CN105990031A - Diaminobenzene functionalized graphene-doped active carbon composite electrode, preparation method thereof and application of diaminobenzene-functionalized graphene-doped active carbon composite electrode to electric adsorption desalination - Google Patents
Diaminobenzene functionalized graphene-doped active carbon composite electrode, preparation method thereof and application of diaminobenzene-functionalized graphene-doped active carbon composite electrode to electric adsorption desalination Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 53
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- 238000007306 functionalization reaction Methods 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003795 desorption Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000002482 conductive additive Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000003292 diminished effect Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229950000845 politef Drugs 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000011780 sodium chloride Substances 0.000 description 10
- -1 graphite Alkene Chemical class 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000000498 cooling water Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 101100121643 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) GEA2 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The present invention discloses a diaminobenzene functionalized graphene-doped active carbon composite electrode, a preparation method thereof and application of the diaminobenzene functionalized graphene-doped active carbon composite electrode to electric adsorption desalination. The preparation method of the diaminobenzene-functionalized graphene-doped active carbon composite electrode includes the following two steps that: (1) diaminobenzene functionalized graphene is prepared; and (2) active carbon is evenly mixed with the diaminobenzene functionalized graphene and a binder, and an obtained mixture is molded in a mold, so that composite electrodes with different specific surface areas and adsorption capacities can be prepared. The composite electrode can be adopted as the positive and negative electrode of an electric adsorption device and can be applied to the two-stage biochemical effluent desalination field and the like, and the desalination efficiency of the composite electrode is significantly better than that of a carbon electrode.
Description
Technical field
The present invention relates to the active carbon combined electrode of a kind of diaminobenzene functionalization graphene doping, preparation and inhale at electricity
Application in attached desalination, belongs to capacitive deionization field.
Background technology
Shortage of water resources has become as the serious problems in the whole world at present, can alleviate showing of shortage of water resources with desalinization
Shape.Contrast traditional technology such as hyperfiltration, electroosmose process and rotary evaporation, due to the high and low energy consumption of desalting efficiency,
Non-secondary pollution, low cost, advantages of environment protection, capacitive deionization (Capacitive deionization, CDI,
Also known as electro-adsorption) method has become as potential desalination process.The process of desalination is to use charge attraction, by ionic adsorption
At electrode surface.When external power supply is connected, the ion with opposite charges can attracted to electrode surface, is formed double
Electric layer.When removing power supply, ion resolves, and comes back in solution, and does not produce secondary pollution.Former based on electric double layer
Reason, the adsorption capacity of CDI has close relationship with the conductivity of electrode and surface nature.
In recent years, there is the activated carbon of different specific surface area and pore structure by wide coverage, including activated carbon,
Carbon aerogels, CNT and some composite activated carbons.Although activated carbon is widely used, but owing to it mostly is micro-
Hole (＜ 2nm) is unfavorable for absorption and the desorption of ion.In order to solve this problem, scientist develops to be had
The Graphene of lamellar structure is as electrode material.Graphene has two-dimensional structure, has big specific surface area, good simultaneously
The advantages such as good electric conductivity, good mechanical performance and chemical stability.Special result and electric property so that graphite
Alkene and composite thereof become the excellent material of energy storage and absorption.Some seminar were had to carry out about graphite in recent years
The work of alkene adsorption desalination, such as: the Li Haibo of East China University of Science (Environ.Sci.Technol., 2010,44,
8692-8697), Zhang of Shanghai University et al. (J.Mater.Chem., 2012,22,14696-14704) is by right
The ratio Graphene electrodes performance of different proportion, optimizes material property, develops the Graphene with electro-adsorption desalting performance
Electrode.Owing to simple Graphene has relatively low electro-adsorption capacity, it is impossible to give full play to its advantage.More work
Concentrate on the exploitation of composite, but seldom have been reported that using after graphene functionalized as adsorption electrode.
Summary of the invention
It is an object of the invention to provide one and have high clearance compound electric adsorption electrode and preparation method thereof, it has
High adsorption capacity and desorption efficiency.
Another object of the present invention is to provide the application of above-mentioned compound electric adsorption electrode.
The technical solution realizing the present invention is: the activated carbon compound electric of a kind of diaminobenzene functionalization graphene doping
Pole, using diaminobenzene functionalization graphene as conductive additive, utilizes binding agent by diaminobenzene functionalization graphene
Build composite with activated carbon homogeneous blend, through press mold molding, this composite is fixed on electrode slice, very
Described combination electrode is i.e. obtained after empty drying.
