CN101912777A - Three-dimensional self-assembly of graphene oxide and preparation method and application thereof - Google Patents
Three-dimensional self-assembly of graphene oxide and preparation method and application thereof Download PDFInfo
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- CN101912777A CN101912777A CN 201010241951 CN201010241951A CN101912777A CN 101912777 A CN101912777 A CN 101912777A CN 201010241951 CN201010241951 CN 201010241951 CN 201010241951 A CN201010241951 A CN 201010241951A CN 101912777 A CN101912777 A CN 101912777A
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Abstract
The invention discloses a three-dimensional self-assembly of graphene oxide and a preparation method and application thereof. The preparation method for the three-dimensional self-assembly of the graphene oxide of the invention comprises the following steps of: dissolving a precious metal compound and reducing substances into the suspension of the graphene oxide to obtain mixed liquid; and thermally treating the mixed liquid in water of 80 to 220 DEG C for 1 to 30 hours to obtain the three-dimensional self-assembly of the graphene oxide, wherein the reducing substances are citric acid and/or polyethylene glycol and the mass ratio of the reducing substances, the precious metal compound to the graphene oxide in the mixed liquid is 0-400:0-10:1. In the three-dimensional porous self-assembly of the graphene oxide prepared by the method, precious metal nano particles are uniformly dispersed on graphene oxide sheets, so that the three-dimensional porous self-assembly of the graphene oxide has good application prospects.
Description
Technical field
The present invention relates to a kind of three-dimensional self-assembly of graphene oxide and preparation method thereof and application.
Background technology
Graphene oxide is at H with graphite
2SO
4, HNO
3Deng strong acid and KMnO
4Under the effect Deng strong oxidizer, through intercalation, hydrolysis, peel off that the back forms contain-C-OH ,-C-O-C even-individual layer and the multiple stratification compound of groups such as COOH.Graphene oxide can be thought functionalized Graphene, owing to have a large amount of oxygen-containing functional groups on the graphene oxide plane, makes it have very strong polarity, and good dispersive property is arranged in water.In addition, the existence that surface pipe can be rolled into a ball combines it easily with other compounds, modified easily.These character of graphene oxide interconnect it easily, form three-dimensional self-assembly.
Summary of the invention
The purpose of this invention is to provide a kind of three-dimensional self-assembly of graphene oxide and preparation method thereof.
Three-dimensional self-assembly of graphene oxide provided by the present invention prepares according to following method: precious metal chemical complex and reducing substances are dissolved in the suspension of graphene oxide, get mixed liquor; And with described mixed liquor at 80-220 ℃ of hydrothermal treatment consists 1-30h, obtain described three-dimensional self-assembly of graphene oxide; Wherein, described reducing substances is citric acid and/or polyethylene glycol; In the described mixed liquor, the mass ratio of reducing substances, precious metal chemical complex and graphene oxide is followed successively by 0-400: 0-10: 1.
Wherein, in the described mixed liquor, the mass ratio of reducing substances, precious metal chemical complex and graphene oxide is preferably 32-86: 0.0286-2.86: 1, further can be 57-86: 0.0286-2.86: and 1, specifically can be 86: 0.0286: 1 or 57: 2.86: 1.The condition of described hydrothermal treatment consists is preferably: 80-200 ℃ of hydrothermal treatment consists 6-15h; Specifically can be 80 ℃ of hydrothermal treatment consists 15h, or 200 ℃ of hydrothermal treatment consists 6h.
Noble metal in the described precious metal chemical complex can be selected from following any one: Au, Ag, Pd, Pt, Ru, Ir and Rh.Described precious metal chemical complex specifically can be palladium bichloride, silver nitrate and gold chloride etc.
The present invention utilizes oxygen-containing functional groups a large amount of on the graphene oxide surface, utilizes the method for hydro-thermal to realize the three-dimensional self assembly of graphene oxide under the promotion of noble metal.Method preparation condition gentleness provided by the present invention, easy and simple to handle, products obtained therefrom have certain intensity, and noble metal nano particles can load on the graphene oxide equably.This method can realize controlling simultaneously the microscopic aperture and the macro-size of porous three-dimensional self-assembly by the concentration and the volume of regulation and control graphene oxide suspension.Because the existence of noble metal makes it become a kind of good catalyst in the three-dimensional porous self-assembly.The present invention has realized the three-dimensional self assembly of graphene oxide first by introducing noble metal, for the further research of Graphene and graphene oxide has important significance for theories.And load has the three-dimensional self-assembly of graphene oxide of noble metal also to have a good application prospect at catalytic field.
Description of drawings
Fig. 1 is the optical photograph of the three-dimensional self-assembly of graphene oxide of embodiment 1 preparation.
Fig. 2 is that the mechanical performance of the sample of embodiment 1 preparation characterizes.
Fig. 3 is that the SEM (SEM) of the sample of embodiment 1 preparation characterizes.
