CN102757041A - Preparation method of graphene/metal oxide nanocomposite powder - Google Patents
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Abstract
The invention relates to a preparation method of graphene/metal oxide nanocomposite powder, and aims to solve the problems that poison is generated in a conventional graphene preparation process, mass production is unavailable and acquiring metal oxide particles with small particle sizes is difficult in the prior art. The preparation method provided by the invention comprises the following steps: I, oxidizing graphite; II, stripping mother liquor of graphite oxide; III, purifying mother liquor of graphene oxide; and IV, preparing graphene/metal oxide nanocomposite powder. The preparation method has the advantages of simple process, innocuity, environmental protection, convenience, high efficiency and energy consumption reduction, and ensures that metal oxide is uniformly and securely coated on the surface of graphene. The graphene/metal oxide nanocomposite material prepared by adopting the method can be widely used in the fields of catalysts, photo-electricity and the like.
Description
Technical field
The present invention relates to the preparation method of Graphene/metal oxide nano composite material.
Background technology
MOX is the compound that metallic element and oxygen element combine formation.MOX of a great variety, except the weak especially metal of minority activities such as Au, Pt, other metals all have corresponding metal oxide.Variable valency metal generally has multiple oxide compound, and for example, ferro element has iron protoxide (FeO), red stone and Z 250 (Fe
3O
4) three kinds of oxide compounds.The status of MOX in catalytic field is very important, and it is widely used as Primary Catalysts, promotor and carrier.With regard to Primary Catalysts, metal oxide catalyst can be divided into catalyst of transition metal oxide and main group metal oxide catalyst, and the latter is mainly solid acid alkali catalytic agent (seeing the acid-base catalysis effect).The particle diameter of metal oxide particle is one of important factor in order that influences its catalytic effect, and particle diameter is more little, and surface-area is big more, and catalytic effect is more excellent.Yet high surface energy has caused the reunion certainly of oxide particle again, therefore, is difficult to obtain the metal oxide particle of small particle size at present.
Graphene is a kind of two-dimentional carbon material of discovered in recent years.It is not only in the known materials the thinnest a kind of, and also unusual rigid has the specific surface area bigger than carbon nanotube.The cellular lattice structure of two-dimension periodic that Graphene is made up of the carbon six-ring, it can warpage becomes the soccerballene of zero dimension, be rolled into the unidimensional carbon nanotube or be stacked to three-dimensional graphite, so Graphene is the elementary cell that constitutes other graphite materials.The basic structural unit of Graphene is a benzene six-ring the most stable in the organic materials, is present optimal two-dimensional nano material.The ideal graphene-structured is the plane hexagonal lattice, can be regarded as the graphite molecule that one deck is stripped from, and each carbon atom is sp
2Hydridization, and contribute the electronics on p track of residue to form big π key, πDian Zi can move freely, and gives the Graphene good electrical conductivity.The compound method of Graphene mainly contains two kinds: mechanical means and chemical process.Mechanical means comprises the method for micromechanics partition method, epitaxy method and heating SiC; Chemical process is chemical reduction method and chemical cleavage method.At present, chemical reduction method is the unique method of a large amount of, cheap preparation Graphene.Just because of the stability of its high specific surface area, superelevation, superpower plurality of advantages such as intensity, make it become the ideal metal oxide carrier.But chemical reduction method needs hydrazine to reduce, and hydrazine has severe toxicity, is unfavorable for the preparation in enormous quantities of Graphene.In addition, need purify during the Graphene powder preparing, operation such as drying, less than serious its productive rate that reduces, operation is also very complicated, and energy consumption is higher.
Summary of the invention
That the present invention will solve is poisonous in the preparation process of existing Graphene, can not scale operation and prior art be difficult to obtain the problem of the metal oxide particle of small particle size, and the preparation method of a kind of Graphene/metal oxide nano composite material powder is provided.
