CN103626173B - Preparation method of low-defect graphene-boron oxide nanocrystal composite material - Google Patents
Preparation method of low-defect graphene-boron oxide nanocrystal composite material Download PDFInfo
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- CN103626173B CN103626173B CN201310632082.7A CN201310632082A CN103626173B CN 103626173 B CN103626173 B CN 103626173B CN 201310632082 A CN201310632082 A CN 201310632082A CN 103626173 B CN103626173 B CN 103626173B
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Abstract
The invention discloses a preparation method of a low-defect graphene-boron oxide nanocrystal composite material. A graphite flake, a graphene flake, graphite oxide or a mixture thereof with any ratio is mixed with boric acid by the mass ratio of (2:1)-(6:1); N-methyl pyrrolidone organic solvent is added to enable the solid content to be 0.1 mg/mL-0.8 mg/mL; the ultrasonic stripping is implemented under the condition of normal temperature; then obtained liquid is centrifugated for 45 min; supernatant liquid is taken; then the obtained supernatant liquid is ultrasonically stripped and centrifugated again to prepare the low-defect graphene-boron oxide nanocrystal composite material. The preparation method has mild conditions, simple process and low energy consumption, and prepares low-defect graphene and boron oxide nanocrystals.
Description
Technical field
The invention relates to nanocrystal, particularly relate to a kind of method preparing Graphene-boron oxide nanocrystal of simple gentleness.
Background technology
Nanocrystal is because of close with atomic size, there is the character such as surface effects, quantum size effect, Dielectric confinement effect, thus derive special optical, electrical, magnetic property, have broad application prospects in optics, catalysis, medicine etc., revolutionary pushing effect is played to development such as future biological medical science, genomics.But technology of preparing nanocrystalline mostly at present is complicated and the high method that consumes energy, and even some preparation method's toxicity is very large.In addition, boron oxide is one of material of the most difficult crystallization at present, and how selecting simple and safe method to prepare boron oxide nanocrystal becomes difficult point.And Graphene can at adatom and molecule with the structure of its uniqueness, the template that can grow as nanocrystal, but also there is many difficult points in the preparation of Graphene simultaneously at present.How to reduce the cost preparing with Graphene the boron oxide nanocrystal being base and become another difficulties.
Summary of the invention
The present invention is in order to overcome the preparation difficult point of existing Graphene and reduce another difficult point preparing with Graphene the boron oxide nanocrystal cost being base, and prepare for prior art the shortcoming that nanocrystal technique is comparatively complicated, toxicity is large, take to add graphite flake/graphene film/graphite oxide and mebor in organic solvent, the method peeled off by low temperature ultrasonic prepares the boron oxide nanocrystal using graphene film as growth substrate, provides that a kind of technique is simple, the nanocrystal preparation method of mild condition.
Low temperature ultrasonic stripping method refers to that the boric acid added then on its surface, dehydration reaction occurs and generates boron oxide nanocrystal by ultrasonic exfoliated graphite/graphene film/graphite oxide generation graphene-structured under normal temperature condition.
The present invention is achieved by following technical solution.
(1) be that 2:1 ~ 6:1 prepares burden by graphite flake and boric acid according to mass ratio, add N-Methyl pyrrolidone organic solvent, after making to add organic solvent, solids content is 0.1mg/mL ~ 0.8mg/mL; Under normal temperature condition, carry out ultrasonic stripping, ultrasonic power is 100W ~ 125W;
(2) liquid that step (1) obtains is carried out centrifugal 45min, centrifugation rate is 1000r/min, gets supernatant liquid;
(3) supernatant liquid that step (2) obtains is carried out ultrasonic stripping again, ultrasonic power is 100W ~ 125W, obtains turbid liquid;
(4) turbid liquid that step (3) obtains is carried out 45min centrifugal, centrifugation rate is 1500r/min, obtains the supernatant liquid containing boron oxide nanocrystal.
The graphite flake of described step (1) also can adopt the mixture of graphene film, graphite oxide or three's arbitrary proportion, and can be realized the preparation of low defect Graphene-boron oxide nanocrystal composite at ambient temperature by ultrasonic stripping method.
The most significant advantage of the present invention is: this method not only equipment is simple, consumes energy low, nontoxic, and namely can react under normal temperature condition; This method, not only can prepare boron oxide nanocrystal, can also prepare other nanocrystal, as titanium oxide, stannic oxide, silver suboxide nanocrystal.
