CN104941686B - Meso-porous nano catalyst of palladium ruthenium bimetallic functionalization a kind of of eggshell structure and preparation method thereof - Google Patents
Meso-porous nano catalyst of palladium ruthenium bimetallic functionalization a kind of of eggshell structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses meso-porous nano catalyst of palladium ruthenium bimetallic functionalization of a kind of eggshell structure and preparation method thereof, the meso-porous nano catalyst is from BTEE and TEOS, Ts DPEN functions silicon source and PdP2Hydrolysis copolymerization obtains the catalyst of the palladium functionalization of eggshell structure in the basic conditions, after forming destination carrier, then by rear grafting metal Ru compounds, finally synthesizes the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of eggshell structure.The catalyst has advantages below：(1) while with the catalysiss being coupled and reduce, can be used for one pot and be catalyzed " coupling catalysed " reaction of series connection；(2) catalyst has the characteristic of obvious hydrophobic performance and high degree of dispersion, may advantageously facilitate the carrying out of organic reaction, improves the reaction rate of catalytic reaction；(3) bottleneck problem of the hardly possible compatibility of conventional dual-metal catalyst is which overcomed, it is achieved that efficiently " coupling catalysed " reaction of the series connection of high selectivity.
Description
Technical field
The present invention relates to catalyst technical field, and in particular to a kind of palladium ruthenium bimetallic functionalization of Novel egg shell structure
Meso-porous nano catalyst and preparation method thereof.
Background technology
The Nano capsule of eggshell-egg yolk structure is the special structure of a class in shell-core nano-particle, and it has moveable
The core of functionalization, external sheath the shell of functionalization, and have space between moveable core and shell parts, form hollow knot
The size of structure, wherein internal cavity is regulatable, and this just imparts eggshell-new characteristic of egg yolk structure Nano capsule so that egg
The Nano capsule of shell-egg yolk structure is in catalysis and nanosecond medical science field (Gao J, Liang G, Zhang of great interest
B,et al.FePt@CoS2yolk-shell nanocrystals as a potent agent to kill HeLa cells
[J].Journal of the American Chemical Society,2007,129(5):1428-1433.).
Since finding ordered nano mesoporous material first from 1992 (C.P.Casey., et al.,
J.Am.Chem.Soc.1992,114:10826-10834.), this material characteristicses are unique：Aligned orderly degree is high, pore diameter range exists
In 2-50nm the advantages of controllable, thus have in fields such as electronic information, biological medicine, environment, chemistry, the energy of crucial importance
Research and using value.Wherein order mesoporous organosilicon material (PMO) is formed due to the regular organic group bridging in its duct,
Thus there is more unique adjustable physics and chemical property (B.Hatton., et al., Acc.Chem.Res.2005,38:
305-312；F.Hoffmann.,et al.,Angew.Chem.Int.Ed.2006,45:3216-3251.).
One pot of series process is that one kind has promising methodology of organic synthesis very much.Multistep reaction in one pot of series process reaction
Baroque molecule can be directly obtained from raw material relatively simple and easy to get without the separation of intermediate.But restrict
The key condition that " one kettle way " is used be requirement each individually react between the step of have compatibility, i.e., will not mutual shadow
Ring.Wherein homogeneous Catalyzed by Pt/M Bimetallic Nano reaction due to interfere one pot of series connection difficult to realize (A.Zanardi,
E.Peris,et al.,J.AM.CHEM.SOC.2009,131,14531–14537；S.Gonell,M.Poyatos,et al.,
Organometallics 2012,31,5606-5614).
Thus the special construction using eggshell structure nano material and with reference to the hydrophobic of orderly mesoporous organosilicon material phase
Property performance, assembling have bimetallic functionalization nano material can interfere efficiently against bimetallic, therefore, study which
In the prospect that one pot of cascade reaction will have very important significance and apply.
In consideration of it, the meso-porous nano catalyst of design and the palladium ruthenium bimetallic functionalization for preparing eggshell structure becomes the present invention
The patent technical issues that need to address.
Content of the invention
It is an object of the present invention to provide a kind of preparation of the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of eggshell structure
Method.
The technical scheme is that：
A kind of preparation method of the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of eggshell structure, including step：
(1) by tetraethoxysilane (TEOS), double (triethoxy silicon substrate) ethane (BTEE) of 1,2- and (N-p- is to (2- tri-
Ethyl-silicone) ethyl benzenesulfonyl -1,2- diphenyl ethylene diamines) Ts-DPEN silicon sources in alkalescence condition, at 80-85 DEG C hydrolyze；
(2) treat that step (1) reactant liquor is cooled to 38-40 DEG C, under ammonia existence condition, Deca tetraethoxysilane
(TEOS), 2-2.5h is stirred；
(3) step (2) reactant liquor Deca 1 under ammonia existence condition, double (triethoxy silicon substrate) ethane (BTEE) of 2-, plus
Enter diphenylphosphine palladium (PdP2), 80-85 DEG C of reaction 3-3.5h；
(4) filter, wash and dry gained solid, surname extraction is carried out to solid with ethanol and ammonium nitrate, is then carried out
Sucking filtration, gained solid is scrubbed and dries, and obtains Pd eggshell structure catalysts；
(5) Pd eggshells structure catalyst and sym-trimethylbenzene. base ruthenic chloride dimer are reacted 20- in anhydrous methylene chloride
24h, removes solvent, through drying after gained solid with methylene chloride surname extraction, obtains the palladium ruthenium bimetallic function of eggshell structure
The meso-porous nano catalyst of change.
