CN103435033B - Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave - Google Patents
Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave Download PDFInfo
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- CN103435033B CN103435033B CN201310350139.4A CN201310350139A CN103435033B CN 103435033 B CN103435033 B CN 103435033B CN 201310350139 A CN201310350139 A CN 201310350139A CN 103435033 B CN103435033 B CN 103435033B
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Abstract
The invention relates to a simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave. The method comprises the following steps: a rolling vibration mill is adopted to grind 150-g normal zinc powder in argon shield for 5 h and seal for standby application; 50 meshes of flake graphite and concentrated nitric acid are mixed according to the mass ratio of 1 to 3, and stirred for 10 minutes at the temperature of 30 DEG C; expandable graphite is obtained after 50 meshes of flake graphite is repeatedly cleaned and filtered, and dried at the temperature of 60 DEG C; after the expandable graphite is treated for 30s in a muffle furnace at the temperature of 900 DEG C, expanded graphite is obtained and sealed for standby application; grinded zinc powder and expandable graphite weighted in proportion are put into distilled water, absolute ethyl alcohol is added and stirred uniformly, ultrasound is performed continuously for 6 to 10 hours in ultrasonic wave, after still standing is performed for 10 minutes, suspended liquid at the upper part is extracted and centrifugally separated, and the graphene based nano-zinc oxide composite material is obtained after vacuum drying is performed at the temperature of 60 DEG C. The method provided by the invention is simple in process, economical and environmental friendly, and can be used for large scale production, the composite material prepared through the method is stable in structure, and the method is important supplement for the preparation method of nano-zinc oxide composite material.
Description
Technical field
The present invention relates to a kind of short-cut method of preparing Graphene zinc-oxide nano rod composite material in ultrasonic wave, belong to nano material preparing technical field.
Background technology
The research and development of field of nanometer technology is maked rapid progress, and new technology and novel material emerge in an endless stream, yet the basis of everything research is the reliability preparation of nano material.Nano-ZnO, as a kind of semiconductor material of broad stopband, has a wide range of applications in photochemical catalysis, piezoelectric, field of electronic devices.But be limited to from as defects such as N-type semiconductor and natural oxygen room, zinc gaps, the characteristics such as its optimized optical, electrical, magnetic, catalysis can't be applied fully.People are just considering mutually compound its larger potentiality of excavating of nano-ZnO and other materials.At present, consider that the compound report of zinc oxide and Graphene is few, and Graphene is owing to having good conductivity and to light absorpting ability, if thereby prepare a kind of novel material for photoelectric field by zinc oxide and Graphene are mutually compound, will there is larger value.But common complicated process of preparation and the energy consumption of Graphene are large, pollute highly, therefore, find the easy and easy control of a kind of process, cost is low, and make zinc oxide be easy to the preparation method compound with Graphene, the popularization and application of the C-base composte material of nano zine oxide is had great importance.
Summary of the invention
The invention discloses a kind of short-cut method of preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave, the condition harshness existing to overcome existing technology of preparing, process is complicated, and energy consumption is polluted the shortcomings such as large.The inventive method adopts nano level zinc particle and the expanded graphite grinding, and directly utilizes ultrasonic technique to prepare Graphene-zinc-oxide nano rod composite material.Process of the present invention is simple, and method is easy, and product is easily controlled.
The present invention is realized by the following technical programs:
A short-cut method of preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave first at room temperature, grinds 5h by 150g general industry zinc powder with rolling-vibrating grinding machine in ar gas environment, prepares nano level zinc particle, and sealing saves backup; By 50 order crystalline flake graphites and concentrated nitric acid in mass ratio 1:3 mix, and stir 10min at 30 ℃, 60 ℃ of dry expansible black leads that make after cleaning and filtering repeatedly, then in retort furnace 900 ℃ process 30s and obtain expanded graphite, seal standby.
