CN108295902B - Immobilized binuclear rhodium metal complex catalyst and preparation method and application thereof - Google Patents
Immobilized binuclear rhodium metal complex catalyst and preparation method and application thereof Download PDFInfo
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- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- C07D203/14—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom with carbocyclic rings directly attached to the ring nitrogen atom
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- B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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Abstract
The invention discloses a preparation method and application of an immobilized binuclear rhodium metal complex catalyst. The immobilized binuclear rhodium metal complex catalyst comprises: zn2+Forming a metal organic framework ZIF-8 serving as a carrier with 2-methylimidazole; and Rh axially modified with 2-methylimidazole2(esp)2Distributed on said vector ZIF-8. The preparation method comprises the following steps: to contain Rh2(esp)2Reacting the mixed system of 2-methylimidazole and solvent at room temperature to form axially modified Rh of 2-methylimidazole2(esp)2Then adding Zn into the mixed system2+And reacting at room temperature to obtain the immobilized binuclear rhodium metal complex catalyst. The invention adopts 2-methylimidazole as an organic ligand for synthesizing ZIF-8, which not only forms a ZIF-8 metal framework by self-assembling with zinc ions, but also forms a ZIF-8 metal framework by self-assembling with Rh2(esp)2Axial coordination occurs, after coordination, Rh is not influenced2(esp)2The reaction activity of the N-H-propyl ring compound is improved, the reaction selectivity of the catalytic synthesis of the N-H-propyl ring compound is improved, and the N-H-propyl ring compound has universality.
Description
Technical Field
The invention particularly relates to an immobilized binuclear rhodium metal complex catalyst and a preparation method and application thereof, belonging to the technical field of material synthesis.
Background
Rh2(esp)2Being a unique homonuclear bimetallic compound, the presence of rhodium-rhodium bonds between the metal nuclei often exhibits a different mode of reaction from that of the mononuclear metal compounds in the catalytic organic reaction. Rh2(esp)2Has high catalytic activity on the catalytic synthesis of carbene and nitrene species, however, Rh2(esp)2The catalyst is very expensive, and can not be recycled because the catalyst is always applied to a homogeneous system in a catalytic reaction, so that precious metals are easily lost and the environment is easily polluted. The metal organic framework ZIF-8 is a rhombic dodecahedron structure with the particle size distribution of 50-80nm and uniform pore diameter, has a larger specific surface area and a stable framework structure, and is also a hot spot problem which is raised in recent years due to a metal organic framework topological structure. Therefore, ZIF-8 is currently widely used as a carrier to support noble metal nanoparticles, metal oxides, bioactive drugs, and the like, but there is no report that ZIF-8 is used as a carrier to support metal complexes.
Disclosure of Invention
The invention mainly aims to provide an immobilized binuclear rhodium metal complex catalyst and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an immobilized binuclear rhodium metal complex catalyst, which comprises the following components in percentage by weight: zn2+Forming a metal organic framework ZIF-8 serving as a carrier with 2-methylimidazole; and Rh axially modified with 2-methylimidazole2(esp)2Distributed on said support.
The embodiment of the invention also provides a preparation method of the immobilized binuclear rhodium metal complex catalyst, which comprises the following steps: to contain Rh2(esp)2Reacting the mixed system of 2-methylimidazole and solvent at room temperature to form axially modified Rh of 2-methylimidazole2(esp)2Then toZn is added into the mixed system2+And reacting at room temperature to obtain the immobilized binuclear rhodium metal complex catalyst.
The embodiment of the invention also provides the immobilized binuclear rhodium metal complex catalyst obtained by the preparation method.
The embodiment of the invention also provides application of the immobilized binuclear rhodium metal complex catalyst in the synthesis reaction of N-H-C cyclic compounds.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides an immobilized binuclear rhodium metal complex catalyst, Rh2(esp)2The solid loading amount is adjustable for the first time, and the solid loading amount is more than 0 and less than or equal to 4.5 percent.
(2) According to the invention, the method for obtaining the immobilized binuclear rhodium metal complex catalyst by adopting a one-step method is adopted, the adopted 2-methylimidazole and zinc nitrate hexahydrate are cheap and easily available compounds, and the ZIF-8 synthesis method is simple, convenient and rapid, large in specific surface area and stable in structure;
(3) 2-methylimidazole as organic ligand for synthesizing ZIF-8, which not only forms ZIF-8 metal skeleton by self-assembling with zinc ion, but also forms ZIF-8 metal skeleton with Rh2(esp)2Axial coordination occurs, after coordination, Rh is not influenced2(esp)2The reaction activity of the N-H-propyl ring compound is improved, the reaction selectivity of the catalytic synthesis of the N-H-propyl ring compound is improved, and the N-H-propyl ring compound has universality;
(4) the direct one-step method for immobilization avoids the complex treatment step of post-grafting, obtains the composite material with high immobilization capacity, simultaneously reserves the skeleton structure of ZIF-8, and meets the requirement of green chemistry.
