CN102580715B - Method for preparing zinc oxide/graphene composite from expanded graphite by stripping - Google Patents
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Abstract
The invention discloses a method for preparing a zinc oxide/graphene composite from expanded graphite by stripping, relating to a preparation method of the zinc oxide/graphene composite and aiming to solve the problem that the conventional zinc oxide nanometer material has relatively low photocatalytic activity. The method disclosed by the invention comprises the steps of: 1, pre-treating the expanded graphite; 2, dissolving a surfactant and a zinc source in a solvent, then adding the pre-treated expanded graphite and injecting the solution in the expanded graphite layer by adopting a vacuum auxiliary mean; 3, performing heat treatment on the solvent; and 4, washing, centrifuging and drying to obtain the needed zinc oxide/graphene composite with high photocatalytic activity. Compared withthe conventional photocatalytic activity, the photocatalytic activity of the zinc oxide/graphene composite of the invention is improved by 30%; and the method for preparing the zinc oxide/graphene composite from expanded graphite by stripping, disclosed by the invention, has the advantages of simple technology, uniform distribution of the zinc oxide, low pollution to environment, low cost and easy implementation of commercialization. The method disclosed by the invention is applied to the preparation field of the zinc oxide nanometer material.
Description
Technical field
The present invention relates to a kind of zinc oxide/graphene complex preparation method.
Background technology
Zinc oxide is as a kind of important semi-conducting material, because its stable performance, avirulence, cheap are widely used at each pollutant of degraded and antibacterial field.Yet the application of zinc oxide also faces worries bottleneck problem to be solved: the photo-generated carrier recombination probability of zinc oxide self is higher; Utilization rate to sunshine is lower.In order to address these problems, the researcher attempts the catalytic efficiency that the whole bag of tricks attempts to improve zinc oxide.For example: people utilize various material with carbon elements (activated carbon, CNT) and zinc oxide to be compounded to form zinc oxide/carbon complex.Material with carbon element has excellent conducting performance and to the strong absorption of light, can promote material to the degraded of organic pollution.
Graphene is a kind of two-dimentional graphite material of novel monatomic thickness.Graphene has excellent crystallinity and unique electronics, thermodynamics, mechanical property, can be applied in many advanced materials and the device, as thin-film material, energy storage material, liquid crystal material, mechanical resonator etc., therefore, more and more scholars participates in the research of the synthetic and performance of graphene composite material.Graphene-based composite shows excellent photocatalysis activity, owing to the material excellent conducting performance with to the strong absorption of light.Obtaining the graphene-based end by chemistry or additive method reduction-oxidation graphite is the method for using usually; because graphite oxide is in oxidizing process; the six-membered ring structure of graphite can be by partial destruction; cause the defective that can't remedy; these defectives also can be inherited by Graphene, and then influence the quality of Graphene, and; the construction method step of graphene-based composite is more, is unfavorable for the scale operation.
Existing sol-gel or hydrothermal method prepare zinc oxide and have the easy photoetch of photocatalytic process, the problem that photocatalytic activity is lower.It is the Graphene source that existing zinc oxide/graphene complex adopts graphite oxide more, and photocatalytic activity is 30%～50%.
Summary of the invention
The objective of the invention is to have the lower problem of photocatalytic activity in order to solve existing nano zinc oxide material, and a kind of method for preparing zinc oxide/graphene complex of being peeled off by expanded graphite is provided.
A kind of method for preparing zinc oxide/graphene complex of being peeled off by expanded graphite of the present invention is finished by following step: one, take by weighing 1～3 part expanded graphite, 0.01～0.1 part surfactant, 0.5～2 part zinc source and 20～50 parts solvent by ratio of weight and the number of copies; Two, expanded graphite preliminary treatment: the expanded graphite that step 1 is taken by weighing is put into high temperature furnace earlier, continues to feed protective gas, is warming up to 800 ℃～1200 ℃ then, and heat treatment 1min～24h is cooled to room temperature again, finishes preliminary treatment; Three, be that the ratio of 1～5g: 100mL is mixed with the pretreated expanded graphite of step 2 and acid solution in mass volume ratio, under 110 ℃～140 ℃ conditions, 6～14h refluxes, collecting precipitation, being precipitated to pH with deionized water or absolute ethanol washing again is 7.0, then vacuum drying 1～48h under 40 ℃～100 ℃ temperature; Four, the surfactant that step 1 is taken by weighing and zinc source are dissolved in the solvent that step 1 takes by weighing, and after mixing, namely get mixed solution; Five, the expanded graphite after step 3 is handled is put into the vacuum filtration device, be 0 in vacuum～-the 0.05MPa condition under, the mixed solution that implantation step four obtains in the vacuum filtration device at 100 ℃～220 ℃ following thermal response 1～24h, namely gets product then; Six, the product that step 5 is obtained with the centrifugal solid formation that obtains vacuum drying 1～48h under 40 ℃～100 ℃ temperature, namely gets highlight catalytic active zinc oxide/graphene complex then with deionized water or absolute ethyl alcohol centrifuge washing 1～5 time; Wherein, the shield gas flow rate in the step 2 is 30～2000mL/min; The described vacuum drying vacuum of step 3 and step 6 is 0～-0.05MPa; The mixed solution that adds in the step 5 is 20～40mL: 0.1g with the volume mass of expanded graphite ratio.
