CN110180587A - The preparation method and applications of functionalized silicon nanometer sheet loaded palladium catalyst - Google Patents
The preparation method and applications of functionalized silicon nanometer sheet loaded palladium catalyst Download PDFInfo
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- CN110180587A CN110180587A CN201910573504.5A CN201910573504A CN110180587A CN 110180587 A CN110180587 A CN 110180587A CN 201910573504 A CN201910573504 A CN 201910573504A CN 110180587 A CN110180587 A CN 110180587A
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- nanometer sheet
- silicon nanometer
- functionalized silicon
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- loaded palladium
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 86
- 239000010703 silicon Substances 0.000 title claims abstract description 86
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 amino silicane Chemical compound 0.000 claims abstract description 31
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000004305 biphenyl Substances 0.000 claims abstract description 4
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 101150003085 Pdcl gene Proteins 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- OOPSAZSKOMIGFX-UHFFFAOYSA-N boric acid;toluene Chemical compound OB(O)O.CC1=CC=CC=C1 OOPSAZSKOMIGFX-UHFFFAOYSA-N 0.000 claims description 10
- 150000001499 aryl bromides Chemical class 0.000 claims description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 2
- 150000003376 silicon Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 229960004756 ethanol Drugs 0.000 description 15
- 238000002156 mixing Methods 0.000 description 6
- 229910004709 CaSi Inorganic materials 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000005347 biaryls Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910021346 calcium silicide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002023 wood Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/44—Palladium
-
- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- 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
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
Abstract
The present invention provides a kind of preparation method and applications of functionalized silicon nanometer sheet loaded palladium catalyst.The present invention is surface modified silicon nanometer sheet using amino silicane coupling agent, then restores successfully synthesis functionalized silicon nanometer sheet loaded palladium catalyst with palladium chloride coordination.The functionalized silicon nanometer sheet of this method preparation has a fabulous crystallinity as carrier loaded nano Pd catalyst, biggish specific surface area and nanoparticle palladium can uniformly disperse.Functionalized silicon nanometer sheet loaded palladium catalyst made from this method shows very superior Hydrogenation and stability in the Suzuki coupling reaction synthesis biphenyl compound for being applied to halogenated aryl hydrocarbon and aryl boric acid.For all either there is good catalytic activity with inhaling still the power Suzuki reaction of halogenated aryl hydrocarbon and aryl boric acid of base of electric base.In addition, the catalyst circulation still keeps good catalytic activity using repeatedly rear its.
Description
Technical field
The invention belongs to loaded noble metal catalyst preparation fields, and in particular to through amino silicane coupling agent chemical modification
The silicon nanometer sheet and palladium chloride of Post functionalization are coordinated, then are prepared for the novel functionalized silicon nanometer sheet supported palladium of one kind through reduction and are urged
Agent, and it is applied to the Suzuki coupling reaction of aryl bromide and aryl boric acid.
Background technique
Catalyst carrier is the important component of loaded catalyst, is mainly used for supporting active component, makes catalyst
With specific physical behavior.There is silica-base material big specific surface area, good mechanical strength and surface to be easy to functionalization etc.
As the carrier of the noble metal catalysts such as palladium high catalytic activity may be implemented, selectivity is good and conversion ratio height etc. is excellent in feature
Point.Silicon nanometer sheet is the new material of scientists study preparation in recent years, is hydrolyzed by calcium silicide and to be obtained in acid condition
Stratified material, it is similar with graphene-structured, there is stratiform, bi-dimensional cellular shape network, compared to traditional nano silicon particles,
The thickness of this silicon nanometer sheet only has 2 ~ 5 nm, has fabulous crystallinity, electric property and big specific surface area, and surface is deposited
In a certain amount of Si-H and Si-OH group, it is modified that surface can be carried out to it with functional group, therefore is highly suitable as loading
The excellent carrier of type catalyst.
