CN114907574B - Metal-organic framework material with controllable morphology and preparation method and application thereof - Google Patents
Metal-organic framework material with controllable morphology and preparation method and application thereof Download PDFInfo
- Publication number
- CN114907574B CN114907574B CN202210673029.0A CN202210673029A CN114907574B CN 114907574 B CN114907574 B CN 114907574B CN 202210673029 A CN202210673029 A CN 202210673029A CN 114907574 B CN114907574 B CN 114907574B
- Authority
- CN
- China
- Prior art keywords
- metal
- organic
- aqueous solution
- ethanol
- framework material
- 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.)
- Active
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 107
- 239000007864 aqueous solution Substances 0.000 claims abstract description 85
- 239000013078 crystal Substances 0.000 claims abstract description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002184 metal Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 150000003839 salts Chemical class 0.000 claims abstract description 55
- 238000002156 mixing Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 36
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 26
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 23
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 23
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 abstract description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 9
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 229910001453 nickel ion Inorganic materials 0.000 description 22
- 230000003287 optical effect Effects 0.000 description 19
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001320 near-infrared absorption spectroscopy Methods 0.000 description 1
- 235000019520 non-alcoholic beverage Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Food Science & Technology (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
Abstract
The invention relates to the technical field of preparation of metal-organic frame materials, and discloses a metal-organic frame material with controllable morphology, a preparation method and application thereof. The method comprises the following steps: (1) Mixing metal salt with water to obtain a metal ion aqueous solution; (2) Mixing an organic ligand with water to obtain an organic ligand aqueous solution; (3) Mixing a metal ion aqueous solution and an organic ligand aqueous solution for reaction to obtain a metal-organic framework material; the metal salt is cobalt salt and/or nickel salt, and the organic ligand is N, N-carbonyl diimidazole, imidazole or imidazole-2-formaldehyde. According to the method, crystals with different morphologies can be obtained by adjusting the molar ratio of the two metal salts to the organic ligand, and the prepared crystals can be used for rapidly detecting the content of ethanol.
Description
Technical Field
The invention relates to the technical field of preparation of metal-organic frame materials, in particular to a metal-organic frame material with controllable morphology, a preparation method and application thereof.
Background
The method for rapidly detecting the alcohol content has important significance for food industries such as alcohol brewing, low-alcohol beverage production, alcohol-free beverage production and the like, and non-food industries such as cosmetics, pharmaceutical manufacturing and the like. The method for measuring ethanol mainly comprises gas chromatography, alcohol meter method, colorimetry, carbon isotope method, chemical oxidation method, density bottle method, nuclear magnetic resonance spectroscopy, near infrared spectroscopy, etc. The gas chromatography has the advantages of accurate measurement results, high selectivity and high sensitivity, but has high detection cost and low detection speed. The alcohol meter method has the advantages of high speed, simple operation and the like, but the pretreatment of the sample is complicated. The near infrared spectrometry is used for measuring the ethanol content, a large amount of experiments are needed to be completed, and the detection period is long.
The metal-organic framework Materials (MOFs) are porous crystal materials formed by self-assembling metal ions or metal clusters and organic ligands in a coordination mode, and have the advantages of large specific surface area, high porosity, multiple structures, easiness in functionalization and the like. MOFs are prepared by a solvothermal method, the synthesis time is long, and the crystal growth cannot be directly observed in the reaction process.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the synthesis time of a metal-organic framework material is long, the crystal growth cannot be directly observed in the reaction process, the alcohol degree detection method is complex, the detection time is long and the like, and provides a metal-organic framework material with controllable morphology, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a metal-organic framework material with controllable morphology, the method comprising the steps of:
(1) Mixing metal salt with water to obtain a metal ion aqueous solution;
(2) Mixing an organic ligand with water to obtain an organic ligand aqueous solution;
(3) Mixing a metal ion aqueous solution and an organic ligand aqueous solution for reaction to obtain a metal-organic framework material;
wherein the metal salt is cobalt salt and/or nickel salt, and the organic ligand is N, N-carbonyl diimidazole, imidazole or imidazole-2-formaldehyde;
when the metal salt is cobalt salt, the molar ratio of cobalt ions to organic ligands in the step (3) is 0.05-0.5:1;
when the metal salt is nickel salt, the molar ratio of nickel ions to organic ligands in the step (3) is 0.05-0.4:1;
when the metal salt is cobalt salt or nickel salt, the molar ratio of cobalt ion, nickel ion and organic ligand in the step (3) is 0.01-0.25:0.02-0.15:1.
