CN104707657A - Preparation and application of noble metal nanoparticles adjustable in sizes, positions and distribution - Google Patents
Preparation and application of noble metal nanoparticles adjustable in sizes, positions and distribution Download PDFInfo
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- CN104707657A CN104707657A CN201510075067.6A CN201510075067A CN104707657A CN 104707657 A CN104707657 A CN 104707657A CN 201510075067 A CN201510075067 A CN 201510075067A CN 104707657 A CN104707657 A CN 104707657A
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Abstract
The invention relates to preparation for a series of homogeneously dispersed loading-type noble metal nanoparticles which are adjustable in sizes and distribution positions. According to the preparation method, through adjusting the steric hindrance of the carrier substituents, noble metal nanoparticles in single distribution inside holes, noble metal nanoparticles in double distribution inside and outside holes and noble metal nanoparticles in single distribution outside holes are obtained. Studies on the performance of the noble metal nanoparticles show that the noble metal nanoparticles in single distribution inside holes have the highest stability and circularity as the confinement effect of micro pores effectively prevents nanoparticles from clustering in the catalytic reaction; the noble metal nanoparticles in single distribution outside holes have the highest catalytic activity, but are relatively poor in stability and circularity; the activity and circularity of the noble metal nanoparticles in double distribution inside and outside holes are between those of the noble metal nanoparticles in single distribution inside holes and the noble metal nanoparticles in single distribution outside holes.
Description
Technical field
The invention belongs to nano particle preparation and catalytic applications, be specifically related to a series of size and the distribute controlled preparation of noble metal nano particles and the application in catalytic reaction.
Background technology
Metal nano material is owing to having quantum effect, small-size effect and skin effect, present much distinctive physics, chemical property, become the study hotspot of the numerous areas such as physics, chemistry, material, and in heterocatalysis, bioengineering, drug delivery and information storage aspect are widely used.Wherein, load type metal nano particle combines the feature of carrier and metal nanoparticle due to it, therefore becomes the material that a class receives much concern, and correspondingly the metal nanoparticle of a series of support type arises at the historic moment, and has application in a lot.But, because carrier structure is different with performance, the form of the metal nanoparticle therefore in load and performance difference are very large, how effectively to regulate and control research emphasis and difficult point that the size of carried noble metal nano particle and distribution are field of nanometer material technology in recent years.
Porous organo polysilica closes (POFs) because of its large specific area, low skeletal density, diversified synthesis strategy, be easy to the advantages such as modification and functionalization, not only can as the effective carrier of metal nanoparticle, also give the certain characteristic of nano particle and function by electronics and stereoeffect, important inducing action is played to the size of nano particle, pattern and performance etc.But, current research to the effect that functional group is incorporated in POFs skeleton, come load and stable metal nano particle by coordination effect and duct confinement effect, these methods have certain defect: the size, distributing position and the degree of scatter that are difficult to regulate and control metal nanoparticle.Therefore in order to make up these defects, we take full advantage of the easy modified of POFs, the fluorenyl POFs that a series of substituting group of design and synthesis varies in size, by changing substituent size, achieve the size of effective regulation and control noble metal nano particles, distributing position and dispersed.
As everyone knows, the size of metal nanoparticle, distributing position and degree of scatter are to catalytic activity, and selective and recyclability has very important effect.At present, in carried noble metal nano-catalytic field, a large amount of patterns has been had, the research of size and distributed controll and discovery.Therefore, a nano particle is example, we use for reference the synthetic method of present existing nano material, by regulating substituent size, control to obtain some row and there is different size size, distributing position and dispersed Pd nano particle, and be applied to olefin hydrogenation reaction in, it shows good catalytic activity and circular form.
Summary of the invention
The invention provides a series of different size size, during it also reacts for olefin hydrogenation by distributing position and dispersed noble metal nano particles.
Noble metal nano particles provided by the invention, is characterized in that: this serial nano particle has different size size, distributing position and to be dispersed in whole POFs skeleton and this serial nano particle has different catalytic activitys, stability and selective.
