CN104164228A - Modification and preparation methods based on IRMOF-3 functional material - Google Patents

Abstract

The invention discloses a modification and preparation method based on IRMOF-3 functional materials, belongs to the technical field of material chemistry, and specifically relates to the preparation and performance characterization of a host-guest composite material. Using IRMOF-3 as raw material, it was pretreated with dichloromethane, and then the guest molecule ferrocene aldehyde (Fe-CHO) was put into the treated IRMOF-3 to make the host-guest undergo affinity addition reaction to generate sub- Amines, resulting in a new IRMOF-3FeCHO material. After pretreatment, it was found that the amber material immersed in ferrocenaldehyde turned black. The elemental, thermogravimetric, PXRD and fluorescence analysis of the material found that about 2.87 ferrocene molecules entered the IRMOF-3 porous material, and the structure of IRMOF-3 remained unchanged before and after the ferrocene entered, and the fluorescence The peak is blue shifted. The invention has low cost and simple and easy preparation process.

Description

A modification and preparation method based on IRMOF-3 functional material

technical field

The invention belongs to the technical field of material chemistry, and in particular relates to the preparation and performance characterization of a host-guest composite material.

Background technique

In recent years, metal-organic frameworks (MOFs) materials have attracted the attention of scientists from various countries because of their high thermal stability, high specific surface area and large porosity. MOFs materials synthesized by traditional methods (such as hydrothermal, diffusion, volatilization, etc.) are increasingly unable to meet people's stringent requirements for materials. It is the dream of scientists to combine guest molecules with special functions and macroporous materials to obtain multifunctional materials. The isoreticular metal-organic framework-3 (IRMOF-3) synthesized by Yaghi's is composed of metal zinc and 2-amino-1,4-phthalic acid in N,N'-dimethylformamide. The hole diameter is 9.7 functional materials. The amine group in the IRMOF-3 structure has no coordination, and because of its high porosity, it has become a carrier for scientists to prepare multifunctional materials.

In 2000, Kimoon Kim et al. reported the first modification of the homochiral MOF material POST-1, by introducing methyl iodide and hexyl iodide to coordinate with the uncoordinated pyridyl group in POST-1, thus achieving Enantioselection on metal complexes. Inspired by this idea, Zhenqiang Wang and Seth M. Cohen carried out a series of modifications to IRMOR-3, thus obtaining new MOFs materials and realizing the transformation from single crystal to single crystal. Because the amine group in the IRMOF-3 structure is not coordinated, Seth M. Cohen's research group introduced a new group through an acylation reaction on the amine group to obtain a new structure. In 2007, Seth M. Cohen reported two methods to modify IRMOR-3. The first is to directly introduce acetic anhydride to acylate it with the amine group, and the second is to introduce crotonic anhydride first, and then introduce bromine , through a series of performance tests, the MOF material was successfully modified. In 2008, Seth M. Cohen's research group modified IRMOR-3 with 10 kinds of branched chain alkyl anhydrides (O(CO(CH ₂ ) _n CH ₃ ) ₂ (n=1to18), and successfully obtained the alkyl chain gradually New MOFs materials with elongated high thermal stability and special properties have opened up a new way for the synthesis of new materials. In 2009, Seth M. Cohen's research group introduced 12 kinds of cyclic anhydrides into IRMOF-3, through acyl The carboxyl-containing, chiral new MOFs were obtained respectively. What's more worth mentioning is that they simultaneously introduced two kinds of anhydrides into the structure of IRMOF-3.

Contents of the invention

Inspired by the above-mentioned materials, the present invention introduces ferrocene aldehyde into the IRMOR-3 structure, causes the aldehyde group and the amine group to undergo nucleophilic addition to generate an imine, and obtains a new IRMOF-3FeCHO structure. The present invention aims to provide a The reaction condition is mild, the preparation process is simple, the cost is low, and at the same time, the method of combining the host and the guest can be well characterized.

The technical scheme adopted in the present invention comprises the following steps:

(1) Soak the prepared IRMOF-3 functional material in an appropriate amount of dichloromethane for three days, and change the dichloromethane once a day during these three days to ensure that the dichloromethane and the solvent in the material are fully exchanged ;

(2) Put 1-10 mg of ferrocene aldehyde (FeCHO) into 1-10 mg of IRMOF-3 fully soaked in dichloromethane in a 10ml dichloromethane beaker solution, and let it stand quietly for 7 days;

(3) After 7 days, the above beaker was put into a vacuum drying oven and dried overnight under reduced pressure to remove the guest molecules attached to the surface. It was found that: IRMOF-3 changed from amber to black.

(4) Elemental analysis and thermogravimetry, fluorescence, and PXRD performance characterization of the above materials were found:

Elemental analysis of IRMOF-3: C.35.42, H.1.85, N.5.17, O.25.58;

Element analysis of IRMOF-3FeCHO: C.26.55, H.1.25, N.2.94, O.17.80

About 2.87 molecules of ferrocenaldehyde enter into the porous material of IRMOF-3.

Compared with the prior art, the present invention has the advantages of finding a new method for synthesizing MOFs, the pretreatment solvent dichloromethane selected for synthesis has no harm to human health, the treatment conditions are mild, the characterization method is simple, and it is easy to operate. The test equipment is simple.

Description of drawings

Figure 1 shows the TGA and PXRD performance characterization of IRMOF-3 and IRMOF-3FeCHO.

Figure 2 shows the fluorescence performance characterization of IRMOF-3 and IRMOF-3FeCHO.

Detailed ways

Below in conjunction with embodiment the present invention is described in further detail.

Divide the prepared IRMOF-3 functional material into several parts with an amount of 9mg-15mg, pretreat it with 5-10ml of dichloromethane for 3-7 days, and then mix 1-10mg of the guest molecule ferrocene aldehyde with the treated The raw materials were put into 5-10ml of dichloromethane for 1-10 days, and the obtained materials were dried under reduced pressure for 1-2 days to remove the remaining guest molecules on the surface of the materials. It was observed in the electron microscope that IRMOF-3 was transformed from the original Amber turns black. Elemental analysis, thermogravimetric analysis, fluorescence analysis, and X-ray powder diffraction (PXRD) analysis and characterization of the material found that about 2.87 ferrocenaldehyde molecules entered the IRMOF-3 porous material.

Claims (1)

1. modification and the preparation method based on isoreticular metal-organic framework (IRMOF-3) functional materials, is characterized in that comprising the following steps and method:

(1) the IRMOF-3 functional materials of preparation is immersed in appropriate methylene dichloride to three days, in these three days, all will change methylene dichloride every day one time, to guarantee that the solvent in methylene dichloride and material exchanges fully;

(2) 1-10mg ferrocene aldehyde is put into the 10ml methylene dichloride beaker solution of the IRMOF-3 that 1-10mg fully soaks with methylene dichloride, silently placed 7 days;

After (3) 7 days, above-mentioned beaker being put into vacuum drying oven drying under reduced pressure a whole night finds to remove after being attached to the guest molecule showing: IRMOF-3 is from the original amber black that becomes;

(4) above-mentioned materials is carried out to ultimate analysis and thermogravimetric, fluorescence, PXRD performance characterization is found:

The ultimate analysis of IRMOF-3: C.35.42, H.1.85, N.5.17, O.25.58

The ultimate analysis of IRMOF-3@FeCHO: C.26.55, H.1.25, N.2.94, O.17.80

Approximately there are 2.87 ferrocene aldehyde molecules to enter in IRMOF-3 porous material, and before and after ferrocene aldehyde enters,

The structure of IRMOF-3 remains unchanged, fluorescence peak generation blue shift.