.Wu, etal.MaterialsScienceinSemiconductorProcessing, 2015,30,476-481) in the upper C002 face of CFs (a).On CFs/GNs/PB (b), except the diffraction maximum in carbon fiber C002 face, visible a series of Prussian blue characteristic peak; Lay respectively at 17.6 °, 25.0 °, 35.5 °, 39.9 °, 43.5 °, 51.2 ° and 57.8 °, respectively the diffraction maximum of corresponding Prussian blue 200,220,400,420,422,440 and 620.
Fig. 3 be acidifying carbon fiber (CFs, a), graphene oxide (GO, b), aminated Graphene (GN, c), the infrared spectrogram of carbon fiber/graphite alkene complex carrier (CFs/GNs, d) and CFs/GNs/PB (e).On curve a, 3430cm
-1locate the stretching vibration peak for hydroxyl (-OH) on CFs, 1646cm
-1locate the asymmetric stretching vibration peak for carboxyl (-COOH) on CFs.On curve b, 1734cm
-1and 1647cm
-1place is respectively the stretching vibration of C=O in carboxyl (-COOH) and the absworption peak of C=C conjugation vibration generation.On curve c, 1440cm
– 1for the characteristic peak of amido link (acid amides II), be made up of N-H flexural vibrations and C-N stretching vibration; 1025cm
– 1for acid amides III is with characteristic peak, i.e. the absworption peak of C-N-H vibration generation.On curve d, 1560cm
-1for the stretching vibration of C=O, 1435cm
– 1for the characteristic peak of amido link (acid amides II), 855cm
– 1for the absworption peak (T.Ramanathan, etal.ChemistryofMaterials, 2005,17,1290-1295) of C-H out-of-plane bending vibration in aldehyde radical (-CHO).On curve e, still visible 3430cm
-1, 855cm
– 1and 1710cm
-1the peak at place, 2079cm
-1place is the characteristic peak of Fe (III)-CN-Fe (II), 593cm
-1for the characteristic absorption peak of Fe-O, 506cm
-1for the characteristic absorption peak (M.Xie, etal.ElectrochemistryCommunications, 2015,59,91-94) of C ≡ N.As can be seen here, carbon fiber and graphite alkene complex carrier deposited Prussian blue.
Fig. 4 is the cyclic voltammetry curve of CFs (a), CFs/GNs (b) and CFs/GNs/PB (c).Solution system: pH1.7,0.1mol/LKCl.As seen from the figure: the background current of CFs/GNs (b) is greater than CFs (a), show that the carbon fiber specific surface modifying Graphene increases.In addition, all without cyclic voltammetric peak on CFs (a), CFs/GNs (b) curve, from curve c
redox peak, show that Prussian blue/graphene/carbon fiber composite (CFs/GNs/PB) is formed.
Five, detailed description of the invention
Embodiment 1:
1, the preparation (CFs/GNs) of carbon fiber/graphite alkene complex carrier
1. the preparation of aminated Graphene: 0.3g graphene oxide is added in 300mL absolute ethyl alcohol, fully be mixed and made into graphene oxide suspension, add 2g1-ethyl-(3-dimethyl aminopropyl) carbodiimide and 200g dimethyl-ethylenediamine, react 1 hour at 70 DEG C, generate aminated Graphene (GN).
2. the preparation of carboxylated carbon fiber: with conducting polypropylene nitrile carbon fiber for working electrode, immersed in the sulfuric acid solution of 9.8g/L, 1.8V anodic oxygenization 30 minutes, generates carboxylated carbon fiber, referred to as CFs;
3. 1gCFs being immersed 300mL concentration is in the aminated Graphene/acetone suspension of 1.5g/L, solution ph is regulated to be 5, add 3gN-HOSu NHS, react 1 hour under temperature 70 C, generate the carbon fiber (CFs/GN) that single-layer graphene is modified.
4. 1gCFs/GN being immersed 300mL concentration is in the graphene oxide/alcohol suspension of 1.2g/L, adds 2g1-ethyl-(3-dimethyl aminopropyl) carbodiimide, reacts 1 hour at 70 DEG C, generates the carbon fiber that bilayer graphene is modified.
