CN104028269A - 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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- CN104028269A CN104028269A CN201410277216.2A CN201410277216A CN104028269A CN 104028269 A CN104028269 A CN 104028269A CN 201410277216 A CN201410277216 A CN 201410277216A CN 104028269 A CN104028269 A CN 104028269A
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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
The present invention relates to nano material preparation and application thereof, be specifically related to a kind of prepare graphene-supported metal nanometer composite material, preparation method and the application in catalytic field thereof.
Background technology
In recent years, carbon nanomaterial becomes the focus of Material Field research, and the discovery of CNT, fullerene has caused countries in the world researchers' extensive concern.Graphene, also can be described as " mono-layer graphite ", is that carbon atom is with sp
2hybridized orbit is the individual layer two dimensional crystal that honeycomb lattice arrangement forms, and due to uniqueness, perfectly structure makes Graphene have characteristic and the king-sized specific areas such as excellent electricity, mechanics, calorifics, optics.These characteristics of Graphene for its excellent carrier that becomes metallic catalyst provide may.
At present, if graphene-supported master metal is mixed by graphene oxide and slaine, add specific reducing agent one step that graphene oxide and slaine are reduced simultaneously and obtain graphene-supported metal.The people such as Sun Xuhui once reported graphene oxide (GO) were mixed with copper salt, obtained graphene-supported copper by sodium borohydride reduction.The people such as Renfeng Nie also report that peroxidating graphene solution mixes with chloroplatinic acid, under reduction of ethylene glycol, successfully synthesize graphene-supported metal platinum, the people such as Lili Jiang have also reported GO have been mixed and added NaOH with metal silver salt, then prepared graphene-supported argentum nano composite material by hydrazine hydrate reduction.But because former three does not all add surfactant and graphene oxide and metal ion sufficient reaction time, too short to cause the easy agglomerated particle of Graphene metal nanoparticle larger.Therefore the present invention has added alkali and surfactant natrium citricum to make metal ion form metal hydroxides nano particle on the former basis in system, that disperses is more even, particle is less, then passes through the reduction of hydrazine hydrate, and a step has generated graphene-supported metal nanometer composite material.
Phenmethylol is synthetic perfume and medical important intermediate, is also widely used in the fields such as sensitization, dyestuff, cosmetics, coating and ink. along with the development of relevant industries and to the opening of international market, both at home and abroad the demand of phenmethylol is constantly increased.The phenmethylol preparation method of industry mainly contains gaseous oxidation toluene method, liquid phase oxidation toluene method, liquid-phase reduction methyl benzoate method at present.But it is too high that vapour phase oxidation process and reduction methyl benzoate method reaction temperature require, and greatly improved reaction cost, makes reaction very uneconomical, wherein liquid-phase oxidation of toluene method reaction condition gentleness is selectively good, technical also the most ripe.Mentioning graphene-supported metal nanoparticle above has fine catalytic action to toluene oxidation, selective preferably.The people such as Amit Dubey make reaction conversion ratio reach 8% with metallic iron load KIT (a kind of silicon nano material), phenmethylol selectively reached to 50%, the people such as Yongjia Li use ferroheme load Graphene liquid-phase catalysis toluene oxidation, conversion ratio reaches 9.6%, but benzyl alcohol selective is only had to 15%.The present invention adopts graphene-supported metal nanoparticle to carry out the reaction of catalysis toluene oxidation on forefathers basis, and conversion ratio can reach 2%-20%, phenmethylol selectively reach 80%-100%.