Drawings
FIG. 1a is a schematic representation of axially modified Rh with 2-methylimidazole in an exemplary embodiment of the present invention2(esp)2Schematic structural diagram of (a);
FIG. 1b is a schematic representation of axially modified Rh with 2-methylimidazole in an exemplary embodiment of the invention2(esp)2Schematic structural diagram of (a);
FIG. 2 shows 2-methylimidazole Rh and Rh in example 1 of the present invention2(esp)2Coordinated X photoelectron spectra;
FIG. 3 shows pure ZIF-8 and Rh-immobilized in example 1 of the present invention2(esp)2An X-ray diffraction pattern of the post ZIF-8 composite;
FIG. 4 shows Rh immobilization in example 1 of the present invention2(esp)2BET plot of post ZIF-8 composites;
FIG. 5 shows Rh immobilization in example 1 of the present invention2(esp)2Transmission electron microscopy of the post ZIF-8 composite.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the invention provides an immobilized binuclear rhodium metal complex catalyst, which comprises the following components in percentage by weight: zn2+Forming a metal organic framework ZIF-8 serving as a carrier with 2-methylimidazole; and Rh axially modified with 2-methylimidazole2(esp)2Distributed on said support.
Further, the immobilized binuclear rhodium metal complex catalyst has a rhombic dodecahedron topology structure.
Furthermore, the particle size of the immobilized binuclear rhodium metal complex catalyst is 50-80 nm.
The embodiment of the invention also provides a preparation method of the immobilized binuclear rhodium metal complex catalyst, which comprises the following steps: to contain Rh2(esp)2Reacting the mixed system of 2-methylimidazole and solvent at room temperature to form axially modified Rh of 2-methylimidazole2(esp)2Then adding Zn into the mixed system2+And reacting at room temperature to obtain the immobilized binuclear rhodium metal complex catalyst.
In some more specific embodiments, the preparation method comprises: at room temperature to Rh2(esp)2Adding 2-methylimidazole into the methanol solution to react until the color of the solution is changed fromChanging green to light red to obtain Rh containing axial modification of 2-methylimidazole2(esp)2And then adding soluble zinc salt into the reaction mixture to react to obtain the immobilized binuclear rhodium metal complex catalyst.
Further, 2-methylimidazole is used in a larger amount than Rh2(esp)2The amount of (A) to (B).
Furthermore, the molar ratio of the soluble zinc salt to the 2-methylimidazole is 1: 2-8.
Further, the Rh is2(esp)2Has a concentration of greater than 0 and less than or equal to 3.0mg/m L.
In some preferred embodiments, the preparation method comprises: slowly dripping a soluble zinc salt solution into the reaction mixture, and continuously stirring for more than 2 hours under the condition that the rotating speed is 400-500 rpm to obtain the immobilized binuclear rhodium metal complex catalyst.
The embodiment of the invention also provides the immobilized binuclear rhodium metal complex catalyst obtained by the preparation method.
The embodiment of the invention also provides application of the immobilized binuclear rhodium metal complex catalyst in the synthesis reaction of N-H-C cyclic compounds.
In particular, in some more specific embodiments, Rh immobilization is performed in a one-step process2(esp)2The preparation method comprises the following steps:
2-methylimidazole and zinc nitrate hexahydrate are taken as raw materials, Rh with different concentrations is obtained at room temperature2(esp)2The methanol solution presents a clear green solution, then 2-methylimidazole is added until the solution turns into light red, zinc nitrate aqueous solution is instantly and slowly dripped, and Rh-containing zinc nitrate aqueous solution is obtained by one-step self-assembly2(esp)2The composite of ZIF-8 (i.e., the immobilized binuclear rhodium metal complex catalyst). The synthesis method is simple and rapid to operate, and the synthesized heterogeneous catalyst has high selectivity and universality for catalyzing N-H-propane cyclic compounds.