5. the carbon fiber that the bilayer graphene that step 4. obtained is modified repeat step 3. with step reaction 4. 3 times, finally generate multi-layer graphene/carbon fiber complex carrier, referred to as CFs/GNs.
2, the preparation of CFs/GNs/PB composite
1. regulate the pH value of potassium ferrocyanide solution to be 3, it is in the potassium ferrocyanide solution of 4.2g/L that 1gCFs/GNs complex carrier is immersed 200mL concentration, soaks 15 minutes, dried for standby at 40 DEG C;
2. be add 0.2g lauryl alcohol polyethenoxy ether sodium sulfate in the ferric chloride solution of 24.0g/L in 200mL concentration, the pH value of this mixed liquor is regulated to be 1, the CFs/GNs having adsorbed potassium ferrocyanide step 1. prepared immerses in this iron chloride mixed solution, soak 10 minutes at temperature 40 DEG C, dry;
3. repeat step 1. immersion process 2. 3 times, finally obtain Prussian blue/graphene/carbon fiber composite (CFs/GNs/PB).
Embodiment 2:
1, the preparation (CFs/GNs) of carbon fiber/graphite alkene complex carrier
1. the preparation of aminated Graphene: 0.6g graphene oxide is added in 300mL dimethyl formamide, fully be mixed and made into graphene oxide suspension, add 1g1-ethyl-(3-dimethyl aminopropyl) carbodiimide and 50g dimethyl-ethylenediamine, react 1.5 hours at 90 DEG C, generate aminated Graphene (GN).
2. the preparation of carboxylated carbon fiber: with conducting polypropylene nitrile carbon fiber for working electrode, immersed in the sulfuric acid solution of 9.8g/L, 1.8V anodic oxygenization 30 minutes, generates carboxylated carbon fiber, referred to as CFs;
3. 1gCFs being immersed 300mL concentration is in the aminated Graphene/dimethylformamide suspension of 2g/L, solution ph is regulated to be 7, add 2gN-HOSu NHS, react 1 hour at 90 DEG C, generate the carbon fiber (CFs/GN) that single-layer graphene is modified.
4. 1gCFs/GN being immersed 300mL concentration is in the graphene oxide/dimethylformamide suspension of 2g/L, adds 2g1-ethyl-(3-dimethyl aminopropyl) carbodiimide, reacts 1.5 hours at 90 DEG C, generates the carbon fiber that bilayer graphene is modified.5. the carbon fiber that the bilayer graphene that step 4. obtained is modified repeat step 3. with step reaction 4. 4 times, finally generate multi-layer graphene/carbon fiber complex carrier, referred to as CFs/GNs.
2, the preparation of CFs/GNs/PB composite
1. regulate the pH value of potassium ferrocyanide solution to be 5,1gCFs/GNs being immersed 250mL concentration is in the potassium ferrocyanide solution of 21.2g/L, soaks 15 minutes, dried for standby at 50 DEG C;
2. be the polyvinylpyrrolidone adding 0.5g in 43.5g/L ferric chloride solution in 250mL concentration, solution ph is regulated to be 1, the CFs/GNs having adsorbed potassium ferrocyanide step 1. prepared immerses in this iron chloride mixed solution, soaks 15 minutes, dried for standby at 50 DEG C;
3. repeat step 1. immersion process 2. 5 times, finally obtain Prussian blue/graphene/carbon fiber composite (CFs/GNs/PB).
Embodiment 3:
1, the preparation (CFs/GNs) of carbon fiber/graphite alkene complex carrier
1. the preparation of aminated Graphene: 0.5g graphene oxide is added in 300mL acetonitrile, fully be mixed and made into graphene oxide suspension, add 1.2g1-ethyl-(3-dimethyl aminopropyl) carbodiimide and 150g Udmh ethylenediamine, react 2 hours at 30 DEG C, generate aminated Graphene (GN).
