CN103879999B - Synchronous in-situ reducing graphene oxide prepares the method for composite - Google Patents
Synchronous in-situ reducing graphene oxide prepares the method for composite Download PDFInfo
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- CN103879999B CN103879999B CN201410075551.4A CN201410075551A CN103879999B CN 103879999 B CN103879999 B CN 103879999B CN 201410075551 A CN201410075551 A CN 201410075551A CN 103879999 B CN103879999 B CN 103879999B
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Abstract
The invention discloses a kind of method that synchronous in-situ reducing graphene oxide prepares composite, after first pulse laser ablation being carried out to the metal targets rotated, obtain the metastable colloid of high reactivity hyperergy; Then mixed with the graphene oxide standby by classical Hummers legal system by highly active metastable nano material colloid after shaking, dark place places more than one week.The nano composite material of preparation is as SnO
2-rGO, ZnO-rGO etc., simple to operate, green high-efficient and universality is strong.
Description
Technical field
The present invention relates to a kind of composite preparation method, particularly relate to a kind of method that synchronous in-situ reducing graphene oxide prepares composite.
Background technology
Graphene is by the cellular two dimensional surface crystal film of sp2 hydridization C atomic building, and single-layer graphene in 2004 is produced and prove can stable existence, and thickness in monolayer is only 0.335nm.Graphene is except having excellent mechanics and thermal property, and the more important thing is also have special electrical properties, as high conductivity, (electronic mobility under room temperature reaches 15000cm
2/ Vs), perfect quantum tunneling effect, large specific surface area (2600m
2/ g) and the behavior of half-integer quantum Hall.This makes Graphene at nano electron device, sensor, pharmaceutical carrier, and the field such as ultracapacitor and stored energy is widely used.And oxidation reduction process is prepared Graphene and is provided technical foundation for preparing Graphene in a large number.Graphene-based matrix material has new performance characteristic and applies more widely, thus receives much concern.In view of what time above, increasing graphene-based matrix material is produced and applies, comprising the compound of inorganic materials, macromolecular material, and the surface modification of Graphene etc.
In prior art, the method commonly used has ultrasonic method, hydrothermal method, electrochemical process, with stage reduction method etc., but all inevitably employ the chemical reagent such as ion source, reductive agent or tensio-active agent in experimentation, and, the anneal that major part method all comprises the later stage is to obtain the graphene composite material of reduction, and step complexity, loaded down with trivial details, the easy residual impurity of process, the product obtained are pure not.
Summary of the invention
The object of this invention is to provide a kind of method that simply effective and pervasive synchronous in-situ reducing graphene oxide prepares composite.
The object of the invention is to be achieved through the following technical solutions:
Synchronous in-situ reducing graphene oxide of the present invention prepares the method for composite, comprises step:
First, after pulse laser ablation is carried out to the metal targets rotated, the metastable nano material colloid of high reactivity hyperergy is obtained;
Then, mixed by the metastable nano material colloid of described high reactivity hyperergy after shaking with graphene oxide, dark place is placed.
As seen from the above technical solution provided by the invention, the synchronous in-situ reducing graphene oxide that the embodiment of the present invention provides prepares the method for composite, first, after pulse laser ablation being carried out to the metal targets rotated, the metastable nano material colloid of high reactivity hyperergy is obtained; Then mixed by the metastable nano material colloid of described high reactivity hyperergy after shaking with graphene oxide, dark place is placed, simple to operate, green high-efficient and universality is strong.
Accompanying drawing explanation
Fig. 1 prepares the schematic flow sheet of the method for composite for synchronous in-situ reducing graphene oxide that the embodiment of the present invention provides;
Fig. 2 is the pictorial diagram in differential responses stage in the embodiment of the present invention;
Fig. 3 a is TEM figure and the SEAD figure of graphene oxide in the embodiment of the present invention;
Fig. 3 b is SnO in the embodiment of the present invention
2tEM figure and the SEAD figure of-rGO nano composite material;
Fig. 3 c is the low power TEM figure of ZnO-rGO matrix material in the embodiment of the present invention and the TEM figure of high power;
Fig. 4 a is SnO in the embodiment of the present invention
2the XRD figure spectrum of-rGO matrix material;
Fig. 4 b is the XRD figure spectrum of ZnO-rGO matrix material in the embodiment of the present invention;
Fig. 5 a is SnO in the embodiment of the present invention
2the UV-Visible absorption comparison diagram of-rGO matrix material;
Fig. 5 b is the UV-Visible absorption comparison diagram of ZnO-rGO matrix material in the embodiment of the present invention;
Fig. 6 a is SnO in the embodiment of the present invention
2the electrical properties of-rGO: glucose detection ability schematic diagram;
Fig. 6 b is SnO in the embodiment of the present invention
2the electrical properties of-rGO: immunity from interference schematic diagram.
Embodiment
To be described in further detail the embodiment of the present invention below.
Synchronous in-situ reducing graphene oxide of the present invention prepares the method for composite, its preferably embodiment comprise step:
First, after pulse laser ablation is carried out to the metal targets rotated, obtain high reactivity hyperergy metastable nano material colloid;
Then, mixed by the metastable nano material colloid of described high reactivity hyperergy after shaking with graphene oxide, dark place is placed.
