CN112920418A - Novel bromine-containing uncoordinated group-containing honeycomb two-dimensional metal organic polyhedral framework compound and synthesis method and application thereof - Google Patents
Novel bromine-containing uncoordinated group-containing honeycomb two-dimensional metal organic polyhedral framework compound and synthesis method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of synthesis of porous coordination polymers, and relates to a novel bromine-containing two-dimensional metal organic polyhedral framework compound which is a honeycomb-shaped compound containing no coordination groups and has a chemical formula as follows: c45.5H27.5Br2.5Cu3.75NO18.755- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid is taken as a ligand, and N, N-dimethylformamide and water are taken as a solventSynthesizing a honeycomb two-dimensional metal organic polyhedral framework compound by adopting a solvothermal method. The invention also relates to a synthesis method of the honeycomb two-dimensional metal organic polyhedral framework compound and application of the compound as carbon dioxide capture. The material of the invention shows high carbon dioxide adsorption selectivity and is expected to be applied to carbon dioxide capture in the flue gas of a thermal power plant.
Description
Technical Field
The invention belongs to the technical field of metal organic framework material synthesis, and particularly relates to a copper-based metal organic polyhedral framework material containing an uncoordinated bromine group based on a 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid ligand.
Background
In recent years, Metal-Organic Frameworks (MOFs) have attracted much attention for applications such as gas storage and separation, heterogeneous catalysis, chemical sensing, light collection, and water collection. Among the MOFs, metal organic polyhedrons having special inner voids and cage-based MOFs have attracted great attention in gas storage and separation. This is because the large voids contained in these metal organic framework compounds can act as traps to selectively adsorb gas molecules depending on their chemical and physical properties. To date, various cage-based MOFs composed of different metal clusters and organic ligands have been described, and these MOFs are typically three-dimensional networks connected by organic linkers. As one of the best known cages, a cuboctahedral nanocage consisting of 24 isophthalate moieties and 12 copper paddlewheel clusters is assembled into a three-dimensional MOF by hydrogen bonding of two separate moieties in the crystal through covalent bonds in an organic linker. In contrast, the low dimensional chain/layered structures composed of these nanocages are rare and their synthesis remains a challenging research topic.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a novel honeycomb-shaped two-dimensional metal organic polyhedral framework compound containing bromine-free uncoordinated groups.
The invention also aims to provide a synthesis method and application of the novel honeycomb two-dimensional metal organic polyhedral framework compound containing the bromine-free uncoordinated groups.
According to the invention, divalent copper ions are used as metal nodes, 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid is used as an organic ligand, N-dimethylformamide and water are used as solvents, and a bromine-containing uncoordinated group-containing honeycomb-shaped two-dimensional metal organic polyhedral framework compound is synthesized by a solvothermal method at a certain temperature.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a novel bromine-containing two-dimensional metal-organic polyhedral skeleton cellular compound with a chemical formula of C45.5H27.5Br2.5Cu3.75NO18.75The method comprises the steps of taking 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid as a ligand, taking N, N-dimethylformamide and water as a solvent, and enabling carboxylic acid groups in the ligand to be completely coordinated to form a binuclear paddled copper cluster with divalent copper ions, so as to construct a bromine-containing uncoordinated two-dimensional network structure, namely the bromine-containing uncoordinated group honeycomb two-dimensional metal organic polyhedral framework compound.
The compound is constructed by Cu (II) and 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid, the crystal structure of the compound belongs to a triclinic crystal system, a P-1 space group, and unit cell parameters are respectively as follows:
α is 85.996(1) °, β is 70.847(1) °, and γ is 71.275(1) °. The equatorial position of all cu (ii) atoms in the crystal structure is occupied by four oxygens from the ligand carboxyl groups, the axial position is the terminal water molecule or the dimethylformamide molecule. Every two adjacent Cu (II) atoms are connected together through four carboxylate groups to form [ Cu2(CO2)4]Paddle type Secondary Building Unit (SBU) (fig. 3 b). SBU general purpose deviceThe ligands are linked together to create a two-dimensional (2D) network. However, due to the disturbed symmetry, the ligand acts as a tetracarboxylate linker, and there are two configurations of organic ligands, each with 50% of the possibilities in the construction of the 2D network (fig. 3 a). From a topology simplification point of view, only 3 connected nodes form the topology, which makes the network hcb (fig. 3 f). Six paddle secondary building units SBUs and twelve ligand linkers were assembled into one elongated triangular gyromagnetic cage with an inner diameter of 1.2nm (fig. 3 d). These nanocages were located in the center of each honeycomb and were aligned in a face-sharing manner to form hcb two-dimensional mesh (fig. 3c, which is the two-dimensional metal-organic polyhedral framework compound of the present invention).
