CN104028269B - Graphene loaded metal nano composite material, and preparation method and application thereof - Google Patents
Graphene loaded metal nano composite material, and preparation method and application thereof Download PDFInfo
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- CN104028269B CN104028269B CN201410277216.2A CN201410277216A CN104028269B CN 104028269 B CN104028269 B CN 104028269B CN 201410277216 A CN201410277216 A CN 201410277216A CN 104028269 B CN104028269 B CN 104028269B
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- GUJOFWGIBDKFJS-UHFFFAOYSA-N Cc(cc1N)cc(N)c1N Chemical compound Cc(cc1N)cc(N)c1N GUJOFWGIBDKFJS-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1cc(*)ccc1 Chemical compound Cc1cc(*)ccc1 0.000 description 1
- JJYPMNFTHPTTDI-UHFFFAOYSA-N Cc1cccc(N)c1 Chemical compound Cc1cccc(N)c1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 1
- QPUYECUOLPXSFR-UHFFFAOYSA-N Cc1cccc2ccccc12 Chemical compound Cc1cccc2ccccc12 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N OC(c1ccccc1)=O Chemical compound OC(c1ccccc1)=O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N OCc1ccccc1 Chemical compound OCc1ccccc1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the chemical field of nano materials, and in particular relates to a graphene loaded metal nano composite material, and a preparation method and application thereof. The invention discloses the graphene loaded metal nano composite material. Under the dispersion and bearing action of graphene, the composite material can be uniformly distributed; the size of the composite material is about 10-100nm. The composite material mainly consists of graphite and simple metal inorganic salt which serve as raw materials, water serving as a solvent, hydrazine hydrate serving as a reducing agent and a proper amount of a surfactant, and is reacted to obtain graphene loaded metal nano particles. The graphene loaded metal nano composite material has the advantages of low cost, high efficiency, energy conservation and the like, and embodiments excellent catalysis activity in benzyl oxidization, so that a low-cost, environment-friendly and high-efficiency nano composite material catalyst is supplied to industrial production.
Description
Technical field
Prepared the present invention relates to nano material and its application field, and in particular to one kind prepares graphene-supported metal and receives
Nano composite material, preparation method and its application in catalytic field.
Background technology
In recent years, carbon nanomaterial turns into the focus of Material Field research, and CNT, the discovery of fullerene cause generation
The extensive concern of various countries of boundary researcher.Graphene, alternatively referred to as " mono-layer graphite " are carbon atoms with sp2Hybridized orbit is in honeybee
The individual layer two dimensional crystal that nest lattice arrangement is constituted, due to unique, perfect structure causes that Graphene has excellent electricity, power
The characteristics such as, calorifics, optics and king-sized specific surface area.These characteristics of Graphene are that it turns into the excellent of metallic catalyst
Carrier is provided may.
At present, graphene-supported metal is mainly and is mixed by graphene oxide and slaine, adds specific reducing agent
Graphene oxide and slaine are reduced and obtain graphene-supported metal by one step simultaneously.Sun Xu brightness et al. was once reported and will aoxidize stone
Black alkene (GO) mixes with copper salt, and graphene-supported copper is obtained by sodium borohydride reduction.Renfeng Nie et al. were also reported
Graphene oxide solution mixes with chloroplatinic acid, and graphene-supported metal platinum, Lili are successfully synthesized under reduction of ethylene glycol
Jiang et al. is also reported and for GO and metal silver salt to be mixed and added into NaOH, then prepares Graphene by hydrazine hydrate reduction
Load argentum nano composite material.But all do not add surfactant and graphene oxide and metal ion to fill due to former three
Divide the reaction time too short cause easy agglomerated particle of Graphene metal nanoparticle larger.Therefore the present invention is on the basis of the former
Metal ion is set to form metal hydroxides nano particle to alkali and surfactant sodium citrate is added in system, it is scattered
More uniform, particle is smaller, then by the reduction of hydrazine hydrate, a step generates graphene-supported metal nanometer composite material.
