CN105772082B - A kind of preparation method and its catalytic applications of the nanocomposite of ruthenium - Google Patents
A kind of preparation method and its catalytic applications of the nanocomposite of ruthenium Download PDFInfo
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- CN105772082B CN105772082B CN201610217534.9A CN201610217534A CN105772082B CN 105772082 B CN105772082 B CN 105772082B CN 201610217534 A CN201610217534 A CN 201610217534A CN 105772082 B CN105772082 B CN 105772082B
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- melon ring
- redox graphene
- melon
- ruthenium
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002114 nanocomposite Substances 0.000 title description 2
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical group N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- -1 aromatic amide compound Chemical class 0.000 claims abstract description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000011943 nanocatalyst Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- ZDOBFUIMGBWEAB-XGFHMVPTSA-N cucurbit[7]uril Chemical compound N1([C@H]2[C@H]3N(C1=O)CN1[C@H]4[C@H]5N(C1=O)CN1[C@H]6[C@H]7N(C1=O)CN1[C@H]8[C@H]9N(C1=O)CN1[C@H]%10[C@H]%11N(C1=O)CN([C@@H]1N(C%12=O)CN%11C(=O)N%10CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@H]6[C@@H]4N2C(=O)N6CN%12[C@@H]1N3C5 ZDOBFUIMGBWEAB-XGFHMVPTSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 229940124530 sulfonamide Drugs 0.000 abstract description 6
- 150000003456 sulfonamides Chemical class 0.000 abstract description 5
- 230000009881 electrostatic interaction Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003223 protective agent Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229910019891 RuCl3 Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 241000219112 Cucumis Species 0.000 description 2
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of synthesis by melon ring and redox graphene as the method that carrier prepares metal ruthenium nanoparticle catalyst altogether, and such catalyst is applied to catalyze and synthesize aromatic amide compound.The chemical component of nanoparticle catalyst of the invention is metal Ru, melon ring and redox graphene.Melon ring and redox graphene effectively prevent the reunion of redox graphene as carrier, the electrostatic interaction and bulk effect of melon ring altogether, and the extra small Ru nano particle grain being prepared is through uniform and be uniformly dispersed.Nanoparticle catalyst prepared by the present invention has excellent catalytic activity and stability, can efficient catalytic sulfonamide and aromatic alcohol reaction prepare aromatic amide compound.The catalyst can be repeated as many times use and activity is not substantially reduced.This method has synthesis simple, and easy to operate, the features such as having a wide range of application, and preparation condition is mild, and method is simple, and without special equipment, cost is cheaper.
Description
Technical field
The present invention relates to the use of melon ring and redox graphene be uniformly dispersed as carrier synthesis altogether, uniform particle diameter it is super
The method of small ruthenium nano-particle.Using the electrostatic interaction and bulk effect of melon ring, intercalation work is carried out to redox graphene
With obtaining the redox graphene that will not reunite.Melon ring and redox graphene have as carrier and protective agent altogether
The reunion and growth of ruthenium nano-particle are limited to effect, obtains the ruthenium nanocatalyst being excellent in organic catalysis.This hair
It is bright to belong to catalysis material field.
Background technique
Effectively construct the hot spot that new carbon-nitrogen bond is always organic catalysis field.Fragrant sulphonyl containing carbon-nitrogen bond
Amine compounds are the basic construction units of many drugs, luminous organic material.Generally synthesized using amine and sulfonic acid chloride as substrate
Corresponding aromatic amide compound, but halogen aromatic compound is more toxic, by-product environmental pollution is serious.It can take
The by-product obtained after the reaction for the aromatic alcohol of sulfonic acid chloride only has water, and nontoxic, is the synthetic route of Atom economy.But
Be aromatic alcohol electrophilicity it is but very weak, so can effectively be catalyzed the reaction catalyst become this circuit combination fragrance sulphonyl
The key of amine compounds.The complex of metal Ru can effectively be catalyzed various organic reactions as homogeneous catalyst, but have
Many and diverse, expensive with production procedure needed for complex, complex itself is also difficult to separate from product, it is difficult to which recycling is sharp again
With.Nano particle specific surface area with higher, is also easy to be surface modified, and can be realized catalytic process as catalyst
Homogeneousization.Meanwhile nano particle can also be separated from reaction system by a variety of methods, such as filtering or magnetic-adsorption
Out, so that the last handling process out-phase of synthesis.Since nano particle is catalyzed while having homogeneous catalysis and heterocatalysis
Advantage, so nano-catalytic becomes the hot spot forward position of industrial production and scientific research.
