CN106732566A - A kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst - Google Patents
A kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 70
- 239000002184 metal Substances 0.000 title claims abstract description 70
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 25
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 60
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000009938 salting Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000000643 oven drying Methods 0.000 claims abstract description 3
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002079 double walled nanotube Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 16
- 238000000746 purification Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- -1 nitric acid ruthenium acetone Chemical compound 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- QINUVAVFJVHWJC-UHFFFAOYSA-K propan-2-one;trichlororuthenium Chemical compound CC(C)=O.Cl[Ru](Cl)Cl QINUVAVFJVHWJC-UHFFFAOYSA-K 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
That will be scattered in metal Ru salting liquid through the CNT of concentrated nitric acid purification process the invention provides a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst, prior to 20 40 DEG C at 2 ~ 6h of ultrasound, then 20 ~ 50h of magnetic agitation, filtering dries；Then it is scattered in KBH under condition of ice bath42 ~ 4h is stirred in solution, oven drying is put into behind suction filtration and washing to filtrate pH=6 ~ 8, obtain the catalyst of CNT outer wall load metal ruthenium nano particle, the catalyst obtains the catalyst filled with metal ruthenium nano particle in CNT chamber through high-temperature process again.The inventive method is simple, efficient, and repeatability is high；The catalyst of preparation has activity high for acetophenone asyininetric hydrogenation, relatively stable in atmosphere；And the wet reducing step for using, avoid and use hydrogen gas reduction step, the danger prepared in catalyst process is reduced, also reduce the preparation difficulty and cost of catalyst.
Description
Technical field
The present invention relates to a kind of carbon nanotube loaded metal Ru nano-particle catalyst and its preparation, it is mainly used in ketone
The asymmetric catalytic hydrogenation reaction of compound, belongs to technical field of composite materials and hydrogenation technical field.
Background technology
Asymmetric catalytic hydrogenation is first asymmetric catalysis industrially applied in the world, because its hand-type increases
The outstanding advantage of value and it is especially noticeable.Almost all of noble metal is used as hydrogenation catalyst, wherein especially with nickel,
Platinum, palladium, rhodium are most widely used.The d electron orbits of transition metal are all unfilled, the easy adsorption reaction thing in their surfaces, are conducive to
The formation of middle " reactive compound ", and with catalysis activity higher, while also having high temperature resistant, anti-oxidant, corrosion-resistant etc.
Good characteristic, the application in hydrogenation reaction is quite extensive.
CNT because of its unique structure and excellent physicochemical properties, using widely.CNT is unique
Quasi-one-dimensional nanoscale luminal structure become a kind of new catalyst carrier, such as research of Li Can academician seminar
Report shows, the catalyst that Pt metal nanoparticles are obtained is filled in CNT chamber, to the asymmetric hydrogenation of a- keto esters
Reaction have active and high enantioselectivity high, equally CNT outer wall load Pt metal nanoparticles catalysis
Agent also shows good catalytic performance.And metallic confinement is in the catalysis activity ordinary circumstance of intraluminal catalyst
The lower catalyst being carried on than metallic outside pipe is high.Bag letter and academician seminar are also reported metallic catalyst nanoparticle
Method of the sub selectively uniform load in carbon nanotubes lumen and outside tube wall.But carbon nanotube cavity will be supported on
When interior metallic catalyst nano-particle is reduced, hydrogen reducing or reducing agent wet reducing, catalyst are either used
Repeatability and stability all can substantially reduce.
Ruthenium is a kind of hard and crisp in grayish multivalence yttrium, is a member in platinum group metal.In the earth's crust
Content is only part per billion, is one of most rare metal, but ruthenium is strictly generally the least expensive a kind of metal in platinum group metal,
Although other metals such as platinum, palladium all enrich than ruthenium.The property of ruthenium is very stable, and corrosion resistance is very strong, normal temperature can resistance to hydrochloric acid,
The corrosion of sulfuric acid, nitric acid and chloroazotic acid.Based on this, we prepare a kind of inside and outside wall loading metal Ru nanoparticle in CNT chamber
Muonic catalysis agent.
The content of the invention
It is an object of the invention to provide a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst.
