CN106179443A - The bimetallic catalyst with core-casing structure of a kind of hexagonal boron nitride nanosheet load and preparation and application thereof - Google Patents
The bimetallic catalyst with core-casing structure of a kind of hexagonal boron nitride nanosheet load and preparation and application thereof Download PDFInfo
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- CN106179443A CN106179443A CN201610523495.5A CN201610523495A CN106179443A CN 106179443 A CN106179443 A CN 106179443A CN 201610523495 A CN201610523495 A CN 201610523495A CN 106179443 A CN106179443 A CN 106179443A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 31
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002135 nanosheet Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 5
- 150000002940 palladium Chemical class 0.000 claims description 5
- 150000001502 aryl halides Chemical class 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical group B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910010277 boron hydride Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052763 palladium Inorganic materials 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005374 membrane filtration Methods 0.000 description 7
- 229950000845 politef Drugs 0.000 description 7
- 229910021065 Pd—Fe Inorganic materials 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- -1 aryl boric acid Chemical compound 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to bimetallic catalyst with core-casing structure and the preparation and application thereof of a kind of hexagonal boron nitride nanosheet load, with Technique of Nano Pd as core, Nanoscale Iron is shell, hexagonal boron nitride nanosheet is carrier, and the catalyst with core-casing structure that described Technique of Nano Pd and described Nanoscale Iron are constituted is anchored on described boron nitride nanosheet carrier.The present invention be a kind of with palladium as core, the ferrum heterogeneous catalyst as shell.Catalyst with core-casing structure is anchored on boron nitride nanosheet, forms a whole, and the introducing of ferrum not only greatly reduces the consumption of palladium, and improves catalysis efficiency by synergism.It is applied to Suzuki coupling reaction, there is high catalysis activity.And the preparation method of the present invention is simple, easily operates.
Description
Technical field
The invention belongs to catalysis technical field, particularly relate to the bimetallic nucleocapsid knot of a kind of hexagonal boron nitride nanosheet load
Structure catalyst and preparation method thereof and the application in Suzuki coupling reaction.
Background technology
Hexagonal boron nitride nanosheet (BNNSs) is the isoelectronic species of Graphene and the two structure is similar to, compared to Graphene,
BNNSs has the character that some are special, as having the strongest non-oxidizability, in atmosphere thermal stable temperature up to 1000 DEG C and and
Acid, alkali are not susceptible to reaction.Based on these advantageous properties, people are with BNNSs for urging that carrier to load metal nanoparticle obtains
Agent, is used in numerous organic reactions.If Lu et al. is that carrier loaded Pd nano particle is for nitro compound with BNNSs
Catalytic hydrogenation reaction, performance is better than business-like Pd/C catalyst.Wang et al. is carrier loaded Zero-valent Iron nanometer with BNNSs
The catalyst that particle obtains achieves the quick debrominate to PBDE.
Suzuki reaction has reaction condition various active functional group gentle, compatible, product less by steric interference
Rate is high and aryl boric acid is to advantages such as aqueous vapor are insensitive and economical and easily available, is the most all pharmaceutical synthesis scholar and chemistry
The object of family's further investigation.Homogeneous catalyst activity is high, applied widely but it typically requires the ginseng of part and surfactant
With and inert gas shielding competence exertion usefulness, and catalyst reclaim difficulty to such an extent as to cannot recycle.Pd nanoparticle
The heterogeneous catalysis being supported on carrier preparation the most easily reclaims, reusable edible, but the usage amount of Pd nanoparticle is past
Toward higher.Therefore, exploitation one combines homogeneous catalyst and heterogeneous catalysis advantage, i.e. Pd usage amount is few and active height, no
Need part, surfactant and inert gas shielding and recyclable catalyst, there is realistic meaning.
Summary of the invention
It is an object of the invention to provide a kind of efficient heterogeneous catalysis being suitable to Suzuki coupling reaction, existing to solve
Some problems.
In order to realize above-mentioned purpose, adopt the following technical scheme that:
A kind of bimetallic catalyst with core-casing structure of hexagonal boron nitride nanosheet load, with Technique of Nano Pd as core, Nanoscale Iron is shell, six
Side's boron nitride nanosheet is carrier, and the catalyst with core-casing structure that described Technique of Nano Pd and described Nanoscale Iron are constituted is anchored on described nitridation
On boron nanometer sheet carrier.