Described graphene oxide is standby by classical Hummers legal system, and the time of described placement is more than one week.
Described metal targets comprise following any one:
Sn、Zn、Ti、Ge、Mg。
Described composite comprise following any one:
SnO
2-rGO、ZnO-rGO、TiO
2-rGO、Ge-rGO、MgO-rGO。
The nano material colloid that the present invention utilizes liquid laser ablation to produce first, as reductive agent, directly mixes dark place with graphene oxide and places and reduce, and obtains composite.Wherein, the chemical reagent such as any other reductive agent, stablizer need not be added, simple to operate, green high-efficient.And accompanying material granule little (<5nm), be evenly distributed, it is little that this method is that the nano material colloid produced based on liquid laser ablation has particle, more Lacking oxygen and defect, high surface reaction activity, the characteristics such as special physicochemical property, in the process of mixing, combine closely with the group of surface of graphene oxide and act on, along with the stable of colloidal solid itself and growth, by synchronous for graphene oxide in-situ reducing, finally form composite.This method is that the Synthesis and applications of composite provides new approach and thinking, meanwhile, is also the application extension that liquid laser ablation technology is new.The active nano material colloids target related to has Sn, Zn, Ti, Ge, Mg etc.
The present invention has expanded the novel method that a kind of synchronous in-situ reducing graphene oxide (GO) prepares composite.The high reaction activity of the colloid utilizing liquid laser ablation to obtain, using colloid as source material simultaneously as reductive agent, after placing with graphene oxide mixing dark place, direct in-situ reduction growth obtains the equally distributed graphene-based matrix material of small size of differing materials load.Due to the single cleaning of colloid obtained, whole experimentation does not have other impurity to originate, to obtain end product efficiently pure, without other by products.One aspect of the present invention has expanded the application of liquid laser ablation technology in materials synthesis, on the other hand also for further investigation composite and application thereof provide new approach and foundation.
Specific embodiment:
With SnO
2-rGO and ZnO-rGO is that example describes procedure in detail.
Concrete experimentation is as shown in Figure 1:
Obtain the metastable nano material colloid of high reactivity hyperergy after adopting rotating metallic target to carry out pulse laser ablation, mix dark place after shaking with the graphene oxide standby by classical Hummers legal system and place.
As shown in Figure 2, after one week, cotton-shaped to change black into cotton-shaped by yellow when mixing at first for product.First the generation of being reduced of graphene oxide and Graphene is demonstrated from color.
As shown in Fig. 3 a, 3b, 3c, in order to characterize the pattern of product, be the TEM of product, (Fig. 3 is a) graphene oxide prepared by classical Hummers method, the even inclusion-free of the graphene oxide obtained as we can see from the figure, the SEAD figure in the upper right corner shows graphene oxide and presents typical hexagonal crystal phase.(Fig. 3 b) is the SnO of preparation
2-rGO nano composite material, find that the material granule in load is even, good crystallinity, size is the quantum stage of about 2-5nm.Illustration is the SEAD figure of product, and crystallization ring from inside to outside represents the SnO obtained in material respectively
2(301), (211), (101), (110) face.(Fig. 3 c) is the low power of ZnO-rGO matrix material and the TEM figure of high power, and as we can see from the figure, on Graphene, the ZnO of load presents sheet, and this flaky material is assembled by the small-particle of about 5nm.And so specific structured material may show special optical property.
As shown in Fig. 4 a, 4b, in order to determine the thing phase of matrix material obtained, be the XRD of respective material, find to obtain material respectively with standard card JCPDSNO.00-046-1088 (SnO
2) and JCPDSNO.01-089-0511 (ZnO) match.From peak shape, the SnO in Fig. 4 a
2wider, this to a certain degree can illustrate acquisition SnO
2particle size smaller, just conform to TEM figure.And Fig. 4 b presents more sharp-pointed peak shape, mainly because the overall pattern of ZnO is the sheet structure that small-particle assembles.
As shown in Fig. 5 a, 5b, be SnO prepared by the present invention
2the UV-vis absorption spectrum figure of-rGO and ZnO-rGO matrix material.As can be seen from the figure, compared to initial graphene oxide and initial colloid, end product has all reflected the result of a reduction and growth.With SnO
2-rGO be example (Fig. 5 a), the characteristic peak of graphene oxide at 230nm and 300nm place replace by the reduction peak at the 258nm place of broadening.In like manner observe the spectrogram (Fig. 5 b) of ZnO-rGO, the peak being all broadening finally obtained, and the peak of the Zn colloid at script 327nm place also there occurs red shift.Demonstrate graphene oxide and there occurs reduction reaction in the growth and stable process of colloid source material, obtain reduced graphene (rGO), namely demonstrate the process of a synchronously reduction.
As shown in Fig. 6 a, 6b, at present with regard to SnO
2-rGO has done a part of work in electrochemical application, explores its ability in glucose detection.Can see from the current time response curve Fig. 6 a, no matter be the glucose at every turn adding 0.05mM at first, or the concentration changing the glucose be added dropwise in process is 0.15mM, this responds the state of held stationary all always, and along with the increase of concentration, made stronger response, the material presenting us (is 1.93A/Mcm after calculating to glucose detection a sensitivity well
2).Meanwhile, mimic biology body environment, We conducted the interference experiment (Fig. 6 b) of possible factor except glucose, finds that our material only has and just can make obvious response to glucose, demonstrates our material to the uniqueness of glucose detection simultaneously.These various composite also having implied that this method obtains are expected to represent different potential in other electricity and optical field.
The present invention design use liquid laser ablation to produce colloid as reductive agent, colloid is utilized to have particle little, more Lacking oxygen and defect, high surface reaction activity, the characteristics such as special physicochemical property, directly mix dark place with graphene oxide and place, after the effect of combining closely of the group with surface of graphene oxide, along with the stable of colloid itself and growth, synchronous for graphene oxide in-situ reducing is obtained composite.Wherein, the chemical reagent such as any other reductive agent, stablizer need not be added, avoid the generation of other impurity product, accompanying material granule little (<5nm), be evenly distributed, be expected to represent different potential in electricity and optical field.This method is simple to operate, green high-efficient, and universality is strong.Not only for the Synthesis and applications of composite provides new approach and thinking, also expand the new opplication of liquid laser ablation technology.The active colloidal target related at present has Sn, Zn, Ti, Ge, Mg etc., and the example presented in specific embodiment is SnO
2-rGO and ZnO-rGO.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (1)
1. synchronous in-situ reducing graphene oxide prepares a method for composite, it is characterized in that, comprises step:
First, after pulse laser ablation is carried out to the metal targets rotated, the metastable nano material colloid of high reactivity hyperergy is obtained;
Then, mixed by the metastable nano material colloid of described high reactivity hyperergy after shaking with graphene oxide, dark place is placed;
Described graphene oxide is standby by classical Hummers legal system, and the time of described placement is more than one week;
Described metal targets comprise following any one:
Sn、Zn、Ti、Ge、Mg；
Described composite comprise following any one:
SnO
2-rGO、ZnO-rGO、TiO
2-rGO、Ge-rGO、MgO-rGO。
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| CN104609407A (en) * | 2015-01-20 | 2015-05-13 | 南昌大学 | Method for preparing graphene through reduction of graphene oxide with magnesium powder |
| CN105021655B (en) * | 2015-07-03 | 2017-08-22 | 西安工业大学 | ZnO nano wall/RGO hetero-junctions gas sensors and preparation method thereof |
| CN105215353B (en) * | 2015-11-09 | 2017-08-25 | 山东大学 | A kind of Metal/grapheme composite and preparation method thereof |
| CN106124496B (en) * | 2016-06-23 | 2018-12-21 | 中国空间技术研究院 | A kind of monitoring material and its preparation method and application based on graphene oxide |
| CN107271488B (en) * | 2017-06-15 | 2019-12-27 | 电子科技大学 | Preparation method of gas-sensitive material with nano composite structure |
| CN107619045B (en) * | 2017-09-21 | 2020-03-31 | 中国科学院合肥物质科学研究院 | Method for in-situ preparation of small-size metal oxide on graphene |
| CN108788135B (en) * | 2018-06-26 | 2021-02-26 | 中国科学院兰州化学物理研究所 | Method for in-situ self-generation of graphene/titanium shell-core structure material |
| CN109179398B (en) * | 2018-10-24 | 2021-01-15 | 国家纳米科学中心 | Noble metal oxide nano composite material, preparation method and application thereof |
| CN111640925A (en) * | 2020-06-12 | 2020-09-08 | 西北工业大学 | SnO (stannic oxide)2Graphene composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102554244A (en) * | 2012-03-12 | 2012-07-11 | 苏州大学 | Self-assembly controllable preparation method of composite of metal nano particles and carbon materials |
| CN102992314A (en) * | 2013-01-04 | 2013-03-27 | 山西大同大学 | Method for preparing graphene |
-
2014
- 2014-03-03 CN CN201410075551.4A patent/CN103879999B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102554244A (en) * | 2012-03-12 | 2012-07-11 | 苏州大学 | Self-assembly controllable preparation method of composite of metal nano particles and carbon materials |
| CN102992314A (en) * | 2013-01-04 | 2013-03-27 | 山西大同大学 | Method for preparing graphene |
Non-Patent Citations (2)
| Title |
|---|
| Assembling Tin Dioxide Quantum Dots to Graphene Nanosheets by a Facile Ultrasonic Route;Chen Chen et al.;《Langmuir》;20131231;第29卷;第4112页第2部分实验部分 * |
| Reactive and photocatalytic degradation of various water contaminants by laser ablation-derived SnOx nanoparticles in liquid;Zhenfei Tian et al.;《Journal of Materials Chemistry》;20111231;第21卷;第18243页第2.1节水中激光制备SnOx 纳米粒子、第18245页第4-7行以及第18247页第4部分结论 * |
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