Fig. 4 is that the HRTEM (high resolution transmission electron microscopy) of the sample of embodiment 1 preparation characterizes; Wherein 4a is the monolithic graphene oxide figure that load has noble metal, and 4b is the electromicroscopic photograph of single nano particle.
Fig. 5 is that the XRD (X-ray diffraction) of embodiment 1 prepared sample characterizes.
The specific embodiment
Experimental technique described in the following embodiment if no special instructions, is conventional method; Described reagent and material if no special instructions, all can obtain from commercial channels.
The three-dimensional self-assembly of embodiment 1, graphene oxide
0.001g palladium bichloride and 3g citric acid are joined in the graphene oxide suspension of 35ml 1mg/ml, stir 30min, hydro-thermal is handled 15h for 80 ℃, obtains the three-dimensional self-assembly of graphene oxide.The exterior appearance of this product is seen Fig. 1, and its mechanical performance as shown in Figure 2.The microscopic appearance of sample is seen Fig. 3 SEM (SEM).HRTEM (high-resolution transmission microscopy) characterizes and sees Fig. 4, and XRD (X-ray diffraction) characterizes and sees Fig. 5.
By shown in Figure 1, the products obtained therefrom diameter is about 1.2cm, the high 2.0cm of being.Can find out intuitively that from the sign of Fig. 2 the three-dimensional self-assembly of graphene oxide can bear the pressure of about 330g.The three-dimensional self-assembly that can be obtained graphene oxide by the SEM photo of sample is a loose structure.The HRTEM photo shows that noble metal nano particles is high degree of dispersion on graphene oxide, and the particle diameter of nano particle is about 10-30nm.The result of XRD figure spectrum shows and contains the very high precious metal palladium of crystallinity in the gained sample.
The three-dimensional self-assembly of embodiment 2, graphene oxide
0.1g silver nitrate and 2g polyethylene glycol (PEG2000) are joined in the graphene oxide suspension of 35ml 1mg/ml, stir 30min, hydro-thermal is handled 6h for 200 ℃, obtains the three-dimensional self-assembly of graphene oxide.
Embodiment 3, the application of three-dimensional self-assembly of graphene oxide in the HECK reaction
Load among the embodiment 1 is had the catalyst of precious metal palladium, and (molar content of palladium is 0.1%, the molar content of palladium obtains by product being done ICP (inductively coupled plasma) analytical calculation in this catalyst) and 5mlNMP (n-formyl sarcolysine base pyrrolidones) place the round-bottomed flask of 25ml, add the 1mmol iodobenzene then, 2mmol methyl acrylate and 2mmol K
2CO
3, flask is sealed in 120 ℃ of heating 2h in the oil bath, detect the product that obtains with GC (gas-chromatography)-MS (mass spectrum).Find that after testing product yield and selectivity that this reaction system obtains are 100%.
Claims (8)
1. a method for preparing three-dimensional self-assembly of graphene oxide comprises the steps: precious metal chemical complex and reducing substances are dissolved in the suspension of graphene oxide, gets mixed liquor; And with described mixed liquor at 80-220 ℃ of hydrothermal treatment consists 1-30h, obtain described three-dimensional self-assembly of graphene oxide; Wherein, described reducing substances is citric acid and/or polyethylene glycol; In the described mixed liquor, the mass ratio of reducing substances, precious metal chemical complex and graphene oxide is for being followed successively by 0-400: 0-10: 1.
2. method according to claim 1 is characterized in that: in the described mixed liquor, the mass ratio of reducing substances, precious metal chemical complex and graphene oxide is followed successively by 32-86: 0.0286-2.86: 1.
3. method according to claim 1 and 2 is characterized in that: the condition of described hydrothermal treatment consists is: 80-200 ℃ of hydrothermal treatment consists 6-15h.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: the noble metal in the described precious metal chemical complex be selected from following any one: Au, Ag, Pd, Pt, Ru, Ir and Rh.
5. method according to claim 4 is characterized in that: the noble metal in the described precious metal chemical complex is Au, Ag or Pd.
6. method according to claim 5 is characterized in that: described precious metal chemical complex is gold chloride, silver nitrate or platinum chloride.
7. the three-dimensional self-assembly of graphene oxide that arbitrary described method prepares among the claim 1-6.
