CN111187423A - Novel stable zirconium-based metal organic framework material, and preparation method and application thereof - Google Patents

Novel stable zirconium-based metal organic framework material, and preparation method and application thereof Download PDF

Info

Publication number
CN111187423A
CN111187423A CN202010066977.9A CN202010066977A CN111187423A CN 111187423 A CN111187423 A CN 111187423A CN 202010066977 A CN202010066977 A CN 202010066977A CN 111187423 A CN111187423 A CN 111187423A
Authority
CN
China
Prior art keywords
acid
temperature
metal organic
based metal
ligand
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202010066977.9A
Other languages
Chinese (zh)
Inventor
王俊豪
李梦娜
张莹
张献明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi University
Original Assignee
Shanxi University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi University filed Critical Shanxi University
Priority to CN202010066977.9A priority Critical patent/CN111187423A/en
Publication of CN111187423A publication Critical patent/CN111187423A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices

Abstract

The invention relates to the field of material preparation, in particular to a novel stable zirconium-based metal organic framework material, and a preparation method and application thereof. The novel stable zirconium-based metal organic framework material is Zr-SXU-2, and Zr is used6O4(OH)4 12+The ligand PBPTTBA is an organic ligand, and is induced and synthesized by introducing a monocarboxylic acid regulator benzoic acid and a second ligand DMTPDC; or 2-fluorobenzoic acid is independently introduced to be used as a monocarboxylic acid regulator for induction synthesis, and the chemical formula of Zr-SXU-2 is Zr6O4(OH)4L3 solvent. The novel stable zirconium-based metal organic framework material is novel in structure, simple in preparation process, low in cost, stable in aqueous solution and capable of being used for gas storage and rapid detection of ferric ions.