Effect of the present invention is: it is the source of Graphene that the present invention adopts expanded graphite, its wide material sources and inexpensive, the photocatalytic activity of the zinc oxide/graphene complex of method preparation of the present invention is compared with existing zinc oxide/graphene complex and has been improved 30%, greatly reduces the cost of synthetic two-dimentional graphene nano material with carbon element on the other hand.The existence of Graphene can obviously improve stability and the photocatalytic activity of zinc oxide; And it is less to prepare the Graphene defective by expanded graphite, the graphite that the obvious excellent oxidation graphite reduction of electric conductivity obtains.Therefore, zinc oxide/graphene composite material of obtaining by the expanded graphite intercalation of the present invention has stable, excellent photocatalysis performance.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the zinc oxide/graphene nano composite of the specific embodiment 12 preparations;
Fig. 2 is the transmission electron microscope photo of the zinc oxide/graphene nano composite of the specific embodiment 12 preparations;
Fig. 3 is the zinc oxide/graphene nano composite of the specific embodiment 12 preparations and the catalytic effect evaluation of Degussa P25 degradable organic pollutant; Wherein
Be the absorbance curve of control group,
Absorbance curve for test group.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: a kind of method for preparing zinc oxide/graphene complex of being peeled off by expanded graphite of present embodiment is finished by following step: one, take by weighing 1～3 part expanded graphite, 0.01～0.1 part surfactant, 0.5～2 part zinc source and 20～50 parts solvent by ratio of weight and the number of copies; Two, expanded graphite preliminary treatment: the expanded graphite that step 1 is taken by weighing is put into high temperature furnace earlier, continues to feed protective gas, is warming up to 800 ℃～1200 ℃ then, and heat treatment 1min～24h is cooled to room temperature again, finishes preliminary treatment; Three, be that the ratio of 1～5g: 100mL is mixed with the pretreated expanded graphite of step 2 and acid solution in mass volume ratio, under 110 ℃～140 ℃ conditions, 6～14h refluxes, collecting precipitation, being precipitated to pH with deionized water or absolute ethanol washing again is 7.0, then vacuum drying 1～48h under 40 ℃～100 ℃ temperature; Four, the surfactant that step 1 is taken by weighing and zinc source are dissolved in the solvent that step 1 takes by weighing, and after mixing, namely get mixed solution; Five, the expanded graphite after step 3 is handled is put into the vacuum filtration device, be 0 in vacuum～-the 0.05MPa condition under, the mixed solution that implantation step four obtains in the vacuum filtration device at 100 ℃～220 ℃ following thermal response 1～24h, namely gets product then; Six, the product that step 5 is obtained with the centrifugal solid formation that obtains vacuum drying 1～48h under 40 ℃～100 ℃ temperature, namely gets highlight catalytic active zinc oxide/graphene complex then with deionized water or absolute ethyl alcohol centrifuge washing 1～5 time; Wherein, the shield gas flow rate in the step 2 is 30～2000mL/min; The described vacuum drying vacuum of step 3 and step 6 is 0～-0.05MPa; The mixed solution that adds in the step 5 is 20～40mL: 0.1g with the volume mass of expanded graphite ratio.
