CN111203274A - Double-channel mixed metal crystalline catalyst and preparation method and application thereof - Google Patents

Double-channel mixed metal crystalline catalyst and preparation method and application thereof Download PDF

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CN111203274A
CN111203274A CN202010072237.6A CN202010072237A CN111203274A CN 111203274 A CN111203274 A CN 111203274A CN 202010072237 A CN202010072237 A CN 202010072237A CN 111203274 A CN111203274 A CN 111203274A
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catalyst
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张建勇
邓维
张娜
谭晶怡
刘青
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Shanghai Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

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Abstract

The invention relates to a double-channel mixed metal crystalline catalyst, a preparation method and application thereof, wherein the catalyst is prepared from Fe (NO)3)3·9H2O and Zn (CCl)3COO)2·2H2O constitutes a precursor with H3BTC is formed by assembling organic bridging ligands; the preparation method comprises the steps of mixing a precursor and an organic bridging ligand to form a precursor solution, and carrying out solvothermal reaction to obtain a solid substance, namely a target product; the catalystThe catalyst may be used to catalyze C-N coupling reactions. Compared with the prior art, the crystalline material has one-dimensional pore channels with two properties of hydrophobicity and hydrophilicity and coordination unsaturated sites, has higher catalytic activity on C-N coupling reaction, and has the highest catalytic efficiency of 98 percent and the selectivity of 100 percent.

