CN103951611B - A kind of spiral shell fluorenes pyridine palladium nano-particles and preparation method thereof - Google Patents

A kind of spiral shell fluorenes pyridine palladium nano-particles and preparation method thereof Download PDF

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CN103951611B
CN103951611B CN201310637491.6A CN201310637491A CN103951611B CN 103951611 B CN103951611 B CN 103951611B CN 201310637491 A CN201310637491 A CN 201310637491A CN 103951611 B CN103951611 B CN 103951611B
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spiral shell
pyridine
nano particle
palladium
shell fluorenes
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CN103951611A (en
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赵秀华
李星
赵亚云
刘素娟
康晶燕
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TONGLING QINGHUABAO ENERGY SOURCES EQUIPMENT Co.,Ltd.
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Ningbo University
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • B82—NANOTECHNOLOGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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    • 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
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    • 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
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    • C07C2531/22—Organic complexes

Abstract

The invention discloses a kind of spiral shell fluorenes pyridine Pd nano particle and preparation method thereof, in the present invention, a certain amount of metal salt solution is joined in the organic ligand that contains pyridine unit, stir at a certain temperature 1～3h, ageing 3～5h, through centrifugation, washing, be dried and make corresponding metal-ligand nano particle, preparation process is simple, and cost is low, is applicable to a large amount of production; By selecting different solvents, control consumption, reaction time and the reaction temperature of reactant, realize size and the dispersed Effective Regulation of spiral shell fluorenes pyridine Pd nano particle particle diameter. The spiral shell fluorenes pyridine Pd nano particle of preparation is a kind of functional nanoparticle that contains palladium, and stable performance, can be used for catalysis C-C key coupling reaction, and catalytic efficiency is high, and productive rate can reach 90～99%. Therefore this spiral shell fluorenes pyridine Pd nano particle has broad application prospects at catalytic field.