Accompanying drawing explanation
Fig. 1 is the TEM low power image of the low defect Graphene-boron oxide nanocrystal composite of embodiment 1;
Fig. 2 is the TEM high power image of the low defect Graphene-boron oxide nanocrystal composite of embodiment 1;
Fig. 3 is the image K-M of the low defect Graphene-boron oxide nanocrystal composite of embodiment 1.
Embodiment
The present invention's graphene film used and graphite flake are Xiamen Kai Na company and produce, and graphite oxide is then the graphite flake of purchase and oxidant reaction are obtained, and other starting material are analytical reagent.Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
(1) ratio getting amount of substance is graphene film and the boric acid of 2:1, adds the suspension that N-Methyl pyrrolidone is mixed with 0.8mg/mL, carries out ultrasonic stripping with the ultrasonic power of 100W under normal temperature condition;
(2) liquid that step (1) obtains is carried out centrifugal 45min, centrifugation rate is 1000r/min, gets supernatant liquid;
(3) supernatant liquid that step (2) obtains is carried out ultrasonic stripping again; Ultrasonic power is 100W, obtains turbid liquid;
(4) turbid liquid that step (3) obtains is carried out 45min centrifugal, centrifugation rate is 1500r/min, obtains the supernatant liquid containing boron oxide nanocrystal.
Embodiment 1 prepares the photo of low defect Graphene-boron oxide nanocrystal composite respectively as shown in Figure 1, Figure 2, Figure 3 shows by taking graphene film as raw material by ultrasonic stripping method.From Fig. 1, be not difficult to find out that graphenic surface has solid particulate to be uniformly distributed, wherein solid grain size is between 3 ~ 5nm.Obviously can seeing lattice fringe from Fig. 2, spacing about 0.23nm again can be drawn by measuring, substantially identical with the spacing of boron oxide crystal; Lattice diffraction ring is obviously seen, by calculating the crystal indices and proving further to obtain boron oxide nanocrystal at graphenic surface with the boron oxide PDF card comparison of standard by electron diffraction (Fig. 3).Be that raw material can prepare boron oxide nanocrystal really by ultrasonic stripping method as can be seen here with graphene film.
Embodiment 2
(1) ratio getting amount of substance is graphene film and the boric acid of 2:1, adds the suspension that N-Methyl pyrrolidone is mixed with 0.1mg/mL, carries out ultrasonic stripping with the ultrasonic power of 100W under normal temperature condition;
(2) liquid that step (1) obtains is carried out centrifugal 45min, get supernatant liquid; Centrifugation rate is 1000r/min;
(3) supernatant liquid that step (2) obtains is carried out ultrasonic stripping again; Ultrasonic power is 100W, obtains turbid liquid;
(4) turbid liquid that step (3) obtains is carried out 45min centrifugal; Centrifugation rate is 1500r/min; Obtain supernatant namely containing boron oxide nanocrystal.
The experimental result obtained under solids concn 0.1mg/mL condition is identical with the experimental result in embodiment 1.
Embodiment 3
(1) ratio getting amount of substance is graphite flake and the boric acid of 2:1, adds the suspension that N-Methyl pyrrolidone is mixed with 0.8mg/mL, carries out ultrasonic stripping with the ultrasonic power of 100W under normal temperature condition;
(2) liquid that step (1) obtains is carried out centrifugal 45min, get supernatant liquid; Centrifugation rate is 1000r/min;
(3) supernatant liquid that step (2) obtains is carried out ultrasonic stripping again; Ultrasonic power is 100W, obtains turbid liquid;
(4) turbid liquid that step (3) obtains is carried out 45min centrifugal; Centrifugation rate is 1500r/min; Obtain supernatant namely containing boron oxide nanocrystal.
The low defect Graphene-boron oxide nanocrystal composite pattern obtained in embodiment 3 is similar to the material morphology obtained in embodiment 1, embodiment 2, but contained amorphous carbon increases.Increasing of amorphous carbon is because the amorphous carbon in raw material is many, but this reaction process still has the generation of nanocrystal, illustrates that this invention still can be starting material synthesis of nano crystal with graphite flake.
Embodiment 4
(1) ratio getting amount of substance is graphite flake and the boric acid of 2:1, adds the suspension that N-Methyl pyrrolidone is mixed with 0.1mg/mL, carries out ultrasonic stripping with the ultrasonic power of 100W under normal temperature condition;
(2) liquid that step (1) obtains is carried out centrifugal 45min, get supernatant; Centrifugation rate is 1000r/min;
(3) supernatant that step (2) obtains is carried out ultrasonic stripping again; Ultrasonic power is 100W, obtains turbid liquid;
(4) turbid liquid that step (3) obtains is carried out 45min centrifugal; Centrifugation rate is 1500r/min; Obtain supernatant liquid namely containing boron oxide nanocrystal.
