CN101912777B - 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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- CN101912777B CN101912777B CN201010241951A CN201010241951A CN101912777B CN 101912777 B CN101912777 B CN 101912777B CN 201010241951 A CN201010241951 A CN 201010241951A CN 201010241951 A CN201010241951 A CN 201010241951A CN 101912777 B CN101912777 B CN 101912777B
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- graphene oxide
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- precious metal
- dimensional self
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 238000001338 self-assembly Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000010970 precious metal Substances 0.000 claims abstract description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical group [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 3
- 150000002736 metal compounds Chemical class 0.000 abstract 2
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
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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 said mixed liquor at 80-220 ℃ of hydrothermal treatment consists 1-30h, obtain said three-dimensional self-assembly of graphene oxide; Wherein, said reducing substances is citric acid and/or polyethylene glycol; In the said 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 said 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 said 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 said precious metal chemical complex can be selected from following any one: Au, Ag, Pd, Pt, Ru, Ir and Rh.Said 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, under the promotion of noble metal, utilizes the method for hydro-thermal to realize the three-dimensional self assembly of graphene oxide.Method preparation condition provided by the present invention is gentle, easy and simple to handle, products obtained therefrom has 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 through 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 through 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 like no specified otherwise, is conventional method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
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 is 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 through 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 through detecting 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 said mixed liquor at 80-220 ℃ of hydrothermal treatment consists 1-30h, obtain said three-dimensional self-assembly of graphene oxide; Wherein, said reducing substances is citric acid and/or polyethylene glycol; In the said 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 said 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 said hydrothermal treatment consists is: 80-200 ℃ of hydrothermal treatment consists 6-15h.
4. method according to claim 1 is characterized in that: the noble metal in the said 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 said precious metal chemical complex is Au, Ag or Pd.
6. method according to claim 5 is characterized in that: said precious metal chemical complex is gold chloride, silver nitrate or platinum chloride.
7. the three-dimensional self-assembly of graphene oxide that arbitrary said 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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| CN101912777B true CN101912777B (en) | 2012-10-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103201216B (en) * | 2010-12-31 | 2015-07-22 | 海洋王照明科技股份有限公司 | Composite material of carbon-coated graphene oxide, preparation method and application thereof |
| CN102515144B (en) * | 2011-12-23 | 2014-04-02 | 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 |
| CA2876930C (en) * | 2012-06-18 | 2016-12-06 | 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 |
| 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 |
| 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 |
| CN104907018B (en) * | 2015-05-25 | 2017-03-01 | 齐鲁工业大学 | A kind of three-dimensional metatitanic acid/graphene oxide pluralgel and preparation method thereof |
| CN105964247B (en) * | 2016-06-12 | 2019-01-25 | 常州大学 | A kind of preparation method of three-dimensional redox graphene load nano Pd particle hydrogenation catalyst |
| 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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| CN101161338B (en) * | 2007-11-16 | 2010-06-02 | 南京理工大学 | Oxidized graphite of loading Cu2O particle and its preparing method |
| CN101161336B (en) * | 2007-11-16 | 2010-06-02 | 南京理工大学 | Oxidized graphite of loading nanometer metallic silver particle and its preparing method |
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Non-Patent Citations (1)
| Title |
|---|
| Zhihong Tang, et al.Noble-Metal-Promoted Three-Dimensional Macroassembly of Single-Layered Graphene Oxide.《Angewandte Chemie》.2010,第122卷(第27期),4707–4711. * |
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