阅读说明：本技术 一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料及其制备方法 (Three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine and preparation method thereof ) 是由 李崧 王宣军 秦向东 彭梦琪 于 2019-11-20 设计创作，主要内容包括：本发明属于金属-有机骨架晶体材料技术领域,具体涉及一种基于延胡索酸及4,4’-联吡啶的三维金属-有机骨架晶体材料及其制备方法。是将延胡索酸、4,4’-联吡啶、硝酸锌、水与乙醇、甲醇或丙酮置于具聚四氟乙烯内衬的高压反应釜中,用NaOH调节pH为9,超声混匀,保持120℃反应三天,自然冷却到室温。经过过滤、洗涤后得到无色块状晶体。本发明是一种新型具有规则孔道结构的三维金属-有机骨架晶体材料,具有较高的比表面积、孔容和良好的热稳定性,可以有效提高甲烷的吸附和存储量。该材料在药物合成、气体存储、捕集、分离,药物输送,光、电、磁,选择性催化,分子识别以及手性拆分等诸多领域都具有应用价值。(The invention belongs to the technical field of metal-organic framework crystal materials, and particularly relates to a three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridyl and a preparation method thereof. Fumaric acid, 4' -bipyridine, zinc nitrate, water, ethanol, methanol or acetone are placed in a high-pressure reaction kettle with a polytetrafluoroethylene lining, pH is adjusted to 9 by NaOH, the mixture is ultrasonically mixed, the mixture is kept at 120 ℃ for reaction for three days, and the mixture is naturally cooled to room temperature. Filtering and washing to obtain colorless blocky crystals. The invention is a novel three-dimensional metal-organic framework crystal material with a regular pore channel structure, has higher specific surface area, pore volume and good thermal stability, and can effectively improve the adsorption and storage capacity of methane. The material has application value in a plurality of fields such as drug synthesis, gas storage, trapping, separation, drug delivery, light, electricity, magnetism, selective catalysis, molecular recognition, chiral resolution and the like.)

1. A three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is characterized in that: the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4 '-bipyridine uses fumaric acid as a ligand A, 4' -bipyridine as a ligand B and is coordinated with metal zinc to form a basic structural unit of the metal-organic framework crystal material; the basic structure unit structure of the metal-organic framework crystal material comprises two divalent zinc ions, four fumaric acid ligands and two 4,4' -bipyridyl ligands; wherein, two zinc ions are both in a six-coordination form, four oxygen atoms and one nitrogen atom which are respectively coordinated with each zinc ion are respectively from four monodentate carboxyl oxygen atoms provided by four fumaric acid ligands and a heterocyclic nitrogen atom provided by a 4,4' -bipyridine ligand, and a coordination bond is formed by direct coordination of two zinc ions; two 4,4' -bipyridyl ligands are mutually vertical and are coordinated and extended with zinc ions along an ab plane, four fumaric acid ligands are coordinated with the zinc ions and are extended towards four directions, and finally, a three-dimensional metal-organic framework material crystal structure with a regular pore channel structure along the c-axis direction is formed, and the chemical molecular formula is as follows: c₁₈H₁₃N₂O_8.50Zn₂Belonging to monoclinic crystal (monoclinic), the space group is: c12/m 1(12) and unit cell parameters of：a=13.4229(11) Å，b= 11.4760(9) Å，c=14.1021(12) Å，α=90°，β= 105.938 (3)°，γ= 90°, V = 2088.8 Å3, Z =4。

2. The crystalline material of three-dimensional metal-organic framework based on fumaric acid and 4,4' -bipyridine according to claim 1, characterized in that: the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4 '-bipyridine is formed by combining fumaric acid ligands, 4' -bipyridine ligands and metal zinc ions according to the molar ratio of 2:2:1, and the specific surface area of the three-dimensional network structure Langmuir is 1025m²Per g, total pore volume 0.389cm³/g。

3. The method for preparing the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine according to claim 1, characterized by comprising the following steps:

(1) adding fumaric acid ligand, 4' -bipyridyl ligand, zinc nitrate and organic solvent in a molar ratio of 0.5:0.5: 1-4: 4:1 into a high-pressure reaction kettle;

(2) placing the high-pressure reaction kettle on an ultrasonic device, and ultrasonically mixing for 1-4 hours at room temperature;

(3) and after stirring is stopped, placing the high-pressure reaction kettle in an oven at the temperature of 40-120 ℃ for 10-40 hours, taking out, cooling to room temperature, and separating out massive colorless crystals, namely the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridyl.