Phenmethylol is the important intermediate of synthetic perfume and medicine, is also widely used in photosensitive, dyestuff, cosmetics, coating
And the field such as ink, with the development of relevant industries and opening to international market, the demand to phenmethylol is continuous both at home and abroad
Increase.The phenmethylol preparation method of industry mainly has gaseous oxidation toluene method, liquid phase oxidation toluene method, liquid-phase reduction benzene first at present
Sour methyl esters method.But vapour phase oxidation process and the reaction temperature requirement of reduction methyl benzoate method are too high, substantially increase reaction cost,
Make reaction very uneconomical, wherein liquid-phase oxidation of toluene method reaction condition is gentle, selectivity is good, it is technically also the most ripe.On
Text mentions graphene-supported metal nanoparticle fine catalytic action to toluene oxidation, preferably selectivity.Amit Dubey
Et al. with metallic iron load KIT (a kind of silicon nano material) reaction conversion ratio is reached 8%, the selectivity to phenmethylol reaches
50%, Yongjia Li et al. loads Graphene liquid-phase catalysis toluene oxidation with ferroheme, conversion ratio up to 9.6%, but to benzene first
Alcohol selectivity but only has 15%.The present invention is to carry out catalysis toluene using graphene-supported metal nanoparticle on the basis of forefathers
Oxidation reaction, conversion ratio can reach 2%-20%, and the selectivity of phenmethylol reaches 80%-100%.
The content of the invention
Present invention aim at providing a kind of metal nanometer composite material being supported on Graphene, preparation method and its should
With.The Graphene carrier specific surface area of the composite is big, and the active component nano-scale of load is small and is uniformly dispersed, stability
Good, preparation process is simple.It is that, up to goal of the invention, the technical solution adopted by the present invention is：Reducing agent is added by oxidation by a step
Graphene aqueous solution and metal salt solution are reduced simultaneously, finally give graphene-supported metal nanoparticle, are specifically included
Following steps：
The preparation of the graphene-supported metal nanometer composite materials of a：
With graphite oxide as raw material, it is dispersed in a certain amount of deionized water, ultrasound is completely dispersed it, aoxidizes stone
Black concentration is 0.1-2mg/mL, is subsequently adding slaine and appropriate surface agent, and the concentration of slaine is 0.1~5mol/L, surface
Surfactant concentration is 0.01-0.02mol/L, 20-40 DEG C of stirring 12-36h, adds alkali, and the concentration of alkali is 0.1~5mol/L,
Its system is transferred in 80-160 DEG C of oil bath again, is slowly added dropwise hydrazine hydrate, hydrazine hydrate volume is 1~10mL, continue to react 1~
10h, centrifugation, filtering is dried and can obtain graphene-supported metal nanometer composite material；
The graphene-supported metal nanometer composite material catalysis benzyl oxidations of b：
In there-necked flask, add 1-5mol/L benzyl aromatic compounds, 50-350mL solvents, wherein solvent for (toluene,
Acetonitrile, ethanol, methyl alcohol, isopropanol, acetic acid, ethylene glycol, tetrahydrofuran, dichloromethane, the one kind in ether), in 50-100mg
Mark thing, wherein internal standard compound are (nitrobenzene, chlorobenzene, bromobenzene, iodobenzene, P-hydroxybenzoic acid, 1, in 3,5- trimethyl toluene one
Kind), graphene-supported metal nanometer composite material catalyst 50-400mg, oxidant is (oxygen, hydrogen peroxide, t-butyl peroxy
Change the one kind in hydrogen), 5-24h is fully reacted, monitored by HPLC liquid phases, gained yield is 5-50%；
In described preparation method, alkali is added first to generate gold hydroxide metal nano-particle, then Graphene is obtained by reduction
Carried metal nano composite material；
The concentration of the alkali is 0.5~5mol/L；
The hydrazine hydrate volume is that mass fraction is 80%1~10mL；
Normal-temperature reaction will reach 12~24h after the addition slaine；
The dropwise addition hydrazine hydrate speed is 0.02-1mL/s；
Added sodium citrate amount concentration is 0.01~0.02mol/L；
During toluene oxidation solvent be toluene, acetonitrile, ethanol, methyl alcohol, isopropanol, acetic acid, ethylene glycol, tetrahydrofuran,
Dichloromethane, one or more mixtures in ether, internal standard compound is nitrobenzene, chlorobenzene, bromobenzene, iodobenzene, para hydroxybenzene
Formic acid, 1,3,5- trimethyl toluene
(1) the just step of metal hydroxides nano particle one is reduced into metal nanoparticle and is supported on the inventive method first
On Graphene, a kind of good method is provided to prepare graphene-supported metal nanoparticle, preparation method of the present invention has
Inexpensively, efficiently, energy-conservation, high-efficient simple the advantages of.