Representational preparation method is as follows for described nano particle:
(1) under the protection of nitrogen by 4-azido Tetrabenzene methane and 2; 7-diacetylene fluorenes or derivatives thereof joins DMF solution; add again 10% cupric sulfate pentahydrate and sodium ascorbate as catalyst, by this mixture under agitation in 100 DEG C reaction 72 hours.Reacted rear gained solid EDTA-Na solution to wash, water, ethanol, oxolane, carrene cleans several times, and under vacuum, drying obtains carrier POFs afterwards
(2) nitrogen content measured by elementary analysis configures different solubility palladium/dichloromethane solution, corresponding POF is joined in palladium solution, reflux 24 hours at 60 DEG C, after question response is complete, precipitation is leached, with carrene, unnecessary palladium is thoroughly cleaned.
(3) POFs of palladium in load is reduced in a hydrogen atmosphere, obtain different size size, distributing position and dispersed Pd nano particle.
Size provided by the invention, position and the controlled nano particle that distributes have following advantage: size is little, is evenly distributed; Stability is high, and cyclicity is good.Pd/POF-1 in the present invention at least can follow seven take turns above, can realize noble metal efficiency utilization thus reduce industrial cost; Catalytic activity is high, and only with 100% hydrogenation that just can realize alkene under the catalyst room temperature of 0.05%, industrial application value is high.
Accompanying drawing explanation
Fig. 1 different size, position and finely dispersed noble metal nano particles prepare schematic diagram
Fig. 2 embodiment Pd/POF-1, the transmission electron microscope picture of Pd/POF-2, Pd/POF-3.
Fig. 3 embodiment Pd/POF-1, the catalytic cycle figure of Pd/POF-2, Pd/POF-3.
More specifically catalyst of the present invention is illustrated below in conjunction with embodiment, but these embodiments are without any restrictions to scope of the present invention.
Embodiment 1 (preparation and application of Pd/POF-1)
The palladium of 100mg is dissolved in 300mL CH
2cL
2in solution, then add 300mg POF-1 by this mixture in 60 DEG C of backflows 24 hours.After question response is complete, precipitation is leached, use CH
2cL
2unnecessary palladium is thoroughly cleaned.By the POF-1 of palladium in load at H
2/ N
2(5%H
2) the lower 200 DEG C of reduction of atmosphere obtain Pd/POF-1 in 4 hours.
Pd nano particle in loading type Pd/POF-1 presents substance distribution (1.6nm), is all evenly distributed in hole.Pd/POF-1 is used in cinnamic hydrogenation, and catalyst amount is 0.05%, and reaction temperature is room temperature, and the reaction time is 6 hours, and conversion ratio is 100%, does not have accessory substance.Can recycle 7 times, and catalytic activity does not obviously reduce.
Embodiment 2 (preparation and application of Pd/POF-2)
The palladium of 92mg is dissolved in 300mL CH
2cL
2in solution, then add 300mg POF-2 by this mixture in 60 DEG C of backflows 24 hours.After question response is complete, precipitation is leached, use CH
2cL
2unnecessary palladium is thoroughly cleaned.By the POF-1 of palladium in load at H
2/ N
2(5%H
2) the lower 200 DEG C of reduction of atmosphere obtain Pd/POF-2 in 4 hours.
Pd nano particle in loading type Pd/POF-2 presents two distribution again (2.2 and 4.5nm), is distributed in hole and outside hole simultaneously.Pd/POF-2 is used in cinnamic hydrogenation, and catalyst amount is 0.05%, and reaction temperature is room temperature, and the reaction time is 6 hours, and conversion ratio is 100%, does not have accessory substance.Can recycle 6 times, and catalytic activity does not obviously reduce.