The preparation method of a kind of Graphene/metal oxide nano composite material powder carries out according to the following steps:
One, graphite oxidation:
Graphite is added in the mixture of strong oxidizing acid and nitrate salt, be cooled to-5 ℃～0 ℃, under agitation add and contain the potassium strong oxidizer, be warming up to 0 ℃～60 ℃ then; And continue to stir 24h～48h, mixed solution, mixed solution poured in 10 ℃～50 ℃ the warm water bath; Continue reaction 40min～60min, add hot water then, make the system boiling and keep 20min～40min; Add ydrogen peroxide 50 again, be stirred to dissolving fully, wash then, be filtered to and do not have SO in the filter cake
4 2-, drying promptly gets graphite oxide, and wherein graphite is 1 with the mass ratio of strong oxidizing acid: (0.025～5); The mass ratio of graphite and nitrate salt is 1: (0.2～8); Graphite is 1 with the mass ratio that contains the potassium strong oxidizer: (0.1～4); The mass ratio of graphite and ydrogen peroxide 50 is 1: (0.125～4); Wherein, described strong oxidizing acid is the vitriol oil or perchloric acid, and the described potassium strong oxidizer that contains is potassium permanganate or potassium perchlorate, and described nitrate salt is SODIUMNITRATE, saltpetre, magnesium nitrate, nitrocalcite or aluminum nitrate;
Two, the graphite oxide mother liquor is peeled off:
The graphite oxide that step 1 is obtained is dissolved in the solvent, and is ultrasonic concussion 0.5h～12h under the condition of 100W～2000W in ultrasonic frequency, obtains graphene oxide solution; Wherein said solvent is water, ethanol, acetone, terepthaloyl moietie, THF or N, dinethylformamide;
Three, the purification of graphene oxide mother liquor:
The graphene oxide solution that step 2 is obtained is centrifugal under the condition of 3000rpm～10000rpm at the whizzer revolution, and the upper solution of centrifugal gained liquid is collected, and lyophilize promptly gets the graphene oxide powder;
Four, the preparation of Graphene/metal oxide nano composite material powder:
Graphene oxide powder that step 3 is obtained and metallic compound are dissolved in the solvent and place in the supercritical reaction still; Feeding gas to pressure is 2～7MPa, and the solvent that heats up, boosts in the reaction kettle reaches supercritical state, behind reaction 0.5～4h; Gas in the still is emitted; After the reaction kettle cooling, with liquid filtering in the still, the oven dry of gained deposition; Obtain Graphene/metal oxide nano composite material powder, wherein the ratio of the amount of substance of the graphene oxide powder that obtains of step 3 and metallic compound is 1: (0.005～10); Said metallic compound is metal itrated compound, Virahol metallic compound or metal chloric acid thing; Said gas is carbonic acid gas, argon gas, nitrogen, neon or hydrogen; Said solvent is water, ethanol, acetone, ether, chloroform, benzene, toluene, ethylbenzene, terepthaloyl moietie, USP Kosher, THF, N, dinethylformamide, sherwood oil, halohydrocarbon, methyl acetate, ETHYLE ACETATE, tetracol phenixin, aliphatic hydrocarbon, aromatic hydrocarbon, organic chloride, pyridine, quadrol or dithiocarbonic anhydride.
The present invention utilizes characteristics such as the super large specific surface of Graphene, superpower hardness, adopts it as substrate, under the supercutical fluid environment, realizes even, the firm coating of MOX on the Graphene surface through the decomposition reaction.The experiment proof adopts Graphene can realize the nanometer and the homodisperse of metal oxide particle as substrate.In addition; The supercutical fluid environment that the present invention is used; The hydrazine of having avoided using severe toxicity is as reductive agent; Can a step realize directly obtaining Graphene/metal oxide nano composite material simultaneously from graphene oxide solution, avoided under many operations such as Graphene cleaning, drying and the productive rate that causes descends and energy consumption, the present invention is a kind of convenience, efficiently, a step obtains the method for Graphene/metal-oxide powder efficiently.The resulting Graphene of the present invention/the burning powder can be good is dispersed in water, ethanol, acetone, THF, sherwood oil, N; In the dinethylformamide equal solvent; Also can directly use as catalyzer; Resulting Graphene/burning powder is the fluffy goose feather shape of brown, and the specific surface of extra-low density and super large is fit to directly use as catalyzer very much.
Prepared graphene/metal oxide nano-material of the present invention can be widely used in fields such as catalyzer, photoelectricity.
