CN112376080B - Two-dimensional conductive metal organic framework material based on tricyclic quinazoline and preparation method thereof - Google Patents
Two-dimensional conductive metal organic framework material based on tricyclic quinazoline and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a tricyclic quinazoline-based two-dimensional conductive metal organic framework material and a preparation method thereof, wherein the preparation method comprises the following steps: 2,3,7,8,12, 13-hexahydroxy tricyclic quinazoline and a divalent metal ion M2+Dissolving in a solvent, and reacting to obtain a tricyclic quinazoline-based two-dimensional conductive metal organic framework material M3(HHTQ)2(M ═ Cu, Ni, Co, Mn, Fe), having the structure shown in formula II:
Description
Technical Field
The invention belongs to the field of metal organic framework materials and electrochemical energy conversion, and particularly relates to a tricyclic quinazoline-based two-dimensional conductive metal organic framework material M3(HHTQ)2(M ═ Cu, Ni, Co, Mn, Fe) and its preparation method and application.
Background
Two-dimensional conductive metal-organic frameworks (2D c-MOFs) are formed by a transition metal node (M ═ Cu, Co, Ni and the like) and an organic linker with multi-vertex ortho-substituted functional groups to form MX (MX)4The (X ═ O, NH, S and Se) plane is geometrically coordinated and connected with each other to construct a two-dimensional material. 2D c-MOFs usually have many attractive properties such as expanded pi-conjugated layers, regular and ordered channel structures, inherent porosity, and good electrical conductivity. The abundant physical and chemical properties of 2D c-MOFs enable the MOFs to have great application potential in the fields of gas adsorption, sensing, energy storage and conversion and the like.
Carbon dioxide, as a product of transitional industrial activities, is one of the booms of the greenhouse effect and many natural disasters. The development of new technologies to store and utilize carbon dioxide is a pressing pursuit. Electrocatalytic reduction of carbon dioxide to produce useful chemicals is an effective strategy to achieve carbon recycling and avoid environmental pollution. Many heterogeneous catalysts, such as metals, metal oxides, graphene-based materials, and the like, are often used as carbon dioxide electrocatalysts, often with excellent performance. From the economic principle, the transition metal is considered to be an effective and economical carbon dioxide electro-reduction catalyst. In particular, Cu-based catalysts can convert carbon dioxide to valuable chemicals such as methanol, ethanol, methane, ethane, etc., but the high overpotential limits their wide-range applications. Secondly, inhibiting the agglomeration of metal clusters and controlling the particle size of the metal are still a problem to be solved. Based on this, it has become a new challenge to develop a carbon dioxide electro-reduction catalyst capable of uniformly dispersing transition metal ions and having high reactivity.
In 2D c-MOFs, a regular and stable dispersion of high content of metal centers in the framework can provide dense catalytically active sites. Second, the porosity and open channels of 2D c-MOFs provide sufficient space for electrolyte ions. In addition, the inherent conductivity of 2D c-MOFs enables rapid transfer of electrons to the active sites, thereby increasing current density. Therefore, it is a major goal to prepare electrocatalyst materials based on 2D c-MOFs with high activity. At present, how to design and construct a two-dimensional conductive metal organic framework material with high catalytic activity still remains a great challenge.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a two-dimensional conductive metal organic framework material based on tricyclic quinazoline.
The second purpose of the invention is to provide a preparation method of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material.
The third purpose of the invention is to provide the application of the two-dimensional conductive metal organic framework material based on the tricyclic quinazoline.
The technical scheme of the invention is summarized as follows:
the tricyclic quinazoline-based two-dimensional conductive metal organic framework material has a structure shown in a formula II:
wherein M is Cu, Ni, Co, Mn or Fe.
The preparation method of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material comprises the following steps:
2,3,7,8,12, 13-hexahydroxy tricyclic quinazoline I and a divalent metal ion M2+Dissolving in solvent, reacting to obtain a tricyclic quinazoline-based two-dimensional catheterAn electro-metal-organic framework material II,
the reaction formula is as follows:
wherein M is Cu, Ni, Co, Mn or Fe;
two-dimensional conductive metal organic framework material II, M for short, based on tricyclic quinazoline3(HHTQ)2(M ═ Cu, Ni, Co, Mn, or Fe)
The solvent is water, N-dimethylformamide aqueous solution with volume concentration less than or equal to 25% or N-methylpyrrolidone aqueous solution with volume concentration less than or equal to 25%.
The application of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material in preparing the carbon dioxide electro-reduction catalyst is provided.