Description

A kind of spiral shell fluorenes pyridine palladium nano-particles and preparation method thereof
Technical field
The invention belongs to metal nanoparticle catalytic field, be specifically related to a kind of spiral shell fluorenes pyrrole for catalytic reactionPyridine palladium nano-particles and preparation method thereof.
Background technology
In a broad sense, nano material refer to wherein the yardstick of one dimension be arbitrarily less than the crystal of 100nm, noncrystal,The material of quasicrystal and interface structure. In the time that small particle size adds nanometer scale, itself has volumeEffect, skin effect, quantum size effect and macro quanta tunnel effect etc. Thereby make it have unusual power, electricity, optics, calorifics, chemism, catalysis and superconducting characteristic, make nano material at various fields toolThere is important using value. Along with nanoparticle particle diameter reduces, specific area increases, surface atom number increases andSurface atom coordination unsaturation causes a large amount of outstanding key and insatiable hunger key etc., and it is high that this just makes nanoparticle haveSurface-active, and particle diameter is less, and the shared ratio of surface atom number is larger; Specific area is larger, smooth surfaceDegree variation, forms rough atomic steps, has increased the contact-making surface of chemical reaction, makes it have goodCatalytic performance.
Nanocatalyst roughly can be divided into support type and the large class of non-loading type two. Common are: noble metal nanoCatalyst, transition metal nano-catalyst, multi-component alloys type nanocatalyst, metal cluster nanocatalyst,Transition metal oxide nano catalyst, nano molecular sieve catalyst and biological nano catalyst. Your gold Au isThe most representative a kind of element in genus, its outer d track has the electronic structure being partly full of, generally not facilitationLearn the little molecule of absorption, and be difficult to make the Au nano particle of high dispersive. But utilize CNT (CNTs)And special interaction between the metal of load, Ma etc. successfully utilize chemical deposit technology by Au loadTo CNTs above, prepared the Au/CNTsNCs of high dispersive. Transition metal all contains not electricity in pairs mostlySon, thereby show certain ferromagnetism or paramagnetism, and the little molecule of chemisorbed very easily, as Fe, Co,Ni is exactly the efficient NCs of preparation CNTs array. The uses such as Yabe are transformed the nanometer obtaining by nanometer Fe filmFe particle, catalyzing acetylene cracking obtains CNTs array. Zhang etc. use by nanometer Ni film pre-through original positionThe nanometer Ni particle that processing obtains, catalytic pyrolysis ethylenediamine makes CNTs array. Cui Shen etc. use through pre-Process and the Ni film of reduction, taking low-carbon alkanes as carbon source, can under differential responses condition, make and to come in every shapeCNTs film.
Although only have TiO at present2、ZnO、SiO2And CaCO3Realize industrialization Deng a few kind,But demonstrate good development prospect. In the nanosecond science and technology seminar finishing for the end of the year 2004, expertThink, nano material has unique crystal structure and surface characteristic, its catalytic activity and being selectively much higher thanTraditional catalyst, can be used as novel catalysis material and is applied to chemical industry. According to commercial communication company, 2004Year global nanocatalyst market reaches nearly 3,700,000,000 dollars. Should although nanocatalyst has been obtained some exploitationsBy achievement, but also have problems at the aspect such as shape, distribution and granularity of controlling nanocatalyst. HeterogeneousIn catalyst, nano particle size is conventionally in 1～20nm left and right, and the particle of 1～50nm left and right showsThe physics and chemistry character going out between minimum chemical element unit and material body, this size rangeParticle, by greatly changing surface texture and the electronic property of catalyst, therefore, significantly affects the catalytic of catalystEnergy. We have prepared a kind of spiral shell fluorenes pyridine palladium nano-particles, and particle diameter is 20～100nm, as nano-catalyticAgent has broad application prospects at catalytic field.
Summary of the invention
Technical problem to be solved by this invention is, for the deficiencies in the prior art, to provide a kind of preparation process letterWhat list and cost were low can be used as spiral shell fluorenes pyridine palladium nano-particles of efficiently urging agent and preparation method thereof.
The present invention for solving the problems of the technologies described above adopted technical scheme is: a kind of spiral shell of efficiently urging agent that can be used asThe preparation method of fluorenes pyridine palladium nano-particles, comprises the following steps:
Spiral shell fluorenes pyridine organic ligand is dissolved in appropriate ethylene glycol or ethyl acetate;
Palladium salt is dissolved in appropriate distilled water;
Palladium saline solution is joined in described machine ligand solution fast to the wherein thing of palladium ion and organic ligandThe ratio of the amount of matter is 1～3:1, at room temperature vigorous stirring after 15 minutes, then carry out microwave back flow reaction 20～40 minutes, cooling rear ageing 3～5h;
By the product centrifugation after ageing, and wash described sediment with deionized water and ethanol, ultrasonic dispersion,Dry, obtain described spiral shell fluorenes pyridine palladium nano-particles.
Preferably, described palladium salt is any one in palladium bichloride or palladium.
Preferably, the amount of substance concentration of described palladium salt is 5.0mmol/L～10mmol/L.
Preferably, the amount of substance concentration of described spiral shell fluorenes pyridine ligand is 1.0mmol/L～5.0mmol/L.
Preferably, the described organic ligand containing pyridine unit is spiral shell fluorenes pyridine, and its name is called 2-bromo-2 ', 7,7 '-tri-(4-pyridine)-9,9 '-spiral shell, two fluorenes, are called for short BTPS, and its molecular formula is C40H24N3Br, structural formula is as follows:
Preferably, the preparation method of described spiral shell fluorenes pyridine comprises:
By 2,2 ', 7,7 '-tetrabromo-9,9 '-spiral shell, two fluorenes, 4-pyridine boric acid, potash, toluene, second alcohol and water joinIn there-necked flask, under nitrogen protection, taking tetra-triphenylphosphine palladium as catalyst, in microwave reactor, reflux anti-Answer 45 minutes;
After finishing, reaction is cooled to room temperature, separatory, water CH2Cl2Extraction, merges organic phase, by organicUse mutually saturated common salt water washing, separatory, then use anhydrous magnesium sulfate drying 10 hours, suction filtration, is spin-dried for, and obtainsThick product;
With column chromatography refined product (ethyl acetate is eluent), obtain bromo-2 ', 7,7 '-tri-(the 4-pyridine)-9,9 ' of 2--Spiral shell two fluorenes net products.
