CN102814198A - Metal/graphene nanometer catalyst, and preparation method and application thereof - Google Patents
Metal/graphene nanometer catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a metal/graphene nanometer catalyst, and a preparation method and an application thereof. The catalyst comprises graphene and metal nanometer particles loaded thereon, and has a high dispersibility in DMF or water. The method comprises the following steps: mixing a graphene oxide or a chemically functionalized graphene with metal ions in a DMF solution containing an organic negative hydrogen donor, and then reducing by the organic negative hydrogen donor under an illumination condition to obtain the metal/graphene nanometer catalyst. The synthetic method has simple steps, and can successfully enable the small-dimension metal nanometer particles to be uniformly loaded on the graphene without the addition of any surfactants. The metal/graphene nanometer catalyst prepared in the invention has excellent catalytic performances in organic synthesis and photic driving hydrogen production.
Description
Technical field
The invention belongs to catalysis technical field, particularly a kind of metal/graphite alkene nanocatalyst.
Background technology
The platinum group metal nano material is like widely used catalyst in petroleum industry, purifying vehicle exhaust, fuel cell equal energy source and the great field of environment.The surface of the platinum of carbon load, ruthenium and palladium metal nano particle has stronger adsorption activity (especially to hydrogen atom and hydrogen) and good electron storge quality and transmission performance; Make it have excellent catalytic performance; Therefore be widely used in the catalyst in the chemical industry, the eelctro-catalyst in the battery that especially acts as a fuel.But because the reserves of platinum group metal are rare, how improving the activity and the selectivity of platinum based catalyst, thereby reduce the consumption of platinum group metal, is the problem that this field receives much concern always.
Research shows that the metallic of nano-scale has very high catalytic activity, especially for electrochemical catalyst.The catalytic activity of metal has very big relation with its size on the one hand.For the platinum group metal, the optimum size that catalytic activity requires is 3nm.Therefore the size of platinum group metal nano particle controlled well can not only improve the utilization rate of this type noble metal, and can make it bring into play best catalytic effect.Though a large amount of research reports about control platinum group metal nano-particles size in solution is arranged at present; The research of the overwhelming majority has all used the surfactant such as the alkyl hydrosulfide that can form micella to assemble to prevent Particle Cluster; But these protectiveness parts can cover some catalytic site of nano particle undoubtedly, can weaken its catalytic effect undoubtedly.Thereby be necessary to seek novel, can synthetic surface method " totally ", undersized metal nanoparticle.
On the other hand, catalyst carrier also has very big influence to the performance of catalyst.Activated carbon, XC-72 nano-sized carbon, CNT etc. all are some catalyst carriers commonly used.CNT can be assembled and transmission electronic because of its conductivity preferably, can suppress compound in semiconductor of electronics and hole effectively, and its this separation of charge effect has been applied to the field that hydrogen is produced in photovoltaic solar cell and the photosensitive catalysis of organic dyestuff.As carrier, different material with carbon elements has very big influence because of the difference of its pattern and electronic transmission performance to the catalytic performance of platinum group metal nano particle, especially for eelctro-catalyst.In order further to strengthen the catalytic performance of platinum group metal nano particle, be necessary to research and develop a kind of new material with carbon element carrier, metal nanoparticle can be distributed on the carrier highly equably.The Graphene of recent findings is a kind of novel two-dimentional material with carbon element, the two dimensional crystal that it is made up of the monolayer carbon atom, and because of it has excellent electrical conductance, thermal conductance and mechanical performance, and very large specific area and receive extensive concern.Thereby we can predict through being one type of novel material with high catalytic activity with Graphene and the compound metal/graphite alkene nanocatalyst that obtains of metallic catalyst.Now developed the method for a lot of graphene-supported metallics; But most research is based on absorption-reducing process; Just mix graphene oxide with the solution of slaine; Thereby make slaine be adsorbed onto the Graphene surface, and then the reducing agent in solution or in reducing atmosphere high temperature reduction, obtain graphene-supported metallic.But this method is difficult to control the size of metal nanoparticle; And often need add dispersant in the reaction; The dispersiveness of Graphene in the aqueous solution that reduction simultaneously obtains is also relatively poor, brings the unfavorable result of following degradation of light scattering, filter effect and catalyst effective ratio area thereupon.
Given this, be necessary to develop under the condition that does not add any surfactant, just can undersized metal nanoparticle be loaded to the straightforward procedure on the carrier equably.
Summary of the invention
First technical problem that the present invention will solve provides a kind of metal/graphite alkene nanocatalyst; This catalyst comprises the metal nanoparticle of Graphene and load on it; This catalyst is at N, and dispersed high in dinethylformamide (DMF) or the water, the fields such as hydrogen, reducing carbon dioxide, organic catalysis of producing in photocatalysis have using value.
Second technical problem that the present invention will solve provides a kind of preparation method of metal/graphite alkene nanocatalyst; This method is through mixing with metal ion Graphene in the DMF/ water mixed solvent, reduction obtains metal/graphite alkene nanocatalyst to body by organic negative hydrogen under illumination condition afterwards; This synthetic method step is simple, under the condition that does not add any surfactant, can successfully undersized metal nanoparticle be loaded on the Graphene equably.
The 3rd technical problem that the present invention will solve provides a kind of application of metal/graphite alkene nanocatalyst; It can be used for organic synthesis and optical drive hydrogen production reaction.
For solving above-mentioned first technical problem, the present invention provides a kind of metal/graphite alkene nanocatalyst, and it comprises the metal nanoparticle of Graphene and load on it; Said Graphene is the graphene oxide of graphene oxide or chemical functionalization; Said metal/graphite alkene nanocatalyst has the surface heterogeneous medium junction structure.
Said graphene oxide can make through other known methods, only needs to satisfy the good dispersion of graphene oxide in water that makes and gets final product, and the present invention provides a kind of preferred manufacturing procedure.
Said graphene oxide makes through the following step:
A. the expansion process of graphite
1.6g potassium persulfate and 1.6g phosphorus pentoxide are joined in 9～15ml concentrated sulfuric acid, be heated to 75～85 ℃ and all dissolve until potassium persulfate and phosphorus pentoxide; Add 1.8～2.2g graphite then, under 75～85 ℃ of temperature, react 4～5h, filter, wash, obtain expanded graphite;
B. the oxidation of expanded graphite
The expanded graphite that step a is obtained joins in 75～85ml concentrated sulfuric acid of ice bath cooling, under magnetic agitation, in this mixture, slowly adds 8～12g potassium permanganate down, and reaction 3～5h under 30～40 ℃ reacts 1.5～2.5h again under the room temperature then; The deionized water that slowly adds 150～170ml keeps temperature to be no more than 50 ℃, continues to stir 1.5～2.5h; Add water and the 30wt% hydrogen peroxide solution 8～12ml of 450～490ml again, produce jonquilleous solution, after this solution is placed 24h; Outwell supernatant,, wash respectively twice with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generator earlier then with remaining liquid; And then with twice of 10wt%HCl washing; Dialysis 6～8 days in water at last, the solid that obtains 45～55 ℃ dry down, make graphite oxide;
C. graphite oxide is peeled off and is the mono-layer graphite olefinic oxide
The graphite oxide that step b is made places deionized water, and through ultrasonic wave effect 10～30min, ultrasonic power is 150W, the graphene oxide solution that dissociates and obtain individual layer; Said graphite oxide: deionized water is 0.3mg～0.6mg: 1mL.
The graphene oxide of said chemical functionalization is on Graphene, to modify P-TOLUENE SULFO ACID 99's base or azacyclo-propyl group acetal chain; Wherein, the structure of P-TOLUENE SULFO ACID 99's base or azacyclo-propyl group acetal chain is following:
1) P-TOLUENE SULFO ACID 99's base:
2) azacyclo-propyl group acetal chain:
Saidly on Graphene, modify P-TOLUENE SULFO ACID 99's base or azacyclo-propyl group acetal chain can obtain through other known methods, the present invention provides a kind of preferable methods.
The said P-TOLUENE SULFO ACID 99's base of on Graphene, modifying is realized through following steps:
Get graphene oxide solution 40ml, with the Na of 5wt%
2CO
3Regulate pH to 9～10, to the sodium borohydride that wherein adds 100～200g, react 1～2h under 80～90 ℃ the condition, centrifugal then, the solid that obtains is distributed to the dispersion liquid of processing 0.3～0.6mg/l in the water again with after washing twice; To wherein adding the hydrochloric acid diazol 3～6ml that contains 0.095M p-sulfonic acid benzene; In ice bath, react 2h; Reaction finishes the back and in this solution, adds 150ml acetone, separates out deposition, and deposition is after centrifugation; Using volume ratio again is 3: 1 acetone mixed solvent washing three times, the solid that obtains ultrasonic again aqueous solution that is dispersed into 0.3～0.6mg/ml after the drying in 50 ℃ baking oven.
The said azacyclo-propyl group acetal chain of on Graphene, modifying is realized through following steps:
Get graphene oxide solution 50ml, the N-methyl pyrrolidone that adds 30～40ml (is called for short later on: NMP) ultrasonic 1h, argon gas bubbling degasification 20min; [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols that add 1～3g under the argon shield condition; Put into oil bath reaction 10～20h for 160 ℃, be cooled to room temperature after, solid is given a baby a bath on the third day after its birth time with DMF; Wash six times the solid that obtains ultrasonic again aqueous solution that is dispersed into 0.3～0.6mg/ml after the drying in 50 ℃ baking oven with acetone.
Further, said metal nanoparticle is platinum, ruthenium or palladium.
For solving above-mentioned second technical problem, the present invention provides a kind of preparation method of metal/graphite alkene nanocatalyst, may further comprise the steps: with the Graphene of graphene oxide or chemical functionalization with contain organic negative hydrogen and mix for the DMF solution of body; The aqueous solution that adds metal ion afterwards; Deoxygenation, this system of illumination adds extractant extraction organic matter; Water is centrifugal with deposition, and the solid that obtains is metal/graphite alkene nanocatalyst.
A kind of preparation method of metal/graphite alkene nanocatalyst specifically may further comprise the steps:
(1) 10ml～20ml is contained 10
-4Mol/l gives the aqueous solution of DMF solution with the Graphene of 5ml, 0.3mg/ml～0.6mg/ml graphene oxide or chemical functionalization of body to the organic negative hydrogen of saturated concentration, stir, and is extremely limpid with ultrasonic Treatment then, obtains uniform dispersion liquid;
(2) in the dispersion liquid that step (1) obtains, add 3ml～4ml, 10
-4Mol/l～10
-2The aqueous solution of mol/l chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium stirs, and obtains uniform dispersion liquid through sonicated again;
(3) this dispersion of ultraviolet-visible light illumination is used in logical argon gas deoxygenation in the dispersion liquid that step (2) obtains in argon gas atmosphere;
(4) add extractant in the dispersion after illumination, the organic matter in the system is fallen in extraction, and the deposition of lower floor's water that obtains and generation is centrifugal, uses water washing, and centrifugation with the solid drying that obtains, obtains metal/graphite alkene nanocatalyst again.
Said graphene oxide can make through other known methods, and the present invention provides a kind of preferred manufacturing procedure.
Said graphene oxide makes through the following step:
A. the expansion process of graphite
1.6g potassium persulfate and 1.6g phosphorus pentoxide are joined in 9～15ml concentrated sulfuric acid, be heated to 75～85 ℃ and all dissolve until potassium persulfate and phosphorus pentoxide; Add 1.8～2.2g graphite then, under 75～85 ℃ of temperature, react 4～5h, filter, wash, obtain expanded graphite;
B. the oxidation of expanded graphite
The expanded graphite that step a is obtained joins in 75～85ml concentrated sulfuric acid of ice bath cooling, under magnetic agitation, in this mixture, slowly adds 8～12g potassium permanganate down, and reaction 3～5h under 30～40 ℃ reacts 1.5～2.5h again under the room temperature then; The deionized water that slowly adds 150～170ml keeps temperature to be no more than 50 ℃, continues to stir 1.5～2.5h; Add water and the 30wt% hydrogen peroxide solution 8～12ml of 450～490ml again, produce jonquilleous solution, after this solution is placed 24h; Outwell supernatant,, wash respectively twice with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generator earlier then with remaining liquid; And then with twice of 10wt%HCl washing; Dialysis 6～8 days in water at last, the solid that obtains 45～55 ℃ dry down, make graphite oxide;
C. graphite oxide is peeled off and is the mono-layer graphite olefinic oxide
The graphite oxide that step b is made places deionized water, and through ultrasonic wave effect 10～30min, ultrasonic power is 150W, the graphene oxide solution that dissociates and obtain individual layer; Said graphite oxide: deionized water is 0.3mg～0.6mg: 1mL.
The graphene oxide of said chemical functionalization is on Graphene, to modify P-TOLUENE SULFO ACID 99's base or azacyclo-propyl group acetal chain; Wherein, the structure of P-TOLUENE SULFO ACID 99's base or azacyclo-propyl group acetal chain is following:
1) P-TOLUENE SULFO ACID 99's base:
2) azacyclo-propyl group acetal chain:
Saidly on Graphene, modify P-TOLUENE SULFO ACID 99's base or azacyclo-propyl group acetal chain can obtain through other known methods, the present invention provides a kind of preferable methods.
The said P-TOLUENE SULFO ACID 99's base of on Graphene, modifying is realized through following steps:
Get graphene oxide solution 40ml, with the Na of 5wt%
2CO
3Regulate pH to 9～10, to the sodium borohydride that wherein adds 100～200g, react 1～2h under 80～90 ℃ the condition, centrifugal then, the solid that obtains is distributed to the dispersion liquid of processing 0.3～0.6mg/l in the water again with after washing twice; To wherein adding the hydrochloric acid diazol 3～6ml that contains 0.095M p-sulfonic acid benzene; In ice bath, react 2h; Reaction finishes the back and in this solution, adds 150ml acetone, separates out deposition, and deposition is after centrifugation; Using volume ratio again is 3: 1 acetone mixed solvent washing three times, the solid that obtains ultrasonic again aqueous solution that is dispersed into 0.3～0.6mg/ml after the drying in 50 ℃ baking oven.
The said azacyclo-propyl group acetal chain of on Graphene, modifying is realized through following steps:
Get graphene oxide solution 50ml, the N-methyl pyrrolidone that adds 30～40ml (is called for short later on: NMP) ultrasonic 1h, argon gas bubbling degasification 20min; [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols that add 1～3g under the argon shield condition; Put into oil bath reaction 10～20h for 160 ℃, be cooled to room temperature after, solid is given a baby a bath on the third day after its birth time with DMF; Wash six times the solid that obtains ultrasonic again aqueous solution that is dispersed into 0.3～0.6mg/ml after the drying in 50 ℃ baking oven with acetone.
Further, said organic negative hydrogen is 1 to body, 4-dihydropyridine, 3,4-dihydropyrimidine-2-keto or 2,3-dihydro-1H-benzimidazole.
Said 1, the 4-dihydropyridine is the compound with following structure:
Wherein R is H, Me, Et or 4-MeO-Ph.
Said 3, the 4-dihydropyrimidine-2-keto is the compound with following structure:
R wherein
1=H, R
2=H; R
1=OMe, R
2=H; R
1=Me, R
2=H; R
1=Br, R
2=H; R
1=NO
2, R
2=H; R
1=OH, R
2=H or R
1=H, R
2=Cl.
Said 2,3-dihydro-1H-benzimidazole is the compound with following structure:
Further, the said metal ion aqueous solution is the aqueous solution of chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium.
Further, said illumination is ultraviolet-visible light illumination, carries out illumination with the 500W high-pressure sodium lamp, wavelength X＞326nm, λ＞355nm or λ＞400nm.
Said deoxygenation is to the logical inert gas of system, like argon gas, and deoxygenation.
Further, said extractant is ethyl acetate, carrene, chloroform, benzene, toluene or ether.
A kind of preparation method of metal/graphite alkene nanocatalyst, may further comprise the steps: 10～20ml contains 10
-4Mol/l gives the aqueous solution of Graphene of DMF solution and the 5ml 0.3～0.6mg/ml graphene oxide or the chemical functionalization of body to saturated organic negative hydrogen; Stir 5～10min; With ultrasonic Treatment to limpid (ultrasonic power is 150W), obtain uniform dispersion liquid then; In the above-mentioned dispersion liquid that obtains, add 3～4ml 10
-4～10
-2The aqueous solution of mol/l chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium stirs 5～10min, and sonicated obtains uniform dispersion liquid again, and logical argon gas deoxygenation is at argon gas atmosphere medium ultraviolet-this dispersion of visible light illumination; Dispersion after the illumination adds ethyl acetate extraction and falls the organic matter in the system, and the deposition of lower floor's water and generation is centrifugal, centrifugalizes with water washing again, and the solid that obtains is dry in 50 ℃ baking oven, obtains metal/graphite alkene nanocatalyst.
For solving above-mentioned the 3rd technical problem, the invention provides the application of metal/graphite alkene nanocatalyst; It can be used in organic synthesis and the optical drive hydrogen production reaction, and catalytic performance is excellent.
The present invention has following beneficial effect:
1) preparation method's step of the present invention is simple; Reaction condition is gentle; Need not to add extra surfactant; Can be on Graphene load high degree of dispersion, undersized metal nanoparticle, especially adopt low-energy light to impinge upon that preparation metal/graphite alkene nanocatalyst can energy savings in the short time.
2) clean metal/graphite alkene nanocatalyst only needs can separate through simple organic post processing, and can in DMF or water, obtain the good catalyst solution of dispersion stabilization.
3) the photochemistry method for preparing catalyst prepares in photoetching and has application prospect aspect the electrode of solar battery.
4) the metal/graphite alkene nanocatalyst catalytic performance of the present invention's preparation is excellent, can be used in organic synthesis and the optical drive hydrogen production reaction.
Description of drawings
Fig. 1 be among the embodiment 1 with 1,4-dihydropyridine (R=H) is a reducing agent, is carrier with the graphene oxide, the transmission electron microscope picture of the platinum/graphene nano catalyst of preparation;
Fig. 2 be among the embodiment 10 with 1,4-dihydropyridine (R=H) is a reducing agent, is carrier through the functionalized Graphene of P-TOLUENE SULFO ACID 99, the transmission electron microscope picture of the platinum/graphene nano catalyst of preparation;
Fig. 3 be among the embodiment 2 with 1,4-dihydropyridine (R=H) is a reducing agent, is carrier with the graphene oxide, the transmission electron microscope picture of the ruthenium of preparation/graphene nano catalyst;
Fig. 4 be among the embodiment 3 with 1,4-dihydropyridine (R=H) is a reducing agent, is carrier with the graphene oxide, the transmission electron microscope picture of the palladium/graphene nano catalyst of preparation.
Fig. 5 is the product hydrogen kinetic curve of the optical drive hydrogen manufacturing system of catalyst for the platinum/graphen compound with embodiment 10 preparations.
The specific embodiment
A kind of preparation method of metal/graphite alkene nanocatalyst may further comprise the steps:
1, graphene oxide is synthetic
A. the expansion process of graphite
The concentrated sulfuric acid of 9ml is heated to 80 ℃, adds 1.6g potassium persulfate and 1.6g phosphorus pentoxide, stirring is dissolved solid entirely under this temperature; Slowly add 2g, 320 purpose crystalline flake graphites then, in 5min, add, this mixed liquor reacts 4.5h down at 80 ℃; Reaction finishes cool to room temperature, adds the 350ml deionized water then, behind the placement 12h; With the membrane filtration of this mixture through 0.2 μ m, go residual acid with a large amount of washings, solid is at room temperature placed 12h.
B. the oxidation of expanded graphite
The concentrated sulfuric acid of getting 80ml places 0 ℃ ice bath, and the expanded graphite that step a is obtained joins in the sulfuric acid solution, under agitation slowly adds the potassium permanganate of 10g then; Guarantee in the process that adds that temperature is no more than 10 ℃; Add the back and react 4h down at 35 ℃, react 2h then under the room temperature again, reaction adds the 160ml deionized water after finishing in batches; Originally can under ice bath, carry out, guarantee that temperature is no more than 50 ℃; At room temperature react 2h after water injection, and then add the water of 470ml, add the hydrogenperoxide steam generator of 10ml, 30wt% after adding again; Produce jonquilleous solution; This solution is outwelled supernatant after placing 24h, then with remaining centrifugal; Elder generation washes twice with the solution that 200ml contains 3wt% sulfuric acid, 1wt% hydrogen peroxide; And then with the 10wt%HCl of 200ml washing twice, each washing is all wanted earlier cleaning solution to be mixed stirring 30min with the solid of graphite oxide, and then the centrifugal cleaning solution that removes; One week of dialysis in deionized water packed coagulant liquid in the bag filter at this moment by the last gel that obtains during again with the washing of 200ml; Coagulant liquid after the dialysis is poured in the culture dish then, and dry 48h obtains graphite oxide in 50 ℃ baking oven.
