CN103626173A - 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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- CN103626173A CN103626173A CN201310632082.7A CN201310632082A CN103626173A CN 103626173 A CN103626173 A CN 103626173A CN 201310632082 A CN201310632082 A CN 201310632082A CN 103626173 A CN103626173 A CN 103626173A
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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, relate in particular to a kind of method of 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, thereby derive special optical, electrical, magnetic property, at aspects such as optics, catalysis, medicine, have broad application prospects, the development such as following biomedicine, genomics are played to revolutionary pushing effect.But nanocrystalline technology of preparing mostly is complicated and the high method that consumes energy at present, and even some preparation method's toxicity is very large.In addition, boron oxide is one of material of at present the most difficult crystallization, and the simple and safe method of How to choose is prepared boron oxide nanocrystal becomes difficult point.And Graphene can be used as the template of nanocrystal growth at adatom and molecule with its unique structure, but also there are many difficult points in the preparation of Graphene simultaneously at present.How reducing preparation take the cost of the boron oxide nanocrystal that Graphene is base and becomes another difficulties.
Summary of the invention
The present invention be take another difficult point of the boron oxide nanocrystal cost that Graphene is base in order to overcome the preparation difficult point of existing Graphene and to reduce preparation, 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, by the ultrasonic method of peeling off of low temperature, prepare and using graphene film as the boron oxide nanocrystal of growth substrate, provide that a kind of technique is simple, the nanocrystal preparation method of mild condition.
The ultrasonic stripping method of low temperature refers under normal temperature condition by ultrasonic exfoliated graphite/graphene film/graphite oxide and generates graphene-structured, and the boric acid adding on its surface, dehydration reaction occurs and generates boron oxide nanocrystal.
The present invention is achieved by following technical solution.
(1) by graphite flake and boric acid, according to mass ratio, be 2:1～6:1 batching, add N-Methyl pyrrolidone organic solvent, making to add solids content after organic solvent is 0.1mg/mL～0.8mg/mL; Under normal temperature condition, carry out ultrasonic peeling off, ultrasonic power is 100W～125W;
(2) liquid step (1) being obtained carries out centrifugal 45min, and centrifugation rate is 1000r/min, gets supernatant liquid;
(3) supernatant liquid step (2) being obtained carries out ultrasonic peeling off again, and ultrasonic power is 100W～125W, obtains turbid liquid;
(4) turbid liquid step (3) being obtained carries out that 45min is centrifugal, and centrifugation rate is 1500r/min, obtains the supernatant liquid that contains 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 by ultrasonic stripping method, realize at ambient temperature the preparation of low defect Graphene-boron oxide nanocrystal matrix material.
The most significant advantage of the present invention is: this method not only equipment is simple, consumes energy low, nontoxic, and 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 low defect Graphene-boron oxide nanocrystal matrix material of embodiment 1;
Fig. 2 is the TEM high power image of low defect Graphene-boron oxide nanocrystal matrix material of embodiment 1;
Fig. 3 is the image K-M of low defect Graphene-boron oxide nanocrystal matrix material 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 that 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) get graphene film and the boric acid that the ratio of amount of substance is 2:1, add N-Methyl pyrrolidone to be mixed with the suspension of 0.8mg/mL, with the ultrasonic power of 100W, under normal temperature condition, carry out ultrasonic peeling off;
(2) liquid step (1) being obtained carries out centrifugal 45min, and centrifugation rate is 1000r/min, gets supernatant liquid;
(3) supernatant liquid step (2) being obtained carries out ultrasonic peeling off again; Ultrasonic power is 100W, obtains turbid liquid;
(4) turbid liquid step (3) being obtained carries out that 45min is centrifugal, and centrifugation rate is 1500r/min, obtains the supernatant liquid that contains boron oxide nanocrystal.
Embodiment 1 is by take photo that graphene film prepares low defect Graphene-boron oxide nanocrystal matrix material by ultrasonic stripping method as raw material respectively as shown in Figure 1, Figure 2, Figure 3 shows.From Fig. 1, be not difficult to find out that Graphene surface has solid particulate to be uniformly distributed, wherein solid grain size is between 3～5nm.From Fig. 2, lattice fringe can be obviously seen, by measuring, spacing 0.23nm left and right again can be drawn, basic identical with the spacing of boron oxide crystal; By electron diffraction (Fig. 3), obviously see lattice diffraction ring, by calculating the crystal indices and comparing further proof with the boron oxide PDF card of standard, on Graphene surface, obtained boron oxide nanocrystal.The graphene film of take as can be seen here can be prepared boron oxide nanocrystal by ultrasonic stripping method really as raw material.
Embodiment 2
(1) get graphene film and the boric acid that the ratio of amount of substance is 2:1, add N-Methyl pyrrolidone to be mixed with the suspension of 0.1mg/mL, with the ultrasonic power of 100W, under normal temperature condition, carry out ultrasonic peeling off;
(2) liquid step (1) being obtained carries out centrifugal 45min, gets supernatant liquid; Centrifugation rate is 1000r/min;
(3) supernatant liquid step (2) being obtained carries out ultrasonic peeling off again; Ultrasonic power is 100W, obtains turbid liquid;
(4) it is centrifugal that turbid liquid step (3) being obtained carries out 45min; Centrifugation rate is 1500r/min; Obtaining the upper strata stillness of night contains boron oxide nanocrystal.