Step (1) alkalescence condition refers to dissolved with the water-soluble of cetyl trimethylammonium bromide (CTAB) and sodium hydroxide
Liquid.
Double (triethoxy silicon substrate) ethane (BTEE) of tetraethoxysilane (TEOS), 1,2- and Ts-DPEN silicon in step (1)
The mol ratio in source is 1:0.23-0.24:0.12-0.13.
In step (2) in added tetraethoxysilane (TEOS) and step (1) added by tetraethoxysilane (TEOS) rub
You are than being 1-1.1:1.
Added 1,4- double (triethoxy silicon substrate) ethane (BTEE) and added tetraethoxy-silicane in step (1) in step (3)
The mol ratio of alkane (TEOS) is 1.20-1.25:1.
Added diphenylphosphine palladium (PdP in step (3)2) with step (1) added tetraethoxysilane (TEOS) mole
Than for 0.07-0.08:1.
The meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of the eggshell structure of the present invention, from BTEE and TEOS, Ts-
DPEN functions silicon source and Pd P2Hydrolysis copolymerization obtains the catalyst of the palladium functionalization of eggshell structure in the basic conditions, forms mesh
After mark carrier, then by rear grafting metal Ru compounds, finally synthesize eggshell structure palladium ruthenium bimetallic functionalization mesoporous
Nanocatalyst.
The catalyst has advantages below：(1) due to containing the double organic metal of palladium-ruthenium, it is coupled so as to have simultaneously and goes back
Former catalysiss, can be used for one pot of catalysis series connection " being coupled-catalysis " reaction, embody bifunctional characteristic.(2) catalyst
There is the characteristic of obvious hydrophobic performance and high degree of dispersion, may advantageously facilitate the carrying out of organic reaction, improve the anti-of catalytic reaction
Answer speed.(3) bottleneck problem of the hardly possible compatibility of conventional dual-metal catalyst is which overcomed, it is achieved that the string of efficient high selectivity
Connection " being coupled-catalysis " reaction, which has potential value at the aspect such as synthesis of chiral medicine and asymmetry catalysis.
Description of the drawings
Fig. 1 is the scanning electron microscope of the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of eggshell structure prepared by the present invention
(SEM).
Fig. 2 is the transmission electron microscope of the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of eggshell structure prepared by the present invention
(TEM).
Fig. 3 is the catalytic reaction of the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of eggshell structure prepared by the present invention
Data.
Specific embodiment
The present invention is specifically described with reference to embodiment and accompanying drawing, it is necessary to it is pointed out here that be the present invention only
It is used to further illustrate the present invention, it is impossible to be interpreted as limiting the scope of the invention.
Embodiment：
(1) 0.1g CTAB are taken, 45mL aqueous solutions are dissolved in, it is placed in 250mL round-bottomed flasks, then Deca 0.35mL
NaOH (2.0M) solution.
(2) after CTAB is uniformly dissolved, slowly Deca 0.43g tetraethoxysilane (TEOS) in stirring
(2.07mmol), and then Deca 0.17g 1,2- double (triethoxy silicon substrate) ethane (BTEE) is (0.48mmol) and 0.125g
Ts-DPEN silicon sources (0.25mmol).
(3) 0.4mL ethyl acetate is added, 2h is stirred in 80 DEG C of oil bath.
(4) question response liquid is cooled to 38 DEG C, then plus 80mL water, 50mL dehydrated alcohol, 300mg CTAB, the ammonia of 1mL
(25wt%).
(5), after stirring 0.5h, Deca 0.47g tetraethoxysilane (2.26mmol) then stirs 2h.
(6) add to reactant liquor and include 80mgCTAB, 40mg FC-4 (Fluorocarbon surfactant), 0.2mL
The 3mL aqueous solutions of ammonia (25wt%).
(7) after stirring, the 2mL of 1,2- of the Deca comprising 0.88g double (triethoxy silicon substrate) ethane (2.49mmol)
Dehydrated alcohol.
150mg diphenylphosphine palladium (PdP are added after (8) two minutes2) (0.16mmol) function silicon source, 1.5h is stirred then,
Heat up 80 DEG C of holding 3h.
(6) from after reaction bulb taking-up, sucking filtration is carried out, by the solid obtained after sucking filtration, deionized water and ethanol are washed again
Wash, be finally placed in 50-55 DEG C of vacuum drying oven and dry, dry 24h.