(2) obtained graphene-supported metal nano particle composite material is applied to benzyl oxidation reaction by the present invention first
In, and show good catalytic performance, be industrial production, the commercial field such as medicine intermediate provide it is a kind of it is cheap, efficiently,
The catalyst of energy-conservation.
Brief description of the drawings
The graphene-supported metal copper nano granules X-ray diffractograms of Fig. 1
The graphene-supported metal copper nano granules scanning electron microscope (SEM) photographs of Fig. 2
The graphene-supported metal copper nano granules transmission electron microscope pictures of Fig. 3
Specific embodiment
Embodiment 1：The preparation of graphene-supported copper nano composite material
Accurate weighing 375mg slaine cupric sulfate pentahydrates are dissolved in deionized water the five water sulfuric acid for being configured to 0.005mol/L
Copper solution and proper amount of surfactant sodium citrate, are mixed and are added in graphene oxide deionized water solution, ultrasonic 1h,
It is completely dispersed it, normal-temperature reaction 12h is obtained graphene oxide metal mixed salt solution.It is molten to above-mentioned mixing with dropping funel
The 50%NaOH aqueous solution, the 4mL80% hydrazine hydrates of 4.8g30mL are sequentially added in liquid, rate of addition is controlled for 1 minute 0.04mL,
12h is reacted under the conditions of 80 DEG C, is filtered, washed with water 3 times, ethanol is washed 3 times, and 60 DEG C of condition vacuum drying obtain graphene-supported gold
Category nano composite material, as a result referring to Fig. 1, the characteristic diffraction peak of graphite oxide disappears, and occurs in that carbon (002) crystal face spreads out at 25 °
Peak is penetrated, the crystallographic plane diffraction peak of copper is occurred in that 43 ° 51 ° 75 ° (003), show that graphite oxide is reduced to Graphene, while obtaining
The nano particle of copper, shows that copper has successfully been supported on the surface of Graphene.Sem test result is shown in Fig. 2, can see
Go out copper nano-particle and be dispersed in graphenic surface, transmissioning electric mirror test result referring to Fig. 3, show copper nano-particle size it is homogeneous and
The surface of Graphene is evenly distributed in, its average grain diameter is in 50nm or so.
Embodiment 2：The preparation of graphene-supported manganese nano particle composite material
According to the reaction condition of embodiment 1, the difference is that slaine cupric sulfate pentahydrate is substituted for into Manganous sulfate monohydrate, pass through
Post-reaction treatment is to obtain graphene-supported manganese metal nano material.
Embodiment 3：The preparation of graphene-supported copper manganese nano particle composite material
According to the reaction condition of embodiment 1, the difference is that slaine cupric sulfate pentahydrate is substituted for into manganese sulfate monohydrate and five
Brochanite mixed metal salt, reacted post processing is to obtain graphene-supported copper manganese Metal nano material.
Embodiment 4：The preparation of graphene-supported silver nano-grain composite
According to the reaction condition of embodiment 1, the difference is that slaine cupric sulfate pentahydrate is substituted for into silver nitrate slaine, pass through
Post-reaction treatment is to obtain graphene-supported silver metal nano material.
Embodiment 5：The preparation of graphene-supported iron nano-particle composite
According to the reaction condition of embodiment 1, the difference is that slaine cupric sulfate pentahydrate is substituted for into six aqueous ferrous sulfates gold
Category salt, reacted post processing is to obtain graphene-supported ferrous metal nano material.