The preferred boron nitride nanosheet of the present invention is as carrier, and preferably ferrum is as the second metal.Because the d of transition metalz 2Rail
Road and the p of B, N in boron nitride nanosheetzTrack has overlap, and the two combination is the most firm；Carrier or the second metal can be simulated simultaneously
Around palladium, the solid of part and electronic environment, carry high catalytic activity by synergism.
Further, the load capacity of described Technique of Nano Pd is 0.05-5wt%, and the load capacity of described Nanoscale Iron is 1-15wt%.
Further, the load capacity of described Technique of Nano Pd is 0.2wt%, and the load capacity of described Nanoscale Iron is 11wt%.Now
It is applied to the Suzuki coupling reaction of iodobenzene and phenylboric acid, its TOF value (reaction substrate converted on every mole of palladium in the unit interval
Amount) up to 30000h-1.
Further, the particle diameter of described Technique of Nano Pd is 0.5-5nm, and the particle diameter of described Nanoscale Iron is 5-20nm.
The preparation method of the bimetallic catalyst with core-casing structure of a kind of above-mentioned hexagonal boron nitride nanosheet load, mainly includes
Following steps:
(1) first hexagonal boron nitride nanosheet is distributed in ethanol and distilled water mixed liquor, then after being separately added into iron salt and palladium salt
Stirring；
(2) at 0-5 DEG C, addition dilute NaOH solution regulation pH value, to 8, continues stirring 1 hour；
(3) at 0-5 DEG C, reducing agent it is added dropwise over, after continuing stirring 1 hour, filtration drying.
Hexagonal boron nitride nanosheet dispersibles in ethanol and distilled water mixed liquor under ultrasound condition, and iron salt and palladium salt are also
May be dissolved in ethanol and distilled water mixed liquor.Based on this, selecting ethanol and distilled water mixed liquor in step (1) is solvent.Step
Suddenly (2) are selected NaOH solution regulation pH value to～8, it is therefore an objective to make palladium, iron particle preferably be deposited on hexagonal nanometer boron nitride
On sheet.In step (2) and (3) preferably 0-5 DEG C, the reunion of metallic can be reduced under cryogenic, advantageously form particle diameter
Less nanoparticle, thus improve catalysis efficiency.
Further, in step (1) volume ratio of ethanol and distilled water mixed liquor at 1:100-100:1.
Further, described in step (3), reducing agent is boron hydride.Because boron hydride can not only reducing metal activity
Component, and reaction condition is relatively mild.
Further, described iron salt be ferrum be FeCl3Or Fe (NO3)3·9H2O, described palladium salt is Na2PdCl4Or PdCl2。
A kind of application of the bimetallic catalyst with core-casing structure of above-mentioned hexagonal boron nitride nanosheet load, even as Suzuki
The catalyst of connection reaction.
Further, described Suzuki coupling reaction is the Suzuki coupling reaction of aryl halides or aryl boric acid.
Compared with prior art, the present invention be a kind of with palladium as core, the ferrum heterogeneous catalyst as shell.Nucleocapsid is tied
Structure catalyst is anchored on boron nitride nanosheet, forms a whole, and the introducing of ferrum not only greatly reduces the consumption of palladium, and
And improve catalysis efficiency by synergism.It is applied to Suzuki coupling reaction, there is high catalysis activity.And the present invention
Preparation method simple, easily operate.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of the Pd-Fe/BNNSs of the embodiment of the present invention 1 preparation；Fig. 2 is this
Scanning transmission electron microscope-the angle of elevation annular dark field of the single-particle nucleocapsid structure of the Pd-Fe/BNNSs of bright embodiment 1 preparation
(STEM-HAADF) Z contrast image.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, the present invention is made into one
Step ground describes in detail.
Embodiment 1
The preparation method of the bimetallic catalyst with core-casing structure of a kind of hexagonal boron nitride nanosheet load, mainly includes following step
Rapid: to take the original hexagonal boron nitride of 500mg and be distributed in 300mL ethanol and distilled water (volume ratio 1:1) mixed liquor, in 240W condition
Under after ultrasonic 15 hours, stand 8 hours, then by the politef membrane filtration that supernatant aperture is 0.22 μm, wash, dry
Dry obtain white solid (BNNSs).Take 60mg BNNSs and join in 80mL ethanol and distilled water (volume ratio 1:1) mixed liquor super
Sound disperses, then by the Na of 60 μ L 30mmol/L2PdCl4Solution and the anhydrous FeCl of 30mg3Add in dispersion liquid and at room temperature
Stir 5 hours.In ice-water bath, be cooled to 0-5 DEG C, with dilute NaOH solution regulation pH value to～8, continue stirring 1 hour, then
The NaBH of 40mL 0.1mol/L it is added dropwise at 0-5 DEG C4Solution, after being further continued for stirring 1 hour, by mixed liquor aperture be
The politef membrane filtration of 0.22 μm, washs, is dried to obtain a kind of catalyst (Pd-Fe/BNNSs).Detect through ICP-AES,
The mass fraction of Pd and Fe is respectively 0.2wt% and 11wt%.The particle diameter of palladium is 0.5-5nm, and the particle diameter of ferrum is 5-20nm.