The Suzuki coupling reaction of halogenated aryl hydrocarbon and aryl boric acid is that the important hand of carbon-carbon bond is constructed in organic chemical synthesis
Section, is one of the most effectual way for constructing biaryl key, and biphenyl compound is widely used in as important Organic Ingredients
Natural products, pharmaceutical intermediate and functional material etc. synthesize field.Currently, there are many kinds of the synthetic methods of biaryl hydrocarbon compound,
Wherein, make catalyst Suzuki coupling reaction using palladium and occupy consequence in synthetic method.However due to homogeneous
Palladium catalyst is difficult to separate, and easily pollutes to product, has the shortcomings that recycling is difficult and can not recycle.It is anti-to limit this
Application industrially is answered, and load type palladium catalyst is then one of the feasible way to solve the above problems.
Summary of the invention
The present invention provides a kind of preparation method and applications of functionalized silicon nanometer sheet loaded palladium catalyst, mainly solves
The technical issues of be: although conventional homogeneous catalyst Suzuki coupling reaction has a very high catalytic activity, but homogeneous
Palladium catalyst is difficult to separate, and easily pollutes to product, has the shortcomings that recycling is difficult and can not recycle, it is anti-to limit this
Answer application industrially
In order to solve the above technical problems, the present invention provides a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst,
The following steps are included:
(1) silicon nanometer sheet is prepared: in 10 mmolCaSi2The middle concentrated hydrochloric acid that 1.2 mol are added, under nitrogen atmosphere, at -15 ~ 0 DEG C
It is stirred to react 3 ~ 5d, is then filtered, methanol is washed 3-5 times, and washing into pH value until filtrate is 6 ~ 7, celadon filter residue is obtained, 80 ~
It is dried in vacuo 2d under the conditions of 100 DEG C of temperature, then grinds, obtains celadon solid powder i.e. silicon nanometer sheet；
(2) the modified functionalized silicon nanometer sheet of preparation: will be added 90 mL alcohol in 1g silicon nanometer sheet described in step (1), ultrasound
Disperse 0.5 ~ 1h, add 10mL water, be then stirred at reflux under the conditions of 70 DEG C of temperature, amino silane coupling is added dropwise
Agent, the reaction was continued 6 ~ 10h are filtered and with ethanol wash 3-5 times, gray solid powder are obtained, then in 60 ~ 80 DEG C of temperature strip
It is dried in vacuo 8 ~ 12h under part, takes out product, grinding obtains the functionalized silicon nanometer sheet of aminosilane coupling agent modifying, wherein institute
The mass ratio for stating silicon nanometer sheet and the amino silicane coupling agent is 1:4 ~ 5；
(3) PdCl is configured2Solution: by PdCl2Middle addition concentrated hydrochloric acid dissolution, adds distilled water, and obtaining palladium content is 10mg/
The PdCl of mL2Solution；
(4) 90 mL dehydrated alcohols, ultrasonic disperse 0.5 will be added in 1 g described in step (2) modified functionalized silicon nanometer sheet
Then PdCl described in 1 ~ 5mL step (3) is added dropwise in ~ 1h2Solution stirs 2.5 ~ 4h, the NaOH solution tune pH value for being 5% with concentration
To 8 ~ 9, the hydrazine hydrate of 10 ~ 20 equivalents is added, continues 2 ~ 5h of stirring, then filter and with ethanol wash 3-5 times, obtains grey
The gray solid powder is placed in a vacuum drying oven dry 8 ~ 12h under the conditions of 60 ~ 80 DEG C of temperature, taken by solid powder
Product out grinds to get functionalized silicon nanometer sheet loaded palladium catalyst is arrived.
It is preferable over, 2 ~ 5 nm of thickness of silicon nanometer sheet described in above-mentioned steps (1).