The experimental result obtaining under solids concn 0.1mg/mL condition is identical with the experimental result in embodiment 1.
Embodiment 3
(1) get graphite flake and the boric acid that the ratio of amount of substance is 2:1, add N-Methyl pyrrolidone to be mixed with the suspension of 0.8mg/mL, with the ultrasonic power of 100W, under normal temperature condition, carry out ultrasonic peeling off;
(2) liquid step (1) being obtained carries out centrifugal 45min, gets supernatant liquid; Centrifugation rate is 1000r/min;
(3) supernatant liquid step (2) being obtained carries out ultrasonic peeling off again; Ultrasonic power is 100W, obtains turbid liquid;
(4) it is centrifugal that turbid liquid step (3) being obtained carries out 45min; Centrifugation rate is 1500r/min; Obtaining the upper strata stillness of night contains boron oxide nanocrystal.
The low defect Graphene-boron oxide nanocrystal matrix material pattern obtaining in embodiment 3 is similar to the material pattern obtaining in embodiment 1, embodiment 2, but contained amorphous carbon increases.Increasing of amorphous carbon is that amorphous carbon due in raw material is many, but this reaction process still has the generation of nanocrystal, illustrates that this invention still can take graphite flake as starting material synthesis of nano crystal.
Embodiment 4
(1) get graphite flake and the boric acid that the ratio of amount of substance is 2:1, add N-Methyl pyrrolidone to be mixed with the suspension of 0.1mg/mL, with the ultrasonic power of 100W, under normal temperature condition, carry out ultrasonic peeling off;
(2) liquid step (1) being obtained carries out centrifugal 45min, gets the upper strata stillness of night; Centrifugation rate is 1000r/min;
(3) upper strata stillness of night step (2) being obtained is carried out ultrasonic peeling off again; Ultrasonic power is 100W, obtains turbid liquid;
(4) it is centrifugal that turbid liquid step (3) being obtained carries out 45min; Centrifugation rate is 1500r/min; Obtain supernatant liquid and contain boron oxide nanocrystal.
The low defect Graphene-boron oxide nanocrystal matrix material obtaining equally in embodiment 4.
Embodiment 5
(1) get graphene film and the boric acid that the ratio of amount of substance is 6:1, add N-Methyl pyrrolidone to be mixed with the suspension of 0.1mg/mL, with the ultrasonic power of 125W, under normal temperature condition, carry out ultrasonic peeling off;
(2) liquid obtaining in (1) is carried out to centrifugal 45min, get the upper strata stillness of night; Centrifugation rate is 1500r/min;
(3) the upper strata stillness of night obtaining in (2) is carried out to ultrasonic peeling off again; Ultrasonic power is 100W, obtains turbid liquid;
(4) turbid liquid obtaining in (3) is carried out to 45min centrifugal; Centrifugation rate is 1500r/min; Obtaining the upper strata stillness of night contains boron oxide nanocrystal.
In the matrix material obtaining in embodiment 5, the content of boron oxide nanocrystal declines to some extent compared with boron oxide nanocrystal content in embodiment 1.It is because boric acid content declines that boron oxide nanocrystal content declines, therefore decline in substrate content distribution, this explanation can obtain different nanocrystal distributions by controlling boric acid consumption.
The above-mentioned description to embodiment is to be convenient to those skilled in the art can understand and apply the invention.Person skilled in the art easily makes various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement of making for the present invention and modification all should be within protection scope of the present invention.
Each cited raw material of the present invention can be realized 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 matrix material, has following steps:
(1) by graphite flake and boric acid, according to mass ratio, be 2:1～6:1 batching, add N-Methyl pyrrolidone organic solvent, making to add solids content after organic solvent is 0.1mg/mL～0.8mg/mL; Under normal temperature condition, carry out ultrasonic peeling off, ultrasonic power is 100W～125W;
(2) liquid step (1) being obtained carries out centrifugal 45min, and centrifugation rate is 1000r/min, gets supernatant liquid;
(3) supernatant liquid step (2) being obtained carries out ultrasonic peeling off again, and ultrasonic power is 100W～125W, obtains turbid liquid;
(4) turbid liquid step (3) being obtained carries out that 45min is centrifugal, and centrifugation rate is 1500r/min, obtains the supernatant liquid that contains boron oxide nanocrystal.
2. according to the preparation method of low defect Graphene-boron oxide nanocrystal matrix material of claim 1, it is characterized in that, the graphite flake of described step (1) also can adopt the mixture of graphene film or three's arbitrary proportion, and can by ultrasonic stripping method, realize at ambient temperature the preparation of low defect Graphene-boron oxide nanocrystal matrix material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109310084A (en) * | 2016-06-01 | 2019-02-05 | 授纳诺有限公司 | Antibacterial agent and preparation method thereof comprising carbon family non-oxide nanoparticles |
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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Patent 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109310084A (en) * | 2016-06-01 | 2019-02-05 | 授纳诺有限公司 | Antibacterial agent and preparation method thereof comprising carbon family non-oxide nanoparticles |
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