CN105312063A - Graphene composite catalyst and preparation method thereof - Google Patents
Graphene composite catalyst and preparation method thereof Download PDFInfo
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- CN105312063A CN105312063A CN201410309339.XA CN201410309339A CN105312063A CN 105312063 A CN105312063 A CN 105312063A CN 201410309339 A CN201410309339 A CN 201410309339A CN 105312063 A CN105312063 A CN 105312063A
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Abstract
The invention discloses a preparation method of a graphene composite catalyst, which includes the steps of 1) preparing single-layer graphene oxide; 2) in-situ growing a magnetic material on the single-layer graphene oxide to prepare a magnetic graphene material; and 3) in-situ growing noble metal particles on the magnetic graphene material to prepare the graphene composite catalyst. In the invention, the noble metal particles being high in catalytic effect and the magnetic material are both supported by the graphene, so that the catalyst is significantly improved in effects and can be separated out from a reaction system effectively without damage of a supporting structure. The graphene can be used in the next reaction high-effectively. The invention develops a supported noble metal catalyst having large contact area and being easy to separate, which saves the production cost of chemical reactions.
Description
Technical field
The present invention relates to noble metal photochemical catalyst and preparation method thereof, particularly relate to a kind of graphene composite catalyst and preparation method thereof.
Background technology
In chemical process, catalyst can reduce activation energy, and reactive chemistry is accelerated, and therefore we usually use catalyst to improve chemical reaction rate.At present, carried noble metal mainly with activated carbon loaded noble metal salt, then is reduced and is obtained, as applied platinum charcoal, palladium carbon etc. very widely in pharmacy and Minute Organic Synthesis.Due to existing loaded noble metal catalyst, to there is surface area large not, much enter carrier inside catalytic activity particle cannot with substrate contact and be difficult to play a role, thus result in the waste of active ingredient.In addition, the separation of loaded noble metal catalyst adopts the method for filtration, the strong mechanical force such as centrifugal usually, and inevitably cause the loss of noble metal, this is also one of reason of inactivation after catalyst recovery.Therefore, a kind of contact area is needed to develop large and be easy to the loaded noble metal catalyst that is separated.
Graphene, as the maximum material of specific area, has broad prospects at catalytic field.If can by together with the noble metal granule of Graphene and high catalysis efficiency and magnetic material load, it is allowed effectively to separate from reaction system while the Be very effective of catalyst is promoted, and do not destroy its support structures, can drop into efficiently in next round reaction.Then can develop a kind of contact area large and be easy to the loaded noble metal catalyst that is separated, thus save chemical reaction production cost.
Summary of the invention
In order to solve the problems of the prior art, the object of the invention is together with the noble metal granule of Graphene and high catalysis efficiency and magnetic material load, it is allowed effectively to separate from reaction system while the Be very effective of catalyst is promoted, and do not destroy its support structures, can drop into efficiently in next round reaction, thus it is large and be easy to graphene composite catalyst be separated and preparation method thereof to develop a kind of contact area.
For achieving the above object, the present invention is by the following technical solutions: a kind of preparation method of graphene composite catalyst comprises the following steps:
Step one, the preparation of single-layer graphene oxide;
Step 2, the growth in situ of magnetic material in single-layer graphene oxide, obtained magnetic oxygenated grapheme material;
Step 3, the growth in situ of noble metal granule on magnetic graphene material is also the obtained of graphene composite catalyst.
Described noble metal comprises platinum, palladium, rhodium, ruthenium, silver.
Described noble metal is silver.
Being prepared as of described step one single-layer graphene oxide:
In graphite powder, add solid sodium chloride fully grind after washing removing sodium chloride, after drying after filtration again, add in the concentrated sulfuric acid and stir, then under the condition of ice bath cooling, add potassium permanganate, to be mixed evenly after again oil bath be warming up to 110 degrees Celsius gradually, and be incubated 5 minutes, slowly add deionized water afterwards and be incubated 10 minutes, continuing to add deionized water and continuous heating seethes with excitement to solution; After solution seethes with excitement 10 minutes, add hydrogen peroxide, then add deionized water and stop heating, make solution naturally cool to normal temperature; Solution is used centrifuge, and the supernatant liquor that inclines also uses salt acid elution, uses deionized water washing instead; Repeated multiple times washing and centrifugal after, when solution can not be centrifuged, gained solution is single-layer graphene oxide solution;
Being prepared as of the magnetic oxygenated grapheme material of described step 2:
In graphene oxide, add ethylene glycol and diglycol, and stirring or the ultrasonic mixture that makes are uniformly dispersed; Then PAA, sodium acetate and Iron(III) chloride hexahydrate solid is added, stir or ultrasonic evenly after mixture is distributed in the stainless steel high temperature autoclave of polytetrafluoro liner and heats up gradually, and add thermal response at 200 degrees celsius and naturally cool to normal temperature after 10 hours; Dividing after being taken out by reacted mixture is filled in centrifuge tube, first ethanol centrifuge washing is added, add deionized water centrifuge washing again, Reusability ethanol and deionized water carry out centrifuge washing successively, can fully be dissolved in water to graphene-based magnetic nanometer composite material, i.e. obtained magnetic oxygenated grapheme material;
The growth in situ of described step 3 noble metal granule on magnetic graphene material, also namely obtaining of graphene composite catalyst is:
In the solution containing magnetic oxygenated Graphene, add solubility containing the salt of noble silver, and it boils and rises, and then adds trisodium citrate, makes solution constantly boiling until solution colour stops heating after no longer changing; Again by centrifugal for solution rotating speed, outwell supernatant, in solution, then add deionized water washing, after repeatedly centrifugal and washing, gained solid is noble metal-magnetic material-graphen catalyst, also i.e. graphene composite catalyst.