Description

Double-channel mixed metal crystalline catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of porous coordination polymers, in particular to a double-channel mixed metal crystalline catalyst and a preparation method and application thereof.
Background
The transition metal catalyzed C-N coupling reaction is a very classical method for constructing aryl carbon-heterobonds and is one of the most important processes in chemical transformation. Simple reaction precursors can be converted into molecules with complex structures by means of these reactions, and transition metal-catalyzed coupling reactions are one of the most powerful approaches. The C-N coupling reaction catalyzed by the transition metal has mild conditions, wide application range, easy product separation, better substrate compatibility and higher yield. Although the coupling reaction has been greatly developed, there are many problems in the reaction process, such as low catalytic efficiency of some catalysts, large amount of catalyst, and complex ligand required for the reaction.
In patent CN 101466715a, aryl halide or aryloxy sulfophthalein based compound and amine form a new method of C-N bond in a specific solvent system under the catalysis of Pd. The method can improve the conversion of substrate amine, but the synthesis steps of the catalyst are complicated, and the catalytic reaction needs to be carried out in a specific solvent, so that the application of the method in the catalytic reaction is limited. The patent CN107803223A discloses a ferrocene cuprous cluster catalyst for catalyzing C-N coupling reaction and a preparation method thereof, the catalyst is a cuprous cluster complex of a ferrocene-based selenium/tellurium ether ligand, the coupling reaction of iodobenzene and imidazole under an alkaline condition is taken as a model reaction, the series of catalysts have high self-stability, and the catalysts can be stored in the air for a long time. However, the selenium/tellurium adopted by the method is expensive, so that the application of the selenium/tellurium in catalytic reaction is limited.
Metal-Organic Frameworks (MOFs) are a class of hot porous materials emerging in recent years. It not only has super large specific surface area and porosity, but also has rich and controllable material structure. The special structure can provide high density of active centers and huge reaction space for reaction, and attracts the research interest of scientists in a plurality of material and chemical fields in the world. The synthesis of MOFs most commonly employs a one-step reaction, i.e. the building of coordination polymers by self-assembly of organic ligands and metal salts, the so-called "one-pot" process. However, the diversity and complexity of coordination modes of metal ions and ligands increase the uncertainty of the self-assembly process, and thus the controllability of the synthesis process is poor, which greatly limits the practical application of the materials in catalysis.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a mixed metal crystalline catalyst which solves the technical problems of uncontrollable assembly process, variable structure, larger unpredictability of the synthesis process of most MOFs in the prior art, poor stability, complicated preparation steps, low activity and the like of the catalyst prepared by the traditional method, and a preparation method and application thereof.
In order to solve the problems in the prior art, the invention explores and utilizes a 'step-by-step assembly' mode to realize the controllable assembly of the porous coordination polymer. Using Fe (NO)3)3With Zn (CCl)3COO)2Synthetic Fe2MO(CCl3COO)6(CH3OH)3And (3) introducing organic bridging ligands such as trimesic acid and the like as a precursor, and assembling to obtain the metal-mixed coordination polymer material.
The purpose of the invention can be realized by the following technical scheme:
a dual-channel mixed metal crystalline catalyst is a three-dimensional mixed metal crystalline catalyst formed by assembling ferric salt and zinc salt serving as precursors and an organic bridging ligand, wherein the molar ratio of the ferric salt to the zinc salt is (1-2) to 1, and the molar ratio of the organic bridging ligand to the zinc salt is (5-10) to 1.
Further, the iron salt comprises Fe (NO)3)3·9H2O, the zinc salt comprises Zn (CCl)3COO)2·2H2O, the organic bridging ligand comprises H3BTC。
A method for preparing a dual-channel mixed-metal crystalline catalyst as described above, comprising the steps of:
(1) mixing Fe (NO)3)3·9H2O and Zn (CCl)3COO)2·2H2Mixing O, adding methanol, heating for reflux reaction, cooling to room temperature, filtering, washing with methanol to obtain mixed precursor, and recording as Fe2ZnO(CCl3COO)6(CH3OH)3；
(2) By reacting an organic bridging ligand H3The BTC and the mixed precursor are dispersed in the mixed solvent to prepare a precursor solution;
(3) and carrying out solvothermal reaction on the precursor solution, and then carrying out suction filtration, washing and drying to obtain the mixed metal crystalline catalyst.