The low defect Graphene-boron oxide nanocrystal composite obtained equally in embodiment 4.
Embodiment 5
(1) ratio getting amount of substance is graphene film and the boric acid of 6:1, adds the suspension that N-Methyl pyrrolidone is mixed with 0.1mg/mL, carries out ultrasonic stripping with the ultrasonic power of 125W under normal temperature condition;
(2) liquid obtained in (1) is carried out centrifugal 45min, get supernatant; Centrifugation rate is 1500r/min;
(3) supernatant obtained in (2) is carried out ultrasonic stripping again; Ultrasonic power is 100W, obtains turbid liquid;
(4) turbid liquid obtained in (3) is carried out 45min centrifugal; Centrifugation rate is 1500r/min; Obtain supernatant namely containing boron oxide nanocrystal.
In the matrix material obtained in embodiment 5 content of boron oxide nanocrystal comparatively in embodiment 1 boron oxide nanocrystal content decline to some extent.It is because boric acid content declines that boron oxide nanocrystal content declines, therefore declines in substrate content distribution, and this explanation can obtain different nanocrystal distribution by controlling boric acid consumption.
The above-mentioned description to embodiment is convenient to those skilled in the art can understand and apply the invention.Person skilled in the art easily makes various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Each raw material cited by the present invention can realize the present invention, and raw material, ultrasonic power, the bound value of solvent load, interval value, can realize the present invention, then this is not illustrated one by one.
Claims (2)
1. a preparation method for low defect Graphene-boron oxide nanocrystal composite, has following steps:
(1) be that 2:1 ~ 6:1 prepares burden by graphite flake and boric acid according to mass ratio, add N-Methyl pyrrolidone organic solvent, after making to add organic solvent, solids content is 0.1mg/mL ~ 0.8mg/mL; Under normal temperature condition, carry out ultrasonic stripping, ultrasonic power is 100W ~ 125W;
(2) liquid that step (1) obtains is carried out centrifugal 45min, centrifugation rate is 1000r/min, gets supernatant liquid;
(3) supernatant liquid that step (2) obtains is carried out ultrasonic stripping again, ultrasonic power is 100W ~ 125W, obtains turbid liquid;
(4) turbid liquid that step (3) obtains is carried out 45min centrifugal, centrifugation rate is 1500r/min, obtains the supernatant liquid containing boron oxide nanocrystal.
2. the preparation method of low defect Graphene-boron oxide nanocrystal composite according to claim 1, it is characterized in that, the graphite flake of described step (1) also can adopt the mixture of graphene film, graphite oxide or three's arbitrary proportion, and can be realized the preparation of low defect Graphene-boron oxide nanocrystal composite at ambient temperature by ultrasonic stripping method.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281323A (en) * | 1999-03-30 | 2000-10-10 | Natl Inst For Res In Inorg Mater | Production of carbon nanotube containing boron |
| JP2004230484A (en) * | 2003-01-28 | 2004-08-19 | National Institute For Materials Science | CNx NANO-COMPOSITION AND BNCx NANO-COMPOSITION, AND METHOD OF MANUFACTURING THE SAME |
| CN1793409A (en) * | 2005-12-02 | 2006-06-28 | 华中师范大学 | Al18B4O33 nano wire uniform cladded with BN and preparation process thereof |
| WO2009052816A2 (en) * | 2007-10-26 | 2009-04-30 | Dirk Lorenzen | Substrate for semiconductor elements |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281323A (en) * | 1999-03-30 | 2000-10-10 | Natl Inst For Res In Inorg Mater | Production of carbon nanotube containing boron |
| JP2004230484A (en) * | 2003-01-28 | 2004-08-19 | National Institute For Materials Science | CNx NANO-COMPOSITION AND BNCx NANO-COMPOSITION, AND METHOD OF MANUFACTURING THE SAME |
| CN1793409A (en) * | 2005-12-02 | 2006-06-28 | 华中师范大学 | Al18B4O33 nano wire uniform cladded with BN and preparation process thereof |
| WO2009052816A2 (en) * | 2007-10-26 | 2009-04-30 | Dirk Lorenzen | Substrate for semiconductor elements |
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