Description

Novel stable zirconium-based metal organic framework material, and preparation method and application thereof
Technical Field
The invention relates to the field of material preparation, in particular to a novel stable zirconium-based metal organic framework material, and a preparation method and application thereof.
Background
Metal Organic Frameworks (MOFs) are a new class of porous crystalline materials, as compared to traditional porous solid materials (e.g., zeolites), due to their high specific surface area, order tunableThe characteristics of pore size, easy functional modification and the like are rapidly developed in the aspects of gas storage, separation, light capture, catalysis and the like in the last two decades. The design of MOFs metal nodes and organic connectors embodies the height adjustability of MOFs on the molecular level. The precise combination of engineered organic ligands with selected inorganic secondary building blocks (SBUs) yields a number of MOFs with different structures. However, the poor stability of most MOFs materials limits their practical application in many areas of research. Due to Zr4+High charge density, easy polarization of bond and the like, and most of Zr-MOFs of carboxylic acids show strong thermodynamic and chemical stability. Zr is widely distributed in nature and is present in all biological systems. The rich Zr content and low toxicity are beneficial to the development and application of Zr-MOFs.
In the synthesis of Zr-MOFs, Zr4+The cation and the carboxylic acid oxygen anion form a strong coordination bond, and the terminal carboxylic acid is added as a regulator to reduce the nucleation and growth rate of the crystal, so that the high-quality Zr-MOFs crystal can be obtained. The Zr-MOFs has high chemical stability, water stability and thermal stability, and has potential application in the fields of catalysis, luminescence, drug delivery and the like. Compared with other transition metals, the Zr-MOFs are still small in quantity, and the synthesis and preparation of the novel Zr-MOFs are of great significance. Meanwhile, iron ions widely exist in a human body and are indispensable substances in a physiological process, and too much or too little iron ions can cause pathological changes of a living organism and threaten the life safety of people, so that the method has important significance for iron ion detection, has small toxic and side effects of Zr-MOFs, has regular pore channels and luminescent properties, can improve the sensitivity and detection limit of iron ion detection by introducing active sites into the Zr-MOFs, and has important research significance.
Disclosure of Invention
The invention aims to use Zr6O4(OH)4 12+For the secondary building unit, the tetracarboxylic acid ligand 4,4' - (1, 4-p-phenylenebis (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid (PBPTTBA) is used as an organic ligand, and the monocarboxylic acid regulator benzoic acid is introduced, and the second ligand is 2',5' -dimethyl-[1,1':4', 1' -triphenyl radicals]4,4' -dicarboxylic acid (DMTPDC), inducing the synthesis of novel highly stable Zr-MOFs; or 2-fluorobenzoic acid is independently introduced as a monocarboxylic acid regulator to induce and synthesize novel high-stability Zr-MOFs. On the basis of intensive research on the adsorption performance, the Zr-SXU-2 can well detect Fe in an aqueous solution3+。
In order to achieve the purpose, the invention adopts the following technical scheme:
the novel stable zirconium-based metal organic framework material is Zr-SXU-2, and the chemical molecular formula of the Zr-SXU-2 is Zr6O4(OH)4L3Solvent, Zr-SXU-2, Zr6O4(OH)4The connection mode of (2) is 12 connections, Zr-SXU-2 is crystallized in the Im-3 space group, and the topology form is expressed by point symbols as {4.5^2}6{4^6.5^24.6^6.7^18.8^12}, which is a 3,12-c two-node network.
The preparation of the novel stable zirconium-based metal organic framework material comprises the following steps:
step 1, dissolving a zirconium salt and a monocarboxylic acid regulator in a solvent, performing ultrasonic treatment until the zirconium salt and the monocarboxylic acid regulator are completely dissolved, heating at a constant temperature, and cooling to room temperature to obtain a first solution;
and 2, dissolving the ligand in a solvent to obtain a second solution, uniformly mixing the first solution and the second solution, carrying out heating reaction under a closed condition, cooling to room temperature, centrifuging the mixed solution to generate a precipitate, filtering, washing the precipitate for the first time and the second time, drying the precipitate at constant temperature in vacuum after washing, and cooling to room temperature to obtain the novel stable zirconium-based metal organic framework material (Zr-SXU-2).