Embodiment 3 (preparation and application of Pd/POF-3)
The palladium of 86mg is dissolved in 300mL CH
2cL
2in solution, then add 300mg POF-3 by this mixture in 60 DEG C of backflows 24 hours.After question response is complete, precipitation is leached, use CH
2cL
2unnecessary palladium is thoroughly cleaned.By the POF-3 of palladium in load at H
2/ N
2(5%H
2) the lower 200 DEG C of reduction of atmosphere obtain Pd/POF-3 in 4 hours.
Pd nano particle in loading type Pd/POF-2 presents substance distribution (2.2 and 4.5nm), is all distributed in outside hole.Pd/POF-3 is used in cinnamic hydrogenation, and catalyst amount is 0.05%, and reaction temperature is room temperature, and the reaction time is 6 hours, and conversion ratio is 100%, does not have accessory substance.Can recycle 4 times, and catalytic activity does not obviously reduce.
The foregoing is only of the present invention and represent embodiment, the modification made in every foundation the present patent application the scope of the claims and change, all should belong to covering scope of the present invention.
Claims (5)
1. a carried noble metal nano particle, is characterized in that: the size of described nano particle, position, and distribution can regulate and control.
2. nano particle according to claim 1, is characterized in that: described noble metal is selected from palladium, platinum, ruthenium, rhodium, iridium.
3. the preparation method of nano particle described in claim 1, is characterized in that, described nano particle by the acetate of the functionalization construction unit in POFs skeleton and noble metal by coordination load, at H
2/ N
2under atmosphere, reduction is obtained.
4. preparation method according to claim 3, it is characterized in that: the porous on the POFs carrier that described nano particle connects at different substituents residing for it is different, is regulated and controled its size, position and distribution etc. by the substituent size regulating POFs skeleton to connect.
5. nano particle according to claim 1 is used for olefin hydrogenation reaction, and catalyst amount is 0.05%, and reaction temperature is room temperature, and the reaction time is 6 hours.
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| CN201510075067.6A CN104707657A (en) | 2015-02-12 | 2015-02-12 | Preparation and application of noble metal nanoparticles adjustable in sizes, positions and distribution |
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| CN201510075067.6A CN104707657A (en) | 2015-02-12 | 2015-02-12 | Preparation and application of noble metal nanoparticles adjustable in sizes, positions and distribution |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721742A (en) * | 2019-10-09 | 2020-01-24 | 中国科学院福建物质结构研究所 | Construction of porous organic framework and application of porous organic framework in hydrodehalogenation reaction |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307571A (en) * | 2014-09-14 | 2015-01-28 | 中国科学院福建物质结构研究所 | Precious metal Carbene polymer catalysts and its preparation method and use |
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2015
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307571A (en) * | 2014-09-14 | 2015-01-28 | 中国科学院福建物质结构研究所 | Precious metal Carbene polymer catalysts and its preparation method and use |
Non-Patent Citations (5)
| Title |
|---|
| HONG ZHONG, ET AL.: "Click-based porous organic framework containing chelating terdentate units and its application in hydrogenation of olefins", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| LI LIUYI, ET AL.: "Facile Fabrication of Ultrafine Palladium Nanoparticles with Size- and Location-Control in Click-Based Porous Organic Polymers", 《ACS NANO》 * |
| LI LIUYI, ET AL.: "Tailorable Synthesis of Porous Organic Polymers Decorating Ultrafine Palladium Nanoparticles for Hydrogenation of Olefins", 《ACS CATALYSIS》 * |
| LI LIUYI，ET AL.: "Spatial control of palladium nanoparticles in flexible click-based porous organic polymers for hydrogenation of olefins and nitrobenzene", 《NANO RESEARCH》 * |
| MD. ANWARUL KARIM, ET AL.: "Comparison of Three Different Click Reaction Methods for the Synthesis of Fluorene-Based Polymers and Performance in Quasi-Solid-State DSSCs", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721742A (en) * | 2019-10-09 | 2020-01-24 | 中国科学院福建物质结构研究所 | Construction of porous organic framework and application of porous organic framework in hydrodehalogenation reaction |
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Application publication date: 20150617 |
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