2. the preparation of carboxylated carbon fiber: with conducting polypropylene nitrile carbon fiber for working electrode, immersed in the sulfuric acid solution of 9.8g/L, 1.8V anodic oxygenization 30 minutes, generates carboxylated carbon fiber, referred to as CFs;
3. 1gCFs being immersed 250mL concentration is in the aminated Graphene/acetonitrile suspension of 1g/L, regulates solution ph to be 6, adds 2gN-HOSu NHS, reacts 1 hour at 30 DEG C, generates the carbon fiber (CFs/GN) that single-layer graphene is modified.
4. 1gCFs/GN being immersed 250mL concentration is in the graphene oxide/acetonitrile suspension of 1g/L, adds 1.2g1-ethyl-(3-dimethyl aminopropyl) carbodiimide, reacts 2 hours at 30 DEG C, generates bilayer graphene/carbon fiber.
5. the carbon fiber that the bilayer graphene that step 4. obtained is modified repeat step 3. with step reaction 4. 4 times, finally generate multi-layer graphene/carbon fiber complex carrier, referred to as CFs/GNs.
2, the preparation of CFs/GNs/PB composite
1. regulate the pH value of potassium ferrocyanide solution to be 2,1gCFs/GNs being immersed 180mL concentration is in the potassium ferrocyanide solution of 10.3g/L, soaks 20 minutes, dried for standby at 25 DEG C;
2. be the dodecyl sodium sulfate adding 0.2g in 15.0g/L ferric chloride solution in 180mL, concentration, solution ph is regulated to be 2, the CFs/GNs having adsorbed potassium ferrocyanide step 1. prepared immerses in this iron chloride mixed solution, soaks 20 minutes, dried for standby at 30 DEG C;
3. repeat step 1. immersion process 2. 4 times, finally obtain Prussian blue/graphene/carbon fiber composite (CFs/GNs/PB).
[maximal absorptive capacity of various material to caesium compares]
From table 1, in various sorbing material, single carbon fiber or carbon fiber/graphite alkene composite all less to caesium absorption property in the aqueous solution.Relative to other same type of material, the present invention prepare Prussian blue/graphene/carbon fiber composite (CFs/GNs/PB) has larger adsorption capacity to caesium in the aqueous solution.
The maximal absorptive capacity of the various material of table 1 to caesium compares.
Claims (10)
1. a preparation method for Prussian blue/graphene/carbon fiber composite, is characterized in that comprising the steps:
(1) preparation of carbon fiber/graphite alkene complex carrier
1. the preparation of aminated Graphene: added by graphene oxide in dispersion solvent, be fully mixed and made into graphene oxide suspension, adds catalyst and diamines subsequently, react 1-5 hour at 20-120 DEG C, filter, absolute ethanol washing, aminated Graphene is obtained, referred to as GN after drying; Wherein the mass ratio of catalyst, graphene oxide suspension and diamines is 1:100:50 ~ 3:500:500;
2. the preparation of carboxylated carbon fiber: with conducting polypropylene nitrile carbon fiber for working electrode, immersed in the sulfuric acid solution of 9.8g/L, 1.8V anodic oxygenization 30 minutes, generates carboxylated carbon fiber, referred to as CFs;
3. immersed by CFs in aminated graphene suspension, adjustment solution ph is 2-6, adds catalyst, reacts 1-5 hour at 20-120 DEG C, generates the carbon fiber that single-layer graphene is modified, referred to as CFs/GN; Wherein the mass ratio of CFs, catalyst and aminated graphene suspension is 1:1:100 ~ 1:3:500;
4. CFs/GN is immersed in graphene oxide suspension, add catalyst, at 20-120 DEG C, react 1-5 hour, generate the carbon fiber that bilayer graphene is modified; Wherein CFs/GN: catalyst: the mass ratio of graphene oxide suspension is 1:1:100-1:3:500;
5. the carbon fiber that obtained bilayer graphene is modified is repeated step 3. with step reaction 4. 2-7 time, finally generate multi-layer graphene/carbon fiber complex carrier, referred to as CFs/GNs;
(2) preparation of CFs/GNs/PB composite
1. regulate the pH value of potassium ferrocyanide solution to be 2-7, CFs/GNs complex carrier is immersed in potassium ferrocyanide solution, at 20-110 DEG C, soaks 10-50 minute, dried for standby;
2. the pH value regulating iron chloride mixed solution is 1-5, is immersed in iron chloride mixed solution by the CFs/GNs adsorbing potassium ferrocyanide, at 10-100 DEG C, soaks 10-50 minute, dry;
3. step 1. immersion process 2. 3-7 time is repeated, the Prussian blue/graphene/carbon fiber composite of final acquisition.