Further, in the step 1, the zirconium salt is one or more of Zr (NO3) 4.5H 2O, ZrOCl 2.8H 2O and ZrCl4 which are mixed according to any proportion.
Further, the solvent in the step 1 is DMF, and the concentration of the DMF solution of zirconium salt is 0.01 mol/L; the constant-temperature heating temperature is 75-85 ℃, and the constant-temperature heating time is 1-2 hours.
Further, the monocarboxylic acid regulator in the step 1 is benzoic acid or 2-fluorobenzoic acid, when the monocarboxylic acid regulator is benzoic acid, the concentration of a DMF solution of the benzoic acid is 1.5-2.1 mol/L, and the ligands in the step 2 are ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid and a second ligand 2',5' -dimethyl- [1,1':4', 1' -triphenyl ] -4, 4' -dicarboxylic acid; when the monocarboxylic acid regulator is 2-fluorobenzoic acid, the concentration of the DMF solution of the 2-fluorobenzoic acid is 1.6-2.3 mol/L, and the ligand in the step 2 is 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid.
Further, in the steps 1 and 2, when the monocarboxylic acid regulator is benzoic acid, the molar ratio of the zirconium salt, the benzoic acid, the ligand 4,4' - (1, 4-terephthalic acid (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid and the second ligand 2',5' -dimethyl- [1,1':4', 1' -triphenyl ] -4, 4' -dicarboxylic acid is 1: 150-210: 0.5: 0.175-0.5; when the monocarboxylic acid regulator is 2-fluorobenzoic acid, the molar ratio of the zirconium salt, the 2-fluorobenzoic acid and the ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid is 1: 160-230: 0.5.
Furthermore, in the step 2, the solvent is DMF, the concentration of the DMF solution of the ligand 4,4' - (1, 4-terephthalic acid (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid is 0.01mol/L, and the concentration of the DMF solution of the second ligand 2',5' -dimethyl- [1,1':4', 1' -triphenyl ] -4, 4' -dicarboxylic acid is 0.0035-0.01 mol/L.
Further, the heating reaction temperature in the step 2 is 100-130 ℃, and the heating reaction time is 24-72 hours; the temperature of the vacuum constant-temperature drying is 30-80 ℃, and the time of the vacuum constant-temperature drying is 1-8 hours.
Further, in the step 2, washing is carried out once by using fresh DMF, the washing times are 4-6 times, soaking is carried out for 1-5 hours by using DMF every time, after soaking is finished, filtering is carried out, the filtered precipitate is re-soaked by using fresh DMF, and the soaking temperature is any temperature within the range of 20-80 ℃; washing with acetone or dichloromethane for the second time, wherein the washing times are 3-5 times, soaking with acetone or dichloromethane for 1-2 hours each time, filtering after soaking, and re-soaking the filtered precipitate with fresh acetone or dichloromethane, wherein the soaking temperature is room temperature.
Application of novel stable zirconium-based metal organic framework material in gas storage and Fe (ferrum) pair3+And (6) detecting.
Compared with the prior art, the invention has the following advantages: the novel Zr-MOFs is synthesized, and the synthesized Zr-MOFs material has high porosity, uniform pore diameter, large specific surface area, and good thermal stability and chemical stability; the synthesis method has the advantages of simple process, good repeatability, high yield and mild process conditions.
Drawings
FIG. 1 is a three-dimensional framework structure diagram and cage dimensions of Zr-SXU-2 synthesized in example 2 of the present invention;
FIG. 2 is a comparison of powder X-ray diffraction (PXRD) pattern and single crystal fit PXRD pattern of Zr-SXU-2 synthesized in example 2 of the present invention;
FIG. 3 is a PXRD pattern of Zr-SXU-2 synthesized in inventive example 2 after treatment with 1M HCl and aqueous pH 10 NaOH;
FIG. 4 is a thermogravimetric analysis plot of Zr-SXU-2 synthesized in example 2 of the present invention;
FIG. 5 shows the N of Zr-SXU-2 synthesized in example 2 under 77K2An isothermal adsorption line;
FIG. 6 shows Zr-SXU-2 synthesized in example 2 under excitation of 320nm at different concentrations of Fe (NO)3)3Fluorescence spectrum in an aqueous solution of (a);
FIG. 7 shows Zr-SXU-2 vs. Fe synthesized in example 2 of the present invention3+SV graph of (1).
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1
The preparation of the novel stable zirconium-based metal organic framework material comprises the following steps:
step 1, metal salt ZrOCl2·8H2Dissolving O (0.0064g, 0.02mmol) and benzoic acid (0.3663g, 3mmol) in 2ml DMF, performing ultrasonic treatment until completely dissolved, placing in an oven at 80 deg.C, heating for 1.5h at constant temperature, and cooling to room temperature to obtain a first solution;
step 2, dissolving 7.1mg and 0.01mmol of ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylcarboxylic acid and 1.7mg and 0.005mmol of second ligand 2',5' -dimethyl- [1,1':4', 1' -triphenyl ] -4, 4' -dicarboxylic acid in 1mL of DMF to obtain a second solution, uniformly mixing the first solution and the second solution, heating the mixture at 120 ℃ in a high-pressure tube for reaction for 48h, cooling the mixture to room temperature, centrifuging the mixed solution to generate precipitate, filtering the precipitate, washing the precipitate with fresh DMF for 5 times, soaking the precipitate with DMF for 3 h each time, filtering the precipitate after the soaking is finished, re-soaking the filtered precipitate with fresh DMF at any temperature in a 50 ℃ interval, washing the second time with acetone, and (3) washing for 4 times, soaking for 1.5 hours in acetone each time, filtering after soaking, re-soaking the filtered precipitate in fresh acetone or dichloromethane at room temperature, washing, putting the precipitate into a drying oven for vacuum constant-temperature drying at 50 ℃ for 4 hours, and cooling to room temperature to obtain Zr-SXU-2.
Example 2
The preparation of the novel stable zirconium-based metal organic framework material comprises the following steps:
step 1, metal salt ZrOCl2·8H2Dissolving O (0.064g, 0.02mmol) and benzoic acid (0.513g, 4.2mmol) in 2mL of DMF, performing ultrasonic treatment until complete dissolution is achieved, placing the solution into an oven at 80 ℃ for heating for 1h at constant temperature, and cooling to room temperature to obtain a first solution;
step 2, dissolving 7.1mg and 0.01mmol of ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylcarboxylic acid and a second ligand 2',5' -dimethyl- [1,1':4', 1' -triphenyl ] -4, 4' -dicarboxylic acid (3.4mg and 0.01mmol) in 1mLDMF to obtain a second solution, uniformly mixing the first solution and the second solution in a high-pressure tube, heating and reacting at 100 ℃ for 72h, cooling to room temperature, centrifuging the mixed solution to generate precipitate, filtering, washing the precipitate with fresh DMF for 4 times, soaking with DMF for 1 hour each time, filtering after soaking, re-soaking the filtered precipitate with fresh DMF at any temperature in a range of 20 ℃, washing with acetone for the second time, and (3) soaking for 1 hour by using acetone for 3 times, filtering after soaking, re-soaking the filtered precipitate by using fresh acetone or dichloromethane at room temperature, washing, putting the precipitate into a drying oven for vacuum constant-temperature drying at 30 ℃ for 8 hours, and cooling to room temperature to obtain the Zr-SXU-2.
Example 3
The preparation of the novel stable zirconium-based metal organic framework material comprises the following steps:
step 1, metal salt ZrOCl2·8H2Dissolving O (0.064g, 0.02mmol) and benzoic acid (0.513g, 4.2mmol) in 2mL of DMF, performing ultrasonic treatment until complete dissolution is achieved, putting the solution into an oven at 85 ℃ for heating for 1h at constant temperature, and cooling to room temperature to obtain a first solution;
step 2, dissolving 7.1mg and 0.01mmol of ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylcarboxylic acid and a second ligand 2',5' -dimethyl- [1,1':4', 1' -triphenyl ] -4, 4' -dicarboxylic acid (1.21mg and 0.0035mmol) in 1mLDMF to obtain a second solution, uniformly mixing the first solution and the second solution, heating and reacting at 100 ℃ in a high-pressure tube for 72h, cooling to room temperature, centrifuging the mixed solution to generate precipitate, filtering, washing the precipitate with fresh DMF for 4 times, soaking with DMF for 1h each time, filtering after soaking, re-soaking the filtered precipitate with fresh DMF at any temperature in the interval of 20 ℃, washing with acetone for the second time, and (3) soaking for 1 hour by using acetone for 3 times, filtering after soaking, re-soaking the filtered precipitate by using fresh acetone or dichloromethane at room temperature, washing, putting the precipitate into a drying oven for vacuum constant-temperature drying at 30 ℃ for 8 hours, and cooling to room temperature to obtain the Zr-SXU-2.
Example 4
The preparation of the novel stable zirconium-based metal organic framework material comprises the following steps:
step 1, metal salt ZrOCl2·8H2Dissolving O (0.064g, 0.02mmol) and benzoic acid (0.488g, 4mmol) in 2mL of DMF, performing ultrasonic treatment until complete dissolution is achieved, placing the solution into a 75 ℃ oven, heating for 2 hours at constant temperature, and cooling to room temperature to obtain a first solution;
step 2, dissolving 7.1mg and 0.01mmol of ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylcarboxylic acid and 2',5' -dimethyl- [1,1':4', 1' -triphenyl ] -4, 4' -dicarboxylic acid (1.39mg and 0.004mmol) of a second ligand in 1mLDMF to obtain a second solution, uniformly mixing the first solution and the second solution, heating the mixture at 130 ℃ in a high-pressure pipe for reaction for 24 hours, cooling the mixture to room temperature, centrifuging the mixed solution to generate precipitate, filtering the precipitate, washing the precipitate with fresh DMF for 6 times, soaking the precipitate with DMF for 5 hours each time, filtering the precipitate after finishing soaking, re-soaking the filtered precipitate with fresh DMF at any temperature within an interval of 80 ℃, washing the second time with acetone, and (3) washing for 5 times, soaking for 2 hours by using acetone each time, filtering after soaking is finished, soaking the filtered precipitate again by using fresh acetone or dichloromethane at room temperature, drying the precipitate in a drying oven at the constant vacuum temperature of 80 ℃ for 1 hour after washing, and cooling to room temperature to obtain the Zr-SXU-2.
Example 5
The preparation of the novel stable zirconium-based metal organic framework material comprises the following steps:
step 1, metal salt ZrOCl2·8H2Dissolving O (0.0064g, 0.02mmol) and 2-fluorobenzoic acid (0.530g, 3.8mmol) in 2mL of DMF, performing ultrasonic treatment until the solution is completely dissolved, putting the solution into an oven at 80 ℃ for heating for 1h at constant temperature, and cooling to room temperature to obtain a first solution;
step 2, dissolving 7.1mg and 0.01mmol of ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenecarboxylic acid in 1mLDMF to obtain a second solution, uniformly mixing the first solution and the second solution, heating the mixture at 120 ℃ in a high-pressure pipe for 24 hours, cooling the mixture to room temperature, centrifuging the mixed solution to generate precipitate, filtering the precipitate, washing the precipitate with fresh DMF for 6 times, soaking the precipitate with DMF for 5 hours each time, filtering the precipitate after soaking, re-soaking the filtered precipitate with fresh DMF at any temperature within the range of 80 ℃, washing the precipitate with acetone for 5 times, soaking the precipitate with acetone for 2 hours each time, filtering the precipitate after soaking, re-soaking the filtered precipitate with fresh acetone or dichloromethane at room temperature, and (3) after washing, putting the precipitate into a drying oven, drying for 1h at the constant temperature of 80 ℃ in vacuum, and cooling to room temperature to obtain Zr-SXU-2.
FIG. 1 is a three-dimensional framework structure diagram of Zr-SXU-2 synthesized in example 2. Zr in Zr-SXU-26O4(OH)4 12+Clusters were linked to 12 PBPTTBA ligands and the Zr-SXU-2 framework comprised cages of two different sizes, the volume of the small cage being 15.3X 15.3
Figure BDA0002376267080000081
The volume of the large cage is 15.560X 21.402X 23.833
Figure BDA0002376267080000082
FIG. 2 is a graph comparing the powder X-ray diffraction pattern and single crystal fit PXRD pattern of Zr-SXU-2 synthesized in example 2. The figure shows that the post-synthesis Zr-SXU-2 corresponds to the peak fitted to the crystal, indicating that the synthesized Zr-SXU-2 is pure phase and has good crystallinity.
FIG. 3 shows a PXRD pattern of Zr-SXU-2 synthesized in example 2 of the present invention after treatment with 1M HCl and pH 10NaOH aqueous solution, which indicates that Zr-SXU-2 has good acid-base stability.
FIG. 4 is a thermogravimetric analysis graph of Zr-SXU-2 synthesized in example 2 of the present invention, which shows that Zr-SXU-2 has excellent thermal stability.
FIG. 5 shows the N of Zr-SXU-2 synthesized in example 2 under 77K2An isothermal adsorption line, the BET specific surface area Zr-SXU-2 calculated from the isothermal adsorption line being 1195m2g-1。
To study Fe3+The influence of the solution on the fluorescence intensity of Zr-MOFs materials with different structures is tested by adding Fe with different concentrations into Zr-SXU-2 prepared in example 23+Fluorescence spectrum of the solution.
FIG. 6 shows Zr-SXU-2 synthesized in example 2 under excitation of 320nm at different concentrations of Fe (NO)3)3The fluorescence spectrum of the aqueous solution of (1). Fe3+In the concentration range of 0-500 mu mol/L with Fe3+As the ion concentration increases, the fluorescence intensity of Zr-SXU-2 gradually decreases at about 386 and 463 nm.
FIG. 7 shows Zr-SXU-2 vs. Fe synthesized in example 2 of the present invention3+SV diagram of (1) for Fe3+Ksv value of ion, Zr-SXU-2 was calculated to be 1.4X 104Calculating Zr-SXU-2 for Fe in water based on Ksv value and standard value (Sb) for measuring fluorescence of three blank solutions3+The limit of detection of the ion (3Sb/Ksv) was 0.214. mu.M.

Claims (10)

1. The novel stable zirconium-based metal organic framework material is characterized in that the chemical molecular formula of the novel stable zirconium-based metal organic framework material is Zr6O4(OH)4L3Solvent, Zr6O4(OH)4L3In a solvent, Zr6O4(OH)4The connection mode of (2) is 12 connections, Zr-SXU-2 is crystallized in the Im-3 space group, and the topology form is expressed by point symbols as {4.5^2}6{4^6.5^24.6^6.7^18.8^12}, which is a 3,12-c two-node network.
2. The preparation method of the novel stable zirconium-based metal organic framework material is characterized by comprising the following steps of:
step 1, dissolving a zirconium salt and a monocarboxylic acid regulator in a solvent, performing ultrasonic treatment until the zirconium salt and the monocarboxylic acid regulator are completely dissolved, heating at a constant temperature, and cooling to room temperature to obtain a first solution;
and 2, dissolving the ligand in a solvent to obtain a second solution, uniformly mixing the first solution and the second solution, carrying out heating reaction under a closed condition, cooling to room temperature, centrifuging the mixed solution to generate a precipitate, filtering, washing the precipitate for the first time and the second time, drying the precipitate at constant temperature in vacuum after washing, and cooling to room temperature to obtain the novel stable zirconium-based metal organic framework material.
3. The method according to claim 2, wherein the zirconium salt in step 1 is Zr (NO)3)4·5H2O、ZrOCl2·8H2O and ZrCl4One or more of them can be mixed according to any proportion.
4. The preparation of a novel stabilized zirconium-based metal organic framework material according to claim 2, wherein the solvent in step 1 is DMF, and the concentration of the DMF solution of zirconium salt is 0.01 mol/L; the constant-temperature heating temperature is 75-85 ℃, and the constant-temperature heating time is 1-2 hours.
5. The method for preparing a novel stabilized zirconium-based metal organic framework material as claimed in claim 2, wherein the monocarboxylic acid modifier is benzoic acid or 2-fluorobenzoic acid in step 1, and when the monocarboxylic acid modifier is benzoic acid, the concentration of the benzoic acid in DMF is 1.5-2.1 mol/L, and the ligands in step 2 are ligand 4,4',4 ", 4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltri)) tetraphenoic acid and second ligand 2',5' -dimethyl- [1,1':4',1 '-triphenyl ] -4, 4' -dicarboxylic acid; when the monocarboxylic acid regulator is 2-fluorobenzoic acid, the concentration of the DMF solution of the 2-fluorobenzoic acid is 1.6-2.3 mol/L, and the ligand in the step 2 is 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid.
6. The preparation method of a novel stable zirconium-based metal organic framework material as claimed in claim 5, wherein in the steps 1 and 2, when the monocarboxylic acid modifier is benzoic acid, the molar ratio of the zirconium salt, benzoic acid, ligand 4,4',4 ", 4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltri)) tetraphenoic acid and the second ligand 2',5' -dimethyl- [1,1':4',1 '-triphenyl ] -4, 4' -dicarboxylic acid is 1: 150-210: 0.5: 0.175-0.5; when the monocarboxylic acid regulator is 2-fluorobenzoic acid, the molar ratio of the zirconium salt, the 2-fluorobenzoic acid and the ligand 4,4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenylbenzoic acid is 1: 160-230: 0.5.
7. The method of claim 2, wherein the solvent used in step 2 is DMF, the concentration of DMF in the ligand 4,4',4 ", 4' - (1, 4-p-phenylene bis (2,4, 6-pyridyltriphenyl)) tetraphenoic acid is 0.01mol/L, and the concentration of DMF in the second ligand 2',5' -dimethyl- [1,1':4',1 '-triphenyl ] -4, 4' -dicarboxylic acid is 0.0035-0.01 mol/L.
8. The preparation method of the novel stable zirconium-based metal organic framework material according to claim 2, wherein the heating reaction in the step 2 is carried out at a temperature of 100-130 ℃ for 24-72 h; the temperature of the vacuum constant-temperature drying is 30-80 ℃, and the time of the vacuum constant-temperature drying is 1-8 hours.
9. The preparation method of the novel stable zirconium-based metal organic framework material according to claim 2, wherein in the step 2, the washing is performed once by using fresh DMF, the washing times are 4-6 times, the soaking is performed for 1-5 hours by using DMF each time, the filtration is performed after the soaking is finished, the filtered precipitate is re-soaked by using fresh DMF, and the soaking temperature is any temperature in the range of 20-80 ℃; washing with acetone or dichloromethane for the second time, wherein the washing times are 3-5 times, soaking with acetone or dichloromethane for 1-2 hours each time, filtering after soaking, and re-soaking the filtered precipitate with fresh acetone or dichloromethane, wherein the soaking temperature is room temperature.
10. The application of the new stable zirconium-based metal organic frame material is characterized in that the material is applied to gas storage and Fe3 +And (6) detecting.
CN202010066977.9A 2020-01-20 2020-01-20 Novel stable zirconium-based metal organic framework material, and preparation method and application thereof Withdrawn CN111187423A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010066977.9A CN111187423A (en) 2020-01-20 2020-01-20 Novel stable zirconium-based metal organic framework material, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010066977.9A CN111187423A (en) 2020-01-20 2020-01-20 Novel stable zirconium-based metal organic framework material, and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN111187423A true CN111187423A (en) 2020-05-22

Family

ID=70706519

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010066977.9A Withdrawn CN111187423A (en) 2020-01-20 2020-01-20 Novel stable zirconium-based metal organic framework material, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111187423A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115613116A (en) * 2022-10-26 2023-01-17 中国石油大学(华东) Method for preparing new single crystal by destroying zirconium-based metal organic framework structure recombination
CN116284830A (en) * 2023-04-06 2023-06-23 福州大学 Zirconium-based metal organic framework material and application thereof in catalytic ring-opening copolymerization
WO2024074141A1 (en) * 2022-10-08 2024-04-11 华为技术有限公司 Porous material and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104607243A (en) * 2014-12-30 2015-05-13 李亚丰 Heteropolyacid or heteropolyacid salt and microporous coordination polymer composite material and preparation method thereof
CN105080495A (en) * 2015-09-16 2015-11-25 北京工业大学 Metal-organic framework material of Zr and preparation method and application thereof
CN105289505A (en) * 2015-11-07 2016-02-03 长春工业大学 Cadmium selenide quantum dot and zirconium base coordination polymer composite material and preparation method
CN105777791A (en) * 2016-03-17 2016-07-20 李亚丰 Preparation method of zirconium-based microporous coordination polymer
WO2019053048A1 (en) * 2017-09-12 2019-03-21 Centre National De La Recherche Scientifique Metal organic frameworks for the capture of volatil organic compounds
CN110833818A (en) * 2019-11-26 2020-02-25 中国石油大学(华东) Preparation method of hierarchical porous metal-organic framework gas chromatography stationary phase material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104607243A (en) * 2014-12-30 2015-05-13 李亚丰 Heteropolyacid or heteropolyacid salt and microporous coordination polymer composite material and preparation method thereof
CN105080495A (en) * 2015-09-16 2015-11-25 北京工业大学 Metal-organic framework material of Zr and preparation method and application thereof
CN105289505A (en) * 2015-11-07 2016-02-03 长春工业大学 Cadmium selenide quantum dot and zirconium base coordination polymer composite material and preparation method
CN105777791A (en) * 2016-03-17 2016-07-20 李亚丰 Preparation method of zirconium-based microporous coordination polymer
WO2019053048A1 (en) * 2017-09-12 2019-03-21 Centre National De La Recherche Scientifique Metal organic frameworks for the capture of volatil organic compounds
CN110833818A (en) * 2019-11-26 2020-02-25 中国石油大学(华东) Preparation method of hierarchical porous metal-organic framework gas chromatography stationary phase material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BIN WANG: "Stable Zr(IV)-Based Metal−Organic Frameworks with Predesigned Functionalized Ligands for Highly Selective Detection of Fe(III) Ions in Water", 《ACS APPL. MATER. INTERFACES》 *
闫淑: "高价（Cr3+和Zr4+）金属有机框架的合成及性质", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024074141A1 (en) * 2022-10-08 2024-04-11 华为技术有限公司 Porous material and application thereof
CN115613116A (en) * 2022-10-26 2023-01-17 中国石油大学(华东) Method for preparing new single crystal by destroying zirconium-based metal organic framework structure recombination
CN116284830A (en) * 2023-04-06 2023-06-23 福州大学 Zirconium-based metal organic framework material and application thereof in catalytic ring-opening copolymerization

Similar Documents

Publication Publication Date Title
CN111253582A (en) Zirconium-based metal organic framework material, preparation method and application
CN111187423A (en) Novel stable zirconium-based metal organic framework material, and preparation method and application thereof
CN102030767B (en) Supramolecular metal-organic framework (MOF) compound material
CN113354825B (en) Zirconium-based metal organic framework material UiO-66(Zr) and room-temperature rapid preparation method and application thereof
CN110339816B (en) Preparation method and application of zirconium-based metal organic framework material
CN106905534B (en) A kind of substep preparation method and application of high stable rare earth organic framework materials
CN110302758A (en) A kind of bimetallic organic framework materials, preparation method and the application of dephosphorization
Yu et al. Novel Eu-MOF-based mixed matrix membranes and 1D Eu-MOF-based ratiometric fluorescent sensor for the detection of metronidazole and PA in water
CN108707238B (en) Metal organic framework material Co-PTTIC-TPB and synthetic method and application thereof
Khosroshahi et al. Fabrication of a novel heteroepitaxial structure from an MOF-on-MOF architecture as a photocatalyst for highly efficient Cr (vi) reduction
CN111471191B (en) Cd-MOF complex and preparation method and application thereof
CN107286185A (en) A kind of cadmium metal organic framework material and preparation method thereof
CN101624183B (en) Method for synthesizing nano-porous zirconium phosphate by using hybridization of ionic liquid
CN108285465A (en) Metal-organic framework material, preparation method, modification metal-organic framework material and preparation method thereof
CN114632550A (en) MOF (Metal organic framework) derived vector and preparation method and application thereof
CN104262275A (en) Silver-azotetrazole metal organic framework material as well as preparation method and application thereof
Molavi et al. Green Synthesis of Cerium-Based Metal–Organic Framework (Ce-UiO-66 MOF) for Wastewater Treatment
CN107398257A (en) A kind of preparation method and application of modified zeolite molecular sieve adsorption particle
CN108586761A (en) A kind of 3-dimensional metal-organic framework material of zirconium, preparation method and water vapor adsorption application
CN116284063A (en) Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof
CN106832326A (en) A kind of high-thermal-stability cerium coordination polymer and its preparation method and application
US20140234624A1 (en) Microporous coordination complex and method of making the same
Dong et al. Ligand “lock and fix” strategy provides stability to metal-organic frameworks for photodegradation processes
CN106928466B (en) Preparation method of Cr-MOFs
Wang et al. In situ rapid versatile method for the preparation of zirconium metal-organic framework filters

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20200522

WW01 Invention patent application withdrawn after publication