CN102580715A - 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 with the 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 the degraded of material to 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; Like 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 through chemistry or additive method reduction-oxidation graphite is usually the method for utilization, 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, and a kind of method for preparing zinc oxide/graphene complex of being peeled off by expanded graphite is provided in order to solve existing nano zinc oxide material.
A kind of method for preparing zinc oxide/graphene complex of being peeled off by expanded graphite of the present invention is accomplished 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 earlier step 1 is taken by weighing is put into high temperature furnace, continues to feed protective gas, is warming up to 800 ℃～1200 ℃ then, and heat treatment 1min～24h is cooled to room temperature again, accomplishes preliminary treatment; Three, by mass volume ratio the mixed of 1～5g: 100mL with pretreated expanded graphite of step 2 and acid solution; Under 110 ℃～140 ℃ conditions; 6～14h refluxes; Collecting precipitation, using deionized water or absolute ethanol washing to be precipitated to pH again is 7.0, then vacuum drying 1～48h under 40 ℃～100 ℃ temperature; Four, 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, promptly 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, promptly 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, promptly 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 the 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 through 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
is the absorbance curve of control group, and
is the absorbance curve of test group.
The specific embodiment
Technical scheme of the present invention is not limited to the following cited specific embodiment, also comprises the combination in any 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 this embodiment is accomplished 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 earlier step 1 is taken by weighing is put into high temperature furnace, continues to feed protective gas, is warming up to 800 ℃～1200 ℃ then, and heat treatment 1min～24h is cooled to room temperature again, accomplishes preliminary treatment; Three, by mass volume ratio the mixed of 1～5g: 100mL with pretreated expanded graphite of step 2 and acid solution; Under 110 ℃～140 ℃ conditions; 6～14h refluxes; Collecting precipitation, using deionized water or absolute ethanol washing to be precipitated to pH again is 7.0, then vacuum drying 1～48h under 40 ℃～100 ℃ temperature; Four, 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, promptly 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, promptly 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, promptly 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 this embodiment adopts expanded graphite; Its wide material sources and inexpensive; The photocatalytic activity of the zinc oxide/graphene complex of the method preparation of this 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 the 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 through the expanded graphite intercalation of this embodiment has stable, excellent photocatalysis performance.
The specific embodiment two: what this 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 this embodiment and the specific embodiment one to two were different is: the said surfactant of step 1 is a 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 this 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 this 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 this 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 kinds by any than mixing.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: what this 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 this 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 this 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 this 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 this 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 this embodiment is accomplished 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 earlier step 1 taken by weighing are put into high temperature process furnances, 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, 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, promptly 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, in the vacuum filtration device, inject the mixed solution that the 40mL step 4 obtains, at 180 ℃ of following thermal response 24h, promptly get product then; Six, the product that step 5 is obtained is with the absolute ethyl alcohol centrifuge washing 15min that under the 12000rpm/min speed conditions, will filtrate, collecting precipitation, then 60 ℃ temperature, vacuum is-condition of 0.05MPa under dry 48h, promptly 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 this 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 this embodiment makes and form as shown in Figure 1ly, as can be seen from the figure Zinc oxide nanoparticle degree of crystallinity is comparatively complete.
The pattern and the structure of zinc oxide/graphene complex that this embodiment of the employing JEOL JEM-2100 of company of NEC transmission electron microscope observing makes; As shown in Figure 2; Can know by Fig. 2; The zinc oxide nano rod that this embodiment makes successfully is inserted in the middle of the Graphene lamella, forms zinc oxide/graphene complex.
Zinc oxide/graphene complex that this embodiment is made carries out application test:
Experimental condition: test group: as photocatalysis target degradation product, put into photo catalysis reactor with methylene blue, the ultraviolet lamp tube that adopts 40W is as ultraviolet source, and the ultraviolet source wavelength is 365nm, and photo catalysis reactor is positioned over the place apart from light source 15cm; Control group: with commercial Degussa P25 powder is photocatalysis target degradation product, and other conditions are consistent with test group;
Concrete test procedure is following:
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 at a distance from 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 its variation in λ=664nm place absorbance.
Simultaneously, control group adopts the condition identical with test group to carry out testing experiment.