(7) surname extraction is carried out to solid with 120mL ethanol and 80mg ammonium nitrates finally, after surname extraction 24-36h, enter
Row sucking filtration, the solid obtained after sucking filtration deionized water and washing with alcohol again are finally placed in 50-55 DEG C of vacuum drying oven
Dry, after drying 24h, obtain the catalyst of the palladium functionalization of the i.e. intended catalyzed agent carrier eggshell structure of buff powder.
(8) catalyst and 100mg sym-trimethylbenzene. base ruthenic chloride dimers of the palladium functionalization of 1g eggshell structures are taken
(Dichloro (mesitylene) ruthenium (II) dimer) is subsequently adding 80mL anhydrous two in 150mL round-bottomed flasks
Chloromethanes, are stirred at room temperature 24-36h, and reaction is spin-dried for solvent after terminating, with dichloromethane surname extraction 10h.50- is finally placed in
Dry in 55 DEG C of vacuum drying ovens, dry the catalyst that 24h obtains the palladium ruthenium bimetallic functionalization of eggshell structure.
Fig. 1 shows that the catalyst is uniformly spherical, and Fig. 2 shows that the catalyst is hollow similar eggshell structure.
The catalyst one pot of cascade reaction of example " Sonogashira coupling reactions and Asymmetric hydrogen transfer reaction " under catalysis
Show preferable activity, reaction conversion ratio reach 99% and chemo-selective Ee values reach 97%.
Claims (6)
1. a kind of preparation method of the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of eggshell structure, it is characterised in that bag
Include step：
(1) by tetraethoxysilane (TEOS), double (triethoxy silicon substrate) ethane (BTEE) of 1,2- and N-p- to (2- triethoxies
Silicon substrate) ethyl benzenesulfonyl -1,2- diphenyl ethylene diamines in alkalescence condition, at 80-85 DEG C hydrolyze；The alkalescence condition refer to dissolved with
Cetyl trimethylammonium bromide (CTAB) and the aqueous solution of sodium hydroxide；
(2) treat that step (1) reactant liquor is cooled to 38-40 DEG C, under ammonia existence condition, Deca tetraethoxysilane (TEOS),
Stirring 2-2.5h；
(3) step (2) reactant liquor Deca 1 under ammonia existence condition, double (triethoxy silicon substrate) ethane (BTEE) of 2-, adds two
Phenyl phosphorus palladium (PdP2) function silicon source, 80-85 DEG C of reaction 3-3.5h；
(4) filter, wash and dry gained solid, surname extraction is carried out to solid with ethanol and ammonium nitrate, then sucking filtration is carried out,
Gained solid is scrubbed and dries, and obtains Pd eggshell structure catalysts；
(5) Pd eggshells structure catalyst and sym-trimethylbenzene. base ruthenic chloride dimer are reacted 20-24h in anhydrous methylene chloride,
Solvent is removed, through drying after gained solid with methylene chloride surname extraction, the palladium ruthenium bimetallic functionalization of eggshell structure is obtained
Meso-porous nano catalyst.
2. the preparation method of meso-porous nano catalyst according to claim 1, it is characterised in that four ethoxies in step (1)
The mol ratio of double (triethoxy silicon substrate) ethane (BTEE) of base silane (TEOS), 1,2- and Ts-DPEN silicon sources is 1:0.23-
0.24:0.12-0.13.
3. the preparation method of meso-porous nano catalyst according to claim 1, it is characterised in that added four in step (2)
Ethoxysilane (TEOS) is 1-1.1 with the mol ratio of added tetraethoxysilane (TEOS) in step (1):1.
4. the preparation method of meso-porous nano catalyst according to claim 1, it is characterised in that added 1 in step (3),
2- double (triethoxy silicon substrate) ethane (BTEE) is 1.20- with the mol ratio of added tetraethoxysilane (TEOS) in step (1)
1.25:1.
5. the preparation method of meso-porous nano catalyst according to claim 1, it is characterised in that added two in step (3)
Phenyl phosphorus palladium (PdP2) mol ratio of added tetraethoxysilane (TEOS) is 0.07-0.08 in function silicon source and step (1):1.
6. the meso-porous nano catalyst of the palladium ruthenium bimetallic functionalization of a kind of eggshell structure, it is characterised in that the catalyst is root
Prepare according to the preparation method described in claim 1-5 any one.
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| CN105289738A (en) * | 2015-11-26 | 2016-02-03 | 上海师范大学 | Chiral ethylenediamine Ru complex modified polyethylene glycol functional meso-porous silicon nanospheres and preparation method thereof |
| CN107008501A (en) * | 2017-02-21 | 2017-08-04 | 上海师范大学 | A kind of hydrophilic mesoporous silicon nanosphere of the bimetallic support type containing palladium and chiral ruthenium complex and preparation method thereof |
| CN115300940B (en) * | 2022-07-19 | 2023-06-06 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Double-layer mesoporous organic silicon hollow sphere solid-phase microextraction probe and preparation method and application thereof |
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