CN108314029A - Hollow bowl-shape graphene oxide micro motor and preparation method thereof - Google Patents
Hollow bowl-shape graphene oxide micro motor and preparation method thereof Download PDFInfo
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- CN108314029A CN108314029A CN201810047672.6A CN201810047672A CN108314029A CN 108314029 A CN108314029 A CN 108314029A CN 201810047672 A CN201810047672 A CN 201810047672A CN 108314029 A CN108314029 A CN 108314029A
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Abstract
The invention discloses a kind of hollow bowl-shape graphene oxide micro motors and preparation method thereof, and hollow bowl-shape graphene oxide micro motor is the asymmetric three-dimensional hollow bowl structure of 30 μm ~ 1.5 mm of diameter.At room temperature, shearing force is provided just with 50 ~ 2800 r/min of electric blender, the capillarity generated in conjunction with drying at room temperature, without freeze-drying, soft template or sacrifice hard template, it is easy to operate, it is of low cost, size is controllable, it is applicable to large-scale industrial production.Prepared hollow bowl-shape graphene oxide micro motor is put into the hydrogenperoxide steam generator that mass percent concentration is 5%, oxygen is generated by catalyzing hydrogen peroxide, self-propelled campaign is realized using oxygen bubble as power, and realize that the simple recycling of micro motor and magnetic field control using hollow bowl-shape graphene oxide micro motor magnetic properties, to achieve the purpose that the positioning operation in the solution containing hydrogen peroxide.
Description
Technical field
The present invention relates to a kind of artificial micro motor and preparation method thereof, providing a kind of easy to operate, of low cost, size can
Control and the hollow bowl-shape graphene oxide micro motor and preparation method thereof suitable for large-scale industrial production.
Background technology
Artificial micro motor is a kind of can to convert chemical energy, luminous energy, the electric energy etc. in environment to having for motion energy
From the micro-nano functional material of drive characteristic, for stock size in nanoscale to micron order, Typical Representative is Janus particles and pipe
Decline motor（Angew. Chem. Int. Ed. 2014, 53, 2）.Several typical building methods are had been developed that at present,
Such as electrochemical deposition（Small 2015, 11, 499）, physical vapour deposition (PVD)（ACS Nano 2012,6,8432）With film roll song
Technology（Chem. Soc. Rev. 2011, 40, 2109）Deng.But existing building method is related to more complex step mostly,
The production equipment for needing some expensive is difficult to realize large-scale industrial production.
Graphene oxide（Graphene oxide, GO）It is the important presoma for preparing graphene, surface exists a large amount of
sp2The functional groups such as the carbon structure unit and hydroxyl (- OH) of hydridization, alkoxy (C-O-C), carboxyl (- COOH) and carbonyl (C=O).
GO has so excellent structural property, be widely used to three-dimensional grapheme and graphene oxide macroscopic material construct and
The fields such as catalysis, the energy, environment show remarkable contribution.It is reported according to existing literature, prepares graphene macroscopic material at present
Frequently with template CVD method (Small 2011,7,3163;Sci. Rep. 2013,3,2125) and hydro-thermal method (ACS
Nano, 2010, 4, 4324; Adv. Mater. 2012, 24, 5124; Sci. Rep. 2013, 3, 2975;
Adv. Mater. 2014, 26, 4789; J. Phys. Chem. C 2015, 119, 24373).Wherein, template CVD method
It is generally necessary to which sacrificing template obtains porous three-dimensional structure, experimental implementation is complicated, and increases operating cost；Hydro-thermal method is using in advance
The graphene hydrogel first prepared removes the solvent in hydrogel in conjunction with Freeze Drying Technique or air drying technology
Obtain the graphene macroform with three-dimensional net structure, however often with the reduction of GO during hydro-thermal method self assembly,
Surface oxygen functional group is caused to reduce (Nanoscale 2012,4,5549).It is bent other than above two self-assembling method
Liang Ti seminars et al. are coupler using aniline, and three-dimensional GO materials (Adv. Mater. are prepared using room temperature self-assembly method
2016,28,10287), gained macrostructure structure is closely knit and diameter is up to several centimeters, symmetrical structure and larger close
Degree, limits its practical application as micro motor.