The result is as shown in Figure 3, can be known by Fig. 3, and zinc oxide/graphene complex that this embodiment makes is degradation of methylene blue effectively, and 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 accomplished 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 earlier step 1 is taken by weighing is put into high temperature furnace, continues to feed protective gas, is warming up to 800 ℃～1200 ℃ then, and heat treatment 1min～24h is cooled to room temperature again, accomplishes preliminary treatment; Three, by mass volume ratio the mixed of 1～5g: 100mL with pretreated expanded graphite of step 2 and acid solution; Under 110 ℃～140 ℃ conditions; 6～14h refluxes; Collecting precipitation, using deionized water or absolute ethanol washing to be precipitated to pH again is 7.0, then vacuum drying 1～48h under 40 ℃～100 ℃ temperature; Four, 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, promptly 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, promptly 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, promptly 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, it is characterized in that the said 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, cetyl benzene sulfonic acid sodium salt, sodium stearyl sulfate, N-oleoyl contract amino acid sodium, sodium sulfate of polyethenoxy ether of fatty alcohol, AEO sulfosuccinic acid monoesters disodium, EO20PO70EO20, EO106PO70EO106, lauryl dimethyl amine oxide, 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, propanediol polyoxypropylene APEO, structure alcohol polyoxyethylene poly-oxygen propylene aether, polyurethane polyureas oxypropylene polyethenoxy ether, polyethylene glycol monooleate, octadecyl ethylene urea, coconut oil also carbinol, 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 more by expanded graphite.
4. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex, 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, 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 by expanded graphite.
5. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex, 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 by expanded graphite.
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 kinds by any than mixing.
7. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex, it is characterized in that the described high temperature furnace of step 2 is high temperature process furnances or Muffle furnace by expanded graphite.
8. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex, it is characterized in that step 2 is described to be warming up to 900 ℃～1000 ℃ by expanded graphite.
9. according to claim 1ly a kind ofly peel off the method for preparing zinc oxide/graphene complex, 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 by expanded graphite.
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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| CN105819428A (en) * | 2014-12-04 | 2016-08-03 | 财团法人工业技术研究院 | Method for graphite delamination |
| CN104475076A (en) * | 2014-12-11 | 2015-04-01 | 上海烟草集团有限责任公司 | Preparation method of graphene-nano zinc oxide composite photocatalytical material for adsorbing and degrading nitrosamine |
| CN104525223A (en) * | 2015-01-05 | 2015-04-22 | 上海纳旭实业有限公司 | Method for preparing high-homodisperse zinc sulfide graphene composite material |
| CN104671228A (en) * | 2015-01-20 | 2015-06-03 | 宁波卡尔新材料科技有限公司 | Method for synthesizing Pt-loaded carbon nanoparticles through microwave irradiation |
| CN104671228B (en) * | 2015-01-20 | 2016-12-07 | 宁波卡尔新材料科技有限公司 | The method of the nano carbon particle of microwave irradiation synthesis supporting Pt |
| CN104667902A (en) * | 2015-03-02 | 2015-06-03 | 哈尔滨理工大学 | Method for preparing ZnO-expanded graphite composite with sol method |
| CN105244502A (en) * | 2015-08-28 | 2016-01-13 | 山东大学 | Method for preparing anode material of lithium ion battery by high-temperature reaction of expansible graphite and zinc powder |
| CN105244502B (en) * | 2015-08-28 | 2017-10-17 | 山东大学 | A kind of method that lithium ion battery negative material is prepared by expansible graphite and zinc powder pyroreaction |
| CN108187653A (en) * | 2018-01-11 | 2018-06-22 | 绍兴文理学院 | Preparation method of graphene-based photocatalytic material |
| CN109046386A (en) * | 2018-08-24 | 2018-12-21 | 秦天 | Manganese doped zinc sulphide/redox graphene composite material and preparation method and application |
| CN109712756A (en) * | 2018-12-28 | 2019-05-03 | 黑龙江科技大学 | A kind of electric conductivity is decided by the preparation method of the conducing composite material of applied electric field |
| CN111905708A (en) * | 2020-08-28 | 2020-11-10 | 阜阳师范大学 | Preparation method and application of solid zinc oxide microspheres |
| CN114054011A (en) * | 2021-11-08 | 2022-02-18 | 惠州市银嘉环保科技有限公司 | Six-component columnar zinc oxide graphene piezoelectric photocatalytic material and preparation method and application thereof |
| CN114054011B (en) * | 2021-11-08 | 2024-01-02 | 惠州市银嘉环保科技有限公司 | Six-component columnar zinc oxide graphene piezoelectric photocatalytic material and preparation method and application thereof |
| CN114242985A (en) * | 2021-12-20 | 2022-03-25 | 南京大学 | Rice hull-based graphene-like loaded zinc silicate composite material block and preparation method and application thereof |
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