It is the source of Graphene that present embodiment adopts expanded graphite, its wide material sources and inexpensive, the photocatalytic activity of the zinc oxide/graphene complex of the method preparation of present embodiment is compared with existing zinc oxide/graphene complex and has been improved 30%, greatly reduces the cost of synthetic two-dimentional graphene nano material with carbon element on the other hand.The existence of Graphene can obviously improve stability and the photocatalytic activity of zinc oxide; And it is less to prepare the Graphene defective by expanded graphite, the graphite that the obvious excellent oxidation graphite reduction of electric conductivity obtains.Therefore, zinc oxide/graphene composite material of obtaining by the expanded graphite intercalation of present embodiment has stable, excellent photocatalysis performance.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: the order number of the described expanded graphite of step 1 is 100,140,200,250,300,350,500,1000,5000 or 8000.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one to two were different is: the described surfactant of step 1 is softex kw; cetyl dimethyl benzyl ammonium bromide; hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride; lauryl alcohol polyoxyethylene ether dimethyl methyl ammonium chloride; OPEO base dimethyl decyl ammonium bromide; OPEO base dimethyl decyl ammonium chloride; hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride; lauryl sodium sulfate; dodecyl sodium sulfate; the cetyl benzene sulfonic acid sodium salt; sodium stearyl sulfate; the N-oleoyl amino acid sodium that contracts more; sodium sulfate of polyethenoxy ether of fatty alcohol; AEO sulfosuccinic acid monoesters disodium; EO20PO70EO20 (P123); EO106PO70EO106 (F127); lauryl dimethyl amine oxide; the cocounut oil alkyl dimethyl amine oxide; DDAO; dodecyl dihydroxy ethyl amine oxide; myristyl dihydroxy ethyl amine oxide; cetyl dihydroxy ethyl amine oxide; octadecyl dimethyl amine oxide; octadecyl dihydroxy ethyl amine oxide; PVP; the propanediol polyoxypropylene APEO; structure alcohol polyoxyethylene poly-oxygen propylene aether; polyurethane polyureas oxypropylene polyethenoxy ether; polyethylene glycol monooleate; the octadecyl ethylene urea; coconut oil is carbinol also; hexadecanol; oleyl alcohol; cetanol; nonyl phenol; octyl phenol; octyl cresol; glycerine; pentaerythrite; sorbierite; monoethanolamine; isopropanolamine; sucrose; laurate; coco-nut oil fatty acid; tetradecylic acid; palmitic acid; oleic acid or stearic acid.Other step and parameter are identical with the specific embodiment one to two.
The specific embodiment four: what present embodiment was different with one of specific embodiment one to three is: the described zinc of step 1 source is zinc chloride, zinc sulfate, zinc nitrate, zinc uranyl acetate, zinc acetate, zinc potassium cyanide, zinc fluoride, zinc fluosilicate, hydrogen zinc hydride, zinc oxide, zinc chloride, zinc cyanide, zinc bromide, zinc sulphide, zinc thiocyanide, zinc stearate, zinc iodide, zinc phosphide, zinc dihydrogen phosphate, trbasic zinc phosphate, zinc peroxide, zinc dithionite or zinc molybdate.Other step and parameter are identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different with one of specific embodiment one to four is: the described solvent of step 1 is that deionized water, mass percentage content are 98% methyl alcohol, absolute ethyl alcohol or acetone.Other step and parameter are identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different with one of specific embodiment one to five is: the described protective gas of step 2 be nitrogen, argon gas, helium, carbon monoxide, hydrogen or wherein several by any than mixing.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: what present embodiment was different with one of specific embodiment one to six is: the described reactor of step 2 is high temperature process furnances or Muffle furnace.Other step and parameter are identical with one of specific embodiment one to six.
The specific embodiment eight: what present embodiment was different with one of specific embodiment one to seven is: step 2 is described to be warming up to 900 ℃～1000 ℃.Other step and parameter are identical with one of specific embodiment one to seven.
The specific embodiment nine: what present embodiment was different with one of specific embodiment one to eight is: the described acid solution of step 3 is nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid or oleum.Other step and parameter are identical with one of specific embodiment one to eight.
The specific embodiment ten: what present embodiment was different with one of specific embodiment one to nine is: step 3 described under 60 ℃～80 ℃ temperature vacuum drying 1～48h.Other step and parameter are identical with one of specific embodiment one to nine.
The specific embodiment 11: what present embodiment was different with one of specific embodiment one to ten is: the described centrifugal condition of step 6 is: centrifugal rotational speed 3000～12000rpm/min, centrifugation time are 1～30min.Other step and parameter are identical with one of specific embodiment one to ten.
