CN104107681A - Preparation method of three-dimensional graphene-protein composite aerogel - Google Patents
Preparation method of three-dimensional graphene-protein composite aerogel Download PDFInfo
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- CN104107681A CN104107681A CN201410272459.7A CN201410272459A CN104107681A CN 104107681 A CN104107681 A CN 104107681A CN 201410272459 A CN201410272459 A CN 201410272459A CN 104107681 A CN104107681 A CN 104107681A
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Abstract
The invention discloses a preparation method of a three-dimensional graphene-protein composite aerogel. The preparation method comprises the following steps: respectively adding oxidized graphite, protein, and a reducing agent into an acidic water solution, an alkaline water solution, and a neutral water solution; then carrying out a supersonic treatment on the three solutions until the added substances are evenly dispersed, mixing the three solutions together, subjecting the mixed solution to water bath heating for 8 to 48 hours at a temperature of 50 to 100 DEG C so as to obtain graphene-protein composite hydrogel, and drying the composite graphene-protein composite hydrogel so as to obtain the graphene-protein composite aerogel, wherein addition of glycerin into the hydrogel can strengthen the flexibility of the aerogel. The prepared composite hydrogel is fluffy and porous, has certain flexibility, and has a very good adsorption effect on pollutants in water.
Description
Technical field
The present invention relates to the preparation method that a kind of simple preparation can be used as three-dimensional grapheme-protein composite aerogel of adsorbent.
Background technology
Absorption method is one of water technology of greatest concern, has advantages of that the control of being easy to and cost are low, and conventional adsorbent has active carbon, silica gel, aluminium oxide, polymer etc. at present.Owing to having larger specific area, nano material has obtained broad research in absorption.Carbon nanomaterial Graphene specific area is in the ideal situation up to 2630m2/g, but its application in absorption still exists limitation, first, only there is the carbon atom of sp2 hydridization in Graphene surface, make it only can be by Van der Waals force in conjunction with pollutant in absorption, thereby faint to pollutant effects such as heavy metals, secondly, Graphene is easily reunited, cause its specific area to decline, finally, as Powdered nano material, after absorption, be not easy to Separation of Solid and Liquid.
Summary of the invention
For the problems referred to above, the present invention discloses the preparation method that a kind of simple preparation can be used as three-dimensional grapheme-protein composite aerogel of adsorbent.By Graphene and polymer being carried out compound and making three dimensional hydrogel and can solve.As natural macromolecular, protein source is extensive, cheap, nontoxic, biocompatibility is high, and has good film forming and hydrophily, but mechanical performance is poor, and itself and Graphene are carried out to recombination energy realization mutual supplement with each other's advantages.
For realizing above object, the technical solution adopted in the present invention is:
(1) in acid, alkalescence or neutral aqueous solution, add successively graphite oxide, protein, reducing agent, every kind of material adds and all carries out ultrasonic until form homogeneous solution afterwards.The concentration of described graphene oxide is 0.1～20mg/mL.Described protein can be a kind of in the protein such as soybean protein, bovine serum albumin, fibroin albumen, collagen, keratin.The mass ratio of Graphene and protein is 1:0～1:100.Reducing agent is hydrazine hydrate, sodium borohydride, sodium acid carbonate, lithium aluminium hydride reduction, formaldehyde, saccharide compound, ascorbic acid, glutathione or amino acid.The mass ratio of Graphene and reducing agent is not less than 1:1.
(2) described mixed solution is carried out to heating water bath, temperature is 50 ℃～100 ℃, and the time is 8～48h, obtains Graphene-protein composite aquogel;
(3) composite aquogel is dried to the rear aeroge that obtains.
Further optimisation technique scheme, in step (3), can strengthen the pliability of aeroge by add the glycerine of proportion 0.1～20% in hydrogel.
Beneficial effect of the present invention is:
1. technique of the present invention simple, be easy to promote, gained three-dimensional grapheme-protein composite aerogel is loose porous, there is the pliability that graphene aerogel does not have, enriched Graphene surface functional group, improved Graphene reunion, increased the hydrophily of material.
2. gained three-dimensional grapheme-protein composite aerogel of the present invention has good adsorption capacity to water pollutant, and by composite as adsorbent than pure Graphene is greatly reduced to cost and toxicity as adsorbent, as three-dimensional aeroge, also solved the problem that nano adsorber is difficult to Separation of Solid and Liquid in addition.
Accompanying drawing explanation
Fig. 1 is the prepared Graphene-protein hydrogel picture of the present invention.
Fig. 2 is the prepared Graphene-protein aeroge ESEM picture of the present invention.
Fig. 3 is the prepared Graphene-protein aeroge of the present invention adsorption curve to methyl orange and tetracycline under different Graphene/protein proportion.
The specific embodiment
The following examples are to further illustrate of the present invention, rather than limit the scope of the invention.