The transmission electron microscope of the bimetallic catalyst with core-casing structure of the hexagonal boron nitride nanosheet load prepared
The scanning transmission electron microscope of figure and single-particle nucleocapsid structure-angle of elevation annular dark field figure is the most as depicted in figs. 1 and 2.
By the bimetallic catalyst with core-casing structure of the hexagonal boron nitride nanosheet load that above-mentioned preparation method obtains, nanometer
The load capacity of palladium can be 0.05-5wt%, and the load capacity of Nanoscale Iron can be 1-15wt%.
Embodiment 2-10
Pd-Fe/BNNSs prepared by embodiment 1 is used for the Suzuki coupling reaction of various aryl halide.Its reaction equation is such as
Under:
Ar-X+Ar′-B(OH)2→Ar-Ar′
Concretely comprise the following steps: 10mg catalyst is distributed in 10mL ethanol and distilled water (volume ratio 1:1), add 1mmol aryl
Halogenide, 2mmol alkali, 1.2mmol phenylboric acid, react under magnetic agitation, counterflow condition, and the reaction mechanism mechanism of reaction passes through thin layer chromatography silicon
Offset plate (TLC) is monitored.After having reacted, mixed liquor aperture is the politef membrane filtration of 0.22 μm, repeatedly washes with ethanol
Washing, filtrate, after anhydrous magnesium sulfate is except water, analyzes its productivity by gas chromatograph (GC).Aryl halide used is with corresponding
Productivity be listed in table 1.
The Suzuki coupling reaction of table 1Pd-Fe/BNNSs catalysis
Embodiment 11-16
The cycle performance test of the Pd-Fe/BNNSs catalyst of embodiment 1 preparation.Its reaction equation is as follows:
Concretely comprise the following steps: take 20mg catalyst and be distributed in 10mL ethanol and distilled water (volume ratio 1:1), addition 1mmol bromobenzene,
2mmol(CH3)3COK, 1.2mmol phenylboric acid, reacts 30min, after having reacted, mixed liquor under magnetic agitation, counterflow condition
With the politef membrane filtration that aperture is 0.22 μm, using ethanol cyclic washing, filtrate is after anhydrous magnesium sulfate is except water, by gas
Chromatography (GC) analyzes its productivity.Solid catalyst is re-dispersed in 40mL ethanol and distilled water (volume ratio 1:1), at 0-
NaBH is used at 5 DEG C4Reduction, filters, washs, is dried, for circulating next time.
Table 2Pd-Fe/BNNSs cycle performance in bromobenzene with phenylboric acid Suzuki coupling reaction
Embodiment 17-21
The cycle performance test of the Pd-Fe/BNNSs catalyst of embodiment 1 preparation.Its reaction equation is as follows:
Concretely comprise the following steps: take 20mg catalyst and be distributed in 10mL ethanol and distilled water (volume ratio 1:1), add 0.5mmol pair
Bromoanisole, 1mmol (CH3)3COK, 0.75mmol1-naphthalene boronic acids, reacts 12h under magnetic agitation, counterflow condition, and reaction completes
After, mixed liquor aperture is the politef membrane filtration of 0.22 μm, uses ethanol cyclic washing.Solid catalyst is re-dispersed into
In 40mL ethanol and distilled water (volume ratio 1:1), at 0-5 DEG C, use NaBH4Reduction, filters, washs, is dried, for next time
Circulation.Filtrate purifies with pillar layer separation, weighs, and calculates productivity.
Table 3Pd-Fe/BNNSs cycle performance in para-bromoanisole with 1-naphthalene boronic acids Suzuki coupling reaction
Embodiment 22
In order to be better understood from the present invention, the solution of the present invention is expanded on further below in conjunction with comparative example.