Described spiral shell fluorenes pyridine Pd nano particle particle diameter is 20～100nm, is that one is efficiently urged agent, can be used for urgingChange coupling reaction.
The pyridine, five-membered ring and the phenyl ring that in this organic ligand, contain have formed delocalized pi-bond, make pyridine nitrogen atomWith the easy coordination of palladium ion, and by electric transmission to palladium ion, change the electron structure of palladium, thereby increase palladiumCatalytic activity.
Compared with prior art, advantage of the present invention is as follows:
(1) described organic ligand spiral shell fluorenes pyridine has the structure of asymmetric uniqueness, contains Br group simultaneously.Br group can increase the dissolubility of part, and Br is electron withdraw group in addition, to the delocalization of part electronics alsoProduce unique impact, thereby the electron structure of part is exerted an influence, thereby the compound forming has solelySpecial physicochemical properties.
(2) delocalization of described spiral shell fluorenes pyrrole electronics is strong and have an asymmetry, can with palladium ion at three notEquidirectional coordination, the formation spiral shell fluorenes pyridine Pd nano particle of carrying out. This nano particle stable performance, catalyzed carbon-In carbon bond coupling reaction, shown higher reactivity, productive rate can reach 70～99%.
(3) preparation process of described spiral shell fluorenes pyridine Pd nano particle is simple, and cost is low, is applicable to a large amount of production.
(3) the present invention, by selecting different palladium salt, controls reaction time, reaction temperature, realizes spiral shell fluorenes pyrroleSize and the dispersed Effective Regulation of pyridine Pd nano particle particle diameter, obtain the different spiral shell fluorenes pyridine palladium nanometer of particle diameterParticle, it has broad application prospects at catalytic field.
Brief description of the drawings
Fig. 1 is bromo-2 ', 7,7 '-tri-(the 4-pyridines)-9 of 2-, the structural formula of 9 '-spiral shell, two fluorenes.
Fig. 2 is the scanning electron microscope (SEM) photograph of spiral shell fluorenes pyridine palladium nano-particles of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The palladium chloride aqueous solution of 10mL5.0mmol/L is joined fast to the spiral shell that contains 10mL5.0mmol/LFluorenes pyridine ethylene glycol solution is put into 50mL there-necked flask, and at room temperature vigorous stirring is after 15 minutes, thenCarry out microwave back flow reaction 20 minutes, ageing 3h under cooling rear room temperature. By the product centrifugation after ageing,And wash described sediment 3 times with deionized water and ethanol, and ultrasonic dispersion, dry, obtain described spiral shell fluorenes pyrrolePyridine Pd nano particle. With the pattern of nano particle described in scanning electron microscopic observation, as shown in Figure 2, nano particle grainFootpath size is 20～100nm.
Wherein, the preparation method of described spiral shell fluorenes pyridine comprises: by 2, and 2 ', 7,7 '-tetrabromo-9,9 '-spiral shell, two fluorenes (3.0mmol,1.91g), 4-pyridine boric acid (9.0mmol, 1.12g), potash (40.0mmol, 5.52g), toluene/ethanol/water(80mL/30mL/20mL) join in the there-necked flask of 250mL, under nitrogen protection with four triphenylphosphinesPalladium (0.3mmol, 0.35g) is catalyst, back flow reaction 45 minutes in microwave reactor. Be cooled to room temperature,Separatory, water CH2Cl2Extract three times, merge organic phase. By saturated common salt water washing three times for organic phase,Use anhydrous magnesium sulfate drying 10h, suction filtration, is spin-dried for again, and obtains thick product. By column chromatography refined product (secondAcetoacetic ester is eluent), obtain bromo-2 ', 7,7 '-tri-(the 4-pyridines)-9 of 2-, 9 '-spiral shell, two fluorenes net products, its structural formula is shown inFig. 1.
Embodiment 2
The palladium chloride aqueous solution of 10mL10mmol/L is joined fast to the spiral shell that contains 10mL5.0mmol/LIn the 50mL there-necked flask of fluorenes pyridylacetic acid ethyl ester solution, at room temperature vigorous stirring is after 15 minutes, thenCarry out microwave back flow reaction 40 minutes, ageing 5h under cooling rear room temperature. By the product centrifugation after ageing,And wash described sediment 3 times with deionized water and ethanol, and ultrasonic dispersion, dry, obtain described spiral shell fluorenes pyrrolePyridine Pd nano particle. With the pattern of nano particle described in scanning electron microscopic observation.
Embodiment 3
The palladium aqueous solution of 10mL5.0mmol/L is joined to the spiral shell that contains 10mL1.0mmol/L fastIn the 50mL there-necked flask of fluorenes pyridine ethylene glycol solution, at room temperature vigorous stirring, after 15 minutes, is then enteredRow microwave back flow reaction 30 minutes, ageing 4h under cooling rear room temperature. By the product centrifugation after ageing, andWash described sediment 3 times with deionized water and ethanol, ultrasonic dispersion, dry, obtain described spiral shell fluorenes pyridinePd nano particle. With the pattern of nano particle described in scanning electron microscopic observation.
With embodiment 1, spiral shell fluorenes pyridine Pd nano particle prepared by embodiment 2 and embodiment 3 is example, urgesChange reaction:
The spiral shell fluorenes pyridine Pd nano particle that uses above-described embodiment 1 to prepare carries out catalytic reaction as catalyst, anti-The condition of answering is: by 1.0mmol4-Brominal, 1.2mmol phenyl boric acid and 3.0mmolK2CO3, at airIn atmosphere in H2In O/EtOH mixed solvent, react, this mixed solvent is by 4mL water and 3mL ethanol (EtOH)Composition, reaction temperature is 50 DEG C, and the reaction time is 4h, adopts column chromatography separated product, and productive rate is 99%.Reaction equation is as follows:
The spiral shell fluorenes pyridine Pd nano particle that uses above-described embodiment 2 to prepare carries out catalytic reaction as catalyst, anti-The condition of answering is: by 1.0mmol iodobenzene, 1.5mmol styrene and 2.0mmolNa2CO3, in air atmosphereReaction in dimethyl formamide (DMF) in enclosing, reaction temperature is 140oC, the reaction time is 24h, adoptsColumn chromatography separated product, productive rate is 70%. Reaction equation is as follows:
The spiral shell fluorenes pyridine Pd nano particle that uses above-described embodiment 3 to prepare carries out catalytic reaction as catalyst, anti-The condition of answering is: by 1.0mmol bromobenzene, 1.2mmol4-methylphenylboronic acid and 3.0mmolK2CO3, at skyAtmosphere enclose in H2In O/EtOH mixed solvent, react, this mixed solvent is by 4mL water and 3mL ethanol(EtOH) composition, reaction temperature is 50oC, the reaction time is 4h, adopts column chromatography separated product,Productive rate is 95%. Reaction equation is as follows:

Claims (4)

1. a preparation method for spiral shell fluorenes pyridine Pd nano particle, is characterized in that, comprises the following steps:
Spiral shell fluorenes pyridine organic ligand is dissolved in ethylene glycol or ethyl acetate, and described spiral shell fluorenes pyridine is 2-bromo-2 ', 7,7 '-tri-(4-pyridine)-9,9 '-spiral shell, two fluorenes, its amount of substance concentration is 1.0mmol/L～5.0mmol/L, structural formula is:
Palladium salt is dissolved in distilled water, and described palladium salt is any one in palladium bichloride or palladium, its amount of substance concentrationFor 5.0mmol/L～10mmol/L;
Palladium saline solution joined in described organic ligand solution fast, wherein the material of palladium ion and organic ligandThe ratio of amount is 1～3:1, at room temperature vigorous stirring after 15 minutes, then carry out microwave back flow reaction 20～40 minutes,Cooling rear ageing 3～5h;
By the product centrifugation after ageing, wash described sediment with deionized water and ethanol respectively, ultrasonic dispersion, dryDry, obtain described spiral shell fluorenes pyridine Pd nano particle.
2. the preparation method of spiral shell fluorenes pyridine Pd nano particle according to claim 1, is characterized in that described 2-Bromo-2 ', 7,7 '-tri-(4-pyridines)-9, the preparation method of 9 '-spiral shell, two fluorenes comprises:
By 2,2 ', 7,7 '-tetrabromo-9,9 '-spiral shell, two fluorenes, 4-pyridine boric acid, potash, toluene, second alcohol and water join three mouthfuls of burningsIn bottle, under nitrogen protection, taking tetra-triphenylphosphine palladium as catalyst, back flow reaction 45 minutes in microwave reactor;
After finishing, reaction is cooled to room temperature, separatory, water CH2Cl2Extraction, merges organic phase, organic phase is used fullWith saline solution washing, separatory, then use anhydrous magnesium sulfate drying 10h, suction filtration, is spin-dried for, and obtains thick product;
Use column chromatography refined product, ethyl acetate is eluent, obtains bromo-2 ', 7,7 '-tri-(the 4-pyridines)-9 of 2-, 9 '-spiral shell, two fluorenesNet product.
3. a spiral shell fluorenes pyridine Pd nano particle, is characterized in that, described spiral shell fluorenes pyridine Pd nano particle is wanted according to rightAsk the preparation method of the spiral shell fluorenes pyridine Pd nano particle described in any one in 1-2 to prepare, described spiral shell fluorenes pyridine palladium is receivedRice corpuscles particle diameter is 20～100nm.
4. spiral shell fluorenes pyridine Pd nano particle as claimed in claim 3 is as an effective catalyst, for catalysis carbon-to-carbonKey coupling reaction.
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