2. preparation method according to claim 1, is characterized in that:
Step (1) 1. described in dispersion solvent be DMF, absolute ethyl alcohol, acetone or acetonitrile; Containing graphene oxide 0.1-2g in 1L graphene oxide suspension.
3. preparation method according to claim 1, is characterized in that:
Step (1) 3. described in the solvent of aminated graphene suspension be one in DMF, absolute ethyl alcohol, acetone, acetonitrile, proportioning is the aminated Graphene/L of 0.1-2g.
4. preparation method according to claim 1, is characterized in that:
Step (1) 4. described in the solvent of graphene oxide suspension be one in DMF, absolute ethyl alcohol, acetone, acetonitrile, proportioning is 0.1-2g graphene oxide/L.
5. preparation method according to claim 1, is characterized in that:
The catalyst used in step (1) is the one in 1-ethyl-(3-dimethyl aminopropyl) carbodiimide, N-hydroxy-succinamide, dicyclohexylcarbodiimide.
6. preparation method according to claim 1, is characterized in that:
Diamines described in step (1) is the one in dimethyl-ethylenediamine, Udmh ethylenediamine, ethylenediamine.
7. preparation method according to claim 1, is characterized in that:
Described in step (2), the concentration of potassium ferrocyanide solution is 4.2-63.2g/L.
8. preparation method according to claim 1, is characterized in that:
The mixed solution that described in step (2), iron chloride mixed solution is made up of iron chloride and surfactant, described surfactant is the one in dodecyl sodium sulfate, lauryl alcohol polyethenoxy ether sodium sulfate, sldium lauryl sulfate, methyl sodiosul foaliphatate, polyvinylpyrrolidone; In described iron chloride mixed solution, the concentration of iron chloride is 2.7-40.5g/L, and in iron chloride mixed solution, the addition of surfactant is the 0.1%-1% of iron chloride mixed solution quality.
9. preparation method according to claim 1, is characterized in that:
In step (2), the mass ratio of potassium ferrocyanide and iron chloride is 1:1-1:6.
10. preparation method according to claim 1, is characterized in that:
In step (2), the mass ratio of CFs/GNs complex carrier and potassium ferrocyanide solution is the mass ratio of 1:150-1:300, CFs/GNs complex carrier and iron chloride mixed solution is 1:150-1:300.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510703334.XA CN105233794B (en) | 2015-10-26 | 2015-10-26 | A kind of preparation method of Prussian blue/graphene/carbon fiber composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510703334.XA CN105233794B (en) | 2015-10-26 | 2015-10-26 | A kind of preparation method of Prussian blue/graphene/carbon fiber composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105233794A true CN105233794A (en) | 2016-01-13 |
| CN105233794B CN105233794B (en) | 2017-11-07 |
Family
ID=55031765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510703334.XA Active CN105233794B (en) | 2015-10-26 | 2015-10-26 | A kind of preparation method of Prussian blue/graphene/carbon fiber composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105233794B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105561928A (en) * | 2016-03-04 | 2016-05-11 | 西南科技大学 | Method for preparing carboxymethyl cellulose/nano-Prussian-blue composite gel microsphere adsorption material |
| CN105771947A (en) * | 2016-05-19 | 2016-07-20 | 天津工业大学 | Graphene-nanometer titanium dioxide composite fabric finishing catalyst and preparation method thereof |
| CN106040190A (en) * | 2016-06-21 | 2016-10-26 | 西南科技大学 | Preparation method of iron ion croscarmellose in-situ growing Prussian-blue microsphere adsorbing material |
| CN106348282A (en) * | 2016-08-23 | 2017-01-25 | 华侨大学 | Double helix carbon fiber graphene composite material and preparation method thereof |
| CN106960954A (en) * | 2017-05-17 | 2017-07-18 | 哈尔滨工业大学 | A kind of preparation method and application of Prussian blue/graphene/sulphur composite |