The specific embodiment 12: a kind of method for preparing zinc oxide/graphene complex of being peeled off by expanded graphite of present embodiment is finished by following step: one, take by weighing the 140 order expanded graphites of 2g, the softex kw of 0.05g, the zinc oxide of 1g and the deionized water of 30g by ratio of weight and the number of copies; Two, expanded graphite preliminary treatment; The 140 order expanded graphites that step 1 is taken by weighing are put into high temperature process furnances earlier, continue to feed nitrogen, are warming up to 1000 ℃ then, and heat treatment 5min is cooled to room temperature again; Three, the 140 order expanded graphites of step 2 heat cooling back 2g and the oleum of 100mL are mixed, under 120 ℃ of conditions, backflow 14h, collecting precipitation, spending deionised water again, to be precipitated to pH be 7.0, then 70 ℃ temperature, vacuum is-condition of 0.05MPa under, vacuum drying 24h; Four, the softex kw that step 1 is taken by weighing and zinc oxide are dissolved in the deionized water that step 1 takes by weighing, and after mixing, namely get mixed solution; Five, the 140 order expanded graphites that step 1 taken by weighing 0.1g are put into the vacuum filtration device, in vacuum be-the 0.05MPa condition under, inject the mixed solution that the 40mL step 4 obtains in the vacuum filtration device, at 180 ℃ of following thermal response 24h, namely get product then; Six, the product that step 5 obtained with absolute ethyl alcohol under the 12000rpm/min speed conditions with filtrate centrifuge washing 15min, collecting precipitation, then 60 ℃ temperature, vacuum is-condition of 0.05MPa under dry 48h, namely get zinc oxide/graphene complex; Wherein, the shield gas flow rate in the step 2 is 1000mL/min.
The structure of the zinc oxide in the present embodiment is the one-dimensional rod-like structure.
Adopt the Japanese D/max-IIIB of company type X-ray diffractometer of science to observe the crystalline phase of zinc oxide/graphene complex that present embodiment makes and form as shown in Figure 1, as can be seen from the figure Zinc oxide nanoparticle degree of crystallinity is comparatively complete.
Pattern and the structure of zinc oxide/graphene complex that the employing JEOL JEM-2100 of company of NEC transmission electron microscope observing present embodiment makes, as shown in Figure 2, as shown in Figure 2, the zinc oxide nano rod that present embodiment makes successfully is inserted in the middle of the Graphene lamella, forms zinc oxide/graphene complex.
Zinc oxide/graphene complex that present embodiment is made carries out application test:
Experimental condition: test group: as photocatalysis target degradation product, put into photo catalysis reactor with methylene blue, adopt the ultraviolet lamp tube of 40W as ultraviolet source, the ultraviolet source wavelength is 365nm, and photo catalysis reactor is positioned over the place apart from light source 15cm; Control group: be photocatalysis target degradation product with commercial Degussa P25 powder, other conditions are consistent with test group;
Concrete test procedure is as follows:
At room temperature, the catalyst mix of the aqueous solution of methylene blue of the 10mg/L of 50mL and 0.1g is even, in dark surrounds, leave standstill, after aqueous solution of methylene blue reaches the adsorption-desorption balance, placing the illumination of photo catalysis reactor medium ultraviolet to penetrate down reacts, every the 10min sampling and testing, with the light degradation experiment of the Japanese SHIMADZU UV-2550 of company ultraviolet-visible spectrophotometric determination methylene blue (MB), observe it in the variation of λ=664nm place absorbance.
Simultaneously, control group adopts the condition identical with test group to carry out testing experiment.
The result as shown in Figure 3, as shown in Figure 3, zinc oxide/graphene complex that present embodiment makes is degradation of methylene blue effectively, photocatalytic activity is 65%.