Embodiment 6：The preparation of graphene-supported nano nickel particles composite
According to the reaction condition of embodiment 1, the difference is that slaine cupric sulfate pentahydrate is substituted for into nickel sulfate hexahydrate metal
Salt, reacted post processing is to obtain graphene-supported nickel metal nano material.
Embodiment 7：The preparation of graphene-supported iridium nano particle composite material
According to the reaction condition of embodiment 1, the difference is that slaine cupric sulfate pentahydrate is substituted for into iridium chloride slaine, pass through
Post-reaction treatment is to obtain graphene-supported iraurite metal nanometer material.
In following application examples, obtained graphene-supported metal nano material is aoxidized in following benzyl in above-described embodiment
As catalyst in reaction, wherein CAT represents graphene-supported metal nano material catalyst.
Application examples 1：The application example illustrates the process and result of graphene-supported copper nano material catalysis oxidation toluene
Toluene 4g, CAT150~400mg, 50~100mL of methyl alcohol is weighed, 1~5mL of hydrogen peroxide reacts 12 under the conditions of 80 DEG C
~36h, conversion ratio can reach 5%~50%, and benzyl alcohol selective is 80%-100%.
Application examples 2：The application example illustrates process and knot of the graphene-supported copper nano material catalysis oxidation to hydroxy-methylbenzene
Really
According to reaction condition in application examples 1, the difference is that substrate is replaced into toluene to hydroxy-methylbenzene, hydroxy-methylbenzene is converted
Rate is 5%-50%, and p-Hydroxybenzylalcohol is selectively 80%-100%.
Application examples 3：The application example illustrates the process and knot of the catalysis oxidation parachlorotoluene of graphene-supported copper nano material
Really
According to reaction condition in application examples 1, the difference is that substrate is replaced into toluene, parachlorotoluene conversion ratio to chloro toluene
It is 5%-50%, is selectively 80%-100% to chlorobenzene methanol.
Application examples 4：The application example illustrate the catalysis oxidation para-nitrotoluene of graphene-supported copper nano material process and
As a result
According to reaction condition in application examples 1, the difference is that substrate para-nitrotoluene is replaced into toluene, para-nitrotoluene conversion
Rate is 5%-50%, and p nitrobenzyl alcohol is selectively 80%-100%.
Application examples 5：The application example illustrates the process and result of graphene-supported copper nano material catalysis oxidation m-chlorotoluene
According to reaction condition in application examples 1, the difference is that substrate is replaced into toluene, m-chlorotoluene conversion ratio to m-chlorotoluene
It is 5%-50%, m-chloro benzyl alcohol selective is 80%-100%.
Application examples 6：The application example explanation catalyst is the process and result of graphene-supported manganese nano material catalysis oxidation
Reaction condition according to application examples 1 is carried out, the difference is that catalyst substitutes stone with graphene-supported manganese nano material
Black alkene supported copper nano material, reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 7：The application example illustrates the process and result of graphene-supported silver nano material catalysis oxidation
Reaction condition according to application examples 1 is carried out, the difference is that catalyst substitutes stone with graphene-supported silver nano material
Black alkene supported copper nano material, reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 8：The application example illustrates the process and result of graphene-supported nickel nano material catalysis oxidation
Reaction condition according to application examples 1 is carried out, the difference is that catalyst substitutes stone with graphene-supported nickel nano material
Black alkene supported copper nano material, reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 9：The application example illustrates the process and result of graphene-supported iridium nano material catalysis oxidation
Reaction condition according to application examples 1 is carried out, the difference is that catalyst substitutes stone with graphene-supported iridium nano material
Black alkene supported copper nano material, reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 10：The application example explanation solvent is the course of reaction and result in the case of acetonitrile
Reaction condition according to application examples 1 is carried out, the difference is that substituting methyl alcohol with acetonitrile solvent, reaction result is that toluene turns
Rate 5%-50%, benzyl alcohol selective is 80%-100%.