Another object of the present invention is to provide a kind of graphene composite catalyst, and this graphene composite catalyst is made by above-mentioned preparation method.
The present invention is by together with the noble metal granule of Graphene and high catalysis efficiency and magnetic material load, it is allowed effectively to separate from reaction system while the Be very effective of catalyst is promoted, and do not destroy its support structures, can drop into efficiently in next round reaction.Have developed a kind of contact area large and be easy to the loaded noble metal catalyst that is separated, save chemical reaction production cost.
Accompanying drawing explanation
The present invention is further described below in conjunction with the drawings and specific embodiments:
Fig. 1 is the AFM schematic diagram of the intermediate product single-layer graphene oxide in the preparation method of a kind of graphene composite catalyst of the present invention;
Fig. 2 be a kind of graphene composite catalyst of the present invention atomic force microscope images schematic diagram.
Detailed description of the invention
As shown in Figure 1 or 2, the preparation method of a kind of graphene composite catalyst of the present invention comprises the following steps: step one, the preparation of single-layer graphene oxide; Step 2, the growth in situ of magnetic material in single-layer graphene oxide, obtained magnetic oxygenated grapheme material; Step 3, the growth in situ of noble metal granule on magnetic graphene material is also the obtained of graphene composite catalyst.
Its detailed step is as follows:
One, the preparation of single-layer graphene oxide
Take 1g graphite powder, add solid sodium chloride and fully grind after washing removing sodium chloride, insert after filtering drying in the 23mL concentrated sulfuric acid to stir and spend the night, then under the condition of ice bath cooling, about about 5g potassium permanganate is added, to be mixed evenly after be warming up to 110 degrees Celsius (speed of intensification is 5 degrees celsius/minute) gradually in oil bath and be incubated 5min, slowly add about 10mL deionized water afterwards and be incubated 10min, then add 40mL deionized water and continuous heating to boiling.After solution boiling 10min, add 10mL30% hydrogen peroxide, add 200mL deionized water after 5min and stop heating, solution is cooled naturally.Solution is placed in centrifuge with the centrifugal 10min of about 8000rpm rotating speed, the supernatant that inclines also uses salt acid elution.Repeatedly use deionized water washing after three times instead, when solution can not be centrifuged substantially, gained solution is single-layer graphene oxide solution.As shown in Figure 1, in Fig. 1, the thickness of visible graphene oxide is about 0.6nm to 0.8nm, meets the thickness 0.6nm to 1.1nm of single-layer graphene for the atomic force microscope images of single-layer graphene oxide.
Two, the growth in situ of magnetic material in single-layer graphene oxide, obtained magnetic oxygenated grapheme material
Get graphene oxide 40mg, add 1mL ethylene glycol and 19mL diglycol and stir and ultrasonicly make it be uniformly dispersed.Then 1.5g PAA, 1.5g sodium acetate and 0.54g Iron(III) chloride hexahydrate solid is added, stir or ultrasonic evenly after mixture is distributed in the stainless steel high temperature autoclave of polytetrafluoro liner, put into baking oven to heat up gradually, add thermal response 10h at 200 DEG C after, naturally cool to room temperature.Question response terminates and point is filled in 2mL centrifuge tube after being taken out by reactant after cooling, and by ethanol and deionized water successively centrifuge washing repeatedly, can fully be dissolved in water to the graphene-based magnetic nanometer composite material of reactant.
