CN108654685B - Method for improving catalytic selectivity of organic matter sites - Google Patents
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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 invention relates to the technical field of selective catalysis, in particular to a method for improving catalytic selectivity of organic matter sites.
Background
Metal-Organic Frameworks (MOFs) are porous materials with a periodic network structure formed by self-assembly of Metal ion centers and Organic ligands. The composite polymer integrates the characteristics of a composite polymer and an organic coordination compound, has the advantages of controllable structure size, adjustable pore channel size, definite pore channel structure, excellent framework rigidity, excellent thermal stability and the like, and has wide application in the fields of material science and energy science.
The catalytic selectivity of organic sites is always a hotspot of research in the scientific and engineering circles, and because a multifunctional group exists in one molecule at the same time, the activity and the steric hindrance are similar, and the directional selective reaction is difficult to realize. At the earliest, researchers utilized the high degree of specificity of enzymes to act only on certain substrates or classes of substrates with specific spatial structures, thereby achieving selective catalysis. The living environment of the enzyme is harsh and the use on a large scale is limited. Later, researchers have realized the selective epoxidation of polyene hydrocarbons by modifying biomacromolecules to activate only a specific functional group or active site in a reactant, and this method makes a significant contribution to the field of organic synthesis. However, these techniques are difficult to scale up industrially due to complex modification and isolation problems. Several heterogeneous catalysts, which are very exponential, have also been used for selective catalysis, on the one hand by modifying the metal ions to provide steric sites by surfactants, but surfactants are also limited to oleic acid, oleylamine and mercaptans and require very long molecular chains. On the other hand, the metal nanoparticles are encapsulated by means of the molecular sieve, and the synthesis conditions of the molecular sieve are complex and harsh, so that the metal nanoparticles are difficult to introduce in the synthesis process, the dispersion disorder of the nanoparticles is caused, and the low selectivity is shown. At present, the problems of low selectivity, difficult separation, complex process, high cost and the like exist when the heterogeneous catalyst is used for realizing the catalytic selectivity of an organic site.
Aiming at the current situation, the invention provides a method for improving the catalytic selectivity of the organic matter sites, and the selective catalysis of the organic matter sites is realized by combining the pore confinement effect of a metal organic framework and the packaging technology of metal nano particles.
Disclosure of Invention
The invention aims to provide a method for improving the catalytic selectivity of organic sites. The method utilizes the special structure of the novel nano-particle @ metal organic framework material, and limits the diffusion movement process of the organic matter through the nano-pore structure of the metal organic framework material, so that only partial functional groups of the organic matter can contact catalytic active sites, and the selectivity of site catalysis is realized.
The invention also aims to provide application of the nanoparticle @ metal organic framework material in selective catalysis of organic sites.
The purpose of the invention is realized by the following technical scheme:
a method for improving catalytic selectivity of organic sites 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.
In the above method, the site-selective catalysis refers to a selective catalytic reaction of functional groups at different positions in an organic substance; preferably the selective hydrogenation of dienes, the selective oxidation of diols, the selective hydrogenation of carbon-carbon double bonds or carbon-oxygen double bonds.
In the method, the nanoparticle @ metal organic framework material is a composite material of the nanoparticle @ metal organic framework material prepared by an in-situ growth method; the in-situ growth method is that the prepared nano particles are dispersed by PVP and then added into the synthetic mother liquor of the metal organic framework material together for growth.
The metal organic framework material is a porous material with a periodic network structure formed by self-assembly of metal ions or clusters and organic ligands through coordination, the pore diameter of the porous material is matched with the size of a reactant, namely the pore diameter can ensure that the steric hindrance of selected site functional groups in the reactant is smaller and the porous material is easier to enter, and because of the limitation of pore channels, the molecules of the reactant cannot be folded or rotated, so that the site functional groups can be contacted with a catalytic active component in the inlet pores, and further site selective catalysis is carried out.
The nanoparticles are nanometer metal or compound thereof with catalytic activity, 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 (1).
The application of the nanoparticle @ metal organic framework material in selective catalysis of organic sites realizes selective catalysis of different sites of organic matters by utilizing the catalytic activity of the nanoparticles in the nanoparticle @ metal organic framework material and the limitation of a nanometer pore channel of the metal organic framework material on the diffusion process of the organic matters;
the site selective catalysis refers to selective catalytic reaction of functional groups at different positions in an organic matter, and comprises selective hydrogenation of diene, selective oxidation of diol, and selective hydrogenation of carbon-carbon double bonds or carbon-oxygen double bonds.
The application takes the nano-particle @ metal organic framework material as a catalyst, and the catalyst is uniformly dispersed in an organic matter catalytic reaction system to carry out organic matter site selective catalytic reaction.
The nanoparticle @ metal organic framework material is a composite material of the nanoparticle @ metal organic framework material prepared by an in-situ growth method; the in-situ growth method is that the prepared nano particles are dispersed by PVP and then added into the synthetic mother liquor of the metal organic framework material together for growth.
The nanoparticles are nano-metals or compounds thereof with catalytic activity, 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 material is matched with the size of organic molecules participating in the reaction in the organic catalytic reaction system.
The invention has the beneficial effects that:
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.
Drawings
FIG. 1 is a schematic representation of the site-selective oxidation of 1, 5-hexanediol by Pt @ ZIF-8 and Pt @ UIO-66
The metal organic framework material ZIF-8 has
Due to the limitation of the steric hindrance of the pore channel, only the terminal hydroxyl group of the 1, 5-hexanediol can enter the pore channel and contact with the reaction active site Pt to carry out selective hydrogenation. And the metal-organic framework material UIO-66 has
The pore diameter of the catalyst is small, and two hydroxyl groups of the glycol can enter the pore channel to carry out hydrogenation reaction.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1: preparation of Pt @ ZIF-8 selective catalyst by in-situ method
Pt nano particles are dispersed in methanol solution by PVP to prepare 0.26 mg-mL-11ml of a methanol solution of Pt, 15ml of a methanol solution of dimethylimidazole (25mM) and 15ml of Zn (NO)3)2·6H2Mixing O (25mM) in methanol, ultrasonically dispersing, soaking for 24h at room temperature, centrifugally separating, washing for 3 times by using methanol, and drying to finally obtain Pt @ ZIF-8. The Pt @ ZIF-8 prepared by Inductively Coupled Plasma (ICP) analysis contained 2 wt% of Pt.
Example 2: preparation of Pt @ UIO-66 selective catalyst by in-situ method
Dispersing Pt nano-particles in N, N' -Dimethylformamide (DMF) by PVP to obtain the concentration of 0.26 mg-mL-1The solution of (1). 5ml of 8.75mM ZrCl were taken4The DMF solution was mixed with 5ml of terephthalic acid DMF solution at a concentration of 8.01mM, followed by the addition of 1.2ml of acetic acid and 0.2ml of Pt in DMF, respectively. The mixed solution is put into an environment with the temperature of 120 ℃ for reaction for 24 hours. Centrifuging, washing with DMF for 3 times, soaking the obtained product in methanol solution at 60 deg.C for 3 days, changing solvent every 24 hr, and drying to obtain Pt @ UIO-66. The Pt @ UIO-66 prepared by ICP analysis had a Pt content of 2 wt%.
Example 3: preparation of Pt/CNT Selective catalyst
The same Pt nanoparticles were dispersed in a methanol solution with PVP to prepare 0.26 mg-mL-1The solution of (1). Dispersing 42.6mg Carbon Nanotube (CNT) treated with concentrated nitric acid in 15ml methanol solution, adding 1ml Pt methanol solution, soaking for adsorption for 24 hr, centrifuging, washing with methanol for 3 times, drying to obtain Pt/CNT, and processing by ICPThe Pt/CNT thus prepared was analyzed to have a Pt content of 2 wt%.
Example 4: selective oxidation of 1, 5-hexanediol
50 mul of 1, 5-hexanediol was added to 15ml of toluene solution, 10mg of the catalyst prepared in examples 1,2 and 3 were added to the solution, the mixture was sonicated for 5min until dispersion was homogeneous, the solution was transferred to the autoclave and reacted for 12h at 120 ℃ under 15bar pure oxygen. The selectivities and conversions obtained are shown in the following table:
example 5: selective hydrogenation of 1, 4-hexadiene
3ml of ethyl acetate is added into a reactor, the air in the reactor is evacuated by pure hydrogen, then 100 mul of 1, 4-hexadiene is added, 10mg of the catalyst prepared in the examples 1,2 and 3 are respectively added into the solution, ultrasonic treatment is carried out for 10min until the catalyst is uniformly dispersed, then pure hydrogen is used for exhausting, and then the reactor is placed at 35 ℃ and reacted for 24h under the hydrogen environment of 1 bar. The selectivities and conversions obtained are shown in the following table:
example 6: selective hydrogenation of cis-4-heptenal
50 mul of cis-4-heptenal and 15ml of toluene solution are added into a high-pressure reaction kettle, 10mg of the catalyst prepared in the examples 1,2 and 3 are respectively added into the solution, and ultrasonic treatment is carried out for 5min until the solution is uniformly dispersed. Discharging the air in the reaction kettle by using pure hydrogen, and reacting for 12 hours at 100 ℃ in a pure hydrogen environment at 15 bar. The selectivities and conversions obtained are shown in the following table: the selectivities and conversions obtained are shown in the following table:
by comparison of the data above, it is readily seen that the nanoparticle @ metal organic framework catalyst has superior site catalysis selectivity over the traditional catalyst.
Claims (4)
1. A method for improving catalytic selectivity of an organic site is characterized by comprising the following steps: the method comprises the following steps of (1) taking nano particles @ metal organic framework materials as catalysts, uniformly dispersing the catalysts in an organic matter catalytic reaction system, and carrying out organic matter site selective catalytic reaction; the site selective catalysis refers to the selective catalytic reaction of functional groups at different positions in an organic matter;
the nano-particle @ metal organic framework material is a composite material of the nano-particle @ metal organic framework material prepared by an in-situ growth method; the in-situ growth method is that the prepared nano particles are dispersed by PVP and then added into the synthetic mother liquor of the metal organic framework material together for growth;
the nano particles are nano metal or compounds thereof with catalytic activity; the aperture of the metal organic framework material should be matched with the size of organic molecules participating in the reaction in an organic catalytic reaction system;
the site-selective catalysis is a selective oxidation of a diol.
2. The method of claim 1, wherein: the nano particles are Pt, Au, Pd, Cu, Fe, Ni, Ru, Ag, Ce, NiO and Fe2O3、CuO、CeO2 、 Co3O4、Au@Pt、Pt@Cu、Au@Cu2O、Pt@NiO、Au@CeO2At least one of (1).
3. The application of the nanoparticle @ metal organic framework material in selective catalysis of organic sites is characterized in that: the selective catalysis of different sites of the organic matter is realized by utilizing the catalytic activity of the nano particles in the nano particles @ metal organic framework material and the limitation of nano pores of the metal organic framework material on the diffusion process of the organic matter; the site selective catalysis refers to the selective catalytic reaction of functional groups at different positions in an organic matter;
the method comprises the following steps of (1) taking nano particles @ metal organic framework materials as catalysts, uniformly dispersing the catalysts in an organic matter catalytic reaction system, and carrying out organic matter site selective catalytic reaction;
the nano-particle @ metal organic framework material is a composite material of the nano-particle @ metal organic framework material prepared by an in-situ growth method; the in-situ growth method is that the prepared nano particles are dispersed by PVP and then added into the synthetic mother liquor of the metal organic framework material together for growth;
the nano particles are nano metal or compounds thereof with catalytic activity; the aperture of the metal organic framework material is matched with the size of organic molecules participating in the reaction in an organic matter catalytic reaction system;
the organic site selective catalysis is the selective oxidation of diol.
4. Use according to claim 3, characterized in that: the nano particles are Pt, Au, Pd, Cu, Fe, Ni, Ru, Ag, Ce, NiO and Fe2O3、CuO、CeO2 、 Co3O4、Au@Pt、Pt@Cu、Au@Cu2O、Pt@NiO、Au@CeO2At least one of them.
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| "Chemoselective reduction of alpha,beta-unsaturated carbonyl compounds with UIO-66 materials";Plessers Eva et al;《JOURNAL OF CATALYSIS》;20160831;第340卷;摘要 * |
| Zhang Weina et al."A family of metal-organic frameworks exhibiting size-selective catalysis with encapsulated noble-metal nanoparticles".《ADVANCED MATERIALS》.2014,第26卷(第24期), * |
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