Application examples 11：The application example explanation solvent is the course of reaction and result in the case of acetic acid
Reaction condition according to application examples 1 is carried out, the difference is that substituting methyl alcohol with acetate solvate, reaction result is that toluene turns
Rate 5%-50%, benzyl alcohol selective is 80%-100%.
Application examples 12：The application example explanation oxidant is the course of reaction and result in the case of oxygen
Reaction condition according to application examples 1 is carried out, the difference is that substituting hydrogen peroxide with oxidant oxygen, reaction result is first
Benzene conversion ratio 5%-50%, benzyl alcohol selective is 80%-100%.
Application examples 13：The application example explanation oxidant is the course of reaction and result in the case of TBHP
Reaction condition according to application examples 1 is carried out, the difference is that hydrogen peroxide is substituted with oxidant TBHP, instead
Should result be toluene conversion 5%-50%, benzyl alcohol selective is 80%-100%.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not intended to limit, for the technology people in this field
For member, the present invention can have a various change, all any modifications made within technical field of the invention, equivalent,
Improve etc., should be included within the scope of the present invention.
Claims (6)
1. graphene-supported metal nanometer composite material is used for the method for preparing fragrant benzylalcohol, it is characterised in that described graphite
In alkene carried metal nano composite material, metal nanoparticle is dispersed on Graphene, and the metal particle diameter is 10-
100nm, metallic particles quality is the 1-10% of composite gross mass, and described method includes procedure below：
Reactant concentration is 1-5mol/L, 150~400mg of graphene-supported metal nanometer composite material catalyst, solvent 10~
12~36h is reacted under the conditions of 500mL, 80-120 DEG C, conversion ratio can reach 5%~50%, and the selectivity of fragrant benzylalcohol reaches
80%-100%；The reactant is
In one or more mixtures.
2. method according to claim 1, it is characterised in that the solvent is toluene, acetonitrile, ethanol, methyl alcohol, isopropyl
Alcohol, acetic acid, ethylene glycol, tetrahydrofuran, dichloromethane, one or more mixtures in ether.
3. method according to claim 1, it is characterised in that oxidant is air, oxygen, hydrogen peroxide, t-butyl peroxy
Change one or more mixtures in hydrogen.
4. method according to claim 1, it is characterised in that the preparation of the graphene-supported metal nanometer composite material
Method is as follows：
(1) add graphene oxide into ultra-pure water, ultrasound is completely dispersed it, be made into the oxidation that concentration is 0.1-5mg/mL
The aqueous solution of Graphene；
(2) stir 12-36h at slaine, 20-40 DEG C to being added in above-mentioned graphene oxide water solution, fill metal cation
That divides is combined with graphene oxide, obtains graphene oxide and metal mixed salt solution；
(3) in above-mentioned mixed solution add surfactant 0.01-0.1mol/L, be sufficiently stirred for 12-36h, prevent metal from
Son is reunited, and adds alkali 0.5-5mol/L, and reaction system is transferred in oil bath, is slowly added dropwise hydrazine hydrate, and rate of addition is
0.02-1mL/ seconds, 60-120 DEG C of reaction 12-24h of control temperature, filtering was dried, and obtains final product graphene-supported metal nano composite wood
Material；
The quality of described slaine is the 1-10% of graphene oxide quality.
5. the method described in claim 4, it is characterised in that the slaine is any one in copper, manganese, silver, iron, iridium, nickel
Kind or the sulfate of more than one alloy, nitrate or hydrochloride.
6. the method described in claim 4, it is characterised in that the alkali is NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate, carbon
Any one in sour hydrogen sodium, potassium carbonate, saleratus or more than one mixtures.
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| CN102350357B (en) * | 2011-07-27 | 2013-06-05 | 天津大学 | Nano-nickel catalyst loaded on grapheme and preparation method thereof |
| CN103191742B (en) * | 2013-04-11 | 2015-04-29 | 济南市供排水监测中心 | Carbon material loaded nano zero valence metal catalyst and preparation method and application thereof |
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