| WO2017136542A1 (en) * | 2016-02-02 | 2017-08-10 | Ohio University | Ionic liquid-functionalized graphene oxide-based nanocomposite anion exchange membranes |
| CN108212072A (en) * | 2016-12-10 | 2018-06-29 | 中国科学院大连化学物理研究所 | It is a kind of to be applied for the adsorbent of cesium ion removal in water and its in Cs absorption |
| CN109110867A (en) * | 2018-08-29 | 2019-01-01 | 合肥工业大学 | A kind of preparation method and applications of ferrocyanide bismuth/heterogeneous carbon composite electrode |
| CN109873187A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | The preparation method and electrode of a kind of zinc-iron flow battery electrode and application |
| CN111286773A (en) * | 2020-02-21 | 2020-06-16 | 石河子大学 | Preparation method for enhancing adsorption performance of graphite felt material by electrochemical anodic oxidation |
| CN116272900A (en) * | 2023-03-06 | 2023-06-23 | 南开大学 | Prussian blue/polyacrylonitrile composite aerogel material, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103005712A (en) * | 2013-01-04 | 2013-04-03 | 江苏中烟工业有限责任公司 | Grapheme type fiber cigarette filter and preparation method thereof |
| CN103787686A (en) * | 2014-01-26 | 2014-05-14 | 四川创越炭材料有限公司 | Carbon fiber composite ball and preparation method thereof |
| CN104464883A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Graphene electrocondution slurry with dispersants adsorbed on surface and manufacturing method and application thereof |
-
2015
- 2015-10-26 CN CN201510703334.XA patent/CN105233794B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103005712A (en) * | 2013-01-04 | 2013-04-03 | 江苏中烟工业有限责任公司 | Grapheme type fiber cigarette filter and preparation method thereof |
| CN103787686A (en) * | 2014-01-26 | 2014-05-14 | 四川创越炭材料有限公司 | Carbon fiber composite ball and preparation method thereof |
| CN104464883A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Graphene electrocondution slurry with dispersants adsorbed on surface and manufacturing method and application thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017136542A1 (en) * | 2016-02-02 | 2017-08-10 | Ohio University | Ionic liquid-functionalized graphene oxide-based nanocomposite anion exchange membranes |
| CN105561928A (en) * | 2016-03-04 | 2016-05-11 | 西南科技大学 | Method for preparing carboxymethyl cellulose/nano-Prussian-blue composite gel microsphere adsorption material |
| CN105771947A (en) * | 2016-05-19 | 2016-07-20 | 天津工业大学 | Graphene-nanometer titanium dioxide composite fabric finishing catalyst and preparation method thereof |
| CN106040190A (en) * | 2016-06-21 | 2016-10-26 | 西南科技大学 | Preparation method of iron ion croscarmellose in-situ growing Prussian-blue microsphere adsorbing material |
| CN106040190B (en) * | 2016-06-21 | 2018-02-16 | 西南科技大学 | A kind of preparation method of the Prussian blue micro-sphere absorption material of iron ion cross-linked carboxymethyl cellulose growth in situ |
| CN106348282A (en) * | 2016-08-23 | 2017-01-25 | 华侨大学 | Double helix carbon fiber graphene composite material and preparation method thereof |
| CN108212072A (en) * | 2016-12-10 | 2018-06-29 | 中国科学院大连化学物理研究所 | It is a kind of to be applied for the adsorbent of cesium ion removal in water and its in Cs absorption |
| CN106960954A (en) * | 2017-05-17 | 2017-07-18 | 哈尔滨工业大学 | A kind of preparation method and application of Prussian blue/graphene/sulphur composite |
| CN109873187A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | The preparation method and electrode of a kind of zinc-iron flow battery electrode and application |
| CN109110867A (en) * | 2018-08-29 | 2019-01-01 | 合肥工业大学 | A kind of preparation method and applications of ferrocyanide bismuth/heterogeneous carbon composite electrode |
| CN109110867B (en) * | 2018-08-29 | 2021-06-04 | 合肥工业大学 | Preparation method and application of bismuth ferrocyanide/heterogeneous carbon composite electrode |
| CN111286773A (en) * | 2020-02-21 | 2020-06-16 | 石河子大学 | Preparation method for enhancing adsorption performance of graphite felt material by electrochemical anodic oxidation |