One of the carboxylate groups of the 5,50- (1, 2-acetylenediyl) bis (1, 3-phthalate) linker based on PCN-16(PCN stands for porous coordination grid, chem. commun.,2010,46,1329) was replaced with Br, eliminating the extension of the 2D network in the vertical direction, and pi-pi interactions between bromobenzene rings (fig. 3i) and Br-pi interactions between bromine atoms and dicarboxylate benzene rings (fig. 3h) such that each adjacent layer is connected in a 3D structure (the bromine is not coordinated to cause formation of an elongated triangular gyromagnetic cage, and the triangular gyromagnetic cages of adjacent layers are connected by pi-pi interaction forces between bromobenzene rings of ligands of adjacent layers and Br-pi interaction forces between bromine atoms of ligands of adjacent layers and dicarboxylate benzene rings, but the 3D structures formed by the force connections are unstable). After removal of the free solvent molecules, the calculation of the PLATON program indicated a pore volume ratio of 56.5%.
A novel synthesis method of a honeycomb two-dimensional metal organic polyhedral framework compound comprises the following steps:
(1) dissolving organic ligand 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid and copper nitrate trihydrate into N, N-dimethylformamide and water, adding a little concentrated nitric acid, and using an ultrasonic oscillator to assist complete dissolution;
(2) transferring the obtained solution to a reaction kettle with a polytetrafluoroethylene lining, sealing, carrying out constant-temperature solvothermal reaction at the temperature of 60-80 ℃ (preferably 65 ℃), wherein the reaction time is 2 days, and cooling to room temperature after the reaction is finished to obtain blue-green pyramid-shaped crystals;
(3) and washing the crystal with N, N-dimethylformamide and water, and drying to obtain the metal organic polyhedral framework compound.
Further, the preparation method of the ligand is as follows:
(1) dissolving 3, 5-dibromobenzoic acid methyl ester in tetrahydrofuran-triethylamine under the protection of nitrogen, adding palladium bis (triphenylphosphine) dichloride and cuprous iodide, stirring, adding 5-ethynyl isophthalic acid dimethyl ester, filtering the filtrate, and drying under reduced pressure to obtain a black solid; then drying the mixture after passing through a column to obtain 5- ((3-bromo-5- (methoxycarbonyl) phenyl) ethynyl) dimethyl isophthalate;
(2) dissolving the 5- ((3-bromo-5- (methoxycarbonyl) phenyl) ethynyl) isophthalic acid dimethyl ester in a methanol-water mixed solution, and adding lithium hydroxide to react to obtain a white solid of 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid.
Further, in the step (1), the molar ratio of the 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid to the copper nitrate trihydrate is 1: 2-5, preferably 1: 5.
further, in the above step (1), the amount ratio of 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid to N, N-dimethylformamide and water and concentrated nitric acid was 0.012 mmol: 2 ml: 0.04 to 1.8 ml, preferably 0.012 mmol: 2 ml: 0.06 ml.
A novel bromine-containing two-dimensional metal organic polyhedral skeleton compound containing no coordination groups is applied to carbon dioxide capture and natural gas purification in flue gas of a thermal power plant.
The beneficial effects of the invention are as follows:
the metal organic polyhedral framework compound material constructed by Cu (II) and 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid prepared by the invention has high carbon dioxide adsorption performance and can selectively separate carbon dioxide.
The preparation method of the metal organic polyhedral framework compound material constructed by Cu (II) and 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid is simple, and the compound has an application value in capturing carbon dioxide in flue gas of a thermal power plant.