First, the preparation of carbon nanotube loaded metal Ru nano-particle catalyst
（1）The pretreatment of CNT：CNT is dipped in the concentrated nitric acid solution of 60 ~ 68wt.%, and 20- is processed in 120 ~ 140 DEG C
24h, filtering, washing, drying.Fig. 1 is the TEM figures of CNT after purification process.As seen from Figure 1, CNT is outer
The equal smoother of wall and inner chamber, a diameter of 30 ~ 50 nm, length is 5 ~ 20 um.Illustrate CNT after treatment, not only
Purifying is arrived, and has been realized control opening and is truncated.
（2）The preparation of carbon nanotube loaded metal ruthenium nano particle：Pretreated CNT is scattered at room temperature
Metal Ru salting liquid, prior to 20 ~ 40 DEG C at 2 ~ 6h of ultrasound, then 20 ~ 50h of magnetic agitation（Mixing speed is 1000 ~ 1500 rpm）,
Filtering, dries；Then it is scattered in KBH under condition of ice bath42 ~ 4h is stirred in solution, is put behind suction filtration and washing to filtrate pH=6 ~ 8
Enter oven drying, obtain the catalyst of CNT outer wall load metal ruthenium nano particle.
The CNT is SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
The metal Ru salt for metal Ru chloride or nitrate, metal Ru salting liquid for metal Ru salt the aqueous solution or
The acetone soln of metal Ru salt；The concentration of metal Ru salting liquid is 0.01 ~ 1 mg/mL.
The ratio of the metal Ru salting liquid and CNT is 100 ~ 200 mL/g.
The KBH4The concentration of solution is 10 ~ 25mg/mL；CNT and KBH4The ratio of solution is 5 ~ 10 mg/mL.
The drying is in 60 ~ 70 DEG C of 14 ~ 16h of drying.
Fig. 2 is this 5%Ru/CNTs（Pipe is outer）TEM figure.As seen from Figure 2, ruthenium nano particle is evenly dispersed in carbon
The outside wall surface of nanotube, it is probably because the present invention is in ultrasonic procedure, in high power（600 W）Ultrasonator（23
KHz）Auxiliary under so that the residue such as empty gas and water in carbon nanotubes lumen can be diffused out, promote RuCl3/ acetone soln
Inside and outside exchange so that ruthenium nano particle is homogeneously dispersed in carbon nanotube outer.Why do not entered into as ruthenium nano particle
Inside CNT, it may be possible to because CNT is sufficient by two ends with concentrated nitric acid processing procedure, there is part to fail
Port is opened, also or CNT is more long, the not particularly apparent reason of capillary condensation phenomenon, so as to cause most of ruthenium to be received
Rice corpuscles is supported on outside CNT.
The catalyst of CNT outer wall load metal ruthenium nano particle is put into tube furnace, under nitrogen protection first from
Room temperature is warming up to 105 ~ 110 DEG C and is incubated 6 ~ 12h with the speed of 0.5 ~ 10 DEG C/min, then is heated up with the speed of 0.5 ~ 10 DEG C/min
To 350 ~ 450 DEG C of 3 ~ 9h of insulation, the catalyst filled with metal ruthenium nano particle in CNT chamber is obtained.
Fig. 3 is 5%Ru@CNTs（In pipe）The TEM figures of catalyst.As seen from Figure 3, most ruthenium nano particles are equal
It is dispersed in the tube chamber of CNT evenly, it is probably because metal ruthenium nano particle ordinary priority is carried on CNT
In defect point, cause that ruthenium nano particle is diffused along these defect sites by the modulation of temperature, into CNT
Inner chamber, so as to form the structure that ruthenium nano particle is carried on carbon tube cavity, and due to N2The protection of atmosphere causes that it retains
Activity after wet reducing.
2nd, the activity of carbon nanotube loaded metal Ru nano-particle catalyst
Acetophenone is used for carbon nanotube loaded metal Ru nano-particle catalyst prepared by the present invention below by specific experiment
Asyininetric hydrogenation in catalysis activity illustrate.
Test method：The asyininetric hydrogenation of acetophenone is carried out in the stainless steel autoclave of 100 mL.Take system
The standby mg of Ru types catalyst 10 for the obtaining and mg of chiral ligand (1S, the 2S)-DPEN 11.7 and mg of TPP 27.5 is in high pressure
In reactor, the acetophenone of 1 mmol is added, be subsequently adding the isopropanol of 4 mL as solvent, charge and discharge is deflated 3 times, to reach row
Go out the purpose of additional air in kettle.Reactant stirs the regular hour in 600 rpm at a set temperature, after question response terminates,
Cooling reactor, it is identical with atmospheric pressure to be first deflated to pressure in kettle, then takes supernatant and survey its selectivity with gas chromatograph
And conversion ratio.