Currently, the stability of less, with higher catalytic activity the nano particle of surface protectant is bad, urged twice one
Change phenomena such as reaction occurs as soon as reunion inactivation later.And the surface of the nanocatalyst of those high stabilities is covered by protective agent
Seriously, so catalytic activity is bad.These problems mostly come from the protective agent that nano particle uses in the synthesis process
And carrier.Redox graphene (rGO) and melon ring (cucurbituril, CB) are to be respectively provided with plane layer structure and ring-type
The two kinds of novel carriers and protective agent of rigid structure.Redox graphene has good electric conductivity, can enhance and be related to electricity
The catalytic performance of the catalysis reaction of son transfer.But the layer of redox graphene is extremely easy to reunite together, weakens significantly
Various performances.Melon ring then can stablize nano material by electrostatic interaction and bulk effect.As emerging in recent years
Carrier type, cricoid melon toroidal molecule, which has, does not dissolve in common solvents, and has higher chemical stability and thermal stability
Etc. advantages.Finely dispersed extra small metal nano is prepared using melon ring and redox graphene as carrier and protective agent altogether
The research of grain catalyst was not yet reported that.By adjusting a variety of reaction conditions, such as the acid-base property of system, metal precursor salt and
Material ratio etc. between carrier, can be prepared and be uniformly dispersed, and grain is through uniform extra small Ru nanoparticle catalyst.The nanometer
Particle prepares aromatic amide compound and shows excellent catalytic activity and stabilization for catalysis sulfonamide and aromatic alcohol reaction
Property.
Summary of the invention
The object of the present invention is to provide one kind to prepare metal Ru nanometer as carrier altogether by melon ring and redox graphene
Beaded catalyst, and the catalysis reaction for being applied to sulfonamide and aromatic alcohol prepares aromatic amide compound.Prepared by the present invention
Nanoparticle catalyst have excellent catalytic activity and stability, can be repeated as many times use.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst.
The chemical component of nanoparticle catalyst of the invention is metal Ru, melon ring and redox graphene.Wherein urge
The content for changing active component Ru can be adjusted from 2% to 30% (mass percent).Melon ring and redox graphene are as load altogether
Body and protective agent, the electrostatic interaction and bulk effect of melon ring effectively prevent the reunion of redox graphene, are prepared
Extra small Ru nano particle grain through uniform and be uniformly dispersed.Melon ring and redox graphene are indispensable, only use a kind of load
The Ru nano particle dispersion that body is prepared is uneven and is easy to reunite, and catalytic activity is not high.Prepare the nanocatalyst
Another key factor is exactly the acid-base property of reaction system, and a large number of experiments determines the Ru/ being prepared in neutral conditions
Melon ring/redox graphene composite Nano catalysis material (Ru/CB/rGO) is to catalysis sulfonamide and aromatic alcohol reaction preparation virtue
Fragrant sulfonamide compounds has most excellent catalytic performance.Nano catalytic material provided by the invention, there is simple process, operation side
Just, the features such as having wide range of applications.
The present invention uses following technical solution:
1. synthesizing to obtain melon ring and graphene oxide according to document providing method.
2. at room temperature, a certain amount of metal precursor salt RuCl3Aqueous solution, regulation system pH value is in particular range；
3. melon ring and graphene oxide solid are added to step 2 into solution, stir 4 hours obtain it is uniformly mixed outstanding
Turbid；
4. by five times of equivalents in metal precursor RuCl3NaBH4Solid is dissolved in ethyl alcohol, obtains reducing agent；
5. the reducing agent of step 4 is added in the suspension of step 3, magnetic agitation 3 hours after sealing；
6. step 5 arrive product centrifugation after, washing twice, ethanol washing it is primary, oven drying.
Nano catalytic material provided by the present invention has the advantage that
(1) particle of active component is extra small, grain through it is uniform, be uniformly dispersed.
(2) adjusting of content of metal may be implemented by adjusting feed ratio.
(3) adjusting of different loads effect may be implemented by the adjusting of ratio between total carrier.
(4) catalytic performance of the nano catalytic material is excellent, catalysis can be completed in the short period under mild conditions
Reaction, and catalytic activity is not decreased obviously after being recycled for multiple times.
Detailed description of the invention
Fig. 1: the transmission electron microscope photo for the Ru/CB/rGO that pH value is prepared when being 7
Fig. 2: Ru/CB/rGO grain is through statistical distribution
Fig. 3: only with a kind of transmission electron microscope photo (Ru/CB) of the Ru nano particle of support C B preparation
Fig. 4: only with a kind of transmission electron microscope photo (Ru/rGO) of the Ru nano particle of carrier rGO preparation.
Fig. 5: the transmission electron microscope photo of Ru/CB/rGO after catalysis.
Fig. 6: catalytic cycle service condition.
Specific embodiment
Embodiment 1:
The preparation of Ru/CB/rGO, by 0.2mL (0.1mmol/mL) RuCl3Aqueous solution be added to the deionized water of 300mL
In, adjusting its pH value with the sodium hydrate aqueous solution of 0.1M is 7；The hexa-atomic melon ring of 50mg (CB [6]) and 50mg graphene oxide
(GO) solid is added in the solution of above-mentioned metal precursor salt, arrives uniform suspension after stirring 4 hours；190mg
NaBH4Fast drop is into above-mentioned suspension after being dissolved in 200mL ethyl alcohol；After persistently being stirred in closed environment 3 hours from
The heart, water washing twice, ethanol washing it is primary.Ethyl alcohol disperses after drying, transmission electron microscope observing product be grain through for 1.25 ±
0.25nm, finely dispersed extra small Ru nano particle (Ru/CB/rGO).Plasma emission spectroscopy (ICP) analysis the result shows that
The content of Ru is 2%.