Comparative example 1
A kind of with preparation method that BNNSs is carrier loaded monometallic palladium catalyst:
Take 60mg BNNSs and join ultrasonic disperse in 80mL ethanol and distilled water (volume ratio 1:1) mixed liquor, then by 50 μ L
The PdCl of 30mmol/L2Solution adds in dispersion liquid and is stirred at room temperature 5 hours.0-5 DEG C it is cooled to, with dilute in ice-water bath
NaOH solution regulation pH value to～8, continue stirring 1 hour, at 0-5 DEG C, be then added dropwise over the NaBH of 30mL 0.1mol/L4
Solution, after being further continued for stirring 1 hour, by the politef membrane filtration that mixed liquor aperture is 0.22 μm, washs, is dried to obtain
A kind of catalyst (Pd/BNNSs).
Comparative example 2
A kind of with preparation method that BNNSs is carrier loaded monometallic iron catalyst:
Take 60mg BNNSs and join ultrasonic disperse in 80mL ethanol and distilled water (volume ratio 1:1) mixed liquor, then by 80mg
Fe(NO3)3·9H2O adds in dispersion liquid and is stirred at room temperature 5 hours.0-5 DEG C it is cooled in ice-water bath, molten with dilute NaOH
Liquid regulation pH value to～8, continue stirring 1 hour, at 0-5 DEG C, be then added dropwise over the KBH of 40mL 0.1mol/L4Solution, then
After continuing stirring 1 hour, by the politef membrane filtration that mixed liquor aperture is 0.22 μm, wash, be dried to obtain one and urge
Agent (Fe/BNNSs).
Comparative example 3-16
The different parameters impact on bromobenzene Yu phenylboric acid Suzuki coupling reaction.Its reaction equation is as follows:
It affects result and is listed in table 4.
Table 4 different parameters affects result to Suzuki coupling reaction
Explained above is only present pre-ferred embodiments, it is impossible to limit the interest field of the present invention with this.Therefore
The equivalent variations made according to the claims in the present invention, still belongs to the scope that the present invention is contained.
Claims (10)
1. the bimetallic catalyst with core-casing structure of a hexagonal boron nitride nanosheet load, it is characterised in that with Technique of Nano Pd as core,
Nanoscale Iron is shell, and hexagonal boron nitride nanosheet is carrier, the catalyst with core-casing structure that described Technique of Nano Pd and described Nanoscale Iron are constituted
It is anchored on described boron nitride nanosheet carrier.
The bimetallic catalyst with core-casing structure of hexagonal boron nitride nanosheet load the most according to claim 1, it is characterised in that
The load capacity of described Technique of Nano Pd is 0.05-5wt%, and the load capacity of described Nanoscale Iron is 1-15wt%.
The bimetallic catalyst with core-casing structure of hexagonal boron nitride nanosheet load the most according to claim 2, it is characterised in that
The load capacity of described Technique of Nano Pd is 0.2wt%, and the load capacity of described Nanoscale Iron is 11wt%.
The bimetallic catalyst with core-casing structure of hexagonal boron nitride nanosheet load the most according to claim 2, it is characterised in that
The particle diameter of described Technique of Nano Pd is 0.5-5nm, and the particle diameter of described Nanoscale Iron is 5-20nm.
5. the bimetallic catalyst with core-casing structure loaded according to hexagonal boron nitride nanosheet described in any one of claim 1-4
Preparation method, it is characterised in that mainly comprise the steps that
(1) first hexagonal boron nitride nanosheet is distributed in ethanol and distilled water mixed liquor, then after being separately added into iron salt and palladium salt
Stirring；
(2) at 0-5 DEG C, addition dilute NaOH solution regulation pH value, to 8, continues stirring 1 hour；
(3) at 0-5 DEG C, reducing agent it is added dropwise over, after continuing stirring 1 hour, filtration drying.
Preparation method the most according to claim 5, it is characterised in that ethanol and the volume of distilled water mixed liquor in step (1)
Ratio is at 1:100-100:1.
Preparation method the most according to claim 5, it is characterised in that described in step (3), reducing agent is boron hydride.
Preparation method the most according to claim 5, it is characterised in that described iron salt be ferrum be FeCl3Or Fe (NO3)3·9H2O,
Described palladium salt is Na2PdCl4Or PdCl2。
9. the bimetallic catalyst with core-casing structure loaded according to hexagonal boron nitride nanosheet described in any one of claim 1-4
Application, it is characterised in that as the catalyst of Suzuki coupling reaction.
Apply the most according to claim 9, it is characterised in that described Suzuki coupling reaction is aryl halides or aryl
The Suzuki coupling reaction of boric acid.
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| CN107774292A (en) * | 2017-10-11 | 2018-03-09 | 中国地质大学（武汉） | A kind of preparation method of oxygen doping boron nitride catalyst carrier carried metal |
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