Experimental result：During CNT outer wall load Ru nano-particle catalysts catalysis acetophenone asyininetric hydrogenation,
The conversion ratio of substrate reaches as high as 99.9%, and the ee values of product a- methylbenzyl alcohols reach as high as 75.8%.Carbon nanotube cavity is born
When carrying Ru nano-particle catalysts catalysis acetophenone asyininetric hydrogenation, substrate conversion efficiency reaches as high as 94.6%, product ee values
Up to 30%.
In sum, the present invention has advantages below compared with the prior art：
1st, the present invention is simply and efficiently prepared for the catalyst of CNT father's carried metal ruthenium nano particle, and the method can be again
Renaturation is high；And the catalyst for preparing has activity higher for asyininetric hydrogenation；
2nd, the wet reducing step for using, avoids and uses hydrogen gas reduction step, reduces the danger prepared in catalyst process
Property, also reduce the preparation difficulty and cost of catalyst；
3rd, the catalyst for preparing at room temperature is relatively stable in atmosphere, it is not necessary to protected using inert gas in use
Shield, thus reduces the use cost of catalyst.
Brief description of the drawings
Fig. 1 is the TEM figures of CNT after purification process.
Fig. 2 is dispersed in the TEM figures of the catalyst of CNT outer wall for ruthenium nano particle.
Fig. 3 is filled in the TEM figures of the catalyst of carbon nanotube cavity for ruthenium nano particle.
Specific embodiment
Below by specific implementation example to a kind of system of carbon nanotube loaded metal Ru nano-particle catalyst of the present invention
Standby and performance is described further.
The preparation of embodiment 1, CNT outside wall surface supported metal ruthenium nano-particle catalyst
（1）The purification process of CNT：By 3 g SWCNs and 150 mL concentrated nitric acids（60~68 wt.%）Mixing, 140
DEG C oil bath flows back 20 h, while magnetic agitation prevents bumping.Suction filtration, deionized water cyclic washing to neutrality, and in 70 DEG C of baking ovens
Middle constant temperature 10 h, it is stand-by.Fig. 1 is the TEM figures of CNT after purification process.
（2）The preparation of CNT outer wall load metal ruthenium nano particle：At room temperature, RuCl is used3 . nH2O and acetone are made into
The ruthenium trichloride acetone soln of 50 mg/mL.0.80 mL ruthenium trichloride acetone solns are taken, after adding 30 mL acetone well mixed,
The CNT for adding 0.40 g to handle well, after stirring 0.5h on magnetic stirring apparatus, is then sonicated 3h, then in magnetic force
25h or so is lentamente stirred on agitator to be volatilized completely to acetone, dries 14h in 70 DEG C in an oven.Take dry after carbon receive
The g of mitron 0.40, is added to the KBH that 20 mL concentration are 12 mg/mL under condition of ice bath42h, suction filtration, washing are stirred in solution
To filtrate pH=7, obtain loading the CNT of ruthenium nano particle；Baking oven is then placed in 24h is dried at 70 DEG C, carbon is obtained
The sample catalyst of nanotube outside wall surface carried metal ruthenium nano particle, the content of metal ruthenium nano particle is 5%, is designated as 5%Ru/
CNTs（Pipe is outer）, its structure and morphology（TEM schemes）See Fig. 2.During the catalyst acetophenone asyininetric hydrogenation, substrate turn
Rate reaches as high as 99.9%, and the ee values of product a- methylbenzyl alcohols reach as high as 75.8%.
The preparation of embodiment 2, CNT outside wall surface supported metal ruthenium nano-particle catalyst
（1）The purification process of CNT：By the original multi-walled carbon nano-tubes of 5 g（Mean inside diameter is 4-8 nm, and external diameter is 10-
20nm）With 200 mL concentrated nitric acids（60-68 wt.%）Mixing, in 140 DEG C of oil bath backflow 24h, stirs, suction filtration, and deionized water is repeatedly
Washing is to neutrality, and the h of constant temperature 12 in 70 DEG C of baking ovens, standby.