4. The method for preparing the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine according to claim 3, wherein the method comprises the following steps: the organic solvent in the step (1) is selected from one or more of methanol, ethanol, isopropanol, ethyl acetate, acetone and acetonitrile.

5. The method for preparing the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine according to claim 3, wherein the method comprises the following steps: the reaction temperature in the step (1) is 40-120 ℃.

6. The crystalline material of three-dimensional metal-organic framework based on fumaric acid and 4,4' -bipyridine according to claim 1, characterized in that: the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to drug synthesis, gas storage, trapping and separation.

7. The crystalline material of three-dimensional metal-organic framework based on fumaric acid and 4,4' -bipyridine according to claim 1, characterized in that: the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to drug delivery.

8. The crystalline material of three-dimensional metal-organic framework based on fumaric acid and 4,4' -bipyridine according to claim 1, characterized in that: the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to the fields of light, electricity and magnetism.

9. The crystalline material of three-dimensional metal-organic framework based on fumaric acid and 4,4' -bipyridine according to claim 1, characterized in that: the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to the fields of selective catalysis, molecular recognition and chiral resolution.

Technical Field

The invention belongs to the technical field of metal-organic framework crystal materials, and particularly relates to a three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridyl and a preparation method thereof.

Background

The metal-organic skeleton crystal material belongs to one kind of supermolecular compound and is the product of the combination of crystal engineering theory and supermolecular chemistry. It has two advantages of inorganic and organic, and the change of organic ligand can make the molecular sieve structure implement diversified structure and adjustable pore channel, so that it can implement directional design. Research on novel molecular functional materials spans a plurality of fields of crystal engineering, material chemistry, topology, inorganic chemistry, organic chemistry, supramolecular chemistry, coordination chemistry, physicochemical, and the like. The material has a crystalline structure with zeolite-like molecular sieve-like pore channel rules, also has a higher specific surface area than that of the traditional porous material, and additionally contains organic components, so that the structure of the material has the characteristics of cuttability, designability, pore channel size adjustment, functional pore channel surface and the like, and the material is excellent in various fields of host-guest chemistry, drug synthesis, gas storage, trapping, separation, drug delivery, optical, electric and magnetic departments, selective catalysis, molecular recognition, chiral resolution and the like. In recent years, metal-organic framework crystalline materials have become one of the hot spots for the research of new functionalized materials. Recently, some metal-organic framework crystalline materials have been successfully commercialized.

Fumaric acid, corynoleic acid or lichenic acid can be used as acidity regulator, acidifying agent, antioxidant auxiliary agent, pickling promoter and perfume, and has antibacterial and antifungal effects. Medical applications are in the treatment of severe psoriasis and may also help prevent multiple sclerosis and the like.

4,4' -bipyridine is a common intermediate for medicine and organic synthesis, and can be used for determining iron content and liquid crystal materials. The zinc metal has good photoelectric and electromagnetic properties and the ability of promoting the growth and development of human body and enhancing immunity.

In view of the above, the inventors of the present invention specifically provide a three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine and a preparation method thereof, which not only retains chemical and pharmacological properties of each ligand, but also forms a three-dimensional metal-organic framework crystal material structure with a regular pore structure, and has application values in various fields such as drug synthesis, gas storage, trapping, separation, drug delivery, optical, electrical, magnetic, selective catalysis, molecular recognition and chiral resolution.