It is preferable over, amino silicane coupling agent described in above-mentioned steps (2) is γ-aminopropyltrimethoxysilane, 3- ammonia third
Ethyl triethoxy silicane alkane, N-(2- aminoethyl) -3- aminopropyl trimethoxysilane, N-(2- aminoethyl) three ethoxy of -3- aminopropyl
Any one in base silane.
It is preferable over, in the obtained functionalized silicon nanometer sheet loaded palladium catalyst of above-mentioned steps (4), nano particle palladium
It is uniformly dispersed in the functionalized silicon nanometer sheet, the particle size of the nano particle palladium is 2 ~ 5 nm.
The present invention also provides the functionalized silicon nanometer sheet loaded palladium catalysts to be applied to halogenated aryl hydrocarbon and aryl boron
The Suzuki coupling reaction of acid synthesizes biphenyl compound, chooses bromobenzene with reacting for toluene boric acid and is used as probe reaction, in bell
Very superior Hydrogenation and stability are shown in wood reaction.
Further, it is catalyzed the reaction condition of the Suzuki coupling reaction of the bromobenzene and toluene boric acid are as follows: by molar ratio
It is mixed for the aryl bromide, aryl boric acid and potassium carbonate of 1:1.2:2, the mixing that the volume ratio for being dissolved in ethanol/water is 1:3 ~ 3:1 is molten
Agent, is added the functionalized silicon nanometer sheet loaded palladium catalyst, and the dosage of the functionalized silicon nanometer sheet loaded palladium catalyst is
Pd is 0.005% ~ 1% with respect to aryl bromide molar ratio, is then stirred to react at 60 DEG C, after 0.5 ~ 3.0h of reaction time, yield
It is 96% ~ 99%.
Compared with prior art, functionalized silicon nanometer sheet loaded palladium catalyst prepared by method of the invention has following
Advantage:
1, there are anchoring groups for the functionalized silicon nanometer sheet obtained through amino silicane coupling agent surface modification, so that the palladium of load is received
Rice grain is not easy to reunite；
2, functionalized silicon nanometer sheet surface can load more Pd nano particle, and palladium particle size is mainly 2 ~ 5 nm,
And dispersion is more uniform, has fabulous crystallinity, biggish specific surface area and nanoparticle palladium can uniformly disperse；
3, functionalized silicon nanometer sheet loaded palladium catalyst has very efficient catalytic activity for Suzuki coupling reaction, for
All either there is good catalysis work with inhaling still the power Suzuki reaction of halogenated aryl hydrocarbon and aryl boric acid of base of electric base
Property, and after being recycled for multiple times, the catalyst is highly stable, still keeps good catalytic activity；
4, functionalized silicon nanometer sheet loaded palladium catalyst has many advantages, such as high activity, Yi Huishou and can be recycled, and makes it have
Good industrial applications prospect, and this method can also be used for preparing other noble metal catalysts.
Detailed description of the invention
The TEM of 1 catalyst of Fig. 1 embodiment schemes.
Specific embodiment
A kind of preparation side of functionalized silicon nanometer sheet loaded palladium catalyst is provided to the present invention in conjunction with the preferred embodiment
Method is further described.