Soft template is generally used at present（Emulsion method）Or hard template method prepares hollow ball or hollow bowl-shape carbon-based material.Such as
Zheng Yuan etc. uses Pickering emulsion methods to prepare size as 25 μm or so of polyaniline-graphite alkene tiny balloon, and this method needs
To the auxiliary of the advance sulfonation modifying of graphene and microemulsion（Chemical journal, 2017,75,391）.Ding Shujiang etc. uses polystyrene
Microballoon is template, prepares the hollow bowl-shape carbon based metal oxide composite of various compositions（Number of patent application
CN201410406726.5）.
Invention content
The present invention is provided a kind of easy to operate, at low cost to solve the above-mentioned technical problem present in the prior art
Honest and clean, size is controllable and the hollow bowl-shape graphene oxide micro motor and preparation method thereof suitable for large-scale industrial production.
Technical solution of the invention is：A kind of hollow bowl-shape graphene oxide micro motor, it is characterized in that asymmetry three
Hollow bowl structure is tieed up, average diameter is 30 μm ~ 1.5 mm.
A kind of preparation method of above-mentioned hollow bowl-shape graphene oxide micro motor, carries out in accordance with the following steps：
A. graphene oxide is prepared, prepared by the method that the prior art can be used；
B. at room temperature, by prepared graphene oxide ultrasonic disperse to water, the suspension of 2 ~ 10 mg/mL is made；So
MnFe is added in backward suspension2O4Powder is ultrasonically formed uniform suspension, the suspension and MnFe2O4The ratio of powder is
10 mL：5~80 mg；Aniline solution is added dropwise again, addition is that 200 mL of μ L ~ 5 are added in every 10 mL suspensions；Finally use
The electric mixer that rotating speed is 50 ~ 2800 r/min stirs 4 ~ 36h, and mixed system becomes flocculent deposit by uniform suspension, from
Heart recycling precipitation, gained are precipitated as the three-dimensional globular macroscopic body of 300 μm ~ 1.5 cm of diameter；
C. after drying at room temperature precipitates for 24 hours, the asymmetric three-dimensional hollow bowl structure of a diameter of 30 μm ~ 1.5 mm is obtained.
The graphene oxide for preparing carries out in accordance with the following steps：
1g graphite is added to 23mL mass percent concentrations as in 98% concentrated sulfuric acid, the lower stirring of ice bath cooling 2 hours slowly adds
Enter 3g potassium permanganate, continue stirring 2 hours in the cooling condition, then mixture is transferred in 35 DEG C of water-baths and is reacted 1 hour,
It is slowly added to the distilled water of 58 mL thereto again, bath temperature is risen to 98 DEG C after stirring evenly, stir 1 hour；From water-bath
The beaker for filling mixture is taken out, is slowly added to the warm water of 60 DEG C of 140 mL under stirring condition, and be cooled under agitation
25℃；The hydrogen peroxide that 5 mL mass percent concentrations are 30% is added into mixture, graphite oxide is obtained after stirring evenly
Alkene suspension, finally by suspension centrifuge washing to neutrality, 80 DEG C of dryings.Dosage in actual production between each reactant can be according to
Aforementioned proportion carries out.
The present invention makes full use of the cooperation mechanism of shearing force and capillarity, using electric stirring and air drying technology,
Can directly preparation structure be 30 μm ~ 1.5 mm of diameter asymmetric three-dimensional hollow bowl structure graphene oxide micro motor,
Without freeze-drying, soft template（Microemulsion）Or hard template is sacrificed, and it is easy to operate, it is of low cost, size is controllable, it is applicable to
Large-scale industrial production.Prepared hollow bowl-shape graphene oxide micro motor is put into the peroxide that mass percent concentration is 5%
Change in hydrogen solution, oxygen is generated by catalyzing hydrogen peroxide, realizes self-propelled campaign using oxygen bubble as power, and utilize
Hollow bowl-shape graphene oxide micro motor magnetic properties realize that the simple recycling of micro motor and magnetic field control, to reach containing
The purpose of positioning operation in the solution of hydrogen peroxide.
Description of the drawings
Fig. 1 is the process flow chart of preparation method of the embodiment of the present invention.
Fig. 2 is the XRD spectra of hollow bowl-shape graphene oxide micro motor in the embodiment of the present invention 1.
Fig. 3 is the stereoscan photograph of hollow bowl-shape graphene oxide micro motor in the embodiment of the present invention 1.