Preferably, the cobalt salt is cobalt nitrate hexahydrate or cobalt chloride hexahydrate;
preferably, the nickel salt is nickel nitrate hexahydrate or nickel chloride hexahydrate.
Preferably, in step (3), the reaction conditions include: the temperature is 5-35 ℃ and the time is 1-2h.
Preferably, when the metal salt is cobalt salt and the molar ratio of cobalt ions to organic ligands is 0.05-0.15:1, a metal-organic framework material with hexagonal prism crystal morphology is obtained;
preferably, when the metal salt is cobalt salt and the molar ratio of cobalt ions to organic ligands is 0.16-0.2:1, a metal-organic framework material with hexagonal prism and hexahedron crystal morphology is obtained;
preferably, when the metal salt is a cobalt salt and when the molar ratio of cobalt ions to organic ligands is 0.21-0.5:1, a metal-organic framework material is obtained with crystal morphology of tetrahedra, hexahedra and hexagonal prisms.
Preferably, when the metal salt is nickel salt and the molar ratio of nickel ions to organic ligands is 0.05-0.1:1, a metal-organic framework material with hexagonal prism crystal morphology is obtained;
preferably, when the metal salt is nickel salt and the molar ratio of nickel ions to organic ligands is 0.11-0.2:1, a metal-organic framework material with hexagonal prism and hexahedron crystal morphology is obtained;
preferably, when the metal salt is a nickel salt and the molar ratio of nickel ions to organic ligands is 0.21-0.4:1, a metal-organic framework material with tetrahedral and hexagonal morphology is obtained.
Preferably, when the metal salts are cobalt salts and nickel salts, the molar ratio of nickel ions to organic ligands is 0.05:1, and the molar ratio of cobalt ions to organic ligands is 0.01-0.03:1, obtaining the metal-organic framework material with hexahedron and hexagonal prism crystal morphology;
preferably, when the metal salts are cobalt salts and nickel salts, the molar ratio of nickel ions to organic ligands is 0.05:1, and the molar ratio of cobalt ions to organic ligands is 0.04-0.08:1, the metal-organic framework material with tetrahedral crystal morphology is obtained;
preferably, when the metal salts are cobalt salts and nickel salts, the molar ratio of nickel ions to organic ligands is 0.05:1, and the molar ratio of cobalt ions to organic ligands is 0.09-0.25:1, a metal-organic framework material with tetrahedral and hexagonal prism crystal morphology is obtained.
Preferably, when the metal salts are cobalt salts and nickel salts, the molar ratio of cobalt ions to organic ligands is 0.05:1, and the molar ratio of nickel ions to organic ligands is 0.01-0.02:1, the metal-organic framework material with hexahedron and hexagonal prism crystal morphology is obtained;
preferably, when the metal salts are cobalt salts and nickel salts, the molar ratio of cobalt ions to organic ligands is 0.05:1, and the molar ratio of nickel ions to organic ligands is 0.03-0.10:1, the metal-organic framework material with tetrahedral and hexahedral crystal morphology is obtained;
preferably, when the metal salts are cobalt salts and nickel salts, the molar ratio of cobalt ions to organic ligands is 0.05:1, and the molar ratio of nickel ions to organic ligands is 0.11-0.15:1, a metal-organic framework material with tetrahedral, hexahedral and hexagonal morphology is obtained.