The invention has the advantages that:
the use of the invention has C3Planar coordination is carried out on symmetrical 2,3,7,8,12, 13-hexahydroxy tricyclic quinazoline ligand and transition metal ions to obtain a tricyclic quinazoline-based two-dimensional conductive metal organic framework material (M)3(HHTQ)2And M is Cu, Ni, Co, Mn or Fe), the material of the invention has simple synthesis steps and mild required conditions. The obtained two-dimensional lamellar structure with honeycomb-shaped pore channels has the advantages of high conductivity, high crystallinity, high stability and the like.
The tricyclic quinazoline-based two-dimensional conductive metal organic framework material obtained by the method is used as a carbon dioxide electro-reduction catalyst for electrochemically reducing carbon dioxide to directionally generate a liquid phase product methanol, and has high current density, high Faraday efficiency and good stability.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of a tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 prepared in example 1.
FIG. 2 is an infrared spectrum of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 and ligand I prepared in example 1.
FIG. 3 is a scanning electron micrograph of the tricyclic quinazoline-based two-dimensional conductive metal-organic framework material II-1 prepared in example 1.
FIG. 4 is a high-resolution TEM image of the tricyclic quinazoline-based two-dimensional conductive metal-organic framework material II-1 prepared in example 1. Fig. 4a is a high-resolution transmission electron micrograph and a structural model of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 prepared in example 1, fig. 4b is a transmission electron micrograph of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 prepared in example 1, and fig. 4c is a selected electron diffraction pattern of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 prepared in example 1.
FIG. 5 is a temperature swing conductivity curve of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 prepared in example 1.
FIG. 6 is a powder X-ray diffraction pattern of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-2 prepared in example 2.
FIG. 7 is an infrared spectrum of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-2 and ligand I prepared in example 2.
FIG. 8 is a scanning electron micrograph of the tricyclic quinazoline-based two-dimensional conductive metal-organic framework material II-2 prepared in example 2.
FIG. 9 is a temperature swing conductivity curve of the tricyclic quinazoline based two-dimensional conductive metal organic framework material II-2 prepared in example 2.
FIG. 10 is a nuclear magnetic diagram of a liquid-phase product of electrocatalytic carbon dioxide of the tricyclic quinazoline-based two-dimensional conductive metal-organic framework material II-1 prepared in example 1.
FIG. 11 is a graph of the change of current with time at a potential of-2.0V (vs SCE) for electrocatalytic carbon dioxide of the tricyclic quinazoline-based two-dimensional conductive metal-organic framework material II-1 prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
Preparation of 2,3,7,8,12, 13-hexahydroxy tricyclic quinazoline:
prepared according to the synthetic method described in Sandeep Kumar, et al, J.org.Chem.1993,58, 3821-S3827.
Example 1
Two-dimensional conductive metal organic framework material II-1 (Cu) based on tricyclic quinazoline3(HHTQ)2) The preparation method comprises the following steps:
33.28 mg of 2,3,7,8,12, 13-hexahydroxy tricyclic quinazoline I and 12 mg of copper nitrate trihydrate were dissolved in 8 ml of 25% by volume aqueous N, N-dimethylformamide, subjected to ultrasonic treatment for 10 minutes, reacted at 85 ℃ for 72 hours, cooled to room temperature, and the reaction solution was centrifuged at 10000 rpm for 3 minutes to obtain a solid, which was washed three times with deionized water and acetone, respectively. Vacuum drying at room temperature for one day to obtain black powder, i.e. two-dimensional conductive metal organic framework material II-1 based on tricyclic quinazoline, i.e. Cu3(HHTQ)2；
The reaction formula is as follows:
see fig. 1, 2,3, 4 and 5.
FIG. 1 demonstrates that the framework material II-1 of this example has good crystallinity and phase purity.
FIG. 2 is an infrared spectrum of a two-dimensional conductive metal organic framework material II-1 based on tricyclic quinazoline prepared in example 1, wherein a vibration peak of hydroxyl group substantially disappears in the spectrum of the complex, thus proving successful coordination between ligand and metal ion.
FIG. 3 demonstrates that complex II-1 prepared in example 1 is rod-shaped crystallites.
Fig. 4 demonstrates that the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 is an AA-stacked two-dimensional lamellar structure with honeycomb-like hexagonal pores. Regular hexagonal pore canals can be seen in the high-resolution transmission electron microscope picture, the size of the regular hexagonal pore canals is consistent with the size of the simulated pore canals, and the regular hexagonal pore canals are basically free of defects.
FIG. 5 is a temperature swing conductivity curve of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 prepared in example 1 at different temperatures (273K-318K), which demonstrates that the conductivity of the framework material prepared in this example is in positive correlation with the ambient temperature.