Fig. 4 is the stereoscan photograph of hollow bowl-shape graphene oxide micro motor in the embodiment of the present invention 2.
Specific implementation mode
Embodiment 1：
A kind of preparation method of above-mentioned hollow bowl-shape graphene oxide micro motor, carries out in accordance with the following steps as shown in Figure 1：
A. graphene oxide is prepared：
1g graphite is added to 23 mL mass percent concentrations as in 98% concentrated sulfuric acid, the lower stirring of ice bath cooling 2 hours slowly adds
Enter 3g potassium permanganate, continue stirring 2 hours in the cooling condition, then mixture is transferred in 35 DEG C of water-baths and is reacted 1 hour,
It is slowly added to the distilled water of 58 mL thereto again, bath temperature is risen to 98 DEG C after stirring evenly, stir 1 hour；From water-bath
The beaker for filling mixture is taken out, is slowly added to the warm water of 60 DEG C of 140 mL under stirring condition, and be cooled under agitation
25℃；To mixture（Graphite oxide, SO4、K+、Mn2+And H+）The middle peroxidating that 5 mL mass percent concentrations are added and are 30%
Hydrogen obtains graphene oxide suspension after stirring evenly, finally by suspension centrifuge washing to neutrality, 80 DEG C of dryings；
B. in room temperature（15-30 DEG C) under, the outstanding of 10 mg/mL in prepared graphene oxide ultrasonic disperse to water, will be made
Turbid；Then 10 mL suspensions are taken, 40 mg MnFe are added thereto2O4Powder is ultrasonically formed uniform suspension；Add dropwise again
Enter 5 mL aniline solutions；The electric mixer that rotating speed is 50 r/min is finally used to stir 36h, mixed system is become by uniform suspension
At flocculent deposit, centrifugation recycling precipitation, gained is precipitated as the three-dimensional globular macroscopic body of moistening；
C. room temperature（15-30 DEG C) it is dry for 24 hours after, obtain asymmetric three-dimensional hollow bowl structure, i.e., hollow bowl-shape graphene oxide
Micro motor.
The average diameter of the three-dimensional globular macroscopic body of the obtained moisture state of b step is 1.5 cm, under the state
Macroscopic body have good ductility, macrostructure of different shapes can be molded.When the three-dimensional globular of moisture state
Macroscopic body is after step c is dried, and with scanning electron microscopic observation, its surface texture shows asymmetric three-dimensional hollow bowl structure, average
Diameter is contracted to 1.5 mm.
The XRD spectra and stereoscan photograph difference of the 1 hollow bowl-shape graphene oxide micro motor of gained of the embodiment of the present invention
As shown in Figure 2 and Figure 3.A in Fig. 3 is the scanning electron microscope (SEM) photograph that the micro motor prepared is shown from " the rim of a bowl " direction；B is in figure a boxes
Partial enlarged drawing.
Embodiment 2：
Preparation method is substantially with embodiment 1, the difference is that the dilute turbid liquid concentration of graphite oxide is diluted to 2 mg/ in b step
5 mg MnFe are added in mL2O4Powder, ultrasound forms uniform suspension in 15 minutes, then 200 μ L aniline, electric mixing is added dropwise
It mixes after device stirs 4h under 2800 r/min speed conditions, recycling precipitation.
Wherein the average diameter of moisture state macroscopic body is 300 μm, and asymmetric hollow bowl structure is showed after dry, is put down
Equal diameter is contracted to 30 μm or so.The stereoscan photograph of the 2 hollow bowl-shape graphene oxide micro motor of gained of the embodiment of the present invention
As shown in Figure 4.
Embodiment 3：
Preparation method is substantially with embodiment 1, the difference is that using electric mixer in 1000 r/min rotating speed items in b step
Precipitation is recycled after stirring 36h under part.
Wherein the average diameter of the macroscopic body of moisture state is 3 mm, and asymmetric hollow bowl structure is showed after dry, is put down
Equal diameter is contracted to 300 μm.
Embodiment 4：
Preparation method is substantially with embodiment 1, the difference is that 80 mg MnFe are added in b step2O4Powder, electric stirring
Device recycles precipitation after stirring 36h under 1000 r/min speed conditions.
