CN108654685A - Method for improving catalytic selectivity of organic matter sites - Google Patents

Method for improving catalytic selectivity of organic matter sites Download PDF

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CN108654685A
CN108654685A CN201710204694.4A CN201710204694A CN108654685A CN 108654685 A CN108654685 A CN 108654685A CN 201710204694 A CN201710204694 A CN 201710204694A CN 108654685 A CN108654685 A CN 108654685A
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organic
framework materials
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organic framework
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CN108654685B (en
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张伟娜
霍峰蔚
张所瀛
王彧
许智玲
陈心怡
郑冰
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Nanjing Tech University
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    • B01J2231/60Reduction reactions, e.g. hydrogenation
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Abstract

The invention discloses a method for improving catalytic selectivity of organic sites, which takes nano particles @ metal organic framework materials as catalysts, and the catalysts are uniformly dispersed in an organic catalytic reaction system to carry out selective catalytic reaction of the organic sites. Compared with the traditional selective catalyst, the site selectivity efficiency can be greatly improved by utilizing the nanometer restricted structure of the metal organic framework material, and the traditional thermodynamic reaction equilibrium limit is broken through.

Description

A method of improving organic matter site catalytic selectivity
Technical field
The present invention relates to selective catalysis technical fields, and in particular to a kind of side for improving organic matter site catalytic selectivity Method.
Background technology
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) be by metal ion center with it is organic Ligand passes through the duct material with periodic network structure that is self-assembly of.It has merged composite high-molecular and organic coordination The characteristics of both compounds, have structure size it is controllable, pore size is adjustable, and pore passage structure is clear, outstanding skeleton rigidity and Many advantages, such as thermal stability, has a wide range of applications in material science and energy science field.
Organic matter site catalytic selectivity is all the hot spot of science and engineering circles research all the time, since polyfunctional group is same When be present in a molecule, activity it is similar with steric hindrance, be difficult to realize directional selectivity react.Earliest, researcher utilizes The specificity of enzyme height only works to certain or certain class substrate with particular space structure, to realize selective catalysis. The living environment of enzyme is harsh, and large-scale use is restricted.Later, researcher made it only by the modification to large biological molecule The specific functional group of some in activated reactant or active site, to realize the selective epoxidation of polyene, the method It is made that major contribution for organic synthesis field.But due to complicated modified and separation problem, these technologies are difficult to carry out Industry amplification.So far, very few several heterogeneous catalysis are also used for selective catalysis, on the one hand, are lived by surface Property agent modified metal ion spatial position be provided realize selective catalysis, but surfactant is also only limited to oleic acid, oleyl amine and Mercaptan and need the strand grown very much.On the other hand, by Zeolite Entrapped metal nanoparticle, due to Zeolite synthesis item Part is complicated harsh, it is difficult to introduce metal nanoparticle in its building-up process, causes the dispersion of nano particle unordered, shows low Selectivity.Nowadays, the catalytic selectivity that organic matter site is realized with heterogeneous catalysis, exist selectivity is low, separation is difficult, The problems such as process is complicated, of high cost.
The present invention is directed to this present situation, and the method for providing a kind of raising organic matter site catalytic selectivity has using metal The encapsulation technology of machine skeleton duct confinement effect and metal nanoparticle is combined, and realizes the selective catalysis in organic matter site.
Invention content
The object of the present invention is to provide a kind of methods of raising organic matter site catalytic selectivity.This method utilizes Performances of Novel Nano-Porous The special construction of rice grain@metal-organic framework materials is limited organic by the nano pore structure of metal-organic framework materials The diffusion motion process of object, enables organic matter to only have part functional group to touch catalytic active site, to realize site catalysis Selectivity.
Another object of the present invention is to provide nano particle@metal-organic framework materials to urge in organic matter site selectivity Application in change.
The purpose of the present invention is achieved through the following technical solutions:
A method of organic matter site catalytic selectivity is improved, is catalysis with nano particle@metal-organic framework materials The catalyst is dispersed in catalytic organism reaction system by agent, carries out the catalysis reaction of organic matter site selectivity.
Above-mentioned method, described in site selectivity catalysis refer to different location in organic matter functional group selectivity Catalysis reaction occurs;The preferably selective hydrogenation of diene, the selection of the selective oxidation of glycol, carbon-carbon double bond or C=O bond Property adds hydrogen.
Above-mentioned method, described in nano particle@metal-organic framework materials be received using prepared by situ synthesis The composite material of rice grain@metal-organic framework materials;The in situ synthesis be will the nano-particle that prepare with PVP into Then row dispersion is added in the synthesis mother liquid of metal-organic framework materials and is grown together.
Above-mentioned metal-organic framework materials are formed by Coordinate self-assembly with organic ligand by metal ion or cluster The porous material with periodical reticular structure, aperture should match with the size of reactant, i.e., pore size can guarantee Selected site functional group steric hindrance smaller in reactant, it is easier to enter, and due to the limitation in duct, reactant molecule It cannot occur to fold or rotate, enable to touch catalytic active component in the site functional group access aperture, and then site choosing occurs Selecting property is catalyzed.