Concrete preparation method is as follows:
(1) with electronic scales, weigh respectively zinc powder and the 5g expanded graphite that 0.2～1.0g ground, mix and be placed in 50～75ml distilled water, and add appropriate dehydrated alcohol, rock evenly.Wherein, zinc powder is 1～5:25 with the quality of expanded graphite than scope.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 20～40KHz, power 300W, under natural light, continuous ultrasound is processed 6～10 hours, during every 15 minutes, take out also and acutely rock 30 seconds;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) precipitation in (3) is placed in to the dry 12h of vacuum drying oven of 60 ℃ and obtains the finished product.
Graphene-zinc-oxide nano the rod composite material making is the surface that corynebacterium Zinc oxide particles is evenly combined in multilayer or single-layer graphene.
The present invention has simple to operate, process is easily controlled, economic environmental protection, low for equipment requirements, the advantage such as can be mass-produced, by changing the ratio of zinc powder and expanded graphite, control the charge capacity of nano zine oxide on Graphene, by changing ultrasonic time and ultrasonic frequency, control the structure of matrix material, Graphene-zinc oxide nano rod composite structure of preparation is stable, to the preparation method of development nano-zinc oxide composite material, is a kind of important supplementing.
Accompanying drawing explanation
Fig. 1 is embodiment 1, the X ray electron-diffraction diagram (XRD) of sample in embodiment 2 and embodiment 4;
Fig. 2 is the scanning electron microscope image (SEM) of sample in embodiment 1;
Fig. 3 is the high power transmission electron microscope micro-image (TEM) of sample in embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail, but the present embodiment can not be for limiting the present invention, and every employing similarity method of the present invention and similar variation thereof, all should list protection scope of the present invention in.
A short-cut method of preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave first at room temperature, grinds 5h by 150g general industry zinc powder with rolling-vibrating grinding machine in ar gas environment, prepares nano level zinc particle, and sealing saves backup; By 50 order crystalline flake graphites and concentrated nitric acid in mass ratio 1:3 mix, and stir 10min at 30 ℃, 60 ℃ of dry expansible black leads that make after cleaning and filtering repeatedly, then in retort furnace 900 ℃ process 30s and obtain expanded graphite, seal standby.
[embodiment 1]
(1) with electronic scales, weigh respectively nano level zinc particle and the 5g expanded graphite that 0.2g ground, mix and be placed in 50ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 20KHz, power 300W, under natural light, continuous ultrasound is processed 6 hours, during every 15 minutes, take out also and acutely rock 30 seconds;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) precipitation in (3) is placed in to the dry 12h of vacuum drying oven of 60 ℃ and obtains the finished product.
[embodiment 2]
(1) with electronic scales, weigh respectively zinc powder and the 5g expanded graphite that 0.4g ground, mix and be placed in 60ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 25KHz, power 300W, under natural light, continuous ultrasound is processed 7 hours, during every 15 minutes, take out also and acutely rock 30 seconds;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) precipitation in (3) is placed in to the dry 12h of vacuum drying oven of 60 ℃ and obtains the finished product.
[embodiment 3]
(1) with electronic scales, weigh respectively zinc powder and the 5g expanded graphite that 0.6g ground, mix and be placed in 65ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 30KHz, power 300W, under natural light, continuous ultrasound is processed 8 hours, during every 15 minutes, take out also and acutely rock 30 seconds;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) precipitation in (3) is placed in to the dry 12h of vacuum drying oven of 60 ℃ and obtains the finished product.
[embodiment 4]
(1) with electronic scales, weigh respectively zinc powder and the 5g expanded graphite that 0.8g ground, mix and be placed in 70ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 40KHz, power 300W, under natural light, continuous ultrasound is processed 9 hours, during every 15 minutes, take out also and acutely rock 30 seconds;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) precipitation in (3) is placed in to the dry 12h of vacuum drying oven of 60 ℃ and obtains the finished product.
[embodiment 5]
(1) with electronic scales, weigh respectively zinc powder and the 5g expanded graphite that 1.0g ground, mix and be placed in 75ml distilled water, and add appropriate dehydrated alcohol, rock evenly.
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 40KHz, power 300W, under natural light, continuous ultrasound is processed 10 hours, during every 15 minutes, take out also and acutely rock 30 seconds;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water.
(4) precipitation in (3) is placed in to the dry 12h of vacuum drying oven of 60 ℃ and obtains the finished product.