Embodiment 1: a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst, its step are as follows,
(1) 100mL concentrated hydrochloric acid is added to the CaSi of 1g2In, and under the protection of nitrogen atmosphere, it is stirred under the conditions of 0 DEG C of temperature
Reaction 4d is mixed, is then filtered, methanol is washed 3-5 times, and washing into pH value until filtrate is 6, celadon filter residue is obtained, in 100 DEG C of temperature
Degree is lower to be dried in vacuo 2d, and grinding obtains celadon solid powder i.e. silicon nanometer sheet；
(2) 90mL alcohol will be added in the obtained 1g silicon nanometer sheet of step (1), then ultrasonic disperse 0.5h is added 10mL's
Water, then be stirred at reflux under the conditions of 70 DEG C of temperature, is added dropwise the γ-aminopropyltrimethoxysilane of 4g, the reaction was continued 6h,
It filters and uses ethanol wash 3-5 times, obtain gray solid powder, be then dried in vacuo 8h under the conditions of 70 DEG C of temperature, take out
Product, grinding, obtains the functionalized silicon nanometer sheet of aminosilane coupling agent modifying；
(3) PdCl is configured2Solution: PdCl is weighed2, add a small amount of concentrated hydrochloric acid to dissolve, add suitable distilled water, obtain palladium content
For the PdCl of 10mg/mL2Solution；
(4) 90mL dehydrated alcohol, ultrasonic disperse will be added in the obtained 1g of step (2) modified functionalized silicon nanometer sheet
Then 1mL step (3) obtained PdCl is added dropwise in 0.5h2Solution stirs 3 h, the dilute NaOH solution tune pH for being 5% with concentration
The hydrazine hydrate of 5 mol is added to 8-9 in value, continues to stir 3 h, then filters and with ethanol wash 3 times, obtains gray solid powder
Obtained gray solid powder is placed in a vacuum drying oven dry 10 h under the conditions of 65 DEG C of temperature, takes out product, grind by end
Mill, obtains functionalized silicon nanometer sheet loaded palladium catalyst.
Tem analysis, as seen from Figure 1, Pd nanometers are carried out to obtained functionalized silicon nanometer sheet loaded palladium catalyst
Grain is uniformly highly dispersed on silicon nanometer sheet surface, and size uniformity, 3 nm of metal nanoparticle size average out to or so.
Be catalyzed the reaction condition of the Suzuki coupling reaction of bromobenzene and toluene boric acid are as follows: by the bromobenzene of 1.0mmol,
The potassium carbonate mixing of the toluene boric acid and 2.0 mmol of 1.2mmol, the mixing for being dissolved in 6mL ethanol/water (volume ratio 1:2) are molten
Agent, is added a certain amount of obtained functionalized silicon nanometer sheet loaded palladium catalyst, and the functionalized silicon nanometer sheet supported palladium is urged
It with respect to aryl bromide molar ratio is 0.5% that agent dosage, which is Pd, is then stirred to react under the conditions of 60 DEG C of temperature, the reaction time
After 1.0h, yield 96.8%.
Embodiment 2: a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst, its step are as follows,
(1) 100mL concentrated hydrochloric acid is added to the CaSi of 1g2In, and under the protection of nitrogen atmosphere, it is stirred under the conditions of 0 DEG C of temperature
Reaction 4d is mixed, is then filtered, methanol is washed 3-5 times, and washing into pH value until filtrate is 6, celadon filter residue is obtained, in 100 DEG C of temperature
Degree is lower to be dried in vacuo 2d, and grinding obtains celadon solid powder i.e. silicon nanometer sheet；
(2) 90mL alcohol will be added in the obtained 1g silicon nanometer sheet of step (1), then ultrasonic disperse 0.5h is added 10mL's
Water, then be stirred at reflux under the conditions of 70 DEG C of temperature, is added dropwise the 3- aminopropyl triethoxysilane of 4g, the reaction was continued 6h,
It filters and uses ethanol wash 3-5 times, obtain gray solid powder, be then dried in vacuo 8h under the conditions of 70 DEG C of temperature, take out
Product, grinding, obtains the functionalized silicon nanometer sheet of aminosilane coupling agent modifying；
(3) PdCl is configured2Solution: 166.6mgPdCl is weighed2, add a small amount of concentrated hydrochloric acid to dissolve, add suitable distilled water, obtain
The PdCl for being 10mg/mL to palladium content2Solution；
(4) 90mL dehydrated alcohol, ultrasonic disperse will be added in the obtained 1g of step (2) modified functionalized silicon nanometer sheet
Then 5mL step (3) obtained PdCl is added dropwise in 0.5h2Solution stirs 3 h, the NaOH solution tune pH value for being 5% with concentration
To 8-9, the hydrazine hydrate of 10mol is added, continue stir 4h, then filter and with ethanol wash 3 times, obtain gray solid powder,
Obtained gray solid powder is placed in a vacuum drying oven dry 8 h under the conditions of 70 DEG C of temperature, takes out product, grinding obtains
To functionalized silicon nanometer sheet loaded palladium catalyst.