Further, the preparation method specifically comprises the following steps:
(1) 2-methylimidazole with Rh2(esp)2Axial coordination: adding Rh to the solution2(esp)2Dissolving in 10m L methanol solution to give clear green solution, adding 4.0mmol 2-methylimidazole until the solution color changes from green to light red, and obtaining axial ligand 2-methylimidazole modified Rh2(esp)2。
(2) Self-assembly to form ZIF-8: slowly dropwise adding zinc nitrate aqueous solution into Rh modified by 2-methylimidazole at room temperature2(esp)2In methanol solution, stirring for 2h by magnetic force to prepare Rh through self-assembly2(esp)2And ZIF-8. Then centrifugally washing the solid with methanol solution to obtain immobilized Rh2(esp)2And (3) placing the composite material in a vacuum drying oven at the temperature of 25 ℃ for more than 24 hours.
The invention selects Rh based on coordination chemistry and MOF self-assembly strategy2(esp)2Taking m-2-methylimidazole and zinc nitrate hexahydrate as raw materials as central active molecules, and simultaneously immobilizing Rh in the process of forming ZIF-8 by self-assembling and combining metal ions and organic ligands2(esp)2By changing Rh2(esp)2Concentration of methanol solution and experimental process conditions to realize Rh2(esp)2Effective regulation and control are carried out to obtain the composite material with high solid loading capacity, large specific surface area and stable structure, namely Rh2(esp)2The @ ZIF-8 composite material (namely the immobilized binuclear rhodium metal complex catalyst) is expected to be widely applied to the aspect of organic catalysis.
The technical solution of the present invention will be described in more detail with reference to the accompanying drawings and specific embodiments.
Example 1: one-step method for loading Rh fixedly2(esp)2The preparation of (1):
step 1: 2-methylimidazole with Rh2(esp)2Axial coordination: adding Rh to the solution2(esp)2Dissolving in 10m L methanol solution to obtain clear green solution with concentration of below 3.0mg/m LSubsequently 4.0mmol of 2-methylimidazole are added, and when the solution changes from green to light red, Rh modified with 2-methylimidazole containing the axial ligand is obtained2(esp)2The reaction mixture of (1), wherein the axial ligand is 2-methylimidazole-modified Rh2(esp)2The spectrum of X photoelectron is shown in FIG. 2.
Step 2: self-assembly to form ZIF-8: slowly dropwise adding zinc nitrate aqueous solution into the reaction mixture at room temperature, and magnetically stirring for 2 hours to prepare Rh through self-assembly2(esp)2And ZIF-8. Then centrifugally washing the solid with methanol solution to obtain immobilized Rh2(esp)2Placing the composite material in a vacuum drying oven at 25 deg.C for more than 24 hr to obtain Rh2(esp)2The X-ray diffraction pattern, BET diagram and transmission electron microscope diagram of the @ ZIF-8 composite material (i.e. the immobilized binuclear rhodium metal complex catalyst) refer to FIG. 3-FIG. 5, respectively.
The methanol is HP L C grade, Rh2(esp)2The concentration of (A) should not be too large, the amount of 2-methylimidazole used is far greater than Rh2(esp)2The amount of (A) to (B).
Example 2: the Rh is added2(esp)2The process of applying @ ZIF-8 to catalytic synthesis of N-H-propisocyclic compounds is as follows:
the reaction was carried out in a 10m L flask, 0.55mmol of 2, 4-dinitrophenylhydroxylamine, 0.005mmol of Rh were weighed out2(esp)2@ ZIF-8 catalyst was charged into a reaction flask, evacuated by an oil pump and charged with nitrogen, so evacuated three times, and then 5.0m L of 2,2, 2-trifluoroethanol solvent and 0.50mmol of 2-methyl-1-phenylpropylene were added by a syringe to react at room temperature for 3 hours.0.60. mu. L of a clear solution of the reaction product was taken, and the reaction product was quantitatively analyzed by gas chromatography, and the results are shown in Table 1:
table 1 shows the results of quantitative analysis of the reaction products by gas chromatography
| Catalyst and process for preparing same | Reaction time (h) | Conversion (%) | Selectivity (%) | Yield (%) |
| 1mol％Rh2(esp)2@ZIF-8 | 3 | 96 | 82 | 79 |
After the reaction is finished, the heterogeneous catalyst is centrifugally separated out, washed by methanol solution and dichloromethane solution for three times respectively, dried in vacuum at the temperature of 25 ℃, and then subjected to mechanical application experiments, and the test results show that Rh is2(esp)2The @ ZIF-8 heterogeneous catalyst still has better catalytic activity after being repeatedly used for four times, and the N-H propylene ring reaction in which the catalyst participates still keeps the product yield close to 70 percent.
According to the invention, the high-efficiency heterogeneous Rh is constructed by selecting the ZIF-8 with high specific surface area and high thermal stability as the carrier2(esp)2The catalyst can effectively solve the defects of the traditional catalyst, and can also solve the problems of separation and recovery of the catalyst, environmental pollution, precious metal loss and the like.