Summary of the invention
The object of the invention is to provide a kind of metal nanometer composite material, preparation method and application thereof loading on Graphene.The Graphene carrier specific area of this composite is large, and the active component nano-scale of load is little and be uniformly dispersed, good stability, and preparation process is simple.For reaching goal of the invention, the technical solution used in the present invention is: add reducing agent that graphite oxide aqueous solution and metal salt solution are reduced by a step simultaneously, finally obtain graphene-supported metal nanoparticle, specifically comprise the following steps:
The preparation of the graphene-supported metal nanometer composite material of a:
Taking graphite oxide as raw material, be dispersed in a certain amount of deionized water, ultrasonic it is disperseed completely, graphite oxide concentration is 0.1-2mg/mL, then add slaine and appropriate surface agent, the concentration of slaine is 0.1～5mol/L, surfactant concentration is 0.01-0.02mol/L, 20-40 DEG C is stirred 12-36h, add again alkali, the concentration of alkali is 0.1～5mol/L, again its system is transferred in 80-160 DEG C of oil bath, slowly drip hydrazine hydrate, hydrazine hydrate volume is 1～10mL, continue reaction 1～10h, centrifugal, filter, be dried and can obtain graphene-supported metal nanometer composite material,
The oxidation of the graphene-supported metal nanometer composite material catalysis of b benzyl:
In there-necked flask, add 1-5mol/L benzyl aromatic compound, 50-350mL solvent, wherein solvent is (toluene, acetonitrile, ethanol, methyl alcohol, isopropyl alcohol, acetic acid, ethylene glycol, oxolane, carrene, one in ether), 50-100mg internal standard compound, wherein internal standard compound is (nitrobenzene, chlorobenzene, bromobenzene, iodobenzene, P-hydroxybenzoic acid, 1, 3, one in 5-trimethyl toluene), graphene-supported metal nanometer composite material catalyst 50-400mg, oxidant is (oxygen, hydrogen peroxide, one in TBHP), fully reaction 5-24h, monitor by HPLC liquid phase, gained productive rate is 5-50%,
In described preparation method, add alkali first to generate gold hydroxide metal nano-particle, then obtain graphene-supported metal nanometer composite material by reduction;
The concentration of described alkali is 0.5～5mol/L;
Described hydrazine hydrate volume is that mass fraction is 80%1～10mL;
Described add slaine after normal-temperature reaction to reach 12～24h;
Described dropping hydrazine hydrate speed is 0.02-1mL/s;
Institute's adding citric acid sodium amount concentration is 0.01～0.02mol/L;
In toluene oxidation process, solvent is toluene, acetonitrile, ethanol, methyl alcohol, isopropyl alcohol, acetic acid, ethylene glycol, oxolane, carrene, one or more mixtures in ether, internal standard compound is nitrobenzene, chlorobenzene, bromobenzene, iodobenzene, P-hydroxybenzoic acid, 1,3,5-trimethyl toluene
(1) the inventive method first just metal hydroxides nano particle one step be reduced into metal nanoparticle and load on Graphene, provide a kind of good method for preparing graphene-supported metal nanoparticle, preparation method of the present invention has the advantages such as cheapness, efficient, energy-conservation, high-efficient simple.
(2) the present invention is applied to the graphene-supported metal nano particle composite material making in benzyl oxidation reaction first, and show good catalytic performance, for industrial production, the commercial fields such as medicine intermediate provide a kind of cheapness, efficient, energy-conservation catalyst.
Brief description of the drawings
The graphene-supported metal copper nano granules X-ray diffractogram of Fig. 1
The graphene-supported metal copper nano granules scanning electron microscope (SEM) photograph of Fig. 2
The graphene-supported metal copper nano granules transmission electron microscope picture of Fig. 3
Detailed description of the invention
Embodiment 1: the preparation of graphene-supported copper nano composite material
Accurate weighing 375mg slaine cupric sulfate pentahydrate is dissolved in the cupric sulfate pentahydrate solution and the proper amount of surfactant natrium citricum that in deionized water, are mixed with 0.005mol/L, be mixed to join in graphene oxide deionized water solution, ultrasonic 1h, it is disperseed completely, normal-temperature reaction 12h, makes graphene oxide slaine mixed solution.With dropping funel to the 50%NaOH aqueous solution that adds successively 4.8g30mL in above-mentioned mixed solution, 4mL80% hydrazine hydrate, controlling rate of addition is 1 minute 0.04mL, under 80 DEG C of conditions, react 12h, filter, wash with water 3 times, ethanol is washed 3 times, 60 DEG C of condition vacuum drying obtain graphene-supported metal nanometer composite material, result is referring to Fig. 1, the characteristic diffraction peak of graphite oxide disappears, there is carbon (002) crystal face diffraction maximum at 25 °, there is the crystal face diffraction maximum of copper 43 ° 51 ° 75 ° (003), show that graphite oxide is reduced to Graphene, obtain the nano particle of copper simultaneously, show that copper has successfully loaded on the surface of Graphene.Sem test the results are shown in Figure 2, can find out that copper nano-particle is dispersed in Graphene surface, and transmissioning electric mirror test result is referring to Fig. 3, shows copper nano-particle size homogeneous and is evenly distributed in the surface of Graphene, and its average grain diameter is in 50nm left and right.
Embodiment 2: the preparation of graphene-supported manganese nano particle composite material
According to the reaction condition of embodiment 1, different is that slaine cupric sulfate pentahydrate is replaced to Manganous sulfate monohydrate, obtains graphene-supported manganese metal nano material through post-reaction treatment.
Embodiment 3: the preparation of graphene-supported copper manganese nano particle composite material
According to the reaction condition of embodiment 1, different is that slaine cupric sulfate pentahydrate is replaced to manganese sulfate monohydrate and cupric sulfate pentahydrate mixed metal salt, obtains graphene-supported copper manganese metal nano material through post-reaction treatment.