Be catalyzed the reaction condition of the Suzuki coupling reaction of bromobenzene and toluene boric acid are as follows: by the bromobenzene of 1.0mmol,
The potassium carbonate mixing of the toluene boric acid and 2.0mmol of 1.2mmol, is dissolved in the mixed solvent of 6mL ethanol/water (volume ratio 1:2),
Quantitative obtained functionalized silicon nanometer sheet loaded palladium catalyst is added, the functionalized silicon nanometer sheet loaded palladium catalyst is used
It with respect to aryl bromide molar ratio is 0.5% that amount, which is Pd, is then stirred to react at 60 DEG C, after reaction time 1.0h, yield is
97.5%。
Embodiment 3: a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst, its step are as follows,
(1) 100mL concentrated hydrochloric acid is added to the CaSi of 1g2In, and under the protection of nitrogen atmosphere, it is stirred under the conditions of 0 DEG C of temperature
Reaction 4d is mixed, is then filtered, methanol is washed 3-5 times, and washing into pH value until filtrate is 6, celadon filter residue is obtained, in 100 DEG C of temperature
Degree is lower to be dried in vacuo 2d, and grinding obtains celadon solid powder i.e. silicon nanometer sheet；
(2) 90mL alcohol will be added in the obtained 1g silicon nanometer sheet of step (1), then ultrasonic disperse 0.5h is added 10mL's
Water, then be stirred at reflux under the conditions of 70 DEG C of temperature, N- (2- aminoethyl) -3- aminopropyl trimethoxy silicon of 4g is added dropwise
Alkane, the reaction was continued 6h are filtered and with ethanol wash 3-5 times, obtain gray solid powder, then under the conditions of 70 DEG C of temperature very
The dry 8h of sky, takes out product, and grinding obtains the functionalized silicon nanometer sheet of aminosilane coupling agent modifying；
(3) PdCl is configured2Solution: 166.6mgPdCl is weighed2, add a small amount of concentrated hydrochloric acid to dissolve, add suitable distilled water, obtain
The PdCl for being 10mg/mL to palladium content2Solution；
(4) 90mL dehydrated alcohol, ultrasonic disperse will be added in the obtained 1g of step (2) modified functionalized silicon nanometer sheet
Then 5mL step (3) obtained PdCl is added dropwise in 0.5h2Solution stirs 3 h, the NaOH solution tune pH value for being 5% with concentration
To 8-9, the hydrazine hydrate of 10mol is added, continue stir 3h, then filter and with ethanol wash 3 times, obtain gray solid powder,
Obtained gray solid powder is placed in a vacuum drying oven dry 12 h under the conditions of 75 DEG C of temperature, product is taken out, grinds,
Obtain functionalized silicon nanometer sheet loaded palladium catalyst.
It is catalyzed the reaction condition of the Suzuki coupling reaction of bromobenzene and phenyl boric acid are as follows: by the bromobenzene of 1.0mmol, 1.2mmol
Toluene boric acid and 2.0mmol potassium carbonate mixing, be dissolved in the mixed solvent of 6mL ethanol/water (volume ratio 1:2), it is fixed to be added
The obtained functionalized silicon nanometer sheet loaded palladium catalyst of amount, the functionalized silicon nanometer sheet loaded palladium catalyst dosage are
Pd is 0.5% with respect to aryl bromide molar ratio, is then stirred to react at 60 DEG C, after reaction time 1.0h, yield 97.2%.