（2）The preparation of CNT outer wall load metal ruthenium nano particle：At room temperature, with Ru (NO) (NO3)3Match somebody with somebody with acetone
Into the nitric acid ruthenium acetone soln of the mg/mL of concentration 20.0.50 mL nitric acid ruthenium acetone solns are taken, adds 30 mL acetone to be well mixed
Afterwards, the treated CNTs of 0.10 g are added, after stirring 1h on magnetic stirring apparatus, 2h is then sonicated, then in magnetic force
Slow stirring 20h or so volatilizees to acetone completely on agitator；In an oven 14h is dried in 70 DEG C.Then take dried
The g of CNT 0.10, is added to the KBH that 20 mL concentration are 1.7 mg/mL under condition of ice bath42h, suction filtration are stirred in solution
And wash to filtrate pH=7, obtain loading the CNT of ruthenium nano particle；Baking oven is then placed in 24h is dried at 70 DEG C, is obtained
To the sample catalyst of CNT outside wall surface carried metal ruthenium nano particle, the content of metal ruthenium nano particle is 3%, is designated as
3%Ru/CNTs（Pipe is outer）, its appearance structure is similar to Example 1.During the catalyst acetophenone asyininetric hydrogenation, bottom
The conversion ratio of thing reaches as high as 99.9%, and the ee values of product a- methylbenzyl alcohols reach as high as 71.1%.
The preparation of embodiment 3, CNT outside wall surface supported metal ruthenium nano-particle catalyst
（1）The purification process of CNT：By the original double-walled carbon nano-tubes of 1 g and 50 mL concentrated nitric acids（60-68 wt.%）Mixing,
In 140 DEG C of oil bath backflow 22h, stir, suction filtration, deionized water cyclic washing is to neutrality, and the constant temperature 11h in 70 DEG C of baking ovens, standby
With.
（2）The preparation of CNT outer wall load metal ruthenium nano particle：At room temperature, RuCl is used3 . nH2O and water are made into dense
Spend the solution of ruthenium trichloride of 50 mg/mL.0.32 mL solution of ruthenium trichloride is taken, after adding 30 mL water well mixed, 0.40 is added
G treated CNT, after stirring 0.5h on magnetic stirring apparatus, is then sonicated 3h, then delays on magnetic stirring apparatus
After slowly stirring 40h or so volatilizees completely to water, 14h is dried in 70 DEG C in an oven.Dried carbon is received under condition of ice bath
The g of the mitron 0.40 and KBH that 20 mL concentration are 4.30 mg/mL4Solution stirring mixing, stirs 2h.Stirring is finished, and suction filtration is simultaneously washed
Wash to filtrate pH=7, the CNT that suction filtration is obtained is put into baking oven in 24h is dried at 70 DEG C, obtain CNT outside wall surface
The sample catalyst of carried metal ruthenium nano particle, the content of metal ruthenium nano particle is 2%, is designated as 2%Ru/CNTs (pipe is outer) and urges
Agent, its appearance structure is similar to Example 1.During the catalyst acetophenone asyininetric hydrogenation, the conversion ratio of substrate
98.1% is reached as high as, the ee values of product a- methylbenzyl alcohols reach as high as 68.6%.
The preparation of embodiment 4, CNT internal face supported metal ruthenium nano-particle catalyst
（1）The purification process of CNT：With embodiment 1；
（2）The preparation of CNT inwall supported metal ruthenium nano-particle catalyst：By the step of embodiment 1（2）The catalysis of preparation
Agent 5%Ru/CNTs（Pipe is outer）It is put into tube furnace, leads to N2110 DEG C of holdings are warming up to the speed of 2 DEG C/min after displaced air
12h, after being warming up to 350 DEG C of holding 7h with the speed of 3 DEG C/min again afterwards, is obtained 5%Ru@CNTs（In pipe）Catalyst.Its pattern
Structure is shown in Fig. 3.During the catalyst acetophenone asyininetric hydrogenation, the conversion ratio of substrate reaches as high as 96.4%, product ee
Value is up to 30%.