C. graphite oxide is peeled off and is the mono-layer graphite olefinic oxide
Graphite oxide is dispersed in the water, and ultrasonic power is 150W, through ultrasonic wave effect 20min, forms the dispersion liquid of 0.5mg/ml.
2, metal nanoparticles loaded Graphene is synthetic
(1) 18ml is contained 1 of 20mg, the 5ml0.5mg/ml graphene oxide dispersion liquid that the DMF solution and the step 1 of 4-dihydropyridine obtains mixes, and stirs 5min, with ultrasonic Treatment to limpid (ultrasonic power is 150W), obtains uniform dispersion liquid then;
(2) in dispersion liquid, add 3ml, 10
-3The aqueous solution of mol/l chloroplatinic acid stirs 5min, and sonicated obtains uniform dispersion liquid again, and logical argon gas deoxygenation adds λ under the optical filter＞400nm illumination 3h at the 500W high-pressure sodium lamp;
(3) adding of the dispersion after illumination ethyl acetate extraction falls the organic matter in the system, and the deposition of lower floor's water and generation is centrifugal, centrifugalizes with water washing again, and the solid that obtains is dry in 50 ℃ baking oven, obtains metal/graphite alkene nanocatalyst.
Embodiment 7
Embodiment 8
Embodiment 9
A kind of preparation method of metal/graphite alkene nanocatalyst may further comprise the steps:
1, graphene oxide is synthetic
Repeat the synthesis step of graphene oxide among the embodiment 1.
2, the Graphene of chemical functionalization---on Graphene, modify P-TOLUENE SULFO ACID 99's base
Get the above-mentioned graphene oxide solution 40ml that obtains, with the Na of 5wt%
2CO
3Regulate pH to 9～10.Add sodium borohydride 160mg, 80 ℃ of reaction 1h, it is centrifugal that reaction finishes the back; Solid is used washing twice, and then is distributed to the dispersion liquid of processing 0.5mg/ml in the water, adds the hydrochloric acid diazol 3.6ml that contains 0.095M p-sulfonic acid benzene then; In ice bath, react 2h; Reaction finishes the back and in this solution, adds 150ml acetone, separates out deposition, after the precipitation and centrifugal separation; Using volume ratio again is 3: 1 acetone mixed solvent washing three times, and the solid that obtains is dispersed into the aqueous solution of (ultrasonic power is 150W) 0.5mg/ml again after the drying in 50 ℃ baking oven.
3, metal nanoparticles loaded Graphene is synthetic
(1) 14ml is contained 1 of 20mg; The dispersion liquid of the 5ml that the DMF solution and the step 2 of 4-dihydropyridine obtains, the Graphene of 0.5mg/ml chemical functionalization mixes; Stir 8min, with ultrasonic Treatment to limpid (ultrasonic power is 150W), obtain uniform dispersion liquid then;
(2) add 3.5ml, 10 in the dispersion liquid
-3The aqueous solution of mol/l chloroplatinic acid stirs 5min, and sonicated obtains uniform dispersion liquid again, and logical argon gas deoxygenation adds λ under the optical filter＞400nm illumination 3h at high-pressure sodium lamp;
(3) adding of the dispersion after illumination ethyl acetate extraction falls the organic matter in the system, and the deposition of lower floor's water and generation is centrifugal, centrifugalizes with water washing again, and the solid that obtains is dry in 50 ℃ baking oven, obtains metal/graphite alkene nanocatalyst.
Embodiment 11
The graphene oxide solution 50ml that obtains adds 35ml NMP (N-methyl pyrrolidone), ultrasonic 1h; Argon gas bubbling degasification 20min; Add 1.1g [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols under the argon shield condition, 160 ℃ of oil baths reaction 18h, be cooled to room temperature after; Solid given a baby a bath on the third day after its birth with DMF time wash six times with acetone, the solid that obtains disperses (ultrasonic power is 150W) to become the aqueous solution of 0.4mg/ml in 50 ℃ baking oven again after the drying.
Embodiment 12
Embodiment 13
Repeat embodiment 11, it only is without part: the last dispersion liquid concentration that forms is 0.6mg/ml in the step 2; Described in the synthesis step (1) of metal nanoparticles loaded Graphene 1, the 4-dihydropyridine is 30mg, and the concentration of the aqueous solution of chloroplatinic acid is 10 in the step (2)
-3Mol/l, illumination wavelength λ＞400nm, the illumination reaction time is 3h.
Embodiment 14
Embodiment 15
Repeat embodiment 11, it only is without part: the last dispersion liquid concentration that forms is 0.5mg/ml in the step 2; Described in the synthesis step (1) of metal nanoparticles loaded Graphene 2,3-dihydro-1H-benzimidazole is 20mg, and the concentration of the aqueous solution of chlorine palladium acid sodium is 10 in the step (2)
-4Mol/l, illumination wavelength λ＞326nm, the illumination reaction time is 3h.
Embodiment 16
A kind of preparation method of metal/graphite alkene nanocatalyst may further comprise the steps:
1, graphene oxide is synthetic
Repeat the synthesis step of graphene oxide among the embodiment 1.
2, the Graphene of chemical functionalization is synthetic-P-TOLUENE SULFO ACID 99's base on Graphene is modified
Get the above-mentioned graphene oxide solution 40ml that obtains, with the Na of 5wt%
2CO
3Regulate pH to 9～10; Add sodium borohydride 100mg, 80 ℃ are reacted 1h down, and it is centrifugal that reaction finishes the back; Solid is used washing twice, and then is distributed to the dispersion liquid of processing 0.6mg/ml in the water, adds the hydrochloric acid diazol 4ml that contains 0.095M p-sulfonic acid benzene then; In ice bath, react 2h; Reaction finishes the back and in this solution, adds 150ml acetone, separates out deposition, after the precipitation and centrifugal separation; Using volume ratio again is 3: 1 acetone mixed solvent washing three times, and the solid that obtains disperses (ultrasonic power is 150W) to become the aqueous solution of 0.4mg/ml in 50 ℃ baking oven again after the drying.
3, metal nanoparticles loaded Graphene is synthetic
(1) 14ml contains 1 of 20mg; The dispersion liquid of the 5ml that the DMF solution and the step 2 of 4-dihydropyridine obtains, 0.5mg/ml chemical functionalization Graphene mixes; Stir 10min, with ultrasonic Treatment to limpid (ultrasonic power is 150W), obtain uniform dispersion liquid then;
(2) add 3.5ml, 10 in the dispersion liquid
-3The aqueous solution of mol/l chloroplatinic acid stirs 5～10min, and sonicated obtains uniform dispersion liquid again, and logical argon gas deoxygenation adds λ under the optical filter＞400nm illumination 3h at high-pressure sodium lamp;
(3) adding of the dispersion after illumination ethyl acetate extraction falls the organic matter in the system, and the deposition of lower floor's water and generation is centrifugal, centrifugalizes with water washing again, and the solid that obtains is dry in 50 ℃ baking oven, obtains metal/graphite alkene nanocatalyst.
Embodiment 17
A kind of preparation method of metal/graphite alkene nanocatalyst may further comprise the steps:
1, graphene oxide is synthetic
Repeat the synthesis step of graphene oxide among the embodiment 1.
2, the synthetic-Graphene of chemical functionalization Graphene is modified and is gone up azacyclo-propyl group acetal chain
Get the above-mentioned graphene oxide solution 50ml that obtains, add 45ml NMP (N-methyl pyrrolidone), ultrasonic 1h; Argon gas bubbling degasification 20min; Add 3g [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols under the argon shield condition, 160 ℃ of oil baths reaction 20h, be cooled to room temperature after; Solid given a baby a bath on the third day after its birth with DMF time wash six times with acetone, the solid that obtains disperses (ultrasonic power is 150W) to become the aqueous solution of 0.4mg/ml in 50 ℃ baking oven again after the drying.
3, metal nanoparticles loaded Graphene is synthetic
Repeat the step among the embodiment 16.
To with 1,4-dihydropyridine (R=H) is that organic negative hydrogen is given body, and without chemical functionalization and metal nanoparticles loaded on the Graphene of chemical functionalization, the composite catalyst that obtains carries out transmission electron microscope and characterizes.
Can find out from the transmission electron microscope picture; Adopt the method for photoreduction; Without chemical functionalization and on the Graphene surface of chemical functionalization all undersized platinum of load and ruthenium nano particle equably, the size of the nano particle that obtains be 3～5nm (like Fig. 1,2; Shown in 3), and Pd nano particle is of a size of 6-10nm (as shown in Figure 4).
From the corresponding HRTEM picture of Pt (Fig. 1 and Fig. 2), can see lattice fringe clearly, wherein the spacing of corresponding Pt (111) crystal face of 0.23nm.
From the corresponding HRTEM picture of Pd (Fig. 4), demonstrate the interplanar distance of 0.23nm, same corresponding Pd (111) crystal face.
In the above embodiments, can wait the degree that graphene oxide is reduced and the load capacity of metal nanoparticle for consumption that the type of body, organic negative hydrogen gives body and reaction condition through changing organic negative hydrogen.
Embodiment 18
The palladium/graphene nano catalyst that obtains with embodiment 3 is a catalyst, studies its catalytic effect in the suzuki coupling reaction, and the structure of reaction system may further comprise the steps:
(1) among the ultrasonic DMF of being distributed to of palladium/graphene nano catalyst that embodiment 3 is obtained (ultrasonic power is 150W), forms the dispersion liquid of 0.3mg/mL;
(2) in the round-bottomed flask of 50ml, add 50mg to methoxyl group iodobenzene, 30mg phenyl boric acid and 83mg anhydrous Na
2CO
3, add above-mentioned palladium/graphene dispersion liquid that obtains of 8ml and 2ml water then;
(3) logical argon gas deoxygenation 30min with the mouth of sealing with wax, behind the reaction 1.5h, stops reaction under oil bath is 85 ℃;
(4) in reactant liquor, add 15ml water; With ethyl acetate extraction three times (each 30ml), upper organic phase with twice of saturated common salt washing (each 20ml), is used anhydrous sodium sulfate drying more at last; Revolving the solid that obtains behind the dried solvent separates with silicagel column; Eluent is a benzinum, obtains p-methoxyphenyl benzene, and productive rate is 80%.
Through catalysis suzuki coupling reaction, can find palladium is loaded on the Graphene, have catalytic performance efficiently, the effect of this enhancing derives from the coupling of the bigger specific area of Graphene and Graphene and nanometer palladium probably.
Embodiment 19
The platinum/graphene nano catalyst that obtains with embodiment 10 is a catalyst, studies its catalytic effect in the solar hydrogen making reaction.
As sensitising agent, as the electronics sacrificial body, as catalyst, the structure of reaction system may further comprise the steps the hydrogen manufacturing system with platinum with triethanolamine with eosin W or W S:
(1) ultrasonic (ultrasonic power is 150W) in the water, the dispersion liquid of formation 0.1mg/ml of being distributed to of platinum/graphene nano catalyst that embodiment 10 is obtained;
(2) in the teat glass of 15ml, add the triethanolamine aqueous solution of the 6ml 0.83M of pH=7.1, and then add the eosin W or W S of 9.3mg, and the catalyst dispersion liquid of the 0.1mg/ml that obtains of 4ml step (1), 5min stirred.Contrasting the hydrogen manufacturing system simultaneously is: do not add platinum/graphen catalyst, other components are identical; The chloroplatinic acid that perhaps adds a great deal of, thus original position produces the platinum nano catalyst by the photosensitizer molecule protection, and other components are all identical;
(3) logical nitrogen deoxygenation 30min, with the mouth of sealing with wax, mark methane 300 microlitres in squeezing into, illumination under wavelength X＞450nm then detects hydrogen growing amount in time with a day U.S. gas-chromatography (TCD is a detector).
As can be seen from Figure 5, the catalyst that makes of the present invention can hydrogen catalyzed effectively generation under the driving of solar energy; Compare with control experiment, can find that Graphene has strengthened the catalysis product hydrogen effect of platinum greatly; This enhancement effect derives from bigger specific area of Graphene and electric transmission speed fast probably, thereby the electronics that has mediated effectively between sensitising agent and the platinum shifts.
Obviously, the above embodiment of the present invention only be for clearly the present invention is described and is done for example, and be not to be qualification to embodiment of the present invention.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (16)
1. a metal/graphite alkene nanocatalyst is characterized in that, comprises the metal nanoparticle of Graphene and load on it; Said Graphene is the graphene oxide of graphene oxide or chemical functionalization.
2. a kind of metal/graphite alkene nanocatalyst according to claim 1 is characterized in that said graphene oxide makes through the following step:
A. the expansion process of graphite
1.6g potassium persulfate and 1.6g phosphorus pentoxide are joined in 9～15ml concentrated sulfuric acid, be heated to 75～85 ℃ and all dissolve until potassium persulfate and phosphorus pentoxide; Add 1.8～2.2g graphite then, under 75～85 ℃ of temperature, react 4～5h, filter, wash, obtain expanded graphite;
B. the oxidation of expanded graphite
The expanded graphite that step a is obtained joins in 75～85ml concentrated sulfuric acid of ice bath cooling, under magnetic agitation, in this mixture, slowly adds 8～12g potassium permanganate down, and reaction 3～5h under 30～40 ℃ reacts 1.5～2.5h again under the room temperature then; The deionized water that slowly adds 150～170ml keeps temperature to be no more than 50 ℃, continues to stir 1.5～2.5h; Add water and the 30wt% hydrogen peroxide solution 8～12ml of 450～490ml again, produce jonquilleous solution, after this solution is placed 24h; Outwell supernatant,, wash respectively twice with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generator earlier then with remaining liquid; And then with twice of 10wt%HCl washing; Dialysis 6～8 days in water at last, the solid that obtains 45～55 ℃ dry down, make graphite oxide;
C. graphite oxide is peeled off and is the mono-layer graphite olefinic oxide
The graphite oxide that step b is made places deionized water, and through ultrasonic wave effect 10～30min, ultrasonic power is 150W, the graphene oxide solution that dissociates and obtain individual layer; Said graphite oxide: deionized water is 0.3mg～0.6mg: 1ml.
3. a kind of metal/graphite alkene nanocatalyst according to claim 1 is characterized in that, the graphene oxide of said chemical functionalization is on Graphene, to modify P-TOLUENE SULFO ACID 99's base or azacyclo-propyl group acetal chain; Wherein, the structure of P-TOLUENE SULFO ACID 99's base and azacyclo-propyl group acetal chain is following:
1) P-TOLUENE SULFO ACID 99's base:
2) azacyclo-propyl group acetal chain:
4. a kind of metal/graphite alkene nanocatalyst according to claim 3 is characterized in that, the said P-TOLUENE SULFO ACID 99's base of on Graphene, modifying is realized through following steps: get graphene oxide solution 40ml, with the Na of 5wt%
2CO
3Regulate pH to 9～10, to the sodium borohydride that wherein adds 100～200g, react 1～2h under 80～90 ℃ the condition, centrifugal then, the solid that obtains is distributed to the dispersion liquid of processing 0.3～0.6mg/l in the water again with after washing twice; To wherein adding the hydrochloric acid diazol 3～6ml that contains 0.095M p-sulfonic acid benzene; In ice bath, react 2h; Reaction finishes the back and in this solution, adds 150ml acetone, separates out deposition, and deposition is after centrifugation; Using volume ratio again is 3: 1 acetone mixed solvent washing three times, the solid that obtains ultrasonic again aqueous solution that is dispersed into 0.3～0.6mg/ml after the drying in 50 ℃ baking oven.
5. a kind of metal/graphite alkene nanocatalyst according to claim 3 is characterized in that, the said azacyclo-propyl group acetal chain of on Graphene, modifying is realized through following steps: get graphene oxide solution 50ml; The ultrasonic 1h of N-methyl pyrrolidone that adds 30～40ml; Argon gas bubbling degasification 20min adds [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols of 1～3g under the argon shield condition, put into oil bath reaction 10～20h for 160 ℃; After being cooled to room temperature; Solid is given a baby a bath on the third day after its birth time with DMF, wash six times, the solid that obtains ultrasonic again aqueous solution that is dispersed into 0.3～0.6mg/ml after the drying in 50 ℃ baking oven with acetone.
6. a kind of metal/graphite alkene nanocatalyst according to claim 1 is characterized in that said metal nanoparticle is platinum, ruthenium or palladium.
7. like the preparation method of the described a kind of metal/graphite alkene nanocatalyst of claim 1-6, it is characterized in that, may further comprise the steps: with the Graphene of graphene oxide or chemical functionalization with contain organic negative hydrogen and mix for the DMF solution of body; The aqueous solution that adds metal ion afterwards; Deoxygenation, this system of illumination adds extractant extraction organic matter; Water is centrifugal with deposition, and the solid that obtains is metal/graphite alkene nanocatalyst.
8. the preparation method of a kind of metal/graphite alkene nanocatalyst according to claim 7 is characterized in that, may further comprise the steps:
(1) 10ml～20ml is contained 10
-4Mol/l gives the aqueous solution of DMF solution with the Graphene of 5ml, 0.3mg/ml～0.6mg/ml graphene oxide or chemical functionalization of body to the organic negative hydrogen of saturated concentration, stir, and is extremely limpid with ultrasonic Treatment then, obtains uniform dispersion liquid;
(2) in the dispersion liquid that step (1) obtains, add 3ml～4ml, 10
-4Mol/l～10
-2The aqueous solution of mol/l metal ion stirs, and obtains uniform dispersion liquid through sonicated again;
(3) this dispersion of ultraviolet-visible light illumination is used in logical argon gas deoxygenation in the dispersion liquid that step (2) obtains in argon gas atmosphere;
(4) add extractant in the dispersion after illumination, the organic matter in the system is fallen in extraction, with the lower floor's water that obtains and precipitate centrifugally, use water washing, centrifugalizes again, with the solid drying that obtains, obtains metal/graphite alkene nanocatalyst.
9. according to the preparation method of claim 7 or 8 described a kind of metal/graphite alkene nanocatalysts, it is characterized in that said organic negative hydrogen is 1 to body, 4-dihydropyridine, 3,4-dihydropyrimidine-2-keto or 2,3-dihydro-1H-benzimidazole.
10. the preparation method of a kind of metal/graphite alkene nanocatalyst according to claim 9 is characterized in that, and is said 1, and the 4-dihydropyridine is the compound with following structure:
Wherein R is H, Me, Et or 4-MeO-Ph.
11. the preparation method of a kind of metal/graphite alkene nanocatalyst according to claim 9 is characterized in that, and is said 3, the 4-dihydropyrimidine-2-keto is the compound with following structure:
R wherein
1=H, R
2=H; R
1=OMe, R
2=H; R
1=Me, R
2=H; R
1=Br, R
2=H; R
1=NO
2, R
2=H; R
1=OH, R
2=H or R
1=H, R
2=Cl.
12. the preparation method of a kind of metal/graphite alkene nanocatalyst according to claim 9 is characterized in that, and is said 2,3-dihydro-1H-benzimidazole is the compound with following structure:
13. the preparation method according to claim 7 or 8 described a kind of metal/graphite alkene nanocatalysts is characterized in that, the said metal ion aqueous solution is the aqueous solution of chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium.
14. the preparation method according to claim 7 or 8 described a kind of metal/graphite alkene nanocatalysts is characterized in that said illumination is to carry out illumination with the 500W high-pressure sodium lamp, wavelength X＞326nm, λ＞355nm or λ＞400nm.
15. the preparation method according to claim 7 or 8 described a kind of metal/graphite alkene nanocatalysts is characterized in that said extractant is ethyl acetate, carrene, chloroform, benzene, toluene or ether.
16. the application of a kind of metal/graphite alkene nanocatalyst as claimed in claim 1 is characterized in that, metal/graphite alkene nanocatalyst is used for organic synthesis and optical drive hydrogen manufacturing system.
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