A second aspect of the present invention provides a metal-organic framework material prepared by the above method.
In a third aspect, the present invention provides a method of detecting the volume fraction of ethanol in an aqueous solution, the method comprising the steps of:
(1) Adding the metal-organic framework material into ethanol-water solutions with volume fractions of 0%, 25%, 50%, 75% and 100% respectively, and detecting the existence time of crystals in the ethanol-water solution to obtain the relationship between the existence time of the crystals and the volume fraction of ethanol;
(2) Adding the same metal-organic framework material as that in the step (1) into the ethanol-water solution to be detected, detecting the existence time of the crystal in the ethanol-water solution, and calculating the volume fraction of the ethanol in the ethanol-water solution to be detected according to the relation between the existence time of the crystal obtained by detection and the volume fraction of the crystal obtained in the step (1);
wherein, the solid-to-liquid ratio of the metal-organic framework material to the ethanol-water solution in the step (1) and the step (2) is the same.
Preferably, the solid to liquid ratio of the metal-organic framework material to the ethanol-water solution in step (1) and step (2) is 1 mg/1 mL.
In the invention, three relatively active organic ligands and two metal salts are selected to be self-assembled into MOFs crystal at normal temperature and normal pressure, the growth of the crystal can be observed in real time under an optical microscope, and the crystals with different morphologies can be obtained by adjusting the molar ratio of the two metal salts to the organic ligands, so that the controllability of the morphology of the organic metal frame material crystal is realized.
The invention also provides a simple and quick method for detecting the ethanol content in the ethanol-water solution, and the method can be used for quickly and conveniently detecting the ethanol content by utilizing the corresponding relation between the existing time of the MOFs crystal prepared by the method in the ethanol-water solution and the volume fraction of the ethanol.
Drawings
FIG. 1 is an optical microscope characterization result of the metal-organic framework material prepared in example 1;
FIG. 2 is an optical microscope characterization result of the metal-organic framework material prepared in example 2;
FIG. 3 is an optical microscope characterization result of the metal-organic framework material prepared in example 3;
FIG. 4 is an optical microscope characterization result of the metal-organic framework material prepared in example 8;
fig. 5 is a fitting result in application example 1.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a method for preparing a metal-organic framework material with controllable morphology, which comprises the following steps:
(1) Mixing metal salt with water to obtain a metal ion aqueous solution;
(2) Mixing an organic ligand with water to obtain an organic ligand aqueous solution;
(3) Mixing a metal ion aqueous solution and an organic ligand aqueous solution for reaction to obtain a metal-organic framework material;
wherein the metal salt is cobalt salt and/or nickel salt, and the organic ligand is N, N-carbonyl diimidazole, imidazole or imidazole-2-formaldehyde;
when the metal salt is cobalt salt, the molar ratio of cobalt ions to organic ligands in the step (3) is 0.05-0.5:1;
when the metal salt is nickel salt, the molar ratio of nickel ions to organic ligands in the step (3) is 0.05-0.4:1;
when the metal salt is cobalt salt or nickel salt, the molar ratio of cobalt ion, nickel ion and organic ligand in the step (3) is 0.01-0.25:0.02-0.15:1.
In a preferred embodiment, the cobalt salt is cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
In a preferred embodiment, the nickel salt is nickel nitrate hexahydrate or nickel chloride hexahydrate.
In a preferred embodiment, in step (3), the reaction conditions include: the temperature is 5-35 ℃ and the time is 1-2h. Specifically, the temperature may be 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃; the time may be 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, or 2h.
In a preferred embodiment, when the metal salt is a cobalt salt and the molar ratio of cobalt ions to organic ligands is 0.05-0.15:1, a metal-organic framework material with hexagonal prism crystal morphology is obtained.