Description of drawings
Fig. 1 is the XPS phenogram of the Graphene/aluminium oxide nano composite material powder of experiment one preparation;
Fig. 2 is the swarming figure of Al peak position among Fig. 1;
Fig. 3 is the TEM figure of graphene oxide of the Graphene/aluminium oxide nano composite material powder of experiment one preparation;
Fig. 4 is the TEM photo of the Graphene/aluminium oxide nano composite material powder of experiment one preparation;
Fig. 5 is the partial enlarged drawing of Fig. 4;
Fig. 6 is the TEM photo of the Graphene/ferric oxide nano composite material powder of experiment two preparations;
Fig. 7 is the XPS phenogram of the Graphene/ferric oxide nano composite material powder of experiment two preparations.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of a kind of Graphene of this embodiment/metal oxide nano composite material powder carries out according to the following steps:
One, graphite oxidation:
Graphite is added in the mixture of strong oxidizing acid and nitrate salt, be cooled to-5 ℃～0 ℃, under agitation add and contain the potassium strong oxidizer, be warming up to 0 ℃～60 ℃ then; And continue to stir 24h～48h, mixed solution, mixed solution poured in 10 ℃～50 ℃ the warm water bath; Continue reaction 40min～60min, add hot water then, make the system boiling and keep 20min～40min; Add ydrogen peroxide 50 again, be stirred to dissolving fully, wash then, be filtered to and do not have SO in the filter cake
4 2-, drying promptly gets graphite oxide, and wherein graphite is 1 with the mass ratio of strong oxidizing acid: (0.025～5); The mass ratio of graphite and nitrate salt is 1: (0.2～8); Graphite is 1 with the mass ratio that contains the potassium strong oxidizer: (0.1～4); The mass ratio of graphite and ydrogen peroxide 50 is 1: (0.125～4); Wherein, described strong oxidizing acid is the vitriol oil or perchloric acid, and the described potassium strong oxidizer that contains is potassium permanganate or potassium perchlorate, and described nitrate salt is SODIUMNITRATE, saltpetre, magnesium nitrate, nitrocalcite or aluminum nitrate;
Two, the graphite oxide mother liquor is peeled off:
The graphite oxide that step 1 is obtained is dissolved in the solvent, and is ultrasonic concussion 0.5h～12h under the condition of 100W～2000W in ultrasonic frequency, obtains graphene oxide solution; Wherein said solvent is water, ethanol, acetone, terepthaloyl moietie, THF or N, dinethylformamide;
Three, the purification of graphene oxide mother liquor:
The graphene oxide solution that step 2 is obtained is centrifugal under the condition of 3000rpm～10000rpm at the whizzer revolution, and the upper solution of centrifugal gained liquid is collected, and lyophilize promptly gets the graphene oxide powder;
Four, the preparation of Graphene/metal oxide nano composite material powder:
Graphene oxide powder that step 3 is obtained and metallic compound are dissolved in the solvent and place in the supercritical reaction still, and feeding gas to pressure is 2～7MPa, and the solvent that heats up, boosts in the reaction kettle reaches supercritical state; Behind reaction 0.5～4h; Gas in the still is emitted, after the reaction kettle cooling, liquid filtering in the still; The oven dry of gained deposition obtains Graphene/metal oxide nano composite material powder.
Wherein the ratio of the amount of substance of the graphene oxide powder that obtains of step 3 and metallic compound is 1: (0.005～10); Said metallic compound is metal itrated compound, Virahol metallic compound or metal chloric acid thing; Said gas is carbonic acid gas, argon gas, nitrogen, neon or hydrogen; Said solvent is water, ethanol, acetone, ether, chloroform, benzene, toluene, ethylbenzene, terepthaloyl moietie, USP Kosher, THF, N, dinethylformamide, sherwood oil, halohydrocarbon, methyl acetate, ETHYLE ACETATE, tetracol phenixin, aliphatic hydrocarbon, aromatic hydrocarbon, organic chloride, pyridine, quadrol or dithiocarbonic anhydride.
Embodiment two: this embodiment and embodiment one are different is to be 25～450 ℃ in temperature in the step 4, and pressure is under 7～50MPa condition, reaction 0.5～4h.Other is identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is that the itrated compound of metal described in the step 4 is iron nitrate, cupric nitrate, Titanium Nitrate, zinc nitrate or zirconium nitrate; Said Virahol metallic compound is a titanium tetraisopropylate; Said metal chloric acid thing is chloric acid gold or chloric acid platinum.Other is identical with embodiment one.