Embodiment 4: the preparation of graphene-supported silver nano-grain composite
According to the reaction condition of embodiment 1, different is that slaine cupric sulfate pentahydrate is replaced to silver nitrate slaine, obtains graphene-supported silver metal nano material through post-reaction treatment.
Embodiment 5: the preparation of graphene-supported iron nano-particle composite
According to the reaction condition of embodiment 1, different is that slaine cupric sulfate pentahydrate is replaced to six aqueous ferrous sulfate slaines, obtains graphene-supported ferrous metal nano material through post-reaction treatment.
Embodiment 6: the preparation of graphene-supported nano nickel particles composite
According to the reaction condition of embodiment 1, different is that slaine cupric sulfate pentahydrate is replaced to nickel sulfate hexahydrate slaine, obtains graphene-supported nickel metal nano material through post-reaction treatment.
Embodiment 7: the preparation of graphene-supported iridium nano particle composite material
According to the reaction condition of embodiment 1, different is that slaine cupric sulfate pentahydrate is replaced to iridium chloride slaine, obtains graphene-supported iridium metals nano material through post-reaction treatment.
In following application examples, the graphene-supported metal nano material making in above-described embodiment is as catalyst in following benzyl oxidation reaction, and wherein CAT represents graphene-supported metal nano material catalyst.
Application examples 1: process and result that graphene-supported copper nano material catalytic oxidation toluene should use-case be described
Take toluene 4g, CAT150～400mg, methyl alcohol 50～100mL, hydrogen peroxide 1～5mL, reacts 12～36h under 80 DEG C of conditions, and conversion ratio can reach 5%～50%, and benzyl alcohol selective is 80%-100%.
Application examples 2: should process and the result of graphene-supported copper nano material catalytic oxidation to hydroxy-methylbenzene be described use-case
According to reaction condition in application examples 1, different is that substrate is replaced to toluene to hydroxy-methylbenzene, is 5%-50% to hydroxy-methylbenzene conversion ratio, and p-Hydroxybenzylalcohol is selectively 80%-100%.
Application examples 3: process and result that the catalytic oxidation parachlorotoluene of graphene-supported copper nano material should use-case be described
According to reaction condition in application examples 1, different is that substrate is replaced to toluene to chloro toluene, and parachlorotoluene conversion ratio is 5%-50%, is selectively 80%-100% to chlorobenzene methanol.
Application examples 4: process and result that the catalytic oxidation para-nitrotoluene of graphene-supported copper nano material should use-case be described
According to reaction condition in application examples 1, different is that substrate para-nitrotoluene is replaced to toluene, and para-nitrotoluene conversion ratio is 5%-50%, and p-nitrophenyl methyl alcohol is selectively 80%-100%.
Application examples 5: process and result that graphene-supported copper nano material catalytic oxidation m-chlorotoluene should use-case be described
According to reaction condition in application examples 1, different is that substrate is replaced to toluene to m-chlorotoluene, and m-chlorotoluene conversion ratio is 5%-50%, and m-chloro benzyl alcohol selective is 80%-100%.
Application examples 6: should use-case explanation catalyst be process and the result of graphene-supported manganese nano material catalytic oxidation
Carry out according to the reaction condition of application examples 1, different is that the graphene-supported manganese nano material of catalyst substitutes graphene-supported copper nano material, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 7: process and result that graphene-supported silver nano material catalytic oxidation should use-case be described
Carry out according to the reaction condition of application examples 1, different is that the graphene-supported silver nano material of catalyst substitutes graphene-supported copper nano material, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 8: process and result that graphene-supported nickel nano material catalytic oxidation should use-case be described
Carry out according to the reaction condition of application examples 1, different is that the graphene-supported nickel nano material of catalyst substitutes graphene-supported copper nano material, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 9: process and result that graphene-supported iridium nano material catalytic oxidation should use-case be described
Carry out according to the reaction condition of application examples 1, different is that the graphene-supported iridium nano material of catalyst substitutes graphene-supported copper nano material, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 10: should course of reaction and the result in the situation that solvent is acetonitrile be described use-case
Carry out according to the reaction condition of application examples 1, different is to use acetonitrile solvent instead of methanol, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 11: should course of reaction and the result in the situation that solvent is acetic acid be described use-case
Carry out according to the reaction condition of application examples 1, different is to use acetate solvate instead of methanol, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 12: should course of reaction and the result in the situation that oxidant is oxygen be described use-case
Carry out according to the reaction condition of application examples 1, different is to substitute hydrogen peroxide with oxidant oxygen, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
Application examples 13: should course of reaction and the result in the situation that oxidant is TBHP be described use-case
Carry out according to the reaction condition of application examples 1, different is to substitute hydrogen peroxide with oxidant TBHP, and reaction result is toluene conversion 5%-50%, and benzyl alcohol selective is 80%-100%.