Drawings
FIG. 1 is a schematic synthesis of 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid ligands of the present invention;
FIG. 2 is a schematic diagram of the synthesis of a bromine-containing uncoordinated group-containing honeycomb two-dimensional metal-organic polyhedral framework compound according to the present invention;
FIG. 3 is a schematic diagram of the three-dimensional structure of the bromine-containing uncoordinated group-containing honeycomb two-dimensional metal-organic polyhedral framework compound of the present invention: wherein, (a) is a ligand of two configurations; (b) is a dual-core wheel paddle copper cluster paddle type two-stage construction unit (SBU) [ Cu ]2(CO2)4](ii) a (c) Two-dimensional (2D) networks, i.e. the compounds of the invention; (d) is a slender triangular gyro nano cage; (e) a single layer mesh structure; (f) a crystal structure visible along the c-axis direction; (g) is a crystal structure visible along the direction of the b axis; (h) is the Br-pi interaction between a bromine atom and a benzene ring of dicarboxylic ester in the structure; (i) is the pi-pi interaction between bromobenzene rings in the structure;
FIG. 4 is an XRD pattern of a bromine uncoordinated group containing cellular two-dimensional metal-organic polyhedral framework compound of the present invention;
FIG. 5 is a graph showing the carbon dioxide adsorption profile of a bromine-containing uncoordinated group-containing honeycomb two-dimensional metal-organic polyhedral framework compound according to the present invention;
FIG. 6 is a diagram showing the selectivity of carbon dioxide adsorption/nitrogen adsorption/carbon dioxide adsorption/methane adsorption of the bromine-containing uncoordinated group-containing cellular two-dimensional metal-organic polyhedral framework compound of the present invention at 298K: (a) carbon dioxide adsorption/nitrogen selectivity profile at 298K; (b) carbon dioxide adsorption/methane selectivity profile at 298K.
Detailed Description
The technical solutions of the present invention are further described in detail by the following specific examples, but it should be noted that the following examples are only used for describing the content of the present invention and should not be construed as limiting the scope of the present invention.
Example 1:
1. a novel process for the preparation of a 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid ligand comprising the steps of:
(1) as shown in the attached FIG. 1, methyl 3, 5-dibromobenzoate (2.7g, 9.3mmol) was taken up in a three-necked flask, dissolved in tetrahydrofuran-triethylamine (160mL, 5:3, v/v) under nitrogen, added with bis (triphenylphosphine) palladium dichloride (652mg, 0.93mmol), cuprous iodide (354mg, 1.86mmol), stirred until clear, and added with dimethyl 5-ethynylisophthalate (4.3g,19.7 mmol). The reaction is carried out for 24h at 50 ℃, and the system is dark brown. Filtering, decompressing and draining the filtrate to obtain a black solid, adding a proper amount of dichloromethane for dissolving, washing with saturated salt for three times, spin-drying the dichloromethane, then passing through a column by using a mixed solvent of petroleum ether and ethyl acetate (20:1, v/v), volatilizing the solvent, and drying to obtain the 5- ((3-bromo-5- (methoxycarbonyl) phenyl) ethynyl) dimethyl isophthalate solid.
(2) Dimethyl 5- ((3-bromo-5- (methoxycarbonyl) phenyl) ethynyl) isophthalate (1g, 2.32mmol) was dissolved in methanol-water (40mL, 1:1, v/v) after which lithium hydroxide (0.29g, 1.2mmol) was added and the reaction stirred at 50 ℃ until clear. The reaction mixture was then concentrated and filtered to remove insoluble impurities, and the filtrate was acidified to pH 2 with concentrated hydrochloric acid to give a light brown flocculent precipitate. Standing, aging, filtering, washing with water until no chloride ion exists, and drying to obtain 0.85g of white solid of 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid.
2. A preparation method of a novel bromine-containing uncoordinated group honeycomb two-dimensional metal organic polyhedral framework compound comprises the following steps:
(1) as shown in figure 2, organic ligand 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid (28mg,0.012mmol) and copper nitrate trihydrate (87mg,0.06mmol) were dissolved in N, N-dimethylformamide-water (2mL, 5:1, v/v), 60 μ l of concentrated nitric acid was added, ultrasonic oscillation aided dissolution completed, and added to a teflon lined reactor;
(2) sealing, reacting at 65 deg.C for 2 days, and cooling to room temperature to obtain blue-green pyramid crystal with yield of about 55%;
(3) and washing the blue-green crystal with N, N-dimethylformamide, and drying to obtain the metal organic polyhedral framework material.
The chemical formula of the metal organic framework material is C45.50H27.50Br2.50Cu3.75NO18.75The method comprises the following steps of taking a 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid ligand as a ligand, and taking N, N-dimethylformamide and water as a solvent. Six paddle type secondary building units SBU in the crystal structure and twelve ligand joints are assembled into an elongated triangular gyroscope nano cage with the inner diameter of 1.2 nm. These nanocages were centered in each cell and aligned in a face-sharing manner to form hcb two-dimensional meshes. One of the carboxylate groups of the PCN-16 based 5,50- (1, 2-acetylenediyl) bis (1, 3-phthalate) linker is replaced by Br, eliminating the extension of the 2D network to the vertical, while pi-pi interactions between bromobenzene rings and Br-pi interactions between bromine atoms and dicarboxylate benzene rings, allow each adjacent layer to join into a 3D structure. After removal of the free solvent molecules, the calculation of the PLATON program indicated a porosity of 56.6%; the XRD pattern of FIG. 3 shows that the purity of the obtained sample of the metal-organic framework material is very high.
2. The prepared metal organic framework material is characterized:
(1) determination of Crystal Structure
Selecting a single crystal with proper size, complete appearance and no crack under a microscope, and collecting data on a single crystal diffractometer by using Mo-K alpha rays monochromatized by a graphite monochromator at the temperature of 296(2) K. All diffraction data were absorption corrected using the SADABS program; the unit cell parameters are determined by a least square method; data reduction and structure analysis was done using SAINT and SHELXTL programs. Firstly, determining the coordinates of all non-hydrogen atoms by using a difference function method and a least square method, obtaining the hydrogen atom position of a main body framework by using a theoretical hydrogenation method, and then refining the crystal structure by using the least square method. Some of the parameters for crystallographic diffraction point data collection and structure refinement are shown in table 1 below.
TABLE 1 Crystal parameter table of the metal organic framework
R1＝Σ||Fo|-|Fc||/|Fo|；wR2＝[Σw(ΣFo 2-Fc 2)2/Σw(Fo 2)2]1/2
(2) Study on adsorption and separation properties of carbon dioxide
The batch samples of the metal organic framework material were subjected to solvent replacement in anhydrous methanol for 72 hours, the anhydrous methanol was replaced every 8 hours, and then degassed at 70 ℃ for 10 hours to obtain fully activated samples. The activated samples were tested for carbon dioxide adsorption at temperatures of 273K and 298K as shown in FIG. 5. Under the conditions of 298K and 1bar, the carbon dioxide adsorption amount of the metal organic framework material is up to 37cm3 g-1The amount of carbon dioxide adsorbed in the two-dimensional metal-organic polyhedral skeleton compound is high. In contrast, its methane and nitrogen adsorption capacity appeared much weaker and the adsorption curve also appeared relatively flat (fig. 6). Therefore, in view of the great difference of the adsorption capacities of the three gases, the Ideal adsorbed adsorption selectivity model (IAST) is adopted to predict the selectivity of the metal organic framework material to carbon dioxide/methane and carbon dioxide/nitrogen according to the adsorption curves of the two gases. FIG. 6 shows that the metal-organic framework material is in CO2:N2The selectivity of the simulated mixed gas of the thermal power plant flue gas is 42, which is much higher than that of some typical porous coordination materials, such as UiO-66(Zr) -NH2(Selectivity: 23.6; adv. Sustainable Syst.,2017,1,1700092), Co-TPA (Selectivity: 28; J.Mater.Chem.A., 2017,5,5402) and HNUST-9 (Selectivity: 22.2; Inorg.Chem.Front,2020,7,1939), among others. Meanwhile, the attached figure 6 shows that the metal organic framework material is in CO2:CH4The selectivity of the natural gas simulated mixed gas is 7.6 which is higher than that of some typical porous coordination materials, such as HHU-5 (selectivity: 6.2; Inorg. chem.,2018,57,14018), [ Zn ] in a 50:50 natural gas simulated mixed gas9(btz)12(atdbc)3(DMF)](Selectivity: 5.2; Inorg. chem.,2019,58,391) andand HNUST-5 (Selectivity: 5.6; chem. Commun.,2016,52, 12988). Further illustrates that the metal organic framework material can also be used for separating CO from flue gas after industrial combustion2Useful materials of (4).