Claims (10)
1. peel off the method for preparing zinc oxide/graphene complex by expanded graphite for one kind, it is characterized in that the method that is prepared zinc oxide/graphene complex by expanded graphite finished by following step: one, take by weighing 1～3 part expanded graphite, 0.01～0.1 part surfactant, 0.5～2 part zinc source and 20～50 parts solvent by ratio of weight and the number of copies; Two, expanded graphite preliminary treatment: the expanded graphite that step 1 is taken by weighing is put into high temperature furnace earlier, continues to feed protective gas, is warming up to 800 ℃～1200 ℃ then, and heat treatment 1min～24h is cooled to room temperature again, finishes preliminary treatment; Three, be that the ratio of 1～5g:100mL is mixed with the pretreated expanded graphite of step 2 and acid solution in mass volume ratio, under 110 ℃～140 ℃ conditions, 6～14h refluxes, collecting precipitation, being precipitated to pH with deionized water or absolute ethanol washing again is 7.0, then vacuum drying 1～48h under 40 ℃～100 ℃ temperature; Four, the surfactant that step 1 is taken by weighing and zinc source are dissolved in the solvent that step 1 takes by weighing, and after mixing, namely get mixed solution; Five, the expanded graphite after step 3 is handled is put into the vacuum filtration device, be 0 in vacuum～-the 0.05MPa condition under, the mixed solution that implantation step four obtains in the vacuum filtration device at 100 ℃～220 ℃ following thermal response 1～24h, namely gets product then; Six, the product that step 5 is obtained with the centrifugal solid formation that obtains vacuum drying 1～48h under 40 ℃～100 ℃ temperature, namely gets highlight catalytic active zinc oxide/graphene complex then with deionized water or absolute ethyl alcohol centrifuge washing 1～5 time; Wherein, the shield gas flow rate in the step 2 is 30～2000mL/min; The described vacuum drying vacuum of step 3 and step 6 is 0～-0.05MPa; The mixed solution that adds in the step 5 is 20～40mL:0.1g with the volume mass of expanded graphite ratio.
2. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, the order number that it is characterized in that the described expanded graphite of step 1 is 100,140,200,250,300,350,500,1000,5000 or 8000.
3. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that the described surfactant of step 1 is softex kw; lauryl alcohol polyoxyethylene ether dimethyl methyl ammonium chloride; OPEO base dimethyl decyl ammonium bromide; OPEO base dimethyl decyl ammonium chloride; hexadecanol polyoxyethylene ether dimethyl-octa alkyl ammomium chloride; lauryl sodium sulfate; dodecyl sodium sulfate; the cetyl benzene sulfonic acid sodium salt; sodium stearyl sulfate; the N-oleoyl amino acid sodium that contracts more; sodium sulfate of polyethenoxy ether of fatty alcohol; AEO sulfosuccinic acid monoesters disodium; EO20PO70EO20; EO106PO70EO106; the cocounut oil alkyl dimethyl amine oxide; DDAO; dodecyl dihydroxy ethyl amine oxide; myristyl dihydroxy ethyl amine oxide; cetyl dihydroxy ethyl amine oxide; octadecyl dimethyl amine oxide; octadecyl dihydroxy ethyl amine oxide; PVP; the propanediol polyoxypropylene APEO; polyethylene glycol monooleate; the octadecyl ethylene urea; coconut oil is carbinol also; oleyl alcohol; cetanol; nonyl phenol; octyl phenol; octyl cresol; glycerine; pentaerythrite; sorbierite; monoethanolamine; isopropanolamine; sucrose; laurate; coco-nut oil fatty acid; tetradecylic acid; palmitic acid; oleic acid or stearic acid.
4. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that the described zinc of step 1 source is zinc chloride, zinc sulfate, zinc nitrate, zinc uranyl acetate, zinc acetate, zinc potassium cyanide, zinc fluoride, zinc fluosilicate, zinc oxide, zinc cyanide, zinc bromide, zinc sulphide, zinc thiocyanide, zinc stearate, zinc iodide, zinc phosphide, zinc dihydrogen phosphate, trbasic zinc phosphate, zinc peroxide, zinc dithionite or zinc molybdate.
5. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that the described solvent of step 1 is that deionized water, mass percentage content are 98% methyl alcohol, absolute ethyl alcohol or acetone.
6. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that the described protective gas of step 2 be a kind of in nitrogen, argon gas, helium, carbon monoxide and the hydrogen or wherein several by any than mixing.
7. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that the described high temperature furnace of step 2 is high temperature process furnances or Muffle furnace.
8. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that step 2 is described to be warming up to 900 ℃～1000 ℃.
9. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that the described acid solution of step 3 is nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid or oleum.
10. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex by expanded graphite, it is characterized in that step 3 described under 60 ℃～80 ℃ temperature vacuum drying 1～48h.
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| CN101696002A (en) * | 2009-10-14 | 2010-04-21 | 苏州纳米技术与纳米仿生研究所 | Graphene and semiconductor nano particle compound system and synthesizing method thereof |
| CN102266764A (en) * | 2011-06-17 | 2011-12-07 | 东华大学 | Expanded graphite/zinc oxide composite photocatalyst and preparation method thereof |
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