CN108654685A - Method for improving catalytic selectivity of organic matter sites - Google Patents
Method for improving catalytic selectivity of organic matter sites Download PDFInfo
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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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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000005416 organic matter Substances 0.000 title claims description 28
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000013105 nano metal-organic framework Substances 0.000 claims description 2
- 239000013289 nano-metal-organic framework Substances 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical class CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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- B01J31/0201—Oxygen-containing compounds
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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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
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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