Embodiment 1
Get five beakers, respectively 40mg graphite oxide is joined in 20mL distilled water and to carry out ultrasonic 6h even to solution, obtain 2mg/L graphene solution.In five groups of beakers, add 40mg ascorbic acid respectively, after ultrasonic 1h is even to solution, add bovine serum albumin 0g, 80mg, 160mg, 240mg, 320mg, 400mg respectively in five groups of beakers, ultrasonic 1h is even to solution.
Solution is put into 80 ℃ of heating water bath 12h.After heating, the water in solution is poured out, poured into distilled water immersion hydrogel 24h, during 12h, change water one time.After immersion, outwell the solution in beaker, hydrogel as shown in Figure 1, by hydrogel freeze drying 24h, obtains composite aerogel, and Electronic Speculum as shown in Figure 2.
The aeroge of five different proteins content is joined in 10mg/L tetracycline, put into 25 ℃ of constant-temperature table vibration 24h, adsorption effect as shown in Figure 3.
Embodiment 2
Get five beakers, respectively 40mg graphite oxide is joined in 20mL distilled water and to carry out ultrasonic 6h even to solution, obtain 2mg/L graphene solution.In five groups of beakers, add 40mg glutathione respectively, after ultrasonic 1h is even to solution, add bovine serum albumin 0g, 80mg, 160mg, 240mg, 320mg, 400mg respectively in five groups of beakers, ultrasonic 1h is even to solution.
Solution is put into 80 ℃ of heating water bath 12h.After heating, the water in solution is poured out, poured into distilled water immersion hydrogel 24h, during 12h, change water one time.After immersion, outwell the solution in beaker, by hydrogel freeze drying 24h, obtain composite aerogel.
Three-dimensional grapheme-protein aeroge is joined in 10mg/L tetracycline, put into 25 ℃ of constant-temperature table vibration 24h, aeroge is good to tetracycline adsorption effect.
Embodiment 3
Get five beakers, respectively 40mg graphite oxide is joined in 20mL distilled water and to carry out ultrasonic 6h even to solution, obtain 2mg/L graphene solution.In five groups of beakers, add 40mg glutathione respectively, after ultrasonic 1h is even to solution, add soybean protein 0g, 80mg, 160mg, 240mg, 320mg, 400mg respectively in five groups of beakers, ultrasonic 1h is even to solution.
Solution is put into 80 ℃ of heating water bath 12h.After heating, the water in solution is poured out, poured into distilled water immersion hydrogel 24h, during 12h, change water one time.After immersion, outwell the solution in beaker, by hydrogel freeze drying 24h, obtain composite aerogel.
Three-dimensional grapheme-protein aeroge is joined in 10mg/L tetracycline, put into 25 ℃ of constant-temperature table vibration 24h, aeroge is good to tetracycline adsorption effect.
Claims (9)
1. three-dimensional grapheme-protein composite aerogel preparation method, is characterized in that, concrete steps are as follows:
(1) in the aqueous solution, add successively graphite oxide, protein, reducing agent, every kind of material adds and all carries out ultrasonic until form homogeneous solution afterwards;
(2) (1) described mixed solution is carried out to heating water bath, obtain Graphene-protein composite aquogel;
(3) composite aquogel is dried to the rear aeroge that obtains.
2. three-dimensional grapheme-protein composite aerogel preparation method according to claim 1, is characterized in that: the concentration of described graphene oxide is 0.1～20mg/mL.
3. three-dimensional grapheme-protein composite aerogel preparation method according to claim 1, is characterized in that: described protein can be a kind of in the protein such as soybean protein, bovine serum albumin, fibroin albumen, collagen, keratin.
4. three-dimensional grapheme-protein composite aerogel preparation method according to claim 1, is characterized in that: the mass ratio of Graphene and protein is 1:0～1:100.
5. three-dimensional grapheme-protein composite aerogel preparation method according to claim 1, is characterized in that: reducing agent is any in hydrazine hydrate, sodium borohydride, sodium acid carbonate, lithium aluminium hydride reduction, formaldehyde, saccharide compound, ascorbic acid, glutathione or amino acid.
6. three-dimensional grapheme-protein composite aerogel preparation method according to claim 1, is characterized in that: the mass ratio of Graphene and reducing agent is not less than 1:1.
7. three-dimensional grapheme-protein composite aerogel preparation method according to claim 1, is characterized in that: the temperature of described mixed solution being carried out to heating water bath is 50 ℃～100 ℃, and the time is 8～48h.
8. three-dimensional grapheme-protein composite aerogel preparation method according to claim 1, is characterized in that: by add the pliability that glycerine can strengthen aeroge in hydrogel.
9. three-dimensional grapheme-protein composite aerogel preparation method according to claim 8, is characterized in that: by the glycerine proportion adding in hydrogel, be 0.1～20%.
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