The preparation of embodiment 5, CNT internal face supported metal ruthenium nano-particle catalyst
（1）The purification process of CNT：With embodiment 4；
（2）The preparation of CNT inwall supported metal ruthenium nano-particle catalyst：By the step of embodiment 1（2）The catalysis of preparation
Agent 5%Ru/CNTs（Pipe is outer）It is put into tube furnace, leads to N2Displaced air, is then warming up to 110 DEG C and keeps 11h with 5 DEG C/min,
After being warming up to 400 DEG C of holding 5h with 5 DEG C/min again afterwards, 5%Ru@CNTs are obtained（In pipe）Catalyst.The catalyst benzene second
During ketone asyininetric hydrogenation, the conversion ratio of substrate reaches as high as 94.8%, and the ee values of product a- methylbenzyl alcohols are reached as high as
16.8%。
The preparation of embodiment 6, CNT internal face supported metal ruthenium nano-particle catalyst
（1）The purification process of CNT：With embodiment 2；
（2）The preparation of CNT inwall supported metal ruthenium nano-particle catalyst：By the step of embodiment 2（2）The catalysis of preparation
Agent 3%Ru/CNTs（Pipe is outer）It is put into tube furnace, leads to N2Displaced air, is then warming up to 110 DEG C of holding 10h with 8 DEG C/min,
After being warming up to 450 DEG C of holding 9h with 7 DEG C/min again afterwards, 3%Ru@CNTs are obtained（In pipe）Catalyst.The catalyst benzene second
During ketone asyininetric hydrogenation, the conversion ratio of substrate reaches as high as 93.5%, and the ee values of product a- methylbenzyl alcohols are reached as high as
16.5%。
Embodiment 7
（1）The purification process of CNT：With embodiment 3；
（2）The preparation of CNT inwall supported metal ruthenium nano-particle catalyst：By the step of embodiment 3（2）The catalysis of preparation
Agent 2%Ru/CNTs（Pipe is outer）It is put into tube furnace, leads to N2Displaced air, is then warming up to 110 DEG C of holding 8h with 2 DEG C/min, it
After being warming up to 400 DEG C of holding 3h with 5 DEG C/min again afterwards, 2%Ru@CNTs are obtained（In pipe）Catalyst.The catalyst acetophenone
During asyininetric hydrogenation, the conversion ratio of substrate reaches as high as 92.5%, and the ee values of product a- methylbenzyl alcohols reach as high as 19%.
Claims (8)
1. a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst, comprises the following steps that：
（1）The pretreatment of CNT：CNT is dipped in the concentrated nitric acid solution of 60 ~ 68wt.%, in 120 ~ 140 DEG C process 20 ~
24h, filtering, washing, drying；
（2）The preparation of carbon nanotube loaded metal ruthenium nano particle：Pretreated CNT is scattered in metal at room temperature
Ruthenium salting liquid, prior to 20-40 DEG C at 2 ~ 6h of ultrasound, then 20 ~ 50h of magnetic agitation, filtering dries；Then divide under condition of ice bath
Dissipate in KBH42 ~ 4h is stirred in solution, oven drying is put into behind suction filtration and washing to filtrate pH=6 ~ 8, obtain CNT outer wall
The catalyst of carried metal ruthenium nano particle.
2. a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst as claimed in claim 1, its feature exists
In：By step（2）The catalyst of the CNT outer wall load metal ruthenium nano particle for obtaining is put into tube furnace, is protected in nitrogen
105 ~ 110 DEG C and 6 ~ 12h of insulation first are warming up to the speed of 0.5 ~ 10 DEG C/min from room temperature under conditions of shield, then with 0.5 ~ 10
DEG C/speed of min is warming up to 350 ~ 450 DEG C of 3 ~ 9h of insulation, obtain being filled with urging for metal ruthenium nano particle in CNT the chamber in
Agent.
3. as claimed in claim 1 or 2 a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst, its feature
It is：Step（2）In, the CNT is SWCN, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
4. a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst as claimed in claim 1 or 2, it is special
Levy and be：Step（2）In, metal Ru salt is the chloride or nitrate of metal Ru, and metal Ru salting liquid is the water of metal Ru salt
The acetone soln of solution or metal Ru salt；The concentration of metal Ru salting liquid is 0.01 ~ 1 mg/mL.
5. as claimed in claim 1 or 2 a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst, its feature
It is：Step（2）In, the ratio of metal Ru salting liquid and CNT is 100 ~ 200 mL/g.
6. a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst as claimed in claim 1 or 2, it is special
Levy and be：Step（2）In, KBH4The concentration of solution is 10 ~ 25mg/mL；CNT and KBH4The ratio of solution is 5 ~ 10 mg/
mL。
7. a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst as claimed in claim 1 or 2, it is special
Levy and be：Step（2）In, magnetic stirring speed is 1000 ~ 1500 rpm.
8. as claimed in claim 1 or 2 a kind of preparation method of carbon nanotube loaded metal Ru nano-particle catalyst, its feature
It is：Step（2）In, the drying is in 60 ~ 70 DEG C of 14 ~ 16h of drying.
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