The foregoing is only the preferred embodiments of the present invention; do not limit the present invention; for the technical staff in this field; the present invention can have various variations; all any amendments of making, be equal to replacement, improvement etc., within protection scope of the present invention all should be included within technical field of the present invention.
Claims (8)
1. a graphene-supported metal nanometer composite material, is characterized in that metal nanoparticle is dispersed on Graphene, and described metal particle diameter is 10-100nm, and metallic particles quality is the 1-10% of composite gross mass.
2. prepare a method for graphene-supported metal nanometer composite material described in claim 1, its operation is as follows:
(1) graphene oxide is joined in ultra-pure water, ultrasonic it is disperseed completely, be made into the aqueous solution that concentration is the graphene oxide of 0.1-5mg/mL;
(2) in the above-mentioned graphene oxide aqueous solution, add slaine, stir 12-36h at 20-40 DEG C, metal cation is combined with graphene oxide fully, obtain graphene oxide and slaine mixed solution;
(3) in above-mentioned mixed solution, add surfactant 0.01-0.1mol/L, fully stir 12-36h, prevent metal ion reunion, then add alkali 0.5-5mol/L, reaction system is transferred in oil bath, slowly drip hydrazine hydrate, rate of addition is 0.02-1mL/ second, controls 60-120 DEG C of reaction 12-24h of temperature, filters, dry, both graphene-supported metal nanometer composite material;
The quality of described slaine is the 1-10% of graphene oxide quality.
3. described in claim 2, in graphene-supported metal nanometer composite material preparation process, slaine is sulfate, nitrate or the hydrochloride of any one or more than one the alloy in copper, manganese, silver, iron, iridium, nickel.
4. described in claim 2, in graphene-supported metal nanometer composite material preparation process, alkali is any one or more than one mixture in NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonate, potash, saleratus.
5. graphene-supported metal nanometer composite material described in claims 1 is for a benzyl oxidation reaction, and its feature comprises following process:
Fragrance benzyl compounds concentration is 1-5mol/L, graphene-supported metal nanometer composite material catalyst 150～400mg, solvent 10～500mL, reacts 12～36h under 80-120 DEG C of condition, conversion ratio can reach 5%～50%, fragrant benzylalcohol selectively reach 80%-100%.
6. described in claim 5, fragrant benzyl is
in one or more mixtures.
7. described in claim 5, solvent is toluene, acetonitrile, ethanol, methyl alcohol, isopropyl alcohol, acetic acid, ethylene glycol, oxolane, carrene, one or more mixtures in ether.
8. described in claim 5, oxidant is one or more mixtures in air, oxygen, hydrogen peroxide, TBHP.
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| CN104475753A (en) * | 2014-12-29 | 2015-04-01 | 黑龙江大学 | Method for preparing nano Cu3.8 Ni alloy loaded on graphene by liquid phase reduction method |
| CN104693002A (en) * | 2015-03-11 | 2015-06-10 | 南京工业大学 | Method for preparing benzaldehyde by toluene oxidation |
| CN105047243A (en) * | 2015-06-08 | 2015-11-11 | 黑龙江大学 | Preparation method of polyaniline-clad graphene nanometer silver-nickel alloy |
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| CN105618779A (en) * | 2014-11-07 | 2016-06-01 | 南京理工大学 | Preparation method of silver/reduced grapheme nanocomposite |
| CN106076342A (en) * | 2016-07-05 | 2016-11-09 | 安徽师范大学 | NiFe alloy nano particle/graphite alkene composite and its preparation method and application |
| CN106077608A (en) * | 2016-06-15 | 2016-11-09 | 苏州洪河金属制品有限公司 | A kind of graphene-supported metallic composite and preparation method thereof |
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| CN107265449A (en) * | 2017-06-16 | 2017-10-20 | 凤台精兴生物科技有限公司 | A kind of preparation method for being electromagnetically shielded graphene |
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| CN108417800A (en) * | 2018-03-07 | 2018-08-17 | 深圳市本征方程石墨烯技术股份有限公司 | A kind of graphene coated graphite/metal composite granule negative material and preparation method |
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| CN115287493A (en) * | 2022-08-08 | 2022-11-04 | 邢台学院 | Preparation method of closed-cell foam metal composite material |
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