In a preferred embodiment, when the metal salt is cobalt salt and the molar ratio of cobalt ions to the organic ligand is 0.16-0.2:1, a metal-organic framework material with hexagonal prism and hexahedron crystal morphology is obtained, and two crystal morphologies exist in the obtained metal-organic framework material at the same time.
In a preferred embodiment, when the metal salt is a cobalt salt and the molar ratio of cobalt ions to organic ligands is 0.21-0.5:1, a metal-organic framework material with tetrahedral, hexahedral and hexagonal crystal morphologies is obtained, and three crystal morphologies simultaneously exist in the obtained metal-organic framework material.
In a preferred embodiment, when the metal salt is a nickel salt and the molar ratio of nickel ions to organic ligands is 0.05-0.1:1, a metal-organic framework material with hexagonal prism morphology is obtained.
In a preferred embodiment, when the metal salt is a nickel salt and the molar ratio of nickel ions to organic ligands is 0.11-0.2:1, a metal-organic framework material with hexagonal prism and hexahedron crystal morphology is obtained, and the obtained metal-organic framework compound has two crystal morphologies at the same time.
In a preferred embodiment, when the metal salt is a nickel salt and the molar ratio of nickel ions to organic ligands is 0.21-0.4:1, a metal-organic framework material with tetrahedron and hexagonal prism crystal morphology is obtained, and two crystal morphologies exist in the obtained metal-organic framework compound at the same time.
In a preferred embodiment, when the metal salt is cobalt salt and nickel salt, the molar ratio of nickel ions to organic ligand is 0.05:1, and the molar ratio of cobalt ions to organic ligand is 0.01-0.03:1, a metal-organic framework material with hexahedron and hexagonal prism crystal morphology is obtained, and two crystal morphologies exist in the obtained metal-organic framework compound at the same time.
In a preferred embodiment, when the metal salts are cobalt salts and nickel salts, the molar ratio of nickel ions to organic ligands is 0.05:1, and the molar ratio of cobalt ions to organic ligands is 0.04-0.08:1, a metal-organic framework material with tetrahedral crystal morphology is obtained;
in a preferred embodiment, when the metal salt is cobalt salt and nickel salt, the molar ratio of nickel ions to organic ligand is 0.05:1, and the molar ratio of cobalt ions to organic ligand is 0.09-0.25:1, a metal-organic framework material with tetrahedron and hexagonal prism crystal morphology is obtained, and two crystal morphologies exist in the obtained metal-organic framework compound at the same time.
In a preferred embodiment, when the metal salt is cobalt salt and nickel salt, the molar ratio of cobalt ion to organic ligand is 0.05:1, and the molar ratio of nickel ion to organic ligand is 0.01-0.02:1, a metal-organic framework material with hexahedron and hexagonal prism crystal morphology is obtained, and two crystal morphologies exist in the obtained metal-organic framework compound at the same time.
In a preferred embodiment, when the metal salt is cobalt salt and nickel salt, the molar ratio of cobalt ion to organic ligand is 0.05:1, and the molar ratio of nickel ion to organic ligand is 0.03-0.10:1, a metal-organic framework material with tetrahedral and hexahedral crystal morphology is obtained, and two crystal morphologies simultaneously exist in the obtained metal-organic framework compound.
In a preferred embodiment, when the metal salt is cobalt salt and nickel salt, the molar ratio of cobalt ion to organic ligand is 0.05:1, and the molar ratio of nickel ion to organic ligand is 0.11-0.15:1, a metal-organic framework material with tetrahedron, hexahedron and hexagonal prism crystal morphology is obtained, and three crystal morphologies exist in the obtained metal-organic framework compound at the same time.
A second aspect of the present invention provides a metal-organic framework material prepared by the above method.