Above-mentioned nano particle be with the nano metal of catalytic activity or its compound, preferably Pt, Au, Pd, Cu, Fe, Ni, Ru、Ag、Ce、NiO、Fe2O3、CuO、CeO2Co3O4、Au@Pt、Pt@Cu、Au@Cu2O、Pt@NiO、Au@CeO2In at least one Kind.
Application of the nano particle@metal-organic framework materials in the catalysis of organic matter site selectivity, utilizes nano particle@ The catalytic activity of nano particle and metal-organic framework materials nano pore diffuse through organic matter in metal-organic framework materials The selective catalysis of organic matter different loci is realized in the limitation of journey;
Above-mentioned site selectivity catalysis refers to the generation catalysis reaction of the functional group selectivity of different location in organic matter, packet Include the selective hydrogenation of diene, the selective hydrogenation of the selective oxidation of glycol, carbon-carbon double bond or C=O bond.
The catalyst is dispersed in organic by above application using nano particle@metal-organic framework materials as catalyst In object catalystic converter system, the catalysis reaction of organic matter site selectivity is carried out.
Above-mentioned nano particle@metal-organic framework materials are organic for the nano particle@metals prepared using in situ synthesis The composite material of framework material;The in situ synthesis is to disperse the nano-particle prepared with PVP, then together It is added in the synthesis mother liquid of metal-organic framework materials and is grown.
Above-mentioned nano-particle be with the nano metal of catalytic activity or its compound, preferably Pt, Au, Pd, Cu, Fe, Ni, Ru、Ag、Ce、NiO、Fe2O3、CuO、CeO2Co3O4、Au@Pt、Pt@Cu、Au@Cu2O、Pt@NiO、Au@CeO2In at least one Kind;
The aperture of above-mentioned metal-organic framework materials should be divided with the organic matter for participating in reacting in catalytic organism reaction system The size of son matches.
Beneficial effects of the present invention:
Compared to traditional catalysts selective, can be greatly improved using the nano-confined structure of metal-organic framework materials Site selectivity efficiency breaks through traditional thermodynamical reaction reaching ability.
Description of the drawings
Fig. 1 is the schematic diagram that Pt@ZIF-8 and Pt@UIO-66 carry out 1,5- hexylene glycols site selectivity oxidation
Metal-organic framework materials ZIF-8 possessesAperture, due to the limitation of duct steric hindrance, 1,5- oneself two Alcohol only terminal hydroxy group can touch reactivity site Pt into duct, and selective hydrogenation occurs.And metal-organic framework materials UIO-66 possessesAperture, two hydroxyls of ethylene glycol can enter duct and hydrogenation reaction occurs.
Specific implementation mode
The following examples are further illustrations of the invention, limitation of the present invention it is not.
Embodiment 1:In-situ method prepares Pt@ZIF-8 catalysts selectives
Pt nano particles are scattered in PVP in methanol solution, 0.26mgmL is prepared-1Solution, by 1ml Pt's Methanol solution, the methanol solution and 15ml Zn (NO of the methylimidazole (25mM) of 15ml3)2·6H2The methanol solution of O (25mM) Mixing, ultrasonic disperse, room temperature immersion for 24 hours, is centrifuged, is washed 3 times with methanol, dry, finally obtains Pt@ZIF-8.Pass through electricity It is 2wt% to feel coupled plasma spectroscopy (ICP) to analyze the content of Pt in obtained Pt@ZIF-8.
Embodiment 2:In-situ method prepares Pt@UIO-66 catalysts selectives
Pt nano particles are scattered in N with PVP, a concentration of 0.26mgmL is made in N '-dimethyl formamide (DMF)-1's Solution.Take the ZrCl of a concentration of 8.75mM of 5ml4The terephthalic acid (TPA) DMF solution of DMF solution and a concentration of 8.01mM of 5ml carries out Mixing, is then separately added into the DMF solution of the acetic acid and 0.2ml Pt of 1.2ml.Mixed solution is put into 120 DEG C of environment and is reacted 24h.It centrifuges, is washed 3 times with DMF, then obtained product is immersed in methanol solution, 60 DEG C impregnate 3 days, per for 24 hours A solvent is replaced, Pt UIO-66 are finally dried to obtain.Content by Pt in the Pt@UIO-66 obtained by icp analysis is 2wt%.
Embodiment 3:Prepare Pt/CNT catalysts selectives
Identical Pt nano particles are scattered in PVP in methanol solution, 0.26mgmL is prepared-1Solution.It takes The carbon nanotube (CNT) that 42.6mg has been handled with concentrated nitric acid is scattered in the methanol solution of 15ml, and the methanol that 1ml Pt are added is molten Liquid, dipping absorption for 24 hours, are centrifuged, are washed 3 times with methanol, obtains Pt/CNT after dry, pass through the Pt/ obtained by icp analysis The content of Pt is 2wt% in CNT.
Embodiment 4:The selective oxidation of 1,5- hexylene glycols
1, the 5- hexylene glycols of 50 μ l are added in the toluene solution of 15ml, 10mg embodiments 1 are taken respectively, obtained by 2,3 Catalyst is added in solution, and ultrasonic 5min shifts the solution in this high-pressure reactor to being uniformly dispersed, at 120 DEG C, 15bar 12h is reacted in purity oxygen environment.Obtained selectivity and conversion ratio is as shown in the table:
Embodiment 5:1,4- hexadiene selective hydrogenations
The ethyl acetate of 3ml is added in reactor, the air in reactor is emptied with pure hydrogen, 100 μ are then added L1,4- hexadiene take 10mg embodiments 1 respectively, and the catalyst obtained by 2,3 is added in solution, and ultrasonic 10min is equal to disperseing It is even, then be exhausted with pure hydrogen, reactor is then placed in 35 DEG C, is reacted for 24 hours under 1bar hydrogen environments.Obtained selectivity It is as shown in the table with conversion ratio:
Embodiment 6:Cis- -4- heptenals selective hydrogenation
The toluene solution of the cis- -4- heptenals of 50 μ l and 15ml are added in autoclave, take 10mg to implement respectively Example 1,2, catalyst obtained by 3 are added in solution, and ultrasonic 5min is to being uniformly dispersed.Air in reaction kettle is arranged with pure hydrogen Go out, reacts 12h in 100 DEG C, 15bar pure hydrogen environment.Obtained selectivity and conversion ratio is as shown in the table:Obtained selection Property and conversion ratio are as shown in the table:
By above-mentioned data comparison, it is seen that nano particle@metal organic framework catalyst compares such as traditional catalyst With superior site catalytic selectivity.

Claims (10)

1. a kind of method improving organic matter site catalytic selectivity, it is characterised in that:With nano particle@metal organic framework materials Material is catalyst, which is dispersed in catalytic organism reaction system, carries out organic matter site selectivity catalysis Reaction.
2. according to the method described in claim 1, it is characterized in that:The site selectivity catalysis refers to different positions in organic matter The generation catalysis reaction of the functional group selectivity set;Preferably the selective hydrogenation of diene, the selective oxidation of glycol, carbon carbon are double The selective hydrogenation of key or C=O bond.
3. according to the method described in claim 1, it is characterized in that:The nano particle@metal-organic framework materials are to adopt With the composite material of nano particle@metal-organic framework materials prepared by situ synthesis;The in situ synthesis is that will make The nano-particle got ready is disperseed with PVP, is then added in the synthesis mother liquid of metal-organic framework materials and is grown together.
4. according to the method described in claim 3, it is characterized in that:The nano-particle is the nano metal with catalytic activity Or its compound, preferably Pt, Au, Pd, Cu, Fe, Ni, Ru, Ag, Ce, NiO, Fe2O3、CuO、CeO2Co3O4、Au@Pt、Pt@Cu、 Au@Cu2O、Pt@NiO、Au@CeO2At least one of;The aperture of the metal-organic framework materials should match organic matter and urge Change the organic molecule size that reaction is participated in reaction system.
5. application of the nano particle@metal-organic framework materials in the catalysis of organic matter site selectivity, it is characterised in that:It utilizes The catalytic activity of nano particle and metal-organic framework materials nano pore are to organic in nano particle@metal-organic framework materials The selective catalysis of organic matter different loci is realized in the limitation of object diffusion process;The site selectivity catalysis refers to organic matter The generation catalysis reaction of the functional group selectivity of middle different location.
6. application according to claim 5, it is characterised in that:The organic matter site selectivity catalysis is the choosing of diene Selecting property adds the selective hydrogenation of hydrogen, the selective oxidation of glycol, carbon-carbon double bond or C=O bond.
7. application according to claim 5, it is characterised in that:Using nano particle@metal-organic framework materials as catalyst, The catalyst is dispersed in catalytic organism reaction system, the catalysis reaction of organic matter site selectivity is carried out.
8. application according to claim 5 or 6, it is characterised in that:The nano particle@metal-organic framework materials are Using the composite material of nano particle@metal-organic framework materials prepared by situ synthesis;The in situ synthesis is will The nano-particle prepared is disperseed with PVP, is then added in the synthesis mother liquid of metal-organic framework materials and is given birth to together It is long.
9. application according to claim 8, it is characterised in that:The nano-particle is the nano metal with catalytic activity Or its compound, preferably Pt, Au, Pd, Cu, Fe, Ni, Ru, Ag, Ce, NiO, Fe2O3、CuO、CeO2Co3O4、Au@Pt、Pt@Cu、 Au@Cu2O、Pt@NiO、Au@CeO2At least one of.
10. application according to claim 8, it is characterised in that:The aperture of the metal-organic framework materials should with it is organic The size that the organic molecule of reaction is participated in object catalystic converter system matches.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117258851A (en) * 2023-11-21 2023-12-22 山东新和成药业有限公司 Copper-based catalyst and preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101426797A (en) * 2006-04-18 2009-05-06 巴斯夫欧洲公司 Methods for producing metal-organic framework materials containing metals of subgroup IV
CN102516274A (en) * 2011-04-25 2012-06-27 中国科学院福建物质结构研究所 Cadmium metal organic frame compound with catalytic performance and preparation method and use thereof
US20130283846A1 (en) * 2012-04-26 2013-10-31 Lawrence Livermore National Security, Llc Adsorption cooling system using metal organic frameworks
CN103949286A (en) * 2014-04-16 2014-07-30 国家纳米科学中心 MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as preparation method and application thereof
US20140221672A1 (en) * 2012-02-28 2014-08-07 Saudi Basic Industries Corporation Process for Preparing Carbonate and Diol Products
CN104069883A (en) * 2014-06-23 2014-10-01 华南理工大学 Cobalt-based catalyst for generating ester by alcohol oxidation, and preparation method and application of cobalt-based catalyst
CN104755531A (en) * 2012-08-27 2015-07-01 拜尔材料科学股份公司 Preparation method of polyether carbonate polyol
CN104857988A (en) * 2015-05-07 2015-08-26 盐城工学院 Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof
CN105237586A (en) * 2015-10-15 2016-01-13 大连理工大学 Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn)