Experiments prove that cobalt acetate tetrahydrate, manganese acetate tetrahydrate and ferrous chloride tetrahydrate are used for replacing copper nitrate trihydrate in the embodiment, and other materials are the same as the embodiment, so that different tricyclic quinazoline-based two-dimensional conductive metal organic framework materials are obtained.
Co3(HHTQ)2、Mn3(HHTQ)2、Fe3(HHTQ)2Characterization and Properties of Cu prepared in example 13(HHTQ)2Similarly.
Experiments prove that, by replacing the 25% by volume aqueous solution of N, N-dimethylformamide in the embodiment with water and an aqueous solution of N, N-dimethylformamide with a volume concentration of less than 25%, such as 1%, 5% or 10%, the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 can be prepared in the same manner as in the embodiment.
Experiments prove that the tricyclic quinazoline based two-dimensional conductive metal organic framework material II-1 can be prepared by replacing the 25% volume concentration N, N-dimethylformamide aqueous solution in the embodiment with the N-methylpyrrolidone aqueous solution with the volume concentration of less than or equal to 25%, such as 1%, 5%, 10% and 25%.
Example 2
Two-dimensional conductive metal organic framework material II-2 (Ni) based on tricyclic quinazoline3(HHTQ)2) The preparation method comprises the following steps:
dissolving 12.48 mg of 2,3,7,8,12, 13-hexahydroxy tricyclic quinazoline I and 22.5 mg of nickel acetate tetrahydrate in 4 ml of 25% N, N-dimethylformamide aqueous solution by volume concentration, performing ultrasonic treatment for 10 minutes, reacting for 72 hours at 85 ℃, cooling to room temperature, and centrifuging the reaction solution at 10000 revolutions per minute for 3 minutes to obtain the compoundThe solid of (a) was washed three times each with deionized water and acetone. Vacuum drying at room temperature for one day to obtain black powder, i.e. two-dimensional conductive metal organic framework material II-2 based on tricyclic quinazoline, i.e. Ni3(HHTQ)2；
The phase, purity, morphology, conductivity and other characteristics of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-2 prepared in example 2 are shown in FIGS. 6-9.
Example 3
The preparation method of the electrocatalyst of the two-dimensional conductive metal organic framework material based on the tricyclic quinazoline and the test of the electrochemical catalytic reduction of carbon dioxide comprise the following steps:
10 mg of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material II-1 powder prepared in example 1 and 3 mg of acetylene black were put in an agate mortar and uniformly ground, and 1 ml of an electrode solution (H) was added2O: isopropyl alcohol: 5 wt% Nafion (perfluorosulfonic acid polytetrafluoroethylene copolymer 5 wt% dispersion (H)2O and isopropanol mixed solution)) ═ 8: 2: 0.05), sampling 0.1 ml after ultrasonic homogenization and dripping and coating on 1 x 1cm2The electrochemical test was performed on carbon paper (not hydrophilic).
The test results are shown in fig. 10 and 11 as characterization data of the electrocatalytic reduction carbon dioxide performance of the tricyclic quinazoline-based two-dimensional conductive metal-organic framework material prepared in example 1. Cu prepared in example 1 under mild conditions3(HHTQ)2Can be used as a catalyst for effectively electro-reducing carbon dioxide to methanol and Cu3(HHTQ)2Shows higher current density, better selectivity and good stability. The results show that the electrocatalytic activity of the catalyst can be effectively adjusted through the change of the functional organic connector and the coordination metal node.
Experiments prove that Ni3(HHTQ)2、Co3(HHTQ)2、Mn3(HHTQ)2、Fe3(HHTQ)2The catalyst shows different electrocatalytic activities and can be used for electrically reducing carbon dioxide to generate methanol.
The above embodiments are illustrative of the embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention are included in the scope of the present invention.
Claims (4)
1. A two-dimensional conductive metal organic framework material based on tricyclic quinazoline is characterized by having a structure shown in formula (II):
wherein M is Cu.
2. The preparation method of the tricyclic quinazoline-based two-dimensional conductive metal organic framework material, according to claim 1, is characterized by comprising the following steps:
2,3,7,8,12, 13-hexahydroxy tricyclic quinazoline (I) and a divalent metal ion M2+Dissolving in a solvent, and reacting to obtain the tricyclic quinazoline-based two-dimensional conductive metal organic framework material (II).
The reaction formula is as follows:
wherein M is Cu.
3. The method according to claim 2, wherein the solvent is water, an aqueous solution of N, N-dimethylformamide having a volume concentration of 25% or less, or an aqueous solution of N-methylpyrrolidone having a volume concentration of 25% or less.
4. The use of a tricyclic quinazoline-based two-dimensional conducting metal organic framework material according to claim 1 for the preparation of carbon dioxide electro-reduction catalysts.
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