Further, said Fe (NO)3)3·9H2O and Zn (CCl)3COO)2·2H2The molar ratio of O is (1-2) to 1.
Further, the reflux reaction time in the step (1) is 6-8 h.
Further, said H3BTC and Fe2ZnO(CCl3COO)6(CH3OH)3The molar ratio of (5-10) to (1).
Furthermore, the mixed solvent is N, N-dimethylformamide and N-propanol with the volume ratio of (10-25): 1.
Further, the temperature of the solvothermal reaction in the step (3) is 70-100 ℃, and the time is 48-120 h.
The application of the double-channel mixed metal crystalline catalyst is to catalyze the C-N coupling reaction.
Further, the catalyst is applied to catalyzing C-N coupling reaction of imine in one-pot preparation of the benzyl amine and the benzyl alcohol.
Compared with the prior art, the invention has the following advantages:
(1) by the step-by-step self-assembly, a double-channel metal-mixed porous coordination polymer material which is difficult to synthesize by a conventional one-pot method is successfully prepared, a new way is opened up for assembling a complex of a dissimilar metal later, a catalyst which is prepared in the application is mainly used for catalyzing C-N coupling reaction, the catalyst is only required to be simultaneously provided with two metal elements of Fe and Zn, if the one-pot method in the prior art is adopted, only one metal element of Fe or Zn is possibly arranged on a ligand, and the catalytic effect on the C-N coupling reaction is very weak, so that the problem can be avoided by step-by-step preparation, and the high-performance catalyst is prepared;
(2) the preparation method of the material is simple, the material structure is controllably assembled, the obtained double-channel mixed metal three-dimensional coordination polymer can catalyze C-N coupling reaction as a heterogeneous catalyst, and the material has the advantages of high catalysis efficiency, mild condition, wide substrate range, high repeated utilization rate and the like, can realize the controllable and ordered assembly of the material, has better selectivity and yield, and simultaneously avoids the problems of overlong synthesis period and large solvent consumption;
(3) the dual-channel heteronuclear mixed metal MOFs catalyst material constructed by the method can overcome the defects that the traditional catalyst is poor in stability, complicated in preparation steps, low in catalytic efficiency, complex in reaction structure and the like, meanwhile, the MOF1 catalyst has the breakthrough of high stability, high yield, short reaction time, high recycling performance and the like, and the application prospect of C-N coupling synthesis is greatly promoted;
(4) the invention can realize the controllable assembly of the porous coordination polymer material, the obtained crystalline material with the mixed metal structure has larger specific surface area and empty active coordination sites, especially has unique catalytic activity on C-N coupling reaction, the highest catalytic efficiency reaches 98 percent, the selectivity reaches 100 percent, and the catalyst can be recycled under the condition of hardly losing the framework integrity and the catalytic activity.
Drawings
FIG. 1 is a single crystal asymmetric unit structure diagram of the two-pass mixed metal crystalline catalyst MOF1 of example 1;
FIG. 2 is a three-core unit structure diagram of the two-pass mixed metal crystalline catalyst MOF1 in example 1;
FIG. 3 is a three-dimensional framework diagram of the two-pass mixed-metal crystalline catalyst MOF1 in example 1;
FIG. 4 is an X-ray energy spectrum of the two-pass mixed metal crystalline catalyst MOF1 in example 1;
FIG. 5 is an X-ray powder diffraction pattern of the two-pass mixed-metal crystalline catalyst MOF1 from example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
(1) According to Fe (NO)3)3·9H2O and Zn (CCl)3COO)2·2H2Weighing raw materials with the molar ratio of O to Fe (NO) of 2:13)3·9H2O (2.0mmol) and Zn (CCl)3COO)2·2H2O (1.0mmol), adding 40mL of methanol, ultrasonically mixing uniformly, transferring the reaction solution to an oil bath, heating for reflux reaction for 7h, cooling to room temperature, filtering, and washing with methanol to obtain a corresponding complex precursor with a molecular formula of Fe2ZnO(CCl3COO)6(CH3OH)3；
(2) According to H3BTC and Fe2ZnO(CCl3COO)6(CH3OH)3The molar ratio of the complex precursor is 10:1, and H is measured3BTC (0.1mmol) and Zn (CCl)3COO)2·2H2O complex precursor (0.01 mmol);
(3) h is to be3Mixing BTC and a complex precursor in 10mL of DMF and 0.5mL of n-propanol under ultrasonic treatment or stirring to prepare a precursor solution, and stirring for 30 minutes at room temperature;
(4) and transferring the precursor solution into a hydrothermal kettle with the volume ratio of 1/3, carrying out solvothermal reaction for 3 days at 70 ℃, and finally, carrying out suction filtration, washing and drying to obtain the mixed metal crystalline catalyst MOF 1.
Diffraction intensity data were collected on a Bruker APEX II diffractometer to obtain the single crystal structure of MOF1, as shown in figure 1, which is a diagram of the asymmetric unit structure of the crystal of example 1. As can be seen from FIG. 1, the material containsIn the presence of FeIIIAnd ZnIITwo metal centers, consistent with the X-ray spectra, are shown in fig. 4.