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101426797A (en) * 2006-04-18 2009-05-06 巴斯夫欧洲公司 Methods for producing metal-organic framework materials containing metals of subgroup IV
CN102516274A (en) * 2011-04-25 2012-06-27 中国科学院福建物质结构研究所 Cadmium metal organic frame compound with catalytic performance and preparation method and use thereof
US20140221672A1 (en) * 2012-02-28 2014-08-07 Saudi Basic Industries Corporation Process for Preparing Carbonate and Diol Products
US20130283846A1 (en) * 2012-04-26 2013-10-31 Lawrence Livermore National Security, Llc Adsorption cooling system using metal organic frameworks
CN104755531A (en) * 2012-08-27 2015-07-01 拜尔材料科学股份公司 Preparation method of polyether carbonate polyol
CN103949286A (en) * 2014-04-16 2014-07-30 国家纳米科学中心 MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as preparation method and application thereof
CN104069883A (en) * 2014-06-23 2014-10-01 华南理工大学 Cobalt-based catalyst for generating ester by alcohol oxidation, and preparation method and application of cobalt-based catalyst
CN104857988A (en) * 2015-05-07 2015-08-26 盐城工学院 Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof
CN105237586A (en) * 2015-10-15 2016-01-13 大连理工大学 Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn)

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
GUO ZHIYONG ET AL: ""Pt nanoclusters confined within metal organic framework cavities for chemoselective cinnamaldehyde hydrogenation"", 《ACS CATALYSIS》 *
PLESSERS EVA ET AL: ""Chemoselective reduction of alpha,beta-unsaturated carbonyl compounds with UIO-66 materials"", 《JOURNAL OF CATALYSIS》 *
STEPHENSON CASEY JET AL: ""Pt@ZIF-8 composite for the regioselective hydrogenation of terminal unsaturations in 1,3-dienes and alkynes"", 《INORGANIC CHEMISTRY FRONTIERS》 *
TORBINA VIKTORIIA V ET AL: ""Propylene glycol oxidation with tert-butyl hydroperoxide over Cr-containing metal-organic frameworks MIL-101 and MIL-100"", 《CATALYSIS TODAY》 *
ZHANG WEINA ET AL: ""A family of metal-organic frameworks exhibiting size-selective catalysis with encapsulated noble-metal nanoparticles"", 《ADVANCED MATERIALS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117258851A (en) * 2023-11-21 2023-12-22 山东新和成药业有限公司 Copper-based catalyst and preparation method and application thereof
CN117258851B (en) * 2023-11-21 2024-02-06 山东新和成药业有限公司 Copper-based catalyst and preparation method and application thereof

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