Three, the growth in situ of noble metal granule on magnetic graphene material, obtaining of graphene composite catalyst
Take the magnetic oxygenated Graphene of 10mg, be dispersed in about 100mL water, add soluble precious-metal salt to be about 0.1g (the present embodiment is for the silver nitrate of silver-colored class salt, the method is equally applicable to the noble metals such as platinum, palladium, rhodium, ruthenium) and boil, then add 1.2g trisodium citrate (being dissolved in a small amount of water) to continue afterwards to boil 30min, after change, do not stop heating until solution colour.This solution is centrifugal with 8000rpm rotating speed, incline supernatant and add deionized water washing, 3 ~ 5 times so repeatedly.Gained solid is noble metal-magnetic material-graphen catalyst, is also graphene composite catalyst.As shown in Figure 2, the graphene composite catalyst atomic force microscope images of this material, in figure, the ag material of visible particulate and magnetic material load are on flake graphite alkene.Synthetic graphene composite catalyst material can at displacement under magnetic field by attraction.
Claims (5)
1. a preparation method for graphene composite catalyst, is characterized in that: it comprises the following steps:
Step one, the preparation of single-layer graphene oxide;
Step 2, the growth in situ of magnetic material in single-layer graphene oxide, obtained magnetic oxygenated grapheme material;
Step 3, the growth in situ of noble metal granule on magnetic graphene material is also the obtained of graphene composite catalyst.
2. the preparation method of a kind of graphene composite catalyst as claimed in claim 1, is characterized in that: described noble metal comprises platinum, palladium, rhodium, ruthenium, silver.
3. the preparation method of a kind of graphene composite catalyst as claimed in claim 2, it is characterized in that: described noble metal is silver.
4. the preparation method of a kind of graphene composite catalyst as claimed in claim 3, is characterized in that: being prepared as of described step one single-layer graphene oxide:
In graphite powder, add solid sodium chloride fully grind after washing removing sodium chloride, after drying after filtration again, add in the concentrated sulfuric acid and stir, then under the condition of ice bath cooling, add potassium permanganate, to be mixed evenly after again oil bath be warming up to 110 degrees Celsius gradually, and be incubated 5 minutes, slowly add deionized water afterwards and be incubated 10 minutes, continuing to add deionized water and continuous heating seethes with excitement to solution; After solution seethes with excitement 10 minutes, add hydrogen peroxide, then add deionized water and stop heating, make solution naturally cool to normal temperature; Solution is used centrifuge, and the supernatant liquor that inclines also uses salt acid elution, uses deionized water washing instead; Repeated multiple times washing and centrifugal after, when solution can not be centrifuged, gained solution is single-layer graphene oxide solution;
Being prepared as of the magnetic oxygenated grapheme material of described step 2:
In graphene oxide, add ethylene glycol and diglycol, and stirring or the ultrasonic mixture that makes are uniformly dispersed; Then PAA, sodium acetate and Iron(III) chloride hexahydrate solid is added, stir or ultrasonic evenly after mixture is distributed in the stainless steel high temperature autoclave of polytetrafluoro liner and heats up gradually, and add thermal response at 200 degrees celsius and naturally cool to normal temperature after 10 hours; Dividing after being taken out by reacted mixture is filled in centrifuge tube, first ethanol centrifuge washing is added, add deionized water centrifuge washing again, Reusability ethanol and deionized water carry out centrifuge washing successively, can fully be dissolved in water to graphene-based magnetic nanometer composite material, i.e. obtained magnetic oxygenated grapheme material;
The growth in situ of described step 3 noble metal granule on magnetic graphene material, also namely obtaining of graphene composite catalyst is:
In the solution containing magnetic oxygenated Graphene, add solubility containing the salt of noble silver, and it boils and rises, and then adds trisodium citrate, makes solution constantly boiling until solution colour stops heating after no longer changing; Again by centrifugal for solution rotating speed, outwell supernatant, in solution, then add deionized water washing, after repeatedly centrifugal and washing, gained solid is noble metal-magnetic material-graphen catalyst, also i.e. graphene composite catalyst.
5. a graphene composite catalyst, is characterized in that: it is made by the preparation method described in Claims 1-4 any one.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106543430A (en) * | 2016-11-10 | 2017-03-29 | 无锡市明盛强力风机有限公司 | A kind of synthetic method of the magnetic oxygenated Graphene of Polyethylene Glycol |
| CN114643050A (en) * | 2022-05-19 | 2022-06-21 | 浙江晟格生物科技有限公司 | Composite catalyst for improving lactose isomerization yield, preparation method and application |
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| CN106543430A (en) * | 2016-11-10 | 2017-03-29 | 无锡市明盛强力风机有限公司 | A kind of synthetic method of the magnetic oxygenated Graphene of Polyethylene Glycol |
| CN114643050A (en) * | 2022-05-19 | 2022-06-21 | 浙江晟格生物科技有限公司 | Composite catalyst for improving lactose isomerization yield, preparation method and application |
| CN114643050B (en) * | 2022-05-19 | 2022-08-23 | 浙江晟格生物科技有限公司 | Composite catalyst for improving lactose isomerization yield, preparation method and application |
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Application publication date: 20160210 |