Adopt following experimental verification effect of the present invention:
Experiment one:
The preparation method of Graphene/aluminium oxide nano composite material powder carries out according to the following steps:
One, graphite oxidation:
10.0g graphite is joined in the mixture of the 200mL vitriol oil and 5g SODIUMNITRATE, be cooled to 0 ℃, under agitation add 30g potassium permanganate; Be warming up to 60 ℃ then, and, continue to stir 24h with the speed of 100r/min; Mixed solution, mixed solution poured in 50 ℃ the warm water bath, continue reaction 40min; Add 500mL, 100 ℃ of hot water then, make the system boiling and keep 20min, add 100mL ydrogen peroxide 50 (ydrogen peroxide 50 is that commercially available volume(tric)fraction is 30% ydrogen peroxide 50) again; Be stirred to dissolving fully, wash then, be filtered to and do not have SO in the filter cake
4 2-, drying promptly gets graphite oxide;
Two, the graphite oxide mother liquor is peeled off:
The graphite oxide that step 1 is obtained is dissolved in the aqueous solvent, and is ultrasonic concussion 1h under the condition of 300W at ultrasonic power, obtains graphene oxide solution;
Three, the purification of graphene oxide mother liquor:
The graphene oxide solution that step 2 is obtained is centrifugal under the condition of 5000rpm at centrifuge speed, and the upper solution of centrifugal gained liquid is collected, and lyophilize promptly gets the graphene oxide powder;
Four, the preparation of Graphene/aluminium oxide nano composite material powder:
Graphene oxide powder that the 0.5g step 3 is obtained and 0.5g aluminum nitrate are dissolved in the alcohol solvent and place in the supercritical reaction still, and feeding carbonic acid gas to pressure is 7MPa, is warming up to 300 ℃, boosts to 40MPa; Behind the reaction 2h; Gas in the reaction kettle is emitted, after the reaction kettle cooling, liquid filtering in the still; The oven dry of gained deposition obtains Graphene/aluminium oxide nano composite material powder.
From Fig. 1 and Fig. 2, can find out and realize the electroless plating of aluminum oxide on the Graphene surface.
The TEM figure of Fig. 3 Graphene can find that Graphene is transparent, the uniform lamella in surface.
From Fig. 4 and Fig. 5, can find out that aluminum oxide has been evenly distributed in the Graphene surface, the particle diameter of products therefrom is about 10nm.
Experiment two:
The preparation method of present embodiment Graphene/red oxide of iron nano composite material powder carries out according to the following steps:
One, graphite oxidation:
10.0g graphite is joined in the mixture of the 200mL vitriol oil and 5g SODIUMNITRATE, be cooled to 0 ℃, under agitation add 30g potassium permanganate, be warming up to 60 ℃ then; And with the speed of 100r/min, continue to stir 24h, mixed solution, mixed solution poured in 50 ℃ the warm water bath; Continue reaction 40min, add 500mL, 100 ℃ of hot water then, make the system boiling and keep 20min; Add the 100mL ydrogen peroxide 50 again, be stirred to dissolving fully, wash then, be filtered to and do not have SO in the filter cake
4 2-, drying promptly gets graphite oxide;
Two, the graphite oxide mother liquor is peeled off:
The graphite oxide that step 1 is obtained is dissolved in the aqueous solvent, and is ultrasonic concussion 1h under the condition of 300W at ultrasonic power, obtains graphene oxide solution;
Three, the purification of graphene oxide mother liquor:
The graphene oxide solution that step 2 is obtained is centrifugal under the condition of 5000rpm at centrifuge speed, and the upper solution of centrifugal gained liquid is collected, and lyophilize promptly gets the graphene oxide powder;
Four, the preparation of Graphene/red oxide of iron nano composite material powder:
Graphene oxide powder that the 0.5g step 3 is obtained and 0.6g iron nitrate are dissolved in the alcohol solvent and place in the supercritical reaction still, and feeding carbonic acid gas to pressure is 7MPa, is warming up to 300 ℃, boosts to 40MPa; Behind the reaction 2h; Gas in the reaction kettle is emitted, after the reaction kettle cooling, liquid filtering in the still; The oven dry of gained deposition obtains Graphene/ferric oxide nano composite material powder.