In above-mentioned combination electrode, binding agent is the one or several of politef, polyvinylidene fluoride and Polyethylene Glycol etc.
The mixture planted.
In above-mentioned combination electrode, electrode slice is aluminum, nickel, titanium, copper or stainless steel, its form be net, paper tinsel film and
One in spongy body.
In above-mentioned combination electrode, diaminobenzene functionalization graphene structure is as follows:
In above-mentioned combination electrode, by quality ratio, activated carbon: diaminobenzene functionalization graphene: binding agent=(99:1:50)
～(19:1:20).
The preparation method of the active carbon combined electrode of diaminobenzene functionalization graphene doping, its step is as follows:
A () is ultrasonic under, prepare the DMF suspension of graphene oxide, by this suspension and diaminobenzene (PA)
DMF solution mixes, and is heated to 70～100 DEG C of stirring reactions, filtration under diminished pressure, washing, i.e. obtains after drying
Diaminobenzene functionalization graphene, wherein, the ratio of graphite oxide and DMF solvent is 7.5～15mg/mL,
Graphene oxide is 1:10～10:1 with the mass ratio of diaminobenzene；
B diaminobenzene functionalization graphene is ground by () after, being blended with activated carbon, preparation has the diaminourea of different proportion
Benzene functionalization graphene and the complex of activated carbon, and be dissolved in organic solvent, mix homogeneously, wherein,
Activated carbon is (99:1)～(19:1) with the mass ratio of diaminobenzene functionalization graphene；
C binding agent is dissolved in organic solvent by (), mix homogeneously, wherein, and diaminobenzene functionalization graphene and binding agent
Mass ratio be (1:50)～(1:20)；
D (b) is mixed homogeneously by () with (c), after grinding ultrasonic 6-8 hour；
E the composite prepared uniformly is coated onto on electrode by (), compressing, and vacuum drying at 60～80 DEG C
16～24h, i.e. can get active carbon combined electrode.
In step (a), ultrasonic time is 2～10h；Diaminobenzene is p-phenylenediamine, m-diaminobenzene. and o-phenylenediamine
In any one；The ratio of diaminobenzene and DMF solvent is 1:10～1:500g/mL；The DMF of diaminobenzene is molten
The temperature range of liquid is 25～80 DEG C；The stirring response time is 5～24h.
In step (b), diaminobenzene functionalization graphene with the mass ratio of activated carbon gross mass with organic solvent is
(1:1～2:1), organic solvent is methanol or ethanol.
In step (c), binding agent is (10:8～2:6) with the mass ratio of organic solvent, and organic solvent is methanol or ethanol.
The application in electro-adsorption desalination of the two-element active charcoal combination electrode of above-mentioned diaminobenzene functionalization graphene doping.
The ion removed includes Na+、Mg2+、Ca2+、F-、NO3 -、NO2 -、HCO3 -、SO4 2-And PO4 3-
Deng, adsorption time is 20～150 minutes, and desorption time is 20～150 minutes, and power-on voltage is 1.0～2.0V.
Compared with prior art, the invention have the advantage that
The present invention utilizes the features such as the electric conductivity of diaminobenzene functionalization graphene is strong and specific surface area is big, prepares diaminourea
The active carbon combined electrode of benzene functionalization graphene doping.Utilize electrode prepared by the method, there is feature: the biggest
Specific surface area；The best electric conductivity；3. high-adsorption-capacity；The highest adsorption efficiency；The most de-
Attached performance.
These features make this composite extensively apply in fields such as municipal sewage and municipal wastewater process.
Accompanying drawing explanation
Fig. 1 is the diaminobenzene functionalization graphene SEM figure in the embodiment of the present invention 1.
Fig. 2 is the infrared spectrogram of the functionalization graphene nano material of synthesis in the embodiment of the present invention 1.
Fig. 3 is the infrared spectrogram of the functionalization graphene nano material of synthesis in the embodiment of the present invention 2.
Fig. 4 is the results of AC impedance of combination electrode in the embodiment of the present invention 6.
Fig. 5 is combination electrode and the absorption situation contrast to NaCl of the simple activity carbon resistance rod of the embodiment of the present invention 7.
Detailed description of the invention
Embodiment 1-3: the preparation of diaminobenzene functionalization graphene:
Embodiment 1
The first step, the preparation of oxidation graphite solid；
At 80 DEG C, with 30mL concentrated sulphuric acid, 10g potassium peroxydisulfate and 10g phosphorus pentoxide by 20g native graphite
After pre-oxidation, being washed to pH=7, normal temperature drying is the most stand-by；
460mL concentrated sulphuric acid is cooled to about 0 DEG C, then the graphite that 20g pre-oxidizes is added thereto, slowly
Add 60g potassium permanganate so that system temperature is less than 20 DEG C, is warmed up to 35 DEG C after interpolation, stir 2h
After, and it being slowly added into 920mL deionized water in batches so that system temperature is less than 98 DEG C, is stirred for 15 points
After clock, add 2.8L deionized water and 50mL 30% hydrogen peroxide.The glassy yellow suspension obtained decompression is taken out
Filter, washing.Until filtrate does not has sulfate ion, and during in neutrality, product is dried in 60 DEG C of vacuum,
Obtain oxidation graphite solid；
Second step, loads round-bottomed flask by 50mg graphite oxide powder, adds 15mL N, N-dimethyl formyl
Amine (DMF) solvent, after ultrasonic 5h, obtains the suspension of graphene oxide (GO)；
3rd step, takes 0.1g p-phenylenediamine and is at room temperature dissolved in 5mL DMF, prepare the DMF of p-phenylenediamine
Solution；
4th step, is slowly dropped to the p-phenylenediamine solution in the 3rd step in second step the GO suspension of preparation, adds
Heat, to 85 DEG C, is stirred vigorously 8h；
5th step, the crude product the 4th step obtained, through sucking filtration, washing, after drying, obtains product.
Functionalization graphene nano material infrared spectrum in a solvent is as shown in Figure 2, it was demonstrated that this nano-hybrid material is
Success synthesizes.Functionalization graphene nano material photo is as shown in the SEM of Fig. 1.
Embodiment 2
The first to second step, with step one in embodiment 1 to two.
3rd step, takes 0.1g m-diaminobenzene. and is at room temperature dissolved in 5mL DMF, prepare the DMF of m-diaminobenzene.
Solution；
4th step, is slowly dropped to the m-phenylenediamine solution in the 3rd step in second step the GO suspension of preparation, adds
Heat, to 85 DEG C, is stirred vigorously 8h；
5th step, with step 5 in embodiment 1.
Functionalization graphene nano material infrared spectrum in a solvent is as shown in Figure 3, it was demonstrated that this nano-hybrid material is
Success synthesizes.
Embodiment 3
The first to second step, with step one in embodiment 1 to two.
3rd step, takes 0.1g o-phenylenediamine and is at room temperature dissolved in 5mL DMF, prepare the DMF of o-phenylenediamine
Solution；
4th step, is slowly dropped to the o-phenylenediamine solution in the 3rd step in second step the GO suspension of preparation, adds
Heat, to 100 DEG C, is stirred vigorously 24h；
5th step, with step 5 in embodiment 1.
Embodiment 4-12: the preparation of combination electrode and application thereof
Embodiment 4
The preparation of combination electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 1 and activated carbon powder respectively
The quality at end is 1g and 19g, according to the ratio mix homogeneously of 1:19；(2) two kinds of material mixing are placed in mortar
Grind 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL methanol, stirring, mix homogeneously are continued；(4)
Ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:2 (quality of PTFE is 66g) and be dissolved in 200mL
In methanol, put it in beaker and disperse 1 hour；(6), after making both mix homogeneously with Glass rod stirring, continue super
Sound 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7) electrode
Air-dry 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.6V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 80%.
Embodiment 5
The preparation of combination electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 2 and activated carbon powder respectively
The quality at end is 0.2g and 19.8g, according to the ratio mix homogeneously of 1:99；(2) mixing of two kinds of materials is placed on grinds
Alms bowl grinds 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL methanol, stirring, mix homogeneously are continued；
(4) ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:1 (quality of PTFE is 33g) to be dissolved in
In 200mL methanol, put it in beaker and disperse 1 hour；(6) after making both mix homogeneously with Glass rod stirring,
Continue ultrasonic 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7)
Electrode air-dries 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.6V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 85%.
Embodiment 6
The preparation of combination electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 2 and activated carbon powder respectively
The quality at end is 2g and 18g, according to the ratio mix homogeneously of 1:9；(2) two kinds of material mixing are placed in mortar
Grind 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL ethanol, stirring, mix homogeneously are continued；(4)
Ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:1 (quality of PTFE is 33g) and be dissolved in 200mL
In ethanol, put it in beaker and disperse 1 hour；(6), after making both mix homogeneously with Glass rod stirring, continue super
Sound 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7) electrode
Air-dry 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.8V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 88%.Fig. 4 is the results of AC impedance of electrode.It can be seen that the less applicable use of this electrode resistance from result
Make electro-adsorption desalination electrode.
Embodiment 7
The preparation of combination electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 2 and activated carbon powder respectively
The quality at end is 1g and 19g, according to the ratio mix homogeneously of 1:19；(2) two kinds of material mixing are placed in mortar
Grind 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL ethanol, stirring, mix homogeneously are continued；(4)
Ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:1 (quality of PTFE is 33g) and be dissolved in 200mL
In ethanol, put it in beaker and disperse 1 hour；(6), after making both mix homogeneously with Glass rod stirring, continue super
Sound 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7) electrode
Air-dry 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.8V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 90%.Fig. 5 is combination electrode (AC/GEA2) and the simple activity carbon resistance rod (AC) absorption to NaCl
Situation contrasts.Result shows that the desalting effect of this combination electrode is substantially better than simple activity carbon resistance rod.
Embodiment 8
The preparation of combination electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 2 and activated carbon powder respectively
The quality at end is 0.2g and 19.8g, according to the ratio mix homogeneously of 1:99；(2) mixing of two kinds of materials is placed on grinds
Alms bowl grinds 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL methanol, stirring, mix homogeneously are continued；
(4) ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:2 (quality of PTFE is 66g) to be dissolved in
In 200mL methanol, put it in beaker and disperse 1 hour；(6) after making both mix homogeneously with Glass rod stirring,
Continue ultrasonic 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7)
Electrode air-dries 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.8V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 87%.
Embodiment 9
The preparation of combination electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 3 and activated carbon powder respectively
The quality at end is 1g and 19g, according to the ratio mix homogeneously of 1:19；(2) two kinds of material mixing are placed in mortar
Grind 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL methanol, stirring, mix homogeneously are continued；(4)
Ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:2 (quality of PTFE is 66g) and be dissolved in 200mL
In methanol, put it in beaker and disperse 1 hour；(6), after making both mix homogeneously with Glass rod stirring, continue super
Sound 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7) electrode
Air-dry 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.6V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 80%.
Embodiment 10
The preparation of combination electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 1 and activated carbon powder respectively
The quality at end is 1g and 19g, according to the ratio mix homogeneously of 1:19；(2) two kinds of material mixing are placed in mortar
Grind 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL methanol, stirring, mix homogeneously are continued；(4)
Ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:1 (quality of PTFE is 33g) and be dissolved in 200mL
In methanol, put it in beaker and disperse 1 hour；(6), after making both mix homogeneously with Glass rod stirring, continue super
Sound 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7) electrode
Air-dry 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.8V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 85%.
Embodiment 11
The preparation of electrode: (1) weighs the diaminobenzene functionalization graphene in embodiment 1 and activated carbon powder respectively
Quality is 0.4g and 19.6g, according to the ratio mix homogeneously of 1:99；(2) two kinds of material mixing are placed in mortar
Grind 30 minutes；(3), during the material of mix homogeneously is dissolved in 300mL methanol, stirring, mix homogeneously are continued；(4)
Ultrasonic 5 hours；(5) weigh binding agent PTFE proportionally 1:2 (quality of PTFE is 66g) and be dissolved in 200mL
In methanol, put it in beaker and disperse 1 hour；(6), after making both mix homogeneously with Glass rod stirring, continue super
Sound 3 hours；(6) material after mix homogeneously is smeared uniformly on electrode slice, with machine press mold molding；(7) electrode
Air-dry 24 hours；(8) dry 24 hours in 80 DEG C of vacuum, standby.
Combination electrode is done electro-adsorption research: taken out from baking oven by freshly prepd combination electrode, cooling, and ultrapure
Water soaks 24 hours.Then assemble electric adsorption device, carry out desalination experiment.Specifically comprise the following steps that prepared by (1)
Composite electrode sheet be installed to make by oneself in electric adsorption device, as both positive and negative polarity；(2) DC source is connected, the two poles of the earth
Power-on voltage is 1.6V；(3) configuration 240mg/L NaCl solution, takes 1000mL solution and does desalination experiment；(4)
Adsorption time is 40 minutes；(5) electrode short circuit desorption, the time is 60 minutes；(6) conditions above salt rejection rate is permissible
Reach 80%.
Claims (10)
1. the active carbon combined electrode of a diaminobenzene functionalization graphene doping, it is characterized in that, using diaminobenzene functionalization graphene as conductive additive, utilize binding agent that with activated carbon homogeneous blend, diaminobenzene functionalization graphene is built composite, through press mold molding, this composite is fixed on electrode slice, after vacuum drying, i.e. obtains described combination electrode.
2. the active carbon combined electrode of diaminobenzene functionalization graphene doping as claimed in claim 1, it is characterised in that binding agent is the mixing of one or more in politef, polyvinylidene fluoride and Polyethylene Glycol.
3. the active carbon combined electrode of diaminobenzene functionalization graphene doping as claimed in claim 1, it is characterised in that electrode slice material is aluminum, nickel, titanium, copper or stainless steel, and it is shaped as the one in net, paper tinsel film and spongy body.
4. the active carbon combined electrode of diaminobenzene functionalization graphene doping as claimed in claim 1, it is characterised in that diaminobenzene functionalization graphene structure is as follows:
。
5. the active carbon combined electrode of diaminobenzene functionalization graphene doping as claimed in claim 1, it is characterised in that by quality ratio, activated carbon: diaminobenzene functionalization graphene: binding agent=(99:1:50) ~ (19:1:20).
6. the preparation method of the active carbon combined electrode of a diaminobenzene functionalization graphene doping, it is characterised in that its step is as follows:
A () is ultrasonic under, prepare the DMF suspension of graphene oxide, this suspension is mixed with the DMF solution of diaminobenzene, it is heated to 70 ~ 100 DEG C of stirring reactions, filtration under diminished pressure, washing, the dried diaminobenzene functionalization graphene that i.e. obtains, graphene oxide is 1:10 ~ 10:1 with the mass ratio of diaminobenzene；
(b)
After diaminobenzene functionalization graphene is ground, it is blended with activated carbon, preparation has the diaminobenzene functionalization graphene of different proportion and the complex of activated carbon, and be dissolved in organic solvent, mix homogeneously, wherein, activated carbon is (99:1) ~ (19:1) with the mass ratio of diaminobenzene functionalization graphene；
C binding agent is dissolved in organic solvent by (), mix homogeneously, and wherein, diaminobenzene functionalization graphene is (1:50) ~ (1:20) with the mass ratio of binding agent；
D step (b) is mixed homogeneously by () with step (c), ultrasonic after grinding obtain composite；
E the composite prepared uniformly is coated onto on electrode by (), compressing, and vacuum drying at 60 ~ 80 DEG C, i.e. can get active carbon combined electrode.
7. the preparation method of the active carbon combined electrode of diaminobenzene functionalization graphene doping as claimed in claim 6, it is characterised in that in step (a), ultrasonic time is 2 ~ 10h；Diaminobenzene is any one in p-phenylenediamine, m-diaminobenzene. and o-phenylenediamine；In the DMF suspension of graphene oxide, the ratio of graphite oxide and DMF solvent is 7.5 ~ 15 mg/mL；The ratio of diaminobenzene and DMF solvent is 1:10 ~ 1:500 g/mL；The temperature range of the DMF solution of diaminobenzene is 25 ~ 80 DEG C；The stirring response time is 5 ~ 24 h.
8. the preparation method of the active carbon combined electrode of diaminobenzene functionalization graphene doping as claimed in claim 6, it is characterized in that, in step (b), diaminobenzene functionalization graphene and the gross mass of activated carbon are (1:1 ~ 2:1) with the mass ratio of organic solvent, and organic solvent is methanol or ethanol；In step (c), binding agent is (10:8 ~ 2:6) with the mass ratio of organic solvent, and organic solvent is methanol or ethanol；In step (d), ultrasonic time is 6-8 hours；In step (e), drying time is 16 ~ 24 h.
9. the two-element active charcoal combination electrode of the diaminobenzene functionalization graphene doping as described in claim 1-8 is arbitrary application in electro-adsorption desalination.
Apply the most as claimed in claim 9, it is characterised in that the ion removed includes Na+、Mg2+、Ca2+、F-、NO3 -、NO2 -、HCO3 -
、SO4 2-And PO4 3-, adsorption time is 20 ~ 150 minutes, and desorption time is 20 ~ 150 minutes, and power-on voltage is 1.0 ~ 2.0 V.
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