The various intermediate and final products (hereinafter collectively referred to as "samples") involved in the above example preparation processes can be structurally characterized by the following means:
analyzing the structural formula of the sample compound on a Bruker SMART APEX II type X-ray single crystal diffractometer;
wide-angle X-ray diffraction structural analysis of the samples was performed on a japanese Rigaku D/Max-RB type X-ray diffractometer;
the transmission electron microscope picture is obtained under a Japanese JEO L JEM2011 type high-resolution transmission electron microscope;
adopting a Perkin Elmer PHI 5000 ESCT System X-ray photoelectron spectrometer, taking PdKa (1486.6eV) as an emission source, measuring the pressure of the analysis chamber at 10-9torr, the flux energy at 46.95eV, and correcting the binding energy by adopting the standard binding energy (CIS at 284.6eV) of the pollution C;
n is measured by a NOVA model 4000 surface area meter manufactured by Kangta, USA2Isothermal adsorption line, the specific surface area of the sample is calculated by BET equation.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. An immobilized binuclear rhodium metal complex catalyst, which is characterized by comprising: zn2+Forming a metal organic framework ZIF-8 serving as a carrier with 2-methylimidazole; and Rh axially modified with 2-methylimidazole2(esp)2Distributed on said support.
2. The immobilized binuclear rhodium metal complex catalyst of claim 1 wherein: the immobilized binuclear rhodium metal complex catalyst has a rhombic dodecahedral topological structure; the particle size of the immobilized binuclear rhodium metal complex catalyst is 50-80 nm.
3. A preparation method of an immobilized binuclear rhodium metal complex catalyst is characterized by comprising the following steps: to contain Rh2(esp)2Reacting the mixed system of 2-methylimidazole and solvent at room temperature to form the axially modified 2-methylimidazoleRh2(esp)2Then adding Zn into the mixed system2+And reacting at room temperature to obtain the immobilized binuclear rhodium metal complex catalyst.
4. The production method according to claim 3, characterized by comprising: at room temperature to Rh2(esp)2Adding 2-methylimidazole into the methanol solution for reaction until the color of the solution is changed from green to light red to obtain Rh containing 2-methylimidazole axial modification2(esp)2And then adding soluble zinc salt into the reaction mixture to react to obtain the immobilized binuclear rhodium metal complex catalyst.
5. The method of claim 4, wherein: the molar ratio of the soluble zinc salt to the 2-methylimidazole is 1: 2-8.
6. The method of claim 4, wherein: the Rh2(esp)2Has a concentration of greater than 0 and less than or equal to 3.0mg/m L.
7. The production method according to claim 4, characterized by comprising: slowly dripping a soluble zinc salt solution into the reaction mixture, and continuously stirring for more than 2 hours under the condition that the rotating speed is 400-500 rpm to obtain the immobilized binuclear rhodium metal complex catalyst.
8. An immobilized dinuclear rhodium metal complex catalyst obtained by the production process according to any one of claims 3 to 7.
9. The use of the supported binuclear rhodium metal complex catalyst of claim 1 or 2 or 8 in the synthesis reaction of N-H-C cyclic compounds.
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|---|---|---|---|---|
| CN103394373A (en) * | 2013-04-27 | 2013-11-20 | 南京工业大学 | Preparation method of hydrogenation catalyst |
| CN106179506A (en) * | 2016-06-24 | 2016-12-07 | 中国科学院福建物质结构研究所 | A kind of support type palladium-based catalyst and its preparation method and application |
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| CN103394373A (en) * | 2013-04-27 | 2013-11-20 | 南京工业大学 | Preparation method of hydrogenation catalyst |
| CN106179506A (en) * | 2016-06-24 | 2016-12-07 | 中国科学院福建物质结构研究所 | A kind of support type palladium-based catalyst and its preparation method and application |
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| A Scalable Rhodium-Catalyzed Intermolecular Aziridination Reaction;David T. Smith等;《Angew. Chem. Int. Ed.》;20140305;第53卷;4278-4280 * |
| Axial Ligand Coordination to the C–H Amination Catalyst Rh2(esp)2: A Structural and Spectroscopic Study;Evan Warzecha等;《Inorg. Chem.》;20150826;第54卷;8817-8824 * |
| Direct and Stereospecific Synthesis of N-H and N-Alkyl Aziridines from Unactivated Olefins Using Hydroxylamine-O-Sulfonic Acids;Zhiwei Ma等;《Angew. Chem. Int. Ed.》;20170614;第56卷;9886-9890 * |
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