Disclosure of Invention

In order to overcome the problems in the background art, the invention provides a three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine and a preparation method thereof, which not only retains the chemical and pharmacological properties of each ligand, but also forms a three-dimensional metal-organic framework crystal material structure with a regular pore channel structure, and has application value in various fields of drug synthesis, gas storage, trapping, separation, drug delivery, light, electricity, magnetism, selective catalysis, molecular recognition, chiral resolution and the like.

In order to realize the purpose, the invention is realized by the following technical scheme:

the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4 '-bipyridine uses fumaric acid as a ligand A, 4' -bipyridine as a ligand B and is coordinated with metal zinc to form a basic structural unit of the metal-organic framework crystal material; the basic structure unit structure of the metal-organic framework crystal material comprises two divalent zinc ions, four fumaric acid ligands and two 4,4' -bipyridyl ligands; wherein, two zinc ions are both in a six-coordination form, four oxygen atoms and one nitrogen atom which are respectively coordinated with each zinc ion are respectively from four monodentate carboxyl oxygen atoms provided by four fumaric acid ligands and a heterocyclic nitrogen atom provided by a 4,4' -bipyridine ligand, and a coordination bond is formed by direct coordination of two zinc ions; two 4,4' -bipyridyl ligands are mutually vertical and are coordinated and extended with zinc ions along an ab plane, four fumaric acid ligands are coordinated with the zinc ions and are extended towards four directions, and finally, a three-dimensional metal-organic framework material crystal structure with a regular pore channel structure along the c-axis direction is formed, and the chemical molecular formula is as follows: c₁₈H₁₃N₂O_8.50Zn₂Belonging to monoclinic crystal (monoclinic), the space group is: c12/m 1(12), unit cell parameters are as follows:

α＝90°，β＝105.938(3)°，γ＝90°,

and Z is 4. The metal-organic framework crystal material is a three-dimensional regular pore system microporous molecular sieve with highly ordered pore structure and 0.38-3.6 nm of pore diameter, the specific surface area of Langmuir is 1025m < 2 >/g, and the total pore volume is 0.389cm < 3 >/g. Thereby showing excellent molecular diffusion and adsorption performance, large adsorption capacity and high methane adsorption and storage capacity under the conditions of temperature change and pressure change.

Furthermore, the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4 '-bipyridyl is formed by combining fumaric acid ligand, 4' -bipyridyl ligand and metal zinc ions according to the molar ratio of 2:2: 1. The specific surface area of the three-dimensional network structure Langmuir is 1025m2/g, and the total pore volume is 0.389cm 3/g.

The preparation method of the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is characterized by comprising the following steps:

(1) adding fumaric acid ligand, 4' -bipyridyl ligand, zinc nitrate and organic solvent in a molar ratio of 0.5:0.5: 1-4: 4:1 into a high-pressure reaction kettle;

(2) placing the high-pressure reaction kettle on an ultrasonic device, and ultrasonically mixing for 1-4 hours at room temperature;

(3) after stirring is stopped, the high-pressure reaction kettle is placed in an oven at the temperature of 40-120 ℃ for 10-40 hours and then taken out, and after the temperature is reduced to room temperature, massive colorless crystals are separated out, namely the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridyl

Further, the organic solvent in step (1) is selected from one or more of methanol, ethanol, isopropanol, ethyl acetate, acetone and acetonitrile.

Further, the reaction temperature in the step (1) is 40-120 ℃.

Further, the ultrasonic blending in the step (2) is 2 hours;

further, the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to drug synthesis, gas storage, trapping and separation.

Further, the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to drug delivery.

Furthermore, the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to the fields of light, electricity and magnetism.

Furthermore, the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is applied to the fields of selective catalysis, molecular recognition and chiral resolution.