| CN116272900A (en) * | 2023-03-06 | 2023-06-23 | 南开大学 | Prussian blue/polyacrylonitrile composite aerogel material, and preparation method and application thereof |
| CN116272900B (en) * | 2023-03-06 | 2024-03-08 | 南开大学 | Prussian blue/polyacrylonitrile composite aerogel material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105233794B (en) | 2017-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105233794A (en) | Preparation method for prussian blue/graphene/carbon fiber composite material | |
| CN102875805B (en) | Three-dimensional graphene-poly dopamine-gold nanoparticle composite material and preparation method thereof | |
| CN109001276B (en) | Construction and application of electrochemical sensor based on COFs (chemical-organic frameworks) material | |
| Long et al. | Magnetic imprinted electrochemical sensor combined with magnetic imprinted solid-phase extraction for rapid and sensitive detection of tetrabromobisphenol S | |
| CN106340399A (en) | Functionalized polydopamine derived carbon layer coated carbon substrate preparation method and application | |
| CN101832965B (en) | Laccase biosensor based on magnetic carbon nano tube and chitosan/silicon dioxide gel and preparation method and application thereof | |
| Yu et al. | Fabrication and evaluation of multilevel Janus-imprinted nanocomposite membranes through a connective method of dip-coating and delayed phase inversion for simultaneous adsorption and separation of tetrabromobisphenol A and cadmium ion | |
| CN103971942B (en) | Graphene/polyaniline/ferric oxide composite material applied to supercapacitor and manufacturing method thereof | |
| CN108339529B (en) | A kind of preparation method and application of the ion blotting composite membrane for Selective Separation palladium ion | |
| CN107703196B (en) | Preparation method of graphene-filter paper and application of graphene-filter paper as self-supporting flexible electrode | |
| Ganjali et al. | Bio-mimetic ion imprinted polymer based potentiometric mercury sensor composed of nano-materials | |
| CN103599763A (en) | Amino-functional ordered mesoporous carbon material and preparation method and application thereof | |
| Xu et al. | Electrochemical preparation of a three dimensional PEDOT–Cu x O hybrid for enhanced oxidation and sensitive detection of hydrazine | |
| Mazloum-Ardakani et al. | Carbon nanotubes in electrochemical sensors | |
| Fan et al. | Synthesis of hierarchical porous ZIF-8/3DCNTs composite sensor for ultrasensitive detection of DA and DFT studies | |
| Jia et al. | The adsorption of nitrogen oxides on noble metal-doped graphene: The first-principles study | |
| Xu et al. | Determination of tannic acid by adsorptive anodic stripping voltammetry at porous pseudo-carbon paste electrode | |
| Khan et al. | Sol–gel synthesis of poly (o-toluidine)@ Sn (II) silicate/CNT composites for ion selective membrane electrodes | |
| Tang et al. | A modified freezing-casted conductive hierarchical porous polymer composite electrode for electrochemical extraction of uranium from water | |
| CN102872834B (en) | Integrated porous polymer adsorption extraction stirring bar and its manufacturing method | |
| Liu et al. | Determination of cadmium (II) using glassy carbon electrodes modified with cupferron, ß-naphthol, and multiwalled carbon nanotubes | |
| CN112098486A (en) | N, P co-doped nano carbon-based framework material modified electrode and preparation method and application thereof | |
| SHANG et al. | An electrochemiluminescence sensor with molecularly imprinted polymer for heroin detection | |
| CN109781807B (en) | Bio-based ion imprinting sensor for detecting copper ions and preparation method thereof | |
| CN111422929B (en) | Preparation method and application of rod-shaped nickel disulfide-molybdenum disulfide nano composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |