CN103073009B - Anionic clay/graphene nanocomposite material and preparation method thereof - Google Patents
Anionic clay/graphene nanocomposite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of nanocomposite materials and discloses an anionic clay/graphene nanocomposite material and a preparation method thereof. The preparation method of the anionic clay/graphene nanocomposite material comprises the following steps of 1, preparing delaminated anionic clay colloid, 2, preparing delaminated electronegative graphene colloid, and 3, preparing the anionic clay/graphene nanocomposite material. The anionic clay/graphene nanocomposite material breaks through the traditional combination way of a semiconductor and graphene. The preparation method realizes fully and effectively combination of a semiconductor and graphene, and performs functions of the two materials to the maximum degree thereby improving photoelectric properties of a semiconductor material.
Description
Technical field
The invention belongs to field of nanocomposite materials, relate to a kind of nano composite material, particularly a kind of anionic clay/graphene nanocomposite material and preparation method thereof.
Background technology
Anionic clay is a kind of porous material with larger specific surface area, can need to carry out according to specific function a kind of stratified material of synthetic.With Zn, the elements such as Ti, as main body, can become the semiconductor material of tool light function by anionic clay design, then add some transition metals to regulate energy gap, make it have good response at visible-range.After the anionic clay semiconductor material of tool light function and Graphene are compound, Graphene can be served as light acceptor, transporting electronics fast again, make light induced electron effectively separate and shift with photohole, and then improved the photoelectric properties of semiconductor material, make this nano composite material produce multiple fields such as oxygen, photocatalysis degradation organic contaminant, photovoltaic cell, solar cell at photocatalytic cleavage aquatic products hydrogen and have a wide range of applications.This nano composite material also can be used as superpower sorbent material use simultaneously.
At present; about the matrix material of semi-conductor and Graphene, there are reports; its preparation method mainly concentrates at Graphene surface growth semiconductor grain or at semiconductor surface growing graphene; but these methods all can not make Graphene be combined fully with semiconductor material, thereby can not effectively bring into play the advantage of the quick transporting electronics of Graphene.Therefore, the combination that must break traditions, finds the combination of new semi-conductor and Graphene, and semiconductor material is combined fully effectively with Graphene.Japan, once reported at some research in nanotechnology centers of Korea S, by the mode of delamination, two kinds of different electrical semiconductor materials of band can be combined by the mode of self-assembly layer by layer.Anionic clay is a kind of stratified material of laminate positively charged, its laminate thickness is about 0.5nm, and graphite is through oxidation or further carboxylated, can obtain leafing, electronegative graphene oxide, and its lamellar spacing is about 0.8～1.2nm.Anionic clay and these two kinds electrical contrary stratified materials of graphene oxide are made to colloidal solution, after mixing, make the anionic clay of unimolecular layer and the graphene oxide of unimolecular layer carry out self-assembly layer by layer by electrostatic interaction, form the nano composite material of anionic clay/graphene oxide.With hydrazine hydrate, graphene oxide is reduced again, can obtain the nano composite material of anionic clay/Graphene, the semi-conductor that this matrix material breaks traditions and the combination of Graphene, semi-conductor is combined fully effectively with Graphene, farthest bring into play the function of bi-material, and then promote the photoelectric properties of semiconductor material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anionic clay/graphene nanocomposite material.
Another object of the present invention is to provide a kind of anionic clay/graphene nanocomposite material being prepared by above-mentioned preparation method.This anionic clay/graphene nanocomposite material is the matrix material with sandwich structure.
Object of the present invention is achieved through the following technical solutions:
A preparation method for anionic clay/graphene nanocomposite material, comprises the following steps:
(1) preparation of the anionic clay colloid of leafing: get anionic clay 0.1～10g, join in the pure formamide soln of 1L, stir, obtaining concentration is the anionic clay colloidal solution of the leafing of 0.1～10g/L;
(2) preparation of the electronegative Graphene colloid of leafing: get the electronegative graphene powder of 5g and join in the pure methane amide liquid of 500mL, stir, obtaining concentration is the electronegative Graphene colloidal solution of the leafing of 1g/L;
(3) anionic clay/Graphene is through the preparation of nano composite material: under the atmosphere at Ar, in the process stirring, the anionic clay colloidal solution of leafing is dropped in the electronegative Graphene colloidal solution of leafing, making the mass ratio of the anionic clay colloid of leafing and the electronegative Graphene colloid of leafing is 0.2:1～20:1; Stir process, obtains flocks, and with dehydrated alcohol, by flocks centrifuge washing, vacuum-drying, obtains anionic clay/electronegative graphene composite material, grinds, and sieves, and obtains anionic clay/electronegative graphene composite material powder; Add 2mL hydrazine hydrate and react 1～5h to 1g anionic clay/electronegative graphene composite material powder, reduction, vacuum-drying, obtain anionic clay/graphene nanocomposite material, grind, cross 200 mesh sieves, obtain anionic clay/Graphene complex material powder.
The preparation process of the anionic clay described in step (1) is: get divalent metal salt and trivalent metal salt and mix, add deionized water, be stirred to metal-salt and dissolve, be designated as solution A; Get urotropin, add deionized water, be stirred to it and dissolve, drip HNO
3solution, regulating pH is 2～5, is designated as solution B; Solution A is mixed with solution B equal-volume, add NaNO
3, shaking up, supersound process, obtains clarifying mixing solutions; Mixing solutions backflow 24～48h, obtains light green turbid solution, cooling rear centrifugal, and washing supernatant liquor is 6.5～8.0 to pH, and institute is precipitated dry, grinds, and sieves, and obtains anionic clay;
Wherein, described divalent metal salt is that amount of substance is the Zn (NO of 0.04～0.048mol
3)
26H
2ni (the NO that O, amount of substance are 0.012～0.02mol
3)
26H
2o; Described divalent metal salt mol ratio Zn
2+: Ni
2+for 2:1～4:1; Described trivalent metal salt is that amount of substance is the Al (NO of 0.02mol
3)
3; Described divalent metal and the mol ratio of trivalent metal are 3:1; The add-on of described deionized water is 125mL; The amount of substance of described urotropin is 0.125mol; Described HNO
3the volumetric molar concentration of solution is 1.0mol/L; Described NaNO
3add-on be 5g; Described supersound process is to process 10～20min under 50KHZ; The temperature of described backflow is 100 DEG C; Described cooling temperature is 20～30 DEG C; Described centrifugal rotating speed is 6000～8000rpm, and the time is 10～20min; Described sieving was 200 object sieves.
Stirring described in step (1) is at 20～30 DEG C, to stir 5～10 days.
Electronegative Graphene described in step (2) is graphene oxide or carboxyl Graphene; Described stirring is at 20～30 DEG C, to stir 5～10 days.
Wherein, the preparation method of described graphene oxide is: 5g graphene powder is joined in the 100mL vitriol oil, stir at 4 DEG C, add 2.5gNaNO in whipping process
3and 15.0gKMnO
4, after stirring 90min, proceed to middle temperature process, stir 30～40min, proceed to hot stage, add deionized water, stir 20～30min, use H
2o
2solution washing once, then with HCl solution washing to without white precipitate generate, by white precipitate vacuum-drying, obtain graphene oxide, grind, sieve, obtain graphene oxide powder.
Wherein, the temperature of described middle temperature process is 30～40 DEG C; The temperature of described hot stage is 80～90 DEG C; The add-on of described deionized water is 200mL; Described H
2o
2the concentration of solution is 30%; The concentration of described HCl solution is 5%; Described sieving was 200 mesh sieves.
The preparation method of described carboxylated Graphene is: graphene oxide powder is joined in NaOH solution, splash into again chloroacetic acid solution, stir, after reaction finishes, use deionized water centrifuge washing, then gained is precipitated to vacuum-drying, obtain carboxylated Graphene, grind, sieve, carboxylated graphene powder.
Wherein, described graphene oxide quality is 2g; The concentration of described NaOH solution is 1.0mmol/L, and volume is 100mL; The concentration of described chloroacetic acid solution is 1.0mmol/L, and volume is 20mL; Described churning time is 2h; Described deionized water wash number of times is 5 times; Described centrifugal rotating speed is 6000rpm, and the time is 10min; Described sieving was 200 object sieves.
The time of the described stir process described in step (3) is 2～6h; Described absolute ethanol washing number of times is 3～5 times, and centrifugal rotating speed is 6000～8000rpm, and the time is 10～20min; Described vacuum drying temperature is 60～80 DEG C; Described sieving was 200 mesh sieves.
Anionic clay/the graphene nanocomposite material being prepared by preparation method described above, this anionic clay/graphene nanocomposite material is by the anionic clay of unimolecular layer and the Graphene of the unimolecular layer matrix material with sandwich structure forming that is layering.
Principle of the present invention is: by the mode of delamination, two kinds of different electrical semiconductor materials of band can be combined by the mode of self-assembly layer by layer.Anionic clay is a kind of stratified material of laminate positively charged, its laminate thickness is about 0.5nm, and graphite is through oxidation or further carboxylated, can obtain leafing, electronegative Graphene, and its lamellar spacing is about 0.8～1.2nm.Anionic clay and these two kinds electrical contrary stratified materials of electronegative Graphene are made to colloidal solution, after mixing, make the anionic clay of unimolecular layer and the graphene oxide of unimolecular layer carry out self-assembly layer by layer by electrostatic interaction, form the nano composite material of anionic clay/graphene oxide.With hydrazine hydrate, graphene oxide is reduced again, can obtain the nano composite material of anionic clay/Graphene.
The present invention's advantage compared with prior art: the matrix material that is applied at present cracking aquatic products hydrogen under visible ray generally needs doped precious metal element, as Ag dopen Nano TiO
2, Pt dopen Nano TiO
2be for transporting electronics effectively Deng, the doping of these precious metals, reduce the compound probability of light induced electron and photohole.But precious metal doping cost is higher, the ability of transporting electronics can not show a candle to lower-cost Graphene.The invention provides a kind of preparation method who can be applicable to the anionic clay/graphene nanocomposite material of cracking aquatic products hydrogen under visible ray, the method can realize the anionic clay of unimolecular layer and the Graphene of unimolecular layer and be layering and form the matrix material of sandwich structure, can make to the full extent anionic clay and Graphene carry out combination.
Brief description of the drawings
Fig. 1. anionic clay/graphene nanocomposite material preparation method schematic diagram.
Fig. 2. the XRD figure of the anionic clay of preparing for embodiment 1.
Fig. 3. the TEM image of the carboxylated Graphene of preparing for embodiment 1.
Fig. 4. the TEM image of anionic clay/graphene nano complex body prepared by embodiment 1.
Fig. 5. anionic clay/graphene nano complex body section high definition TEM and schematic diagram.
Fig. 6. solid UV-vis spectral scan figure: (a) anionic clay; (b) anionic clay/graphene nanocomposite material.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) preparation of anionic clay: take respectively 11.90g (0.040mol) Zn (NO
3)
26H
2o, 5.82g (0.020mol) Ni (NO
3)
26H
2o, 7.50g (0.020mol) Al (NO
3)
3, be placed in 300mL beaker, add 125mL deionized water, be stirred to solid and dissolve completely, be designated as solution A, in solution A, the mol ratio (Zn of divalent metal and trivalent metal
2++ Ni
2+): Al
3+=3:1, wherein Zn
2+: Ni
2+=2:1.Take 17.50g (0.125mol) urotropin, be placed in 300mL beaker, add 125mL deionized water, after being stirred to solid and dissolving completely, drip 1.0mol/L HNO
3solution, makes pH be down to 2, is designated as solution B.
By above-mentioned A, B solution, in two mouthfuls of medium volume mixture of additional examination flask of 500mL, adds 5.00gNaNO
3shake up, then two mouthfuls of additional examination flasks are placed in to 50kHz ultrasonic washer and process 10min, obtain the mixing solutions of clarification.
Two mouthfuls of additional examination flasks are put into electric heating device, 24h refluxes under 100 DEG C of conditions, obtain light green suspension liquid, after being cooled to 25 DEG C with the centrifugal 10min of deionized water 6000rpm wash to supernatant liquor be pH to 6.5, the lyophilize of gained precipitation, after dry, grind, cross 200 mesh sieves, obtain anionic clay.The XRD figure of prepared anionic clay can be referring to Fig. 2, it is characterized in that occurring a sharp-pointed peak near 2 θ=10 °.
(2) preparation of the anionic clay colloid of leafing: get the anionic clay that 1.0g prepares, join in the pure methane amide liquid of 1.0L, stir 5 days at 20 DEG C, obtaining concentration is the anionic clay colloidal solution of the leafing of 1.0g/L.Available Tyndall effect judges whether to form colloidal solution.
(3) preparation of graphene oxide: prepare graphene oxide by improved Hummers method.Preparation process is as follows: 5.0g graphene powder (Shanghai Aladdin company buys) is joined to the dense H of 100mL
2sO
4in, under 4 DEG C of conditions, stir, in whipping process, add again 2.5g NaNO
3and 15.0gKMnO
4, after stirring 90min, proceeding to middle temperature process (35 DEG C), middle temperature proceeds to hot stage (80 DEG C) after stirring 30min again, then adds 200mL deionized water, and hot stage stirs 30min.After reaction, first use 30%H
2o
2solution washing once, then with 5%HCL solution washing when generating without white precipitate, by white precipitate vacuum-drying, obtain graphene oxide, ground 200 orders for subsequent use, obtain graphene oxide powder.
(4) preparation of the graphene oxide colloidal solution of leafing: get the graphene oxide powder that 0.5g prepares and join in the pure methane amide liquid of 500mL, stir 7 days at 20 DEG C, obtaining concentration is the graphene oxide colloidal solution of the leafing of 1.0g/L.Available Tyndall effect judges whether to form colloidal solution.
(5) anionic clay/Graphene is through the preparation of nano composite material: the graphene oxide colloidal solution of the 500mL leafing of gained is transferred in the round-bottomed flask of 3L, under the atmosphere of Ar, in the process stirring, dropwise add the anionic clay colloidal solution of the leafing of 1.0L, the mass ratio that makes the anionic clay of leafing and the graphene oxide of leafing is 2:1, stir 2h, obtain flocks.
With straight alcohol by the flocks centrifuge washing of gained 3 times, centrifugal rotational speed is 6000rpm, and gained is deposited in 60 DEG C of vacuum-dryings, obtains anionic clay/graphene oxide complex material, grind again 100 orders, obtained anionic clay/graphene oxide complex material powder.
Get anionic clay/graphene oxide complex body powder of 1.0g gained, add 2.0mL hydrazine hydrate reaction 1h, make its reduction, 60 DEG C of vacuum-dryings, obtain anionic clay/graphene nano complex material, ground 200 orders, Fig. 1 is shown in by the powder anionic clay/graphene nanocomposite material preparation method schematic diagram that obtains anionic clay/graphene nano complex material again.
Embodiment 2
(1) preparation of anionic clay: take respectively 11.90g (0.040mol) Zn (NO
3)
26H
2o, 5.82g (0.020mol) Ni (NO
3)
26H
2o, 7.50g (0.020mol) Al (NO
3)
3, be placed in 300mL beaker, add 125mL deionized water, be stirred to solid and dissolve completely, be designated as solution A, in solution A, the mol ratio (Zn of divalent metal and trivalent metal
2++ Ni
2+): Al
3+=3:1, wherein Zn
2+: Ni
2+=2:1.Take 17.50g (0.125mol) urotropin, be placed in 300mL beaker, add 125mL deionized water, after being stirred to solid and dissolving completely, drip 1.0mol/L HNO
3solution, makes pH be down to 5, is designated as solution B.
By above-mentioned A, B solution, in two mouthfuls of medium volume mixture of additional examination flask of 500mL, adds 5.00gNaNO
3shake up, then two mouthfuls of additional examination flasks are placed in to 50kHz ultrasonic washer and process 10min, obtain the mixing solutions of clarification.
Two mouthfuls of additional examination flasks are put into electric heating device, make its 48h that refluxes under 100 DEG C of conditions, obtain light green suspension liquid, after being cooled to 20 DEG C with centrifugal 20min under deionized water 8000rpm wash to supernatant liquor be pH to 8.0, the lyophilize of gained precipitation, after dry, grind, cross 200 mesh sieves, obtain anionic clay.
(2) preparation of the anionic clay colloid of leafing: get the anionic clay that 0.1g prepares, join in the pure methane amide liquid of 1.0L, stir 10 days at 25 DEG C, obtaining concentration is the anionic clay colloidal solution of the leafing of 0.1g/L.Available Tyndall effect judges whether to form colloidal solution.
(3) preparation of carboxylated Graphene: prepare graphene oxide by improved Hummers method.Preparation process is as follows: 5.0g graphene powder (Shanghai Aladdin company buys) is added to the dense H of 100mL
2sO
4under 4 DEG C of conditions, stir, in whipping process, add again 2.5g NaNO
3and 15.0gKMnO
4, after stirring 90min, proceeding to middle temperature process, temperature is being controlled at 35 DEG C, after stirring 30min, proceeds to hot stage again, and 80 DEG C of temperature controls, then add 200mL deionized water, stir 30min.After reaction, first use 30%H
2o
2solution washing once, then with 5%HCL solution washing to generating without white precipitate.By white precipitate vacuum-drying, obtain graphene oxide, ground 200 orders, obtain graphene oxide powder.Take the graphene oxide powder that 2.0g prepares, joining 100mL concentration is in 1.0mmol/LNaOH solution, splash into again the chloroacetic acid solution that 20mL concentration is 1.0mmol/L, stir 2h, after reaction finishes, use centrifugal 10min under deionized water 6000rpm to wash centrifuge washing 5 times, again gained is precipitated to vacuum-drying, obtain carboxylated Graphene, ground 200 orders, obtain carboxylated graphene powder.
(4) get the carboxylated Graphene that 0.5g prepares and join in the pure methane amide liquid of 500mL, stir 10 days at 25 DEG C, obtaining concentration is the carboxylated Graphene colloidal solution of the leafing of 1.0g/L.Available Tyndall effect judges whether to form colloidal solution.The carboxylated Graphene colloid TEM image of its leafing can be referring to Fig. 3.
(5) anionic clay/Graphene is through the preparation of nano composite material: the carboxylated Graphene colloidal solution of the 500mL leafing of gained is transferred in the round-bottomed flask of 3L, under the atmosphere of Ar, in the process stirring, dropwise add the anionic clay colloidal solution of the leafing of 1.0L, the mass ratio that makes the anionic clay of leafing and the carboxylated Graphene of leafing is 1:5, stir 6h, obtain flocks.
With straight alcohol by the flocks centrifuge washing of gained 4 times, centrifugal rotational speed is 8000rpm, and gained is deposited in 70 DEG C of vacuum-dryings, obtains anionic clay/carboxylated Graphene complex material, grind again 100 orders, obtained anionic clay/carboxylated Graphene complex material powder.
Get the anionic clay/carboxylated Graphene complex body powder of 1.0g gained, add 2.0mL hydrazine hydrate reaction 3h, make its reduction, 70 DEG C of vacuum-dryings, obtain anionic clay/graphene nano complex material, then ground 200 orders, obtain the powder of anionic clay/graphene nano complex material, its TEM image can be referring to Fig. 4 and Fig. 5, and the solid UV-vis spectral scan figure of its anionic clay and anionic clay/graphene nano complex material can be referring to Fig. 6.
Embodiment 3
(1) preparation of anionic clay: take 13.38g (0.045mol) Zn (NO
3)
26H
2o, 4.36g (0.015mol) Ni (NO
3)
26H
2o, 7.50g (0.02mol) Al (NO
3)
3, be placed in 300mL beaker, add 125mL deionized water, be stirred to solid and dissolve completely, be designated as solution A, in solution A, the mol ratio (Zn of divalent metal and trivalent metal
2++ Ni
2+): Al
3+=3:1, wherein Zn
2+: Ni
2+=3:1.Take 17.50g (0.125mol) urotropin, be placed in 300mL beaker, add 125mL deionized water, after being stirred to solid and dissolving completely, drip 1.0mol/L HNO
3solution, makes pH be down to 2.5, is designated as solution B.By above-mentioned A, B solution, in two mouthfuls of medium volume mixture of additional examination flask of 500mL, adds 5.00g NaNO
3shake up, then flask is placed in to 50kHz ultrasonic washer processes 20min, obtain the mixing solutions of clarification.
Two mouthfuls of additional examination flasks are put into electric heating device, make its 36h that refluxes under 100 DEG C of conditions, obtain light green suspension liquid, after being cooled to 30 DEG C under deionized water 6000rpm centrifugal 10min to wash supernatant liquor be pH to 7, the lyophilize of gained precipitation, after dry, grind, cross 200 mesh sieves, obtain anionic clay.
(2) preparation of the anionic clay colloid of leafing: get the anionic clay that 10g prepares, join in the pure methane amide liquid of 1.0L, stir 7 days at 30 DEG C, obtaining concentration is the anionic clay colloidal solution of the leafing of 10g/L.Available Tyndall effect judges whether to form colloidal solution.
(3) preparation of graphene oxide: prepare graphene oxide by improved Hummers method.Preparation process is as follows: 5.0g graphene powder (Shanghai Aladdin company buys) is added to the dense H of 100mL
2sO
4under 4 DEG C of conditions, stir, in whipping process, add again 2.5g NaNO
3and 15.0gKMnO
4, after stirring 90min, proceeding to middle temperature process, temperature is being controlled at 30 DEG C, after stirring 40min, proceeds to hot stage again, and 85 DEG C of temperature controls, then add 200mL deionized water, stir 25min.After reaction, first use 30%H
2o
2solution washing once, then with 5%HCL solution washing to generating without white precipitate.By white precipitate vacuum-drying, obtain graphene oxide, ground 200 orders for subsequent use, obtain graphene oxide powder.
(4) get the graphene oxide that 0.5g prepares and join in the pure methane amide liquid of 500mL, stir 5 days at 30 DEG C, obtaining concentration is the graphene oxide colloidal solution of the leafing of 1.0g/L.Available Tyndall effect judges whether to form colloidal solution.
(5) anionic clay/Graphene is through the preparation of nano composite material: the graphene oxide colloidal solution of the 500mL leafing of gained is transferred in the round-bottomed flask of 3L, under the atmosphere of Ar, in the process stirring, dropwise add the anionic clay colloidal solution of 1.0L, the mass ratio that makes the anionic clay of leafing and the graphene oxide of leafing is 20:1, stir 4h, obtain flocks.
With straight alcohol by the flocks centrifuge washing of gained 5 times, centrifugal rotational speed is 5000rpm, and gained is deposited in 80 DEG C of vacuum-dryings, obtains anionic clay/graphene oxide complex material, grind again 100 orders, obtained anionic clay/graphene oxide complex material powder.
Get anionic clay/graphene oxide complex body powder of 1.0g gained, add 2.0mL hydrazine hydrate reaction 1h, make its reduction, 80 DEG C of vacuum-dryings, obtain anionic clay/graphene nano complex material, grind again 200 orders, obtained the powder of anionic clay/graphene nano complex material.
Embodiment 4
(1) preparation of anionic clay: take respectively 14.28g (0.048mol) Zn (NO
3)
26H
2o, 3.49g (0.012mol) Ni (NO
3)
26H
2o, 7.50g (0.02mol) Al (NO
3)
3, be placed in 300mL beaker, add 125mL deionized water, be stirred to solid and dissolve completely, be designated as solution A, in solution A, the mol ratio (Zn of divalent metal and trivalent metal
2++ Ni
2+): Al
3+=3:1, wherein Zn
2+: Ni
2+=4:1.Take 17.50g (0.125mol) urotropin, be placed in 300mL beaker, add 125mL deionized water, after being stirred to solid and dissolving completely, drip 1.0mol/L HNO
3solution, makes pH be down to 2.5, is designated as solution B.
By above-mentioned A, B solution, in two mouthfuls of medium volume mixture of additional examination flask of 500mL, adds 5.00gNaNO
3shake up, then flask is placed in to 50kHz ultrasonic washer processes 10min, obtain the mixing solutions of clarification.
Two mouthfuls of additional examination flasks are put into electric heating device, make its 48h that refluxes under 100 DEG C of conditions, obtain light green suspension liquid, after being cooled to 25 DEG C under 6000rpm centrifugal 10min to wash supernatant liquor be pH to 8.0, the lyophilize of gained precipitation, grinds after dry, cross 200 mesh sieves, obtain anionic clay.
(2) preparation of the anionic clay colloid of leafing: get the anionic clay that 1.0g prepares, join in the pure methane amide liquid of 1.0L, stir 10 days at 25 DEG C, obtaining concentration is the anionic clay colloidal solution of the leafing of 1g/L.Available Tyndall effect judges whether to form colloidal solution.
(3) preparation of graphene oxide: prepare graphene oxide by improved Hummers method.Preparation process is as follows: 5.0g graphene powder (Shanghai Aladdin company buys) is added to the dense H of 100mL
2sO
4under 4 DEG C of conditions, stir, in whipping process, add again 2.5g NaNO
3with 15.0g KMnO
4, after stirring 90min, proceeding to middle temperature process, temperature is being controlled at 40 DEG C, after stirring 25min, proceeds to hot stage again, and 90 DEG C of temperature controls, then add 200mL deionized water, stir 20min.After reaction, first use 30%H
2o
2solution washing once, then with 5%HCL solution washing to generating without white precipitate.By white precipitate vacuum-drying, obtain graphene oxide, ground 200 orders for subsequent use, obtain graphene oxide powder.
(4) get the graphene oxide that 0.5g prepares and join in the pure methane amide liquid of 500mL, stir 7 days at 25 DEG C, obtaining concentration is the graphene oxide colloidal solution of the leafing of 1.0g/L.Available Tyndall effect judges whether to form colloidal solution.
(5) anionic clay/Graphene is through the preparation of nano composite material: the graphene oxide colloidal solution of the 500mL leafing of gained is transferred in the round-bottomed flask of 3L, under the atmosphere of Ar, in the process stirring, dropwise add the anionic clay colloidal solution of the leafing of 1.0L, the mass ratio that makes the graphene oxide of anionic clay and leafing is 2:1, stir 2h, obtain flocks.
With straight alcohol by the flocks centrifuge washing of gained 3 times, centrifugal rotational speed is 6000rpm, and gained is deposited in 60 DEG C of vacuum-dryings, obtains anionic clay/carboxylated Graphene complex material, grind again 100 orders, obtained anionic clay/carboxylated Graphene complex material powder.
Get anionic clay/graphene oxide complex body powder of 1.0g gained, add 2.0mL hydrazine hydrate reaction 5h, make its reduction, 60 DEG C of vacuum-dryings, obtain anionic clay/graphene nano complex material, grind again 200 orders, obtained the powder of anionic clay/graphene nano complex material.
Can be found out by accompanying drawing: the prepared anionic clay/graphene nano complex material of the present invention has been realized the anionic clay of unimolecular layer and the Graphene of unimolecular layer and has been layering and forms the matrix material of sandwich structure, can make to the full extent anionic clay and Graphene carry out combination.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a preparation method for anionic clay/graphene nanocomposite material, is characterized in that: comprise the following steps:
(1) preparation of the anionic clay colloidal solution of leafing: get anionic clay 0.1～10g, join in the pure formamide soln of 1L, stir, obtaining concentration is the anionic clay colloidal solution of the leafing of 0.1～10g/L;
(2) preparation of the electronegative Graphene colloidal solution of leafing: get the electronegative graphene powder of 0.5g and join in the pure methane amide liquid of 500mL, stir, obtaining concentration is the electronegative Graphene colloidal solution of the leafing of 1g/L;
(3) preparation of anionic clay/graphene nanocomposite material: under the atmosphere of Ar, in the process stirring, the anionic clay colloidal solution of leafing is dropped in the electronegative Graphene colloidal solution of leafing, making the mass ratio of the anionic clay colloid of leafing and the electronegative Graphene colloid of leafing is 0.2:1～20:1, stir process, obtain flocks, with dehydrated alcohol by flocks centrifuge washing, vacuum-drying, obtain anionic clay/electronegative graphene composite material, grind, sieve, obtain anionic clay/electronegative graphene composite material powder, add 2mL hydrazine hydrate and react 1～5h to 1g anionic clay/electronegative graphene composite material powder, reduction, vacuum-drying, obtain anionic clay/graphene nanocomposite material, grind, cross 200 mesh sieves, obtain anionic clay/Graphene complex material powder.
2. preparation method according to claim 1, it is characterized in that: the preparation process of the anionic clay described in step (1) is: get divalent metal salt and trivalent metal salt and mix, add deionized water, be stirred to metal-salt and dissolve, be designated as solution A; Get urotropin, add deionized water, be stirred to it and dissolve, drip HNO
3solution, regulating pH is 2～5, is designated as solution B; Solution A is mixed with solution B equal-volume, add NaNO
3, shaking up, supersound process, obtains clarifying mixing solutions; Mixing solutions backflow 24～48h, obtains light green turbid solution, cooling rear centrifugal, and washing supernatant liquor is 6.5～8.0 to pH, and institute is precipitated dry, grinds, and sieves, and obtains anionic clay;
Stirring described in step (1) is at 20～30 DEG C, to stir 5～10 days.
3. preparation method according to claim 1, is characterized in that: the electronegative Graphene described in step (2) is graphene oxide or carboxyl Graphene; Described stirring is at 20～30 DEG C, to stir 5～10 days.
4. preparation method according to claim 1, is characterized in that: the time of the described stir process described in step (3) is 2～6h; Described absolute ethanol washing number of times is 3～5 times, and centrifugal rotating speed is 6000～8000rpm, and the time is 10～20min; Described vacuum drying temperature is 60～80 DEG C; Described sieving was 200 mesh sieves.
5. preparation method according to claim 2, is characterized in that: described divalent metal salt is that amount of substance is the Zn (NO of 0.04～0.048mol
3)
26H
2ni (the NO that O, amount of substance are 0.012～0.02mol
3)
26H
2o; Described divalent metal salt mol ratio Zn
2+: Ni
2+for 2:1～4:1; Described trivalent metal salt is that amount of substance is the Al (NO of 0.02mol
3)
3; Described divalent metal and the mol ratio of trivalent metal are 3:1; The add-on of described deionized water is 125mL; The amount of substance of described urotropin is 0.125mol; Described HNO
3the volumetric molar concentration of solution is 1.0mol/L; Described NaNO
3add-on be 5g; Described supersound process is to process 10～20min under 50KHz; The temperature of described backflow is 100 DEG C; Described cooling temperature is 20～30 DEG C; Described centrifugal rotating speed is 6000～8000rpm, and the time is 10～20min; Described sieving was 200 object sieves.
6. preparation method according to claim 3, it is characterized in that: the preparation method of described carboxylated Graphene is: graphene oxide powder is joined in NaOH solution, splash into again chloroacetic acid solution, stir, after reaction finishes, use deionized water centrifuge washing, again gained is precipitated to vacuum-drying, obtain carboxylated Graphene, grind, sieve, obtain carboxylated graphene powder.
7. according to the preparation method described in claim 3 or 6, it is characterized in that: the preparation process of described graphene oxide is: 5g graphene powder is joined in the 100mL vitriol oil, stir at 4 DEG C, in whipping process, add 2.5gNaNO
3with 15.0g KMnO
4, after stirring 90min, proceed to middle temperature process, stir 30～40min, proceed to hot stage, add deionized water, stir 20～30min, use H
2o
2solution washing once, then with HCl solution washing to without white precipitate generate, by white precipitate vacuum-drying, obtain graphene oxide, grind, sieve, obtain graphene oxide powder.
8. preparation method according to claim 6, is characterized in that: described graphene oxide quality is 2g; The concentration of described NaOH solution is 1.0mmol/L, and volume is 100mL; The concentration of described chloroacetic acid solution is 1.0mmol/L, and volume is 20mL; Described churning time is 2h; Described deionized water wash number of times is 5 times; Described centrifugal rotating speed is 6000rpm, and the time is 10min; Described sieving was 200 object sieves.
9. preparation method according to claim 7, is characterized in that: the temperature of described middle temperature process is 30～40 DEG C; The temperature of described hot stage is 80～90 DEG C; The add-on of described deionized water is 200mL; Described H
2o
2the concentration of solution is 30%; The concentration of described HCl solution is 5%; Described sieving was 200 mesh sieves.
10. anionic clay/the graphene nanocomposite material being prepared by the preparation method described in claim 1～9 any one, is characterized in that: this anionic clay/graphene nanocomposite material is by the anionic clay of unimolecular layer and the Graphene of the monoatomic layer matrix material with sandwich structure forming that is layering.
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