8. the described three-dimensional self-assembly of graphene oxide of claim 7 is as the application of catalyst in the precious metal catalyst reaction.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102515144A (en) * | 2011-12-23 | 2012-06-27 | 哈尔滨工业大学 | Method for preparing porous carbon microspheres converted from graphene |
| CN102580714A (en) * | 2012-02-09 | 2012-07-18 | 江苏大学 | Graphene oxide/silver phosphate composite visible light catalyst and preparation method thereof |
| CN102581297A (en) * | 2012-02-06 | 2012-07-18 | 上海交通大学 | Method for preparing controllable green synthetic metallic nano-materials based on graphene oxide |
| CN102897756A (en) * | 2012-09-19 | 2013-01-30 | 电子科技大学 | Preparation method of graphene |
| CN103286318A (en) * | 2013-04-03 | 2013-09-11 | 华中科技大学 | Preparation method of nano precious metal-carbon nano tube-graphene composite and nano precious metal-carbon nano tube-graphene composite product |
| CN103449577A (en) * | 2013-09-16 | 2013-12-18 | 湖南大学 | Method for efficiently and quickly killing bacteria in water |
| WO2013191654A1 (en) * | 2012-06-18 | 2013-12-27 | National University Of Singapore | Porous graphene oxide materials |
| CN104332637A (en) * | 2014-09-20 | 2015-02-04 | 杭州电子科技大学 | Preparation method of catalyst of porous graphene loading precious metal nano particles |
| CN104907018A (en) * | 2015-05-25 | 2015-09-16 | 齐鲁工业大学 | Three-dimensional titanic acid/graphene oxide composite gel, and preparation method thereof |
| CN105312063A (en) * | 2014-07-01 | 2016-02-10 | 韩爱英 | Graphene composite catalyst and preparation method thereof |
| EP2660199A4 (en) * | 2010-12-31 | 2016-06-15 | Ocean S King Lighting Science&Technology Co Ltd | Composite material of carbon-coated graphene oxide, preparation method and application thereof |
| CN105964247A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Preparation method of nano-Pd hydrogenation catalyst loaded with three-dimensional reduction graphene oxide |
| CN107322004A (en) * | 2017-06-07 | 2017-11-07 | 安徽师范大学 | A kind of silver/redox graphene nano composite material and application |
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| CN101161338A (en) * | 2007-11-16 | 2008-04-16 | 南京理工大学 | Oxidized plumbago of loading Cu*O corpuscule and its preparing method |
| CN101161336A (en) * | 2007-11-16 | 2008-04-16 | 南京理工大学 | Oxidized plumbago of loading nanometer metallic silver corpuscle and its preparing method |
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2010
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| CN101161338A (en) * | 2007-11-16 | 2008-04-16 | 南京理工大学 | Oxidized plumbago of loading Cu*O corpuscule and its preparing method |
| CN101161336A (en) * | 2007-11-16 | 2008-04-16 | 南京理工大学 | Oxidized plumbago of loading nanometer metallic silver corpuscle and its preparing method |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102115069B (en) * | 2010-12-20 | 2012-09-05 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| EP2660199A4 (en) * | 2010-12-31 | 2016-06-15 | Ocean S King Lighting Science&Technology Co Ltd | Composite material of carbon-coated graphene oxide, preparation method and application thereof |
| CN102515144A (en) * | 2011-12-23 | 2012-06-27 | 哈尔滨工业大学 | Method for preparing porous carbon microspheres converted from graphene |
| CN102581297A (en) * | 2012-02-06 | 2012-07-18 | 上海交通大学 | Method for preparing controllable green synthetic metallic nano-materials based on graphene oxide |
| CN102580714A (en) * | 2012-02-09 | 2012-07-18 | 江苏大学 | Graphene oxide/silver phosphate composite visible light catalyst and preparation method thereof |
| WO2013191654A1 (en) * | 2012-06-18 | 2013-12-27 | National University Of Singapore | Porous graphene oxide materials |
| US9180442B2 (en) | 2012-06-18 | 2015-11-10 | National University Of Singapore | Porous graphene oxide materials |
| CN102897756A (en) * | 2012-09-19 | 2013-01-30 | 电子科技大学 | Preparation method of graphene |
| CN103286318A (en) * | 2013-04-03 | 2013-09-11 | 华中科技大学 | Preparation method of nano precious metal-carbon nano tube-graphene composite and nano precious metal-carbon nano tube-graphene composite product |
| CN103286318B (en) * | 2013-04-03 | 2014-11-12 | 华中科技大学 | Preparation method of nano precious metal-carbon nano tube-graphene composite and nano precious metal-carbon nano tube-graphene composite product |
| CN103449577A (en) * | 2013-09-16 | 2013-12-18 | 湖南大学 | Method for efficiently and quickly killing bacteria in water |
| CN105312063A (en) * | 2014-07-01 | 2016-02-10 | 韩爱英 | Graphene composite catalyst and preparation method thereof |
| CN104332637A (en) * | 2014-09-20 | 2015-02-04 | 杭州电子科技大学 | Preparation method of catalyst of porous graphene loading precious metal nano particles |
| CN104332637B (en) * | 2014-09-20 | 2016-08-17 | 杭州电子科技大学 | A kind of noble metal nano particles is carried on the method for preparing catalyst of porous graphene |
| CN104907018A (en) * | 2015-05-25 | 2015-09-16 | 齐鲁工业大学 | Three-dimensional titanic acid/graphene oxide composite gel, and preparation method thereof |
| CN105964247A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Preparation method of nano-Pd hydrogenation catalyst loaded with three-dimensional reduction graphene oxide |
| CN107322004A (en) * | 2017-06-07 | 2017-11-07 | 安徽师范大学 | A kind of silver/redox graphene nano composite material and application |
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