In a third aspect, the present invention provides a method of detecting the volume fraction of ethanol in an aqueous solution, the method comprising the steps of:
(1) Adding the metal-organic framework material into ethanol-water solutions with volume fractions of 0%, 25%, 50%, 75% and 100% respectively, and detecting the existence time of crystals in the ethanol-water solution to obtain the relationship between the existence time of the crystals and the volume fraction of ethanol;
(2) Adding the same metal-organic framework material as that in the step (1) into the ethanol-water solution to be detected, detecting the existence time of the crystal in the ethanol-water solution, and calculating the volume fraction of the ethanol in the ethanol-water solution to be detected according to the relation between the existence time of the crystal obtained by detection and the volume fraction of the crystal obtained in the step (1);
wherein, the solid-to-liquid ratio of the metal-organic framework material to the ethanol-water solution in the step (1) and the step (2) is the same.
In the present invention, the time for which the crystals are present in the ethanol-water solution means the time required for the crystals to be completely dissolved in the above solution.
In a preferred embodiment, the fitting is performed according to the presence times of crystals in ethanol-water solutions with volume fractions of 0%, 25%, 50%, 75% and 100%, respectively, the volume fraction x% and the presence time Y satisfying the following relationship: y=11.67 x exp (x/17.39) +341.70.
Preferably, the solid-to-liquid ratio of the metal-organic framework material to the ethanol-water solution in step (1) and step (2) is 1mg/mL.
In a preferred embodiment, the method of preparing the metal-organic framework material in step (1) comprises the steps of:
(1) Cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is dissolved in water to prepare Co (NO) 3 ) 2 An aqueous solution;
(2) Dissolving N, N-carbonyl diimidazole in water to prepare an organic ligand solution;
(3) Co (NO) 3 ) 2 The aqueous solution was mixed with an aqueous solution of N, N-carbonyldiimidazole, and Co (NO) 3 ) 2 The mixture reacts with N, N-carbonyl diimidazole for 2 hours at normal temperature (25 ℃) with the molar ratio of 0.15:1, pink precipitate is separated out from the solution, and the pink crystal is obtained after the precipitate is filtered and dried.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
Example 1
(1) Metal salt (Co (NO) 3 ) 2 ·6H 2 O) is mixed with water to obtain a metal ion aqueous solution with the concentration of 0.2 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 25 ℃ to obtain the metal-organic framework material.
As a result of observation by an optical microscope (a short time microscope E5 biological microscope) during the reaction, as shown in FIG. 1, it was observed that crystals having a hexagonal prism shape were produced.
Example 2
(1) Metal salt (Co (NO) 3 ) 2 ·6H 2 O) is mixed with water to obtain a metal ion aqueous solution with the concentration of 0.36 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 25 ℃ to obtain the metal-organic framework material.
During the reaction, the generation of crystals having hexahedral and hexagonal shapes was observed by observation with an optical microscope (a short time period microscope E5 biological microscope) as shown in FIG. 2.
Example 3
(1) Metal salt (Co (NO) 3 ) 2 ·6H 2 O) is mixed with water to obtain a metal ion aqueous solution with the concentration of 0.8 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting at 30 ℃ for 1.5h to obtain the metal-organic framework material.
During the reaction, the generation of crystals having tetrahedra, hexahedron and hexagonal prism can be observed by observation under an optical microscope (a short time period microscope E5 biological microscope) as shown in FIG. 3.
Comparative example 1
(1) Metal salt (Co (NO) 3 ) 2 ·6H 2 O) is mixed with water to obtain a metal ion aqueous solution with the concentration of 1.2 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 25 ℃ to obtain the metal-organic framework material.
During the reaction, the reaction was observed by an optical microscope, and the generation of crystals was not observed.
Example 4
(1) Metal salt (Ni (NO) 3 ) 2 ·6H 2 O) is mixed with water to obtain a metal ion aqueous solution with the concentration of 0.16 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 20 ℃ to obtain the metal-organic framework material.
During the reaction, crystals having a hexagonal prism shape were observed to be produced by observation with an optical microscope.
Example 5
(1) Metal salt (Ni (NO) 3 ) 2 ·6H 2 O) is mixed with water to obtain a metal ion aqueous solution with the concentration of 0.3 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 25 ℃ to obtain the metal-organic framework material.
Crystals having hexahedral and hexagonal shapes were observed to be generated by observation with an optical microscope during the reaction.
Example 6
(1) Metal salt (Ni (NO) 3 ) 2 ·6H 2 O) is mixed with water to obtain a metal ion aqueous solution with the concentration of 0.6 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 20 ℃ to obtain the metal-organic framework material.
During the reaction, the generation of crystals having tetrahedral and hexagonal shapes was observed by observation under an optical microscope (a short time microscope E5 biomicroscope).
Comparative example 2
(1) Metal salt (Ni (NO) 3 ) 2 ·6H 2 O) mixing with water to obtain a metal ion aqueous solution with the concentration of 1 mmol/mL;
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 25 ℃ to obtain the metal-organic framework material.
During the reaction, no crystal generation was observed by observation under an optical microscope (short time microscope E5 biomicroscope).
Example 7
(1) Metal salt (Ni (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 O) was mixed with water to give a molar concentration of 0.1mmol/mLNi (NO) 3 ) 2 And 0.04mmol/mL Co (NO) 3 ) 2 Metal ion aqueous solution of (a);
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 25 ℃ to obtain the metal-organic framework material.
During the reaction, the generation of crystals having hexahedral and hexagonal shapes was observed by observation under an optical microscope (a short time period microscope E5 biological microscope).
Example 8
(1) Metal salt (Ni (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 O) was mixed with water to give a molar concentration of 0.1mmol/mLNi (NO) 3 ) 2 And 0.1mmol/mL Co (NO) 3 ) 2 Metal ion aqueous solution of (a);
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 20 ℃ to obtain the metal-organic framework material.
During the reaction, the generation of crystals having a tetrahedral shape was observed by observation under an optical microscope (a short time microscope E5 biological microscope) as shown in FIG. 4.
Example 9
(1) Metal salt (Ni (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 O) was mixed with water to give a molar concentration of 0.1mmol/mLNi (NO) 3 ) 2 And 0.3mmol/mL Co (NO) 3 ) 2 Metal ion aqueous solution of (a);
(2) Mixing an organic ligand (N, N-carbonyl diimidazole) with water to obtain an organic ligand aqueous solution with a concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 15 ℃ to obtain the metal-organic framework material.
During the reaction, the generation of crystals having tetrahedral and hexagonal shapes was observed by observation under an optical microscope (a short time microscope E5 biomicroscope).
Example 10
(1) Metal salt (Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O) was mixed with water to give Co (NO) at a molar concentration of 0.1mmol/mL 3 ) 2 And 0.04mmol/mLNi (NO) 3 ) 2 Metal ion aqueous solution of (a);
(2) Mixing an organic ligand (imidazole-2-formaldehyde) with water to obtain an organic ligand aqueous solution with the concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting at 25 ℃ for 1.5h to obtain the metal-organic framework material.
During the reaction, the generation of crystals having hexahedral and hexagonal shapes was observed by observation under an optical microscope (a short time period microscope E5 biological microscope).
Example 11
(1) Metal salt (Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O) was mixed with water to give Co (NO) at a molar concentration of 0.1mmol/mL 3 ) 2 And 0.1mmol/mLNi (NO) 3 ) 2 Metal ion aqueous solution of (a);
(2) Mixing an organic ligand (imidazole-2-formaldehyde) with water to obtain an organic ligand aqueous solution with the concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 25 ℃ to obtain the metal-organic framework material.
During the reaction, the generation of crystals having tetrahedral and hexahedral shapes was observed by observation under an optical microscope (a short duration microscope E5 biomicroscope).