Wherein Zn isIIThe ion being saturated, hexacoordinated, being surrounded by four carboxyl oxygen atoms, one mu3-the O atom coordinates to a terminal coordinated n-propanol molecule. Fe in the structureIIIThe ions being randomly distributed, being bound by three carboxyl oxygen atoms and one mu3the-O atom coordinates to form a coordinatively unsaturated model, and the remaining two coordination sites thereof can participate in the organocatalytic oxidation reaction as coordinatively unsaturated sites.
Two Fe symmetrically relatedIIIIons and a ZnIIIon passing through quadruple of carboxyl groups and mu3the-O bridge constituting Fe2Zn(μ3-O)(COO)4Further linked by deprotonated trimesic acid ligands to form a three-dimensional framework of crystalline material.
As shown in fig. 3, two kinds of one-dimensional channels with different properties are formed in the crystallographic c direction, one is a hydrophobic channel a constructed by benzene ring carbon atoms, and the channel size is larger; the other is a hydrophilic pore passage B with pore walls constructed by carboxyl oxygen atoms, the pore passage size is smaller, and two pore passages with different properties are used as double channels to provide possibility for further catalytic reaction.
FIG. 5 is an X-ray powder diffraction pattern of the sample obtained in example 1, and it can be seen from FIG. 5 that the sample has high crystallinity and exhibits an ordered porous structure.
The mixed metal crystalline catalyst MOF1 prepared in example 1 was applied to the C-N coupling reaction of benzylamine with benzyl alcohol.
Before the catalytic reaction, the freshly prepared MOF1 catalyst was previously heat treated in an oven at 100 ℃ to give an activated catalyst.
In the C-N coupling reaction of benzylamine with benzyl alcohol, using KOH as the base, benzylamine (2mmol) and benzyl alcohol (4mmol) as the reaction substrates, pyrene (400. mu.L) as the internal standard was added, and 0.2 mol% of the crystalline catalyst MOF1 of example 1 was added in a 25mL round bottom flask.
The reaction mixture was reacted for 12 hours under heating stirring reflux on an oil bath, immediately after the reaction was completed, a sample was taken and the content of the product was measured by GC-MS of SHIMADZU-QP2010 type, and the conversion of the reaction was calculated to be 98%.
After the reaction is finished, the catalyst can be separated and washed through simple filtration, the next round of catalyst recycling experiment is carried out, and the specific reaction steps are as above. The catalyst can be recycled for more than 5 times, and the catalytic conversion efficiency is basically kept unchanged and still reaches more than 90 percent.
Under similar reaction conditions, the catalytic efficiency of the catalyst for catalyzing C-N coupling reaction containing different substituents is considered, and the reaction equation is represented by the following formula:
Figure BDA0002377597520000061
the experimental results are shown in table 1, the catalyst has extremely high catalytic efficiency and selectivity for the coupling reaction of benzyl alcohol and benzyl amine with different substituents, when the para-position is the substituent of an electron-withdrawing group, the catalytic efficiency is slightly reduced but still reaches over 86%, and the catalytic material has excellent catalytic performance for the reactions.
TABLE 1
R group Conversion rate Selectivity is
4-H 98％ 100％
4-OCH3 97％ 99％
4-CH3 95％ 99％
4-NO2 86％ 97％
4-Br 92％ 98％
4-CF3 88％ 96％
Example 2
(1) According to Fe (NO)3)3·9H2O and Zn (CCl)3COO)2·2H2Weighing raw material Fe (NO) with O molar ratio of 1:23)3·9H2O (1.0mmol) and Zn (CCl)3COO)2·2H2O (2.0mmol), adding 40mL of methanol, ultrasonically mixing uniformly, transferring the reaction solution to an oil bath, heating for reflux reaction for 7h, cooling to room temperature, filtering, and washing with methanol to obtain a corresponding complex precursor with a molecular formula of Fe2ZnO(CCl3COO)6(CH3OH)3；
(2) According to H3BTC and Fe2ZnO(CCl3COO)6(CH3OH)3H is weighed according to the molar ratio of 5:1 of the complex precursor3BTC (0.1mmol) and Zn (CCl)3COO)2·2H2O complex precursor (0.02 mmol);
(3) h is to be3Mixing BTC and a complex precursor in DMF (10mL) and n-propanol (0.5mL) under ultrasonic treatment or stirring to prepare a precursor solution, and stirring at room temperature for 30 minutes;
(4) and transferring the precursor solution into a hydrothermal kettle with the volume ratio of 1/3, carrying out solvothermal reaction for 4 days at 85 ℃, and finally, carrying out suction filtration, washing and drying to obtain the mixed metal crystalline catalyst MOF 1.
Example 3
(1) According to Fe (NO)3)3·9H2O and Zn (CCl)3COO)2·2H2Weighing raw material Fe (NO) with O molar ratio of 1:23)3·9H2O (1.0mmol) and Zn (CCl)3COO)2·2H2O (2.0mmol), adding 40mL of methanol, ultrasonically mixing uniformly, transferring the reaction solution to an oil bath, heating for reflux reaction for 7h, cooling to room temperature, filtering, and washing with methanol to obtain a corresponding complex precursor with a molecular formula of FeIII 2ZnIIO(CCl3COO)6(CH3OH)3；