The invention has the beneficial effects that:

the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine prepared by the invention not only retains the chemical and pharmacological properties of each ligand, but also forms a three-dimensional metal-organic framework crystal material structure with a regular pore structure, and has application value in various fields such as drug synthesis, gas storage, trapping, separation, drug delivery, light, electricity, magnetism, selective catalysis, molecular recognition, chiral resolution and the like.

Drawings

FIG. 1: the invention discloses a schematic diagram of a metal-organic framework crystal material structural unit;

FIG. 2: the invention relates to a microscope structure diagram of a metal-organic framework crystal material;

FIG. 3: a spatial three-dimensional network diagram of the metal-organic framework crystal material of the invention;

FIG. 4: the metal-organic framework crystal material is simulated to obtain an XRD spectrogram;

FIG. 5: TG plot of metal-organic framework crystalline material of the invention;

FIG. 6: the nitrogen adsorption isotherm of the metal-organic framework crystal material is at 77K and 0-1 atm;

FIG. 7: at 298K, 323K; the methane storage capacity isotherm of the metal-organic framework material of the metal-organic framework crystal material is 0-10 bar.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.

The invention selects fumaric acid as ligand A, 4,4' -bipyridyl as ligand B to coordinate with metal zinc and prepares a novel three-dimensional metal-organic framework crystal material with a regular pore structure in solvents such as water, ethanol, methanol or acetone and the like.

Fumaric acid and 4,4' -bipyridine are organic carboxylic acids which are clinical drugs and drug synthesis precursors, and the molecular formulas are respectively: c₄H₄O₄；C₁₀H₈N₂The structural formula is shown as formulas a and b.

The three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4 '-bipyridine uses fumaric acid as a ligand A, 4' -bipyridine as a ligand B and is coordinated with metal zinc to form a basic structural unit of the metal-organic framework crystal material; the basic structure unit structure of the metal-organic framework crystal material comprises two divalent zinc ions, four fumaric acid ligands and two 4,4' -bipyridyl ligands; wherein, two zinc ions are both in a six-coordination form, four oxygen atoms and one nitrogen atom which are respectively coordinated with each zinc ion are respectively from four monodentate carboxyl oxygen atoms provided by four fumaric acid ligands and a heterocyclic nitrogen atom provided by a 4,4' -bipyridine ligand, and a coordination bond is formed by direct coordination of two zinc ions; two 4,4' -bipyridyl ligands are mutually vertical and are coordinated and extended with zinc ions along an ab plane, four fumaric acid ligands are coordinated with the zinc ions and are extended towards four directions, and finally, a three-dimensional metal-organic framework material crystal structure with a regular pore channel structure along the c-axis direction is formed, and the chemical molecular formula is as follows: c₁₈H₁₃N₂O_8.50Zn₂Belonging to monoclinic crystal (monoclinic), the space group is: c12/m 1(12), unit cell parameters are as follows:

α＝90°，β＝105.938(3)°，γ＝90°,and Z is 4. The three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4 '-bipyridine is formed by combining fumaric acid ligand, 4' -bipyridine ligand and metal zinc ions according to the molar ratio of 2:2: 1. Its crystal structure is characterized as follows:

the crystal structure was determined using a Bruker Apex II CCD diffractometer at 296(2)Using MoK α radiation monochromatized with graphite at K

Diffraction points were collected in an omega scan fashion, and the collected data were reduced by the SAINT program and corrected for semi-empirical absorption using the SADABS method. The structure analysis and the refinement are respectively completed by using SHELXS and SHELXL of a SHELXTL program, and F2 is corrected by a full matrix least square method to obtain the coordinates and the anisotropic parameters of all non-hydrogen atoms. All hydrogen atoms are theoretically fixed on the parent atom during the structure refinement process, giving an isotropic displacement parameter slightly (C-H, 1.2 or O/N-H, 1.5 times) larger than the parent atom displacement parameter. Detailed crystal determination data are shown in table 1, a schematic diagram of the structural units is shown in figure 1,

the microscopic structure diagram of the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridyl is shown in figure 2, the spatial three-dimensional network diagram of the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridyl is shown in figure 3, and the simulated powder diffraction diagram of the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridyl is shown in figure 4.