Embodiment 4: a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst, its step are as follows,
(1) 100mL concentrated hydrochloric acid is added to the CaSi of 1g2In, and under the protection of nitrogen atmosphere, it is stirred under the conditions of 0 DEG C of temperature
Reaction 4d is mixed, is then filtered, methanol is washed 3-5 times, and washing into pH value until filtrate is 6, celadon filter residue is obtained, in 100 DEG C of temperature
Degree is lower to be dried in vacuo 2d, and grinding obtains celadon solid powder i.e. silicon nanometer sheet；
(2) 90mL alcohol will be added in the obtained 1g silicon nanometer sheet of step (1), then ultrasonic disperse 0.5h is added 10mL's
Water, then be stirred at reflux under the conditions of 70 DEG C of temperature, N- (2- aminoethyl) -3- aminopropyl trimethoxy silicon of 5g is added dropwise
Alkane, the reaction was continued 6h are filtered and with ethanol wash 3-5 times, obtain gray solid powder, then under the conditions of 70 DEG C of temperature very
The dry 8h of sky, takes out product, and grinding obtains the functionalized silicon nanometer sheet of aminosilane coupling agent modifying；
(3) PdCl is configured2Solution: 166.6mgPdCl is weighed2, add a small amount of concentrated hydrochloric acid to dissolve, add suitable distilled water, obtain
The PdCl for being 10mg/mL to palladium content2Solution；
(4) 90mL dehydrated alcohol, ultrasonic disperse will be added in the obtained 1g of step (2) modified functionalized silicon nanometer sheet
Then 1mL step (3) obtained PdCl is added dropwise in 0.5h2Solution stirs 3 h, the NaOH solution tune pH value for being 5% with concentration
To 8-9, the hydrazine hydrate of 5mol is added, continue stir 2.5h, then filter and with ethanol wash 3 times, obtain gray solid powder,
Obtained gray solid powder is placed in a vacuum drying oven dry 8 h under the conditions of 70 DEG C of temperature, takes out product, grinding obtains
To functionalized silicon nanometer sheet loaded palladium catalyst.
It is catalyzed the reaction condition of the Suzuki coupling reaction of bromobenzene and phenyl boric acid are as follows: by the bromobenzene of 1.0mmol, 1.2mmol
Toluene boric acid and 2.0mmol potassium carbonate mixing, be dissolved in the mixed solvent of 6mL ethanol/water (volume ratio 1:2), it is fixed to be added
The obtained functionalized silicon nanometer sheet loaded palladium catalyst of amount, the functionalized silicon nanometer sheet loaded palladium catalyst dosage are
Pd is 0.5% with respect to aryl bromide molar ratio, is then stirred to react at 60 DEG C, after reaction time 1.0h, yield 98.8%.
Selection example 1 ~ 4 carries out reuse experiment under similarity condition, and experimental result is shown in Table shown in 1:
1 catalyst stability experimental result of table
| Catalyst | Use the 1st yield | Use the 10th yield |
| Embodiment 1 | 96.8% | 88.6% |
| Embodiment 2 | 97.2% | 89.9% |
| Embodiment 3 | 97.9% | 90.7% |
| Embodiment 4 | 98.8% | 91.8% |
Claims (7)
1. a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst, which comprises the following steps:
(1) silicon nanometer sheet is prepared: in 10 mmolCaSi2The middle concentrated hydrochloric acid that 1.2 mol are added, under nitrogen atmosphere, at -15 ~ 0 DEG C
It is stirred to react 3 ~ 5d, is then filtered, methanol is washed 3-5 times, and washing into pH value until filtrate is 6 ~ 7, celadon filter residue is obtained, 80 ~
It is dried in vacuo 2d under the conditions of 100 DEG C of temperature, then grinds, obtains celadon solid powder i.e. silicon nanometer sheet；
(2) the modified functionalized silicon nanometer sheet of preparation: will be added 90 mL alcohol in 1g silicon nanometer sheet described in step (1), ultrasound
Disperse 0.5 ~ 1h, add 10mL water, be then stirred at reflux under the conditions of 70 DEG C of temperature, amino silane coupling is added dropwise