(2) According to H3BTC and FeIII 2ZnIIO(CCl3COO)6(CH3OH)3The molar ratio of the complex precursor is 10:1, and H is measured3BTC H3BTC (0.1mmol) and Zn (CCl)3COO)2·2H2O complex precursor (0.01 mmol);
(3) h is to be3Mixing BTC and a complex precursor in DMF (10mL) and n-propanol (1mL) under ultrasonic treatment or stirring to prepare a precursor solution, and stirring at room temperature for 30 min;
(4) and transferring the precursor solution into a hydrothermal kettle with the volume ratio of 1/3, carrying out solvothermal reaction for 5 days at 100 ℃, and finally, carrying out suction filtration, washing and drying to obtain the mixed metal crystalline catalyst MOF 1.
Example 4
This example is substantially the same as example 1, except that in this example, Fe (NO) is used3)3·9H2O and Zn (CCl)3COO)2·2H2The molar ratio of O is 1:1.
Example 5
This example is substantially the same as example 1, except that in this example, Fe (NO) is used3)3·9H2O and Zn (CCl)3COO)2·2H2The molar ratio of O is 1: 1.5.
Example 6
This example is substantially the same as example 1, except that in this example, H3BTC and medium Fe2ZnO(CCl3COO)6(CH3OH)3The molar ratio of the precursors is 8: 1.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The double-channel mixed metal crystalline catalyst is characterized in that iron salt and zinc salt are used as precursors and are assembled with an organic bridging ligand to form the mixed metal crystalline catalyst with a three-dimensional structure, the molar ratio of the iron salt to the zinc salt is (1-2):1, and the molar ratio of the organic bridging ligand to the zinc salt is (5-10): 1.
2. The dual channel mixed metal crystalline catalyst as claimed in claim 1, wherein the iron salt comprises Fe (NO)3)3·9H2O, the zinc salt comprises Zn (CCl)3COO)2·2H2O, the organic bridging ligand comprises H3BTC。
3. A method for preparing a dual channel mixed metal crystalline catalyst as claimed in claim 1, comprising the steps of:
(1) mixing Fe (NO)3)3·9H2O and Zn (CCl)3COO)2·2H2Mixing O, adding methanol, heating for reflux reaction, cooling to room temperature, filtering, washing with methanol to obtain mixed precursor, and recording as Fe2ZnO(CCl3COO)6(CH3OH)3；
(2) By reacting an organic bridging ligand H3The BTC and the mixed precursor are dispersed in the mixed solvent to prepare a precursor solution;
(3) and carrying out solvothermal reaction on the precursor solution, and then carrying out suction filtration, washing and drying to obtain the mixed metal crystalline catalyst.
4. The method of claim 3, wherein the Fe (NO) is Fe3)3·9H2O and Zn (CCl)3COO)2·2H2The molar ratio of O is (1-2) to 1.
5. The method for preparing the dual-channel mixed-metal crystalline catalyst as claimed in claim 3, wherein the reflux reaction time in the step (1) is 6-8 h.
6. The method as claimed in claim 3, wherein the H is selected from the group consisting of3BTC and Fe2ZnO(CCl3COO)6(CH3OH)3The molar ratio of (5-10) to (1).
7. The method for preparing the dual-channel mixed-metal crystalline catalyst as claimed in claim 3, wherein the mixed solvent is N, N-dimethylformamide and N-propanol with a volume ratio of (10-25): 1.
8. The method for preparing the dual-channel mixed-metal crystalline catalyst as claimed in claim 3, wherein the temperature of the solvothermal reaction in the step (3) is 70-100 ℃ and the time is 48-120 h.
9. Use of a dual channel mixed metal crystalline catalyst as claimed in claim 1 for catalysing C-N coupling reactions.
10. The use of the dual-channel mixed-metal crystalline catalyst as claimed in claim 9, wherein the catalyst is used for catalyzing the C-N coupling reaction of imine in the one-pot preparation of phenylmethylamine and benzyl alcohol.
CN202010072237.6A 2020-01-21 2020-01-21 Double-channel mixed metal crystalline catalyst and preparation method and application thereof Pending CN111203274A (en)

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CN107774234A (en) * 2016-08-29 2018-03-09 中国石油化工股份有限公司 A kind of metal-organic framework materials and preparation method and application
CN109575296A (en) * 2017-09-28 2019-04-05 天津工业大学 A kind of transition metal Zn complex and Fe3+The photocatalysis performance of modified composite material
CN110124738A (en) * 2019-05-28 2019-08-16 上海应用技术大学 A kind of Fe-Zn bimetallic crystalline-state catalyst and its preparation method and application

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN107774234A (en) * 2016-08-29 2018-03-09 中国石油化工股份有限公司 A kind of metal-organic framework materials and preparation method and application
CN109575296A (en) * 2017-09-28 2019-04-05 天津工业大学 A kind of transition metal Zn complex and Fe3+The photocatalysis performance of modified composite material
CN110124738A (en) * 2019-05-28 2019-08-16 上海应用技术大学 A kind of Fe-Zn bimetallic crystalline-state catalyst and its preparation method and application

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Application publication date: 20200529