Wherein the average diameter of moisture state macroscopic body is 1.5 mm, and asymmetric hollow bowl structure is showed after dry, is put down
Equal diameter is contracted to 150 μm.
Claims (3)
1. a kind of hollow bowl-shape graphene oxide micro motor, it is characterized in that asymmetric three-dimensional hollow bowl structure, average diameter are
30 μm ~1.5 mm。
2. a kind of preparation method of hollow bowl-shape graphene oxide micro motor as described in claim 1, it is characterised in that according to such as
Lower step carries out：
A. graphene oxide is prepared；
B. at room temperature, by prepared graphene oxide ultrasonic disperse to water, the suspension of 2 ~ 10 mg/mL is made；So
MnFe is added in backward suspension2O4Powder is ultrasonically formed uniform suspension, the suspension and MnFe2O4The ratio of powder is
10 mL：5~80 mg；Aniline solution is added dropwise again, addition is that 200 mL of μ L ~ 5 are added in every 10 mL suspensions；Finally use
Rotating speed stirs for the electric mixer of 50 ~ 2800 r/min to mixed system becomes flocculent deposit by uniform suspension, and recycling is heavy
It forms sediment；
C. drying at room temperature precipitates, and obtains the asymmetric three-dimensional hollow bowl structure of a diameter of 30 μm ~ 1.5 mm.
3. the preparation method of hollow bowl-shape graphene oxide micro motor according to claim 2, it is characterised in that the preparation
Graphene oxide carries out in accordance with the following steps：
1g graphite is added to 23 mL mass percent concentrations as in 98% concentrated sulfuric acid, the lower stirring of ice bath cooling 2 hours slowly adds
Enter 3g potassium permanganate, continue stirring 2 hours in the cooling condition, then mixture is transferred in 35 DEG C of water-baths and is reacted 1 hour,
It is slowly added to the distilled water of 58 mL thereto again, bath temperature is risen to 98 DEG C after stirring evenly, stir 1 hour；From water-bath
The beaker for filling mixture is taken out, is slowly added to the warm water of 60 DEG C of 140 mL under stirring condition, and be cooled under agitation
25℃；The hydrogen peroxide that 5 mL mass percent concentrations are 30% is added into mixture, graphite oxide is obtained after stirring evenly
Alkene suspension, finally by suspension centrifuge washing to neutrality, 80 DEG C of dryings.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109292889A (en) * | 2018-11-14 | 2019-02-01 | 伊犁师范学院 | A kind of graphene robot |
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| KR20140118064A (en) * | 2013-03-28 | 2014-10-08 | 한국지질자원연구원 | Manufacturing method for graphene hollow particle and graphene hollow particle using the same |
| CN105331999A (en) * | 2015-10-13 | 2016-02-17 | 湖南农业大学 | Preparing method for hollow graphene |
| CN106129373A (en) * | 2016-08-25 | 2016-11-16 | 陕西科技大学 | A kind of hollow ball Fe2o3the preparation method of/rGO lithium ion battery negative material |
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Patent Citations (4)
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| CN103121672A (en) * | 2013-03-20 | 2013-05-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide microsphere and graphene microsphere and preparation methods thereof |
| KR20140118064A (en) * | 2013-03-28 | 2014-10-08 | 한국지질자원연구원 | Manufacturing method for graphene hollow particle and graphene hollow particle using the same |
| CN105331999A (en) * | 2015-10-13 | 2016-02-17 | 湖南农业大学 | Preparing method for hollow graphene |
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| CN109292889A (en) * | 2018-11-14 | 2019-02-01 | 伊犁师范学院 | A kind of graphene robot |
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Application publication date: 20180724 Assignee: Yangjiang jiyoulan Electronic Technology Co.,Ltd. Assignor: DONGGUAN University OF TECHNOLOGY Contract record no.: X2022980027700 Denomination of invention: Hollow bowl-shaped graphene oxide micromotor and its preparation method Granted publication date: 20190312 License type: Common License Record date: 20221230 |
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Application publication date: 20180724 Assignee: Guangdong Meisong New Material Co.,Ltd. Assignor: DONGGUAN University OF TECHNOLOGY Contract record no.: X2023980030287 Denomination of invention: Hollow bowl-shaped graphene oxide micromotor and its preparation method Granted publication date: 20190312 License type: Common License Record date: 20230110 |
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