Accompanying drawing 1 is the X ray electron-diffraction diagram (XRD) of embodiment 1, embodiment 2 and example 4 gained samples, is not difficult to find out the diffraction peak of the ZnO phase that all can see hexagonal wurtzite structure in sample and the diffraction peak of the carbon phase that multi-layer graphene forms.Illustrate that this inventive method successfully prepared carbon-based nano zinc oxide composite.
Accompanying drawing 2 is the scanning electron microscope image (SEM) of embodiment 1 gained sample, can find out easily, and nano granular of zinc oxide is combined in the surface of multi-layer graphene equably.
Accompanying drawing 3 is the electron projection MIcrosope image (TEM) of embodiment 1 gained sample, can find out, Graphene matrix presents the structure of individual layer or multilayer, nano zine oxide is corynebacterium, be attached to the surface of Graphene matrix, although be subject to the bombardment of electron beam in observation process, material sample is still keeping stable intimate-association state, further illustrates this method and successfully prepares Graphene-zinc-oxide nano rod composite material.
Claims (2)
1. in ultrasonic wave, prepare a short-cut method for Graphene-zinc-oxide nano rod composite material, it is characterized in that:
First at room temperature with rolling-vibrating grinding machine, in ar gas environment, 150g general industry zinc powder is ground to 5h, prepare nano level zinc particle, sealing saves backup; By 50 order crystalline flake graphites and concentrated nitric acid in mass ratio 1:3 mix, and stir 10min at 30 ℃, repeatedly after cleaning and filtering 60 ℃ dryly make expansible black lead, then in retort furnace, 900 ℃ of processing obtain expanded graphite in 30 seconds, seal standby; Concrete preparation method is as follows:
(1) with electronic scales, weigh respectively nano level zinc particle and the 5g expanded graphite that 0.2～1.0g ground, mix and be placed in 50～75ml distilled water, and add dehydrated alcohol, rock evenly; Wherein, the mass ratio of nano level zinc particle and expanded graphite is 1～5:25;
(2) mixture in (1) is placed in to ultrasonic device, settings ultrasonic frequency is 20～40KHz, power 300W, under natural light, continuous ultrasound is processed 6～10 hours, during every 15 minutes, take out also and acutely rock 30 seconds;
(3) supersound process finishes rear standing 10min, gets mixing solutions upper part in clean centrifuge tube; Centrifugation goes out the precipitation of black, and repeatedly cleans with distilled water;
(4) precipitation in (3) is placed in to the dry 12h of vacuum drying oven of 60 ℃ and obtains the finished product.
2. according to a kind of short-cut method of preparing Graphene-zinc-oxide nano rod composite material in ultrasonic wave described in claims 1, it is characterized in that: the Graphene-zinc-oxide nano rod composite material making is the surface that corynebacterium Zinc oxide particles is evenly combined in multilayer or single-layer graphene.
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| CN104891485A (en) * | 2015-06-08 | 2015-09-09 | 哈尔滨工业大学（威海） | Method for preparing nano graphite sheet |
| CN105498689B (en) * | 2015-12-09 | 2018-03-06 | 唐山冀东石墨烯科技发展有限公司 | Graphene-supported nano-ZnO/Ag composites and preparation method thereof |
| CN106517167B (en) * | 2016-10-25 | 2018-05-04 | 成都新柯力化工科技有限公司 | A kind of method and graphene microchip that graphene microchip is prepared by setting rotary screw in vibromill |
| CN111040324A (en) * | 2019-12-31 | 2020-04-21 | 深圳第三代半导体研究院 | Composite heat dissipation material for semiconductor and preparation method thereof |
| CN113800476B (en) * | 2021-08-30 | 2023-09-12 | 宁波工程学院 | Ultrasonic preparation method of nano metal oxide |
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| KR20130048056A (en) * | 2011-11-01 | 2013-05-09 | 한국과학기술연구원 | Tunable light emitting diode using graphene conjugated metal oxide semiconductor-graphene core-shell quantum dots and its fabrication process thereof |
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| CN102464315A (en) * | 2010-11-18 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
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