The honeycomb-shaped two-dimensional metal organic polyhedral framework compound containing the bromine-free coordination groups in the embodiment has high adsorption capacity and separation performance on carbon dioxide at normal temperature, and can be applied to carbon dioxide capture and natural gas purification in flue gas of a thermal power plant.
Claims (10)
1. A novel bromine-containing two-dimensional metal organic polyhedral skeleton compound containing no coordination groups is characterized in that: the chemical formula of the metal organic polyhedral framework compound is C45.5H27.5Br2.5Cu3.75NO18.75The method comprises the steps of taking 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid as a ligand, taking N, N-dimethylformamide and water as a solvent, and enabling carboxylic acid groups in the ligand to be completely coordinated to form a binuclear paddled copper cluster with divalent copper ions, so as to construct a bromine-containing uncoordinated two-dimensional network structure, namely the bromine-containing uncoordinated group honeycomb two-dimensional metal organic polyhedral framework compound.
2. The novel bromine uncoordinated group-containing cellular two-dimensional metal-organic polyhedral framework compound as recited in claim 1, wherein: the bromine is not coordinated to cause the formation of elongated triangular gyroscope nanocages, and the triangular gyroscope nanocages of adjacent layers are connected by the pi-pi interaction force between bromobenzene rings of the ligands of adjacent layers and the Br-pi interaction force between bromine atoms of the ligands of adjacent layers and benzene rings of dicarboxylic ester.
3. The novel bromine uncoordinated group-containing honeycomb two-dimensional metal-organic polyhedral framework compound as set forth in claim 1 or 2, wherein: the crystal of the metal organic framework belongs to a triclinic crystal system, a P-1 space group, and the unit cell parameters are respectively as follows:
α＝85.996(1)°，β＝70.847(1)°，γ＝71.275(1)°。
4. the method for synthesizing the novel bromine-containing uncoordinated group honeycomb two-dimensional metal organic polyhedral framework compound as claimed in claim 1, wherein: the method comprises the following steps:
1) dissolving ligand 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid and copper nitrate trihydrate into N, N-dimethylformamide, adding concentrated nitric acid, and performing ultrasonic oscillation to assist complete dissolution;
2) transferring and sealing the prepared solution, carrying out constant-temperature solvothermal reaction at 60-80 ℃, and cooling to room temperature after the reaction is finished to obtain a blue-green pyramid-shaped crystal;
3) and washing with N, N-dimethylformamide and water, and drying to obtain the bromine-containing two-dimensional metal organic polyhedral skeleton compound containing no coordination groups.
5. The method of synthesis of claim 4, wherein: the preparation method of the ligand comprises the following steps:
1) dissolving 3, 5-dibromobenzoic acid methyl ester in tetrahydrofuran-triethylamine under the protection of nitrogen, adding palladium bis (triphenylphosphine) dichloride and cuprous iodide, stirring, adding 5-ethynyl isophthalic acid dimethyl ester, filtering the filtrate, and drying under reduced pressure to obtain a black solid; then drying the mixture after passing through a column to obtain 5- ((3-bromo-5- (methoxycarbonyl) phenyl) ethynyl) dimethyl isophthalate;
2) dissolving the 5- ((3-bromo-5- (methoxycarbonyl) phenyl) ethynyl) isophthalic acid dimethyl ester in a methanol-water mixed solution, and adding lithium hydroxide to react to obtain a white solid of 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid.
6. The method of synthesis of claim 4 or 5, wherein: in the step 1), the molar ratio of 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid to copper nitrate trihydrate is 1:2 to 5.
7. The method of synthesis of claim 6, wherein: the molar ratio of the 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid to the copper nitrate trihydrate is 1: 5.
8. the method of synthesis of claim 4 or 5, wherein: in the step 1), the use amount ratio of 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid to N, N-dimethylformamide and concentrated nitric acid is 0.012 millimole: 2 ml: 0.04-1.8 ml.
9. The method of synthesis of claim 8, wherein: the dosage ratio of the 5- ((3-bromo-5-carboxyphenyl) ethynyl) isophthalic acid to the N, N-dimethylformamide and the concentrated nitric acid is 0.012 millimole: 2 ml: 0.06 ml.
10. A novel bromine-containing uncoordinated group-containing cellular two-dimensional metal organic polyhedral framework compound as defined in claim 1, which is used for capturing carbon dioxide in flue gas of a thermal power plant.
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