CN106311223A - Preparation method of precious metal/graphene nanocomposite - Google Patents
Preparation method of precious metal/graphene nanocomposite Download PDFInfo
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- CN106311223A CN106311223A CN201610670705.3A CN201610670705A CN106311223A CN 106311223 A CN106311223 A CN 106311223A CN 201610670705 A CN201610670705 A CN 201610670705A CN 106311223 A CN106311223 A CN 106311223A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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Abstract
The invention discloses a preparation method of a precious metal/graphene nanocomposite. The method comprises the following steps that 1, according to the loading capacity of precious metal on graphene and the preparation quantity of target products, a corresponding quantity of precious metal soluble compounds are weighed and dissolved in a small amount of water, and the mixture is added into a corresponding volume of graphene oxide aqueous dispersion liquid with the concentration of 0.5-5 g/L; 2, a proper amount of organic fuel and ammonium nitrate are added into the dispersion liquid in step 1, and the mixture is stirred and subjected to ultrasound treatment for 15-90 minutes; 3, the mixed dispersion liquid in step 2 is heated and concentrated to be thick and then placed in a heating furnace at the temperature of 300-900 DEG C for ignition, and after combustion is completed, the product is cooled to room temperature, washed and dried. The preparation method is short in synthesis time and easy to implement, a poisonous and harmful reducing agent or stabilizing agent does not need to be added, the particle sizes of platinum nano-particles are uniform and controllable, the platinum nano-particles are uniform in dispersity on graphene, and the preparation method is a new method which is fast and efficient and makes industrial preparation of the platinum/graphene nanocomposite easy.
Description
Technical field
The invention belongs to field of material synthesis technology, relate to preparation method prepared by carbon-based nano composite.
Technical background
It is high that precious metal catalyst has catalysis activity, and selectivity is strong, and catalyst is easy to make, and usage amount is few, it is possible to anti-
The features such as multiple regeneration and activation use, life-span length, are mainly used in ammoxidation, petroleum hydrocarbon reformation, unsaturated compound oxidation and add
The process such as the removing of carbon monoxide, nitrogen oxides in hydrogen, gas is chemistry, oil and chemical reaction process through frequently with one
Plant catalyst.Noble metal nano catalyst is compared body phase noble metal catalyst and is had higher catalysis activity, and consumption is less, selects
The higher characteristic of property.But noble metal nano catalyst is little due to granule, surface can cause granule unstable greatly, easily coagulates
Poly-so that most noble metal granule is capped and fails to make full use of, cause the activity reduction of catalyst.Graphene has
Greatly specific surface area, by they compound catalytic performance and reusings that can significantly improve noble metal, current noble metal/
Graphene nanocomposite material has obtained preferably application in fields such as fuel cell biosensors.Therefore by noble metal nano
Catalyst be supported on Graphene can be good at solving noble metal nano catalyst because surface can be high and be prone to reunite and reduce catalysis
The problem of activity, can also solve the overlapping agglomeration traits of two-dimensional graphene simultaneously, have extraordinary utilization prospect.
At present, the preparation method of noble metal/graphene nanocomposite material mainly has coprecipitation and electrochemical deposition method.
Coprecipitation is first to be mixed with graphene oxide solution by precious metal salt, adds the strong reductants such as sodium borohydride hydrazine hydrate, expensive
Slaine and graphene oxide are reduced into metal nanoparticle and Graphene simultaneously, and co-precipitation precipitation obtains expensive from aqueous solution
Metal/grapheme composite.The method is simple to operate, but need to use the reducing agent that toxicity is bigger in a large number, is good for operator
Health and environment bring bigger harm.Additionally, graphite oxide is different and the most original with the reduction complexity of precious metal presoma
The water solublity difference of thing is big, and in noble metal/graphene composite material that co-precipitation obtains, noble metal is hard to be uniformly dispersed in
Between graphene sheet layer, thus cause the catalytic performance of material unsatisfactory.Electrochemical deposition method is frequently with by graphene oxide
Being applied to electrode surface in advance, then electrode is placed on controlled potential eletrolysis in the electrolyte solution containing noble metal precursor body, by metal
Ion reduction becomes metal nanoparticle and is deposited on electrode surface.Electrodeposition process is simple, environmental protection.But obtained composite wood
Material metal nanoparticle does not penetrate in graphene sheet layer, and is deposited on Graphene coating surface, the most undesirable.Visible open
Send out a kind of green, efficient and reliable noble metal/graphene composite material preparation method and there is very important realistic meaning.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of noble metal/graphene nanocomposite material, method is simple,
Mild condition, the time is short, it is not necessary to organic solvent or additive, pollution-free and consume energy low, and noble metal nano particles is on Graphene
Soilless sticking and distribution all hook, the green of the one-step synthesis of noble metal/graphene nanocomposite material that granularity is controlled, efficiently and can
By method.
The preparation method of a kind of noble metal/graphene nanocomposite material of the present invention, is characterized in that including following
Step.
(1) according to noble metal load capacity on Graphene and the preparation amount of target product, your gold of respective amount is weighed
Belonging to soluble compound to be dissolved in a small amount of water, the graphene oxide that concentration is 0.5 ~ 5 g/L adding respective amount volume is water-dispersible
In liquid.
(2) in the dispersion liquid that step (1) obtains, appropriate organic-fuel and ammonium nitrate are added, stirring ultrasonic 15 ~ 90
Minute obtain uniform dispersion.
(3) dispersion liquid heating step (2) obtained is concentrated into thickness, puts into the heating furnace that temperature is 300 ~ 900 DEG C
Ignite, after having burnt, be cooled to room temperature, scrubbed after drying, i.e. obtain end product.
In the step (1) of preparation method of the present invention, described noble metal load capacity on Graphene is 10 ~ 50%
(mass ratio).
Noble metal described in step (1) is one or both in gold or platinum.
Precious metal soluble compound described in step (1), wherein platinum soluble compound is Tetrachloroplatinate lithium, tetrachloro
Sodium platinate, Platinous Potassium Chloride, Tetrachloroplatinate ammonium, sodium chloroplatinate, potassium platinic chloride, chloroplatinic acid or platinum tetrachloride.Jin Ke
Soluble compound is sodium chloraurate, potassium chloroaurate, ammonium chloraurate, gold chloride or Auric chloride..
The molal quantity of the ammonium nitrate described in step (2) is 2 ~ 8 times of precious metal soluble compound molal quantity.
Organic-fuel described in step (2) is one or both in glycine, carbamide or ethylene glycol, added organic combustion
Molal quantity is ammonium nitrate molal quantity 0.5 ~ 5 times of material.
Washing described in step (3) refers to be less than by the electrical conductivity of deionized water and washing with alcohol product to cleaning mixture
10μs/cm2。
The present invention is based on surface of graphene oxide rich in oxygen-containing functional group, and wherein hydroxyl can reduce chlorine platinum (golden) acid group,
And platinum (golden) nanoparticle reduction obtained the most uniformly is fixed on the surface of graphene oxide, due to graphene oxide table
The hydroxyl in face can only reduce part chlorine platinum (golden) acid group, but platinum (golden) particle of these early stages reduction is the least.Due to solution
In with the addition of ammonium nitrate, it is provided that the necessary nitrate anion of oxidoreduction in burning.In combustion, remaining chlorine platinum (golden) acid
It is obtained for reduction with graphene oxide, and platinum (golden) particle that platinum (golden) particle that thermal reduction is out reduces with early stage is for brilliant
Core is grown up, and solving can not be well real because of Coulomb repulsion between the electronegative graphene oxide of chlorine platinum (golden) acid group and surface
Existing platinum (golden) nanoparticle uniform load on Graphene, has finally given high-quality noble metal/graphene nano and has been combined
Material.Generated time of the present invention is short, implements simple, it is not necessary to add poisonous deleterious reduction agent or stabilizer, platinum (golden) nanoparticle
Uniform particle sizes is controlled, and on Graphene, dispersibility is uniform, be a kind of green, quickly, efficiently, be prone to preparation of industrialization noble metal/
The new method of graphene nanocomposite material.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the embodiment of the present invention 1 sample, and the feature of corresponding metal platinum and Graphene is spread out respectively
Penetrate peak, wherein the appearance explanation platinum/graphene nano of the characteristic diffraction peak that JCPDS card number is 04-0802, platinum and Graphene of platinum
The formation of composite.
Fig. 2 be the relatively low amplification of the embodiment of the present invention 1 sample saturating penetrate electromicroscopic photograph, as it can be seen, platinum nanometer
Be distributed in is on Graphene uniform particle.
Fig. 3 is the transmission electron microscope photo of the more high-amplification-factor of the embodiment of the present invention 1 sample, as it can be seen, platinum particles
Mean diameter be 25nm, be evenly distributed on Graphene.
Detailed description of the invention
The present invention will be described further by following example.
Embodiment 1.
Weigh 0.4258 g K2PtCl4It is dissolved in a small amount of water, joins the graphene oxide that 400 ml concentration are 0.5 g/L
In aqueous dispersions, add 0.1346g ammonium nitrate and 0.3435g glycine, stir all and after ultrasonic 30 minutes, obtain uniformly
Dispersion liquid, heating is concentrated into thickness, puts into the Muffle furnace that temperature is 500 DEG C and ignite, after having burnt, be cooled to room temperature, uses
Deionized water and washing with alcohol product to the electrical conductivity of cleaning mixture less than 10 μ s/cm2Rear dry, i.e. obtain platinum/graphene nano
Composite.
Embodiment 2.
Weigh 0.3709 g NaAuCl4It is dissolved in a small amount of water, joins the graphite oxide that 400 ml concentration are 0.5 g/L
In alkene aqueous dispersions, add 0.1346g ammonium nitrate and 0.2748 g carbamide, stir all and after ultrasonic 30 minutes, obtain uniformly
Dispersion liquid, heating is concentrated into thickness, puts into the Muffle furnace that temperature is 500 DEG C and ignite, after having burnt, be cooled to room temperature, uses
Deionized water and washing with alcohol product to the electrical conductivity of cleaning mixture less than 10 μ s/cm2Rear dry, i.e. obtain gold/graphene nano
Composite.
Claims (1)
1. a preparation method for noble metal/graphene nanocomposite material, is characterized in that comprising the following steps:
(1) according to noble metal load capacity on Graphene and the preparation amount of target product, the noble metal weighing respective amount can
Soluble compound is dissolved in a small amount of water, adds the graphene oxide aqueous dispersions that concentration is 0.5 ~ 5 g/L of respective amount volume
In；
(2) in the dispersion liquid that step (1) obtains, appropriate organic-fuel and ammonium nitrate are added, stirring ultrasonic 15 ~ 90 minutes
Obtain uniform dispersion；
(3) dispersion liquid heating step (2) obtained is concentrated into thickness, puts into the heating furnace that temperature is 300 ~ 900 DEG C and ignites,
After having burnt, be cooled to room temperature, scrubbed after drying, i.e. obtain end product；
The noble metal described in step (1) load capacity on Graphene is mass ratio 10 ~ 50%；
Noble metal described in step (1) is one or both in gold or platinum；
Precious metal soluble compound described in step (1), wherein platinum soluble compound is Tetrachloroplatinate lithium, Tetrachloroplatinate
Sodium, Platinous Potassium Chloride, Tetrachloroplatinate ammonium, sodium chloroplatinate, potassium platinic chloride, chloroplatinic acid or platinum tetrachloride；Gold solubility
Compound is sodium chloraurate, potassium chloroaurate, ammonium chloraurate, gold chloride or Auric chloride.；
The molal quantity of the ammonium nitrate described in step (2) is 2 ~ 8 times of precious metal soluble compound molal quantity；
Organic-fuel described in step (2) is one or both in glycine, carbamide or ethylene glycol, added organic-fuel
Molal quantity is 0.5 ~ 5 times of ammonium nitrate molal quantity；
Washing described in step (3) refers to use deionized water and washing with alcohol product to the electrical conductivity of cleaning mixture less than 10 μ
s/cm2。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117061A (en) * | 2018-01-26 | 2018-06-05 | 中冶华天工程技术有限公司 | The method for producing grapheme foam |
| CN108658059A (en) * | 2018-05-02 | 2018-10-16 | 南昌大学 | A kind of preparation method of tungstic acid/nitrogen-doped graphene compound |
| CN109187510A (en) * | 2018-09-05 | 2019-01-11 | 浙江理工大学 | A method of ancient times woolen knitwear is detected based on Electrochemiluminescince |
| CN109594068A (en) * | 2018-12-26 | 2019-04-09 | 郑州师范学院 | A kind of preparation method of noble-metal-supported grapheme material |
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| CN102826546A (en) * | 2012-09-28 | 2012-12-19 | 哈尔滨工业大学 | Method for preparing graphene powder by combustion synthesis |
| CN104815983A (en) * | 2015-04-20 | 2015-08-05 | 齐鲁工业大学 | Carbon-coated nickel oxide/metallic nickel and simple synthesis method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117061A (en) * | 2018-01-26 | 2018-06-05 | 中冶华天工程技术有限公司 | The method for producing grapheme foam |
| CN108658059A (en) * | 2018-05-02 | 2018-10-16 | 南昌大学 | A kind of preparation method of tungstic acid/nitrogen-doped graphene compound |
| CN108658059B (en) * | 2018-05-02 | 2021-10-22 | 南昌大学 | Preparation method of tungsten trioxide/nitrogen-doped graphene compound |
| CN109187510A (en) * | 2018-09-05 | 2019-01-11 | 浙江理工大学 | A method of ancient times woolen knitwear is detected based on Electrochemiluminescince |
| CN109187510B (en) * | 2018-09-05 | 2020-10-16 | 浙江理工大学 | Method for detecting ancient wool fabric based on electrochemical luminescence method |
| CN109594068A (en) * | 2018-12-26 | 2019-04-09 | 郑州师范学院 | A kind of preparation method of noble-metal-supported grapheme material |
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