Agent, the reaction was continued 6 ~ 10h are filtered and with ethanol wash 3-5 times, gray solid powder are obtained, then in 60 ~ 80 DEG C of temperature strip
It is dried in vacuo 8 ~ 12h under part, takes out product, grinding obtains the functionalized silicon nanometer sheet of aminosilane coupling agent modifying, wherein institute
The mass ratio for stating silicon nanometer sheet and the amino silicane coupling agent is 1:4 ~ 5；
(3) PdCl is configured2Solution: by PdCl2Middle addition concentrated hydrochloric acid dissolution, adds distilled water, and obtaining palladium content is 10mg/mL
PdCl2Solution；
(4) 90 mL dehydrated alcohols, ultrasonic disperse 0.5 will be added in 1 g described in step (2) modified functionalized silicon nanometer sheet
Then PdCl described in 1 ~ 5mL step (3) is added dropwise in ~ 1h2Solution stirs 2.5 ~ 4h, the NaOH solution tune pH value for being 5% with concentration
To 8 ~ 9, the hydrazine hydrate of 10 ~ 20 equivalents is added, continues 2 ~ 5h of stirring, then filter and with ethanol wash 3-5 times, obtains grey
The gray solid powder is placed in a vacuum drying oven dry 8 ~ 12h under the conditions of 60 ~ 80 DEG C of temperature, taken by solid powder
Product out grinds to get functionalized silicon nanometer sheet loaded palladium catalyst is arrived.
2. a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst according to claim 1, which is characterized in that
2 ~ 5 nm of thickness of silicon nanometer sheet described in above-mentioned steps (1).
3. a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst according to claim 2, which is characterized in that
Amino silicane coupling agent described in above-mentioned steps (2) be γ-aminopropyltrimethoxysilane, 3- aminopropyl triethoxysilane,
N-(2- aminoethyl) -3- aminopropyl trimethoxysilane, N-(2- aminoethyl) it is any one in -3- aminopropyl triethoxysilane
Kind.
4. a kind of preparation method of functionalized silicon nanometer sheet loaded palladium catalyst according to claim 3, which is characterized in that
In the obtained functionalized silicon nanometer sheet loaded palladium catalyst of above-mentioned steps (4), nano particle palladium is uniformly dispersed in institute
It states in functionalized silicon nanometer sheet, the particle size of the nano particle palladium is 2 ~ 5 nm.
5. a kind of functionalized silicon nanometer sheet loaded palladium catalyst described in any one of -4 according to claim 1 is applied to halogenated
The Suzuki coupling reaction of aromatic hydrocarbons and aryl boric acid synthesizes biphenyl compound, and selection bromobenzene reacts conduct with toluene boric acid
Probe reaction.
6. functionalized silicon nanometer sheet loaded palladium catalyst according to claim 5 is in halogenated aryl hydrocarbon and aryl boric acid
Application in Suzuki coupling reaction, it is characterised in that: be catalyzed the Suzuki coupling reaction of the bromobenzene and toluene boric acid
Reaction condition are as follows: aryl bromide, aryl boric acid and potassium carbonate that molar ratio is 1:1.2:2 are mixed, the volume of ethanol/water is dissolved in
Than the mixed solvent for 1:3 ~ 3:1, the functionalized silicon nanometer sheet loaded palladium catalyst is added, the functionalized silicon nanometer sheet is negative
It with respect to aryl bromide molar ratio is 0.005% ~ 1% that the dosage of carried palladium catalyst, which is Pd, is then stirred to react at 60 DEG C.
7. functionalized silicon nanometer sheet loaded palladium catalyst according to claim 6 is in halogenated aryl hydrocarbon and aryl boric acid
Application in Suzuki coupling reaction, it is characterised in that: after 0.5 ~ 3.0h of reaction time, yield is 96% ~ 99%.
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