As can be seen from Figure 6 red stone has been plated in the Graphene surface uniformly, and the particle diameter of products therefrom is 30-50nm.
As can be seen from Figure 7 red stone be plated in Graphene surface.
Claims (3)
1. the preparation method of Graphene/metal oxide nano composite material powder is characterized in that the preparation method of Graphene/metal oxide nano composite material powder carries out according to the following steps:
One, graphite oxidation:
Graphite is added in the mixture of strong oxidizing acid and nitrate salt, be cooled to-5 ℃～0 ℃, under agitation add and contain the potassium strong oxidizer, be warming up to 0 ℃～60 ℃ then; And continue to stir 24h～48h, mixed solution, mixed solution poured in 10 ℃～50 ℃ the warm water bath; Continue reaction 40min～60min, add hot water then, make the system boiling and keep 20min～40min; Add ydrogen peroxide 50 again, be stirred to dissolving fully, wash then, be filtered to and do not have SO in the filter cake
42-, drying promptly gets graphite oxide, and wherein graphite is 1 with the mass ratio of strong oxidizing acid: (0.025～5); The mass ratio of graphite and nitrate salt is 1: (0.2～8); Graphite is 1 with the mass ratio that contains the potassium strong oxidizer: (0.1～4); The mass ratio of graphite and ydrogen peroxide 50 is 1: (0.125～4); Wherein, described strong oxidizing acid is the vitriol oil or perchloric acid, and the described potassium strong oxidizer that contains is potassium permanganate or potassium perchlorate, and described nitrate salt is SODIUMNITRATE, saltpetre, magnesium nitrate, nitrocalcite or aluminum nitrate;
Two, the graphite oxide mother liquor is peeled off:
The graphite oxide that step 1 is obtained is dissolved in the solvent, and is ultrasonic concussion 0.5h～12h under the condition of 100W～2000W in ultrasonic frequency, obtains graphene oxide solution; Wherein said solvent is water, ethanol, acetone, terepthaloyl moietie, THF or N, dinethylformamide;
Three, the purification of graphene oxide mother liquor:
The graphene oxide solution that step 2 is obtained is centrifugal under the condition of 3000rpm～10000rpm at the whizzer revolution, and the upper solution of centrifugal gained liquid is collected, and lyophilize promptly gets the graphene oxide powder;
Four, the preparation of Graphene/metal oxide nano composite material powder:
Graphene oxide powder that step 3 is obtained and metallic compound are dissolved in the solvent and place in the supercritical reaction still; Feeding gas to pressure is 2～7MPa, and the solvent that heats up, boosts in the reaction kettle reaches supercritical state, behind reaction 0.5～4h; Gas in the still is emitted; After the reaction kettle cooling, with liquid filtering in the still, the oven dry of gained deposition; Obtain Graphene/metal oxide nano composite material powder, wherein the ratio of the amount of substance of the graphene oxide powder that obtains of step 3 and metallic compound is 1: (0.005～10); Said metallic compound is metal itrated compound, Virahol metallic compound or metal chloric acid thing; Said gas is carbonic acid gas, argon gas, nitrogen, neon or hydrogen; Said solvent is water, ethanol, acetone, ether, chloroform, benzene, toluene, ethylbenzene, terepthaloyl moietie, USP Kosher, THF, N, dinethylformamide, sherwood oil, halohydrocarbon, methyl acetate, ETHYLE ACETATE, tetracol phenixin, aliphatic hydrocarbon, aromatic hydrocarbon, organic chloride, pyridine, quadrol or dithiocarbonic anhydride.
2. the preparation method of a kind of Graphene according to claim 1/metal oxide nano composite material powder is characterized in that in the step 4 in temperature being 25～450 ℃, and pressure is under 7～50MPa condition, reaction 0.5～4h.
3. the preparation method of a kind of Graphene according to claim 1/metal oxide nano composite material powder is characterized in that the itrated compound of metal described in the step 4 is iron nitrate, cupric nitrate, Titanium Nitrate, zinc nitrate or zirconium nitrate; Said Virahol metallic compound is a titanium tetraisopropylate; Said metal chloric acid thing is chloric acid gold or chloric acid platinum.
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