Embodiment 2:
By 3mL (0.1mmol/mL) RuCl3Aqueous solution be added in the deionized water of 300mL, with the hydroxide of 0.1M
It is 7 that sodium water solution, which adjusts its pH value,；The hexa-atomic melon ring of 50mg (CB [6]) and 50mg graphene oxide (GO) solid are added to above-mentioned gold
In the solution for belonging to precursor salt, uniform suspension is arrived after stirring 4 hours；2.85g NaBH4It is fast after being dissolved in 400mL ethyl alcohol
Speed is added drop-wise in above-mentioned suspension；Be centrifuged after persistently stirring 3 hours in closed environment, water washing twice, ethanol washing one
It is secondary.Icp analysis is the result shows that the content of Ru is 30%.
Embodiment 3:
All steps are same as Example 1, in addition to hexa-atomic melon ring changes eight yuan of melon rings into, obtain Ru/CB [8]/rGO, ICP divides
Analysis is the result shows that the content of Ru is 12%.
Embodiment 4:
All steps are same as Example 1, in addition to pH value does not have to adjust, obtain Ru/CB/rGO-2.
Embodiment 5:
Ru/CB/rGO catalysis sulfonamide and aromatic alcohol prepare aromatic amide compound, 138mg K2CO3, to methylbenzene sulphur
Amide (1mmol), 1mL benzyl alcohol and 10mg Ru/CB/rGO are added in 35mL pressure resistance reaction flask, it is closed after at 130 degrees Celsius
Under the conditions of react 6 hours.5mL water is added after reaction, organic phase is then extracted with ethyl acetate.Water phase contains catalyst powder
Catalyst is recycled after dry by separating and respectively washed once with water, ethyl alcohol in the part at end.Organic phase is obtained by column chromatography for separation
To product, separating yield is 98%.Using preparation-obtained material in embodiment 4 as catalyst, urge under the same conditions
Changing yield is 60%.
Above said content is only the basic explanation under present inventive concept, and what technical solution according to the present invention was done appoints
What equivalent transformation, is within the scope of protection of the invention.
Claims (4)
1. a kind of ruthenium nanoparticle catalyst for being carried on melon ring and redox graphene, chemical skeleton symbol are as follows: Ru/CB/rGO,
Wherein the mass content of active component Ru is 2% to 30%；Wherein melon ring and redox graphene are as carrier altogether；It is described to urge
The partial size of agent is 0.6nm~2.0nm；
The preparation method of the catalyst, includes the following steps:
(1) melon ring and graphene oxide are synthesized first；
(2) pH value of metal Ru precursor salt aqueous solution is adjusted in neutrality with sodium hydrate aqueous solution；
(3) the melon ring of step (1) synthesis and graphene oxide and metal Ru precursor salt are added according to certain mass ratio and are walked
Suddenly it in the solution of (2), stirs 4 hours, dispersion obtains mixture；
(4) sodium borohydride that molar ratio is five times in ruthenium precursor salt is dissolved in ethyl alcohol, obtains reducing agent；
(5) reducing agent of step (4) is rapidly injected in the mixture of step (3), and magnetic agitation 3 hours；
(6) step (5) product by centrifugation, washing twice, ethanol washing it is primary after, oven drying obtains final nano-catalytic material
Material；The amount of each substance must be added in step (2), (3) according to a certain percentage；Be added the melon ring of different proportion, graphene oxide and
Metal precursor, a series of different nanocatalyst of available active component contents.
2. the ruthenium nanoparticle catalyst according to claim 1 for being carried on melon ring and redox graphene, feature
Be: the type for the melon ring being added in the step (3) is different, and the ruthenium nanometer that can obtain different loads and catalytic effect is urged
Change material, wherein the type of melon ring is five yuan of melon rings, hexa-atomic melon ring, cucurbit(7)uril and eight yuan of melon rings.
3. the ruthenium nanoparticle catalyst according to claim 1 for being carried on melon ring and redox graphene, feature
Be: the mass ratio of the melon ring and graphene oxide that are added in the step (3) can be adjusted within the scope of full scale, be born
It carries and the different nano catalytic material of catalytic effect.
4. the ruthenium nanoparticle catalyst described in claim 1 for being carried on melon ring and redox graphene is for being catalyzed sulphonyl
Amine and aromatic alcohol reaction prepare aromatic amide compound.
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| CN201610217534.9A CN105772082B (en) | 2016-04-08 | 2016-04-08 | A kind of preparation method and its catalytic applications of the nanocomposite of ruthenium |
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