Table 1 cocrystal principal crystallographic data

The three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine is characterized by thermal stability, low-temperature nitrogen adsorption and methane gas adsorption:

thermogravimetric analysis of a crystalline material of three-dimensional metal-organic framework based on fumaric acid and 4,4' -bipyridine in a nitrogen atmosphere at a temperature ranging from 0 ℃ to 600 ℃. FIG. 5 is a TG test chart, from which it can be seen that a three-dimensional metal-organic framework crystalline material based on fumaric acid and 4,4' -bipyridine can be stabilized to 380 ℃; the first weight loss occurs in the range of 50-260 ℃, the weight loss proportion is 31.99 percent, and the loss can be attributed to the loss of guest molecules and terminal coordination molecules. While the framework collapse occurs within the range of 260-380 ℃ and the weight loss is 34.22 percent, and the final decomposition product is 33.69 percent.

The three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine was vacuum-activated at 100 ℃ for 3 hours, and the activated sample was subjected to low-temperature nitrogen adsorption at a temperature of 77K, with the results shown in fig. 6. And measured the BET area 754.4m2/g, the corresponding Langmuir area 1025m2/g, and the total pore volume 0.389cm3/g of a three-dimensional metal-organic framework crystalline material based on fumaric acid and 4,4' -bipyridine.

FIG. 7 is a graph of adsorption curves of three-dimensional metal-organic framework crystalline materials based on fumaric acid and 4,4' -bipyridine at 298K and 323K on methane. It can be seen from fig. 7 that the adsorption amount of methane increases with the increase in pressure. When the pressure was increased to 10bar, the material adsorbed 2.02mmol/g methane at 298K. When the temperature was raised to 323K, the methane adsorption amount was 1.57 mmol/g.

Preparation method example 1: a preparation method of a three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine comprises the following steps:

adding 0.2mmol of fumaric acid, 0.2mmol of 4,4' -bipyridine and 0.1mmol of zinc nitrate into a mixed solvent consisting of 3ml of water and 3ml of ethanol, placing the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and ultrasonically mixing the mixture for 2 hours at room temperature; after the ultrasonic treatment is stopped, the high-pressure reaction kettle is placed in an oven at the temperature of 80 ℃ and is placed for 20 hours, then the high-pressure reaction kettle is taken out, and after the high-pressure reaction kettle is cooled to room temperature, massive colorless crystals are separated out, and the molar yield is 87%.

Preparation method example 2: the preparation method of the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine comprises the following steps:

adding 0.2mmol of fumaric acid, 0.2mmol of 4,4' -bipyridine and 0.1mmol of zinc nitrate into a mixed solvent consisting of 3ml of water and 3ml of methanol, placing the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and ultrasonically mixing the mixture for 2 hours at room temperature; after the ultrasonic treatment is stopped, the high-pressure reaction kettle is placed in an oven at the temperature of 80 ℃ and is placed for 20 hours, then the high-pressure reaction kettle is taken out, and after the high-pressure reaction kettle is cooled to room temperature, massive colorless crystals are separated out, and the molar yield is 85%.

Preparation method example 3: the preparation method of the three-dimensional metal-organic framework crystal material based on fumaric acid and 4,4' -bipyridine comprises the following steps:

adding 0.2mmol of fumaric acid, 0.2mmol of 4,4' -bipyridine and 0.1mmol of zinc nitrate into a mixed solvent consisting of 3ml of water and 3ml of acetone, placing the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and ultrasonically mixing the mixture for 2 hours at room temperature; after the ultrasonic treatment is stopped, the high-pressure reaction kettle is placed in an oven at the temperature of 80 ℃ and is placed for 20 hours, then the high-pressure reaction kettle is taken out, and after the high-pressure reaction kettle is cooled to room temperature, massive colorless crystals are separated out, and the molar yield is 84%.

Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.