Example 12
(1) Metal salt (Co (NO) 3 ) 2 ·6H 2 O and Ni (NO) 3 ) 2 ·6H 2 O) was mixed with water to give Co (NO) at a molar concentration of 0.1mmol/mL 3 ) 2 And 0.24mmol/mLNi (NO) 3 ) 2 Metal ion aqueous solution of (a);
(2) Mixing an organic ligand (imidazole-2-formaldehyde) with water to obtain an organic ligand aqueous solution with the concentration of 2 mmol/mL;
(3) And (3) mixing the metal ion aqueous solution obtained in the step (1) and the organic ligand aqueous solution obtained in the step (2) in equal volume, and reacting for 2 hours at 20 ℃ to obtain the metal-organic framework material.
During the reaction, the generation of crystals having tetrahedral, hexahedral and hexagonal shapes was observed by observation under an optical microscope (a short time period microscope E5 biomicroscope).
Application example 1
Preparation of metal-organic framework materials:
(1) 267.0mg of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) was dissolved in 1mL of water to prepare Co (NO) having a molar concentration of 0.75mmol/mL 3 ) 2 An aqueous solution;
(2) 811mg of N, N-carbonyldiimidazole was dissolved in 4mL of the aqueous solution to prepare an organic ligand solution having a molar concentration of 1.25 mmol/mL;
(3) The above 1mL of Co (NO 3 ) 2 Mixing the aqueous solution with 4mL of N, N-carbonyl diimidazole aqueous solution, reacting for 2 hours at normal temperature (25 ℃), precipitating pink precipitate in the solution, filtering the precipitate, and drying to obtain pink crystal Co-CDI;
and (3) detecting the volume fraction of ethanol:
(1) Providing 5 clean glass bottles, wherein each glass bottle contains 5mL of ethanol aqueous solution, the volume fraction of ethanol in the ethanol aqueous solution is respectively 0%, 25%, 50%, 75% and 100%, 5mg of Co-CDI is added into each glass bottle, and the existence time of Co-CDI in each group of solutions is recorded;
(2) The data obtained in step (1) are shown in table 1, and according to the data in table 1, a mapping analysis is performed with the volume fraction (x%) of ethanol as an abscissa and the presence time (y) as an ordinate, and the result is shown in fig. 5, and the data in the graph are fitted, where the fitting result is: y=11.67 x exp (x/17.39) +341.70, r 2 ＝0.99605。
(3) 5mL of ethanol water solutions with the volume fractions of 40% and 60% are respectively prepared as solutions to be tested, 5mg of Co-CDI is respectively added into the two groups of solutions, the existence time of crystals is recorded, the recorded existence time is substituted into y=11.67 x exp (x/17.39) +341.70, and the volume fraction of the measured ethanol is calculated, and the results are shown in Table 2.
TABLE 1
| Ethanol volume fraction/% | 0 | 25 | 50 | 75 | 100 |
| Time of existence/s | 225 | 453 | 668 | 1153 | 4020 |
TABLE 2
| Theoretical value of ethanol volume fraction | 40％ | 60％ |
| Ethanol volume fraction measurement | 38.09％ | 59.16％ |
| Error of | 4.78％ | 1.4％ |
From the data in Table 2, it can be seen that the volume fraction of ethanol in the aqueous ethanol solution can be detected using the methods described herein.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (4)
1. Use of a metal-organic framework material for detecting the volume fraction of ethanol in an aqueous solution, characterized in that the method for detecting the volume fraction of ethanol in an aqueous solution comprises the steps of:
(1) Adding a metal-organic framework material into ethanol-water solutions with volume fractions of 0%, 25%, 50%, 75% and 100% respectively, and detecting the existence time of crystals in the ethanol-water solutions to obtain the relationship between the existence time of the crystals and the volume fraction of ethanol;
(2) Adding the same metal-organic framework material as that in the step (1) into the ethanol-water solution to be detected, detecting the existence time of the crystal in the ethanol-water solution, and calculating the volume fraction of the ethanol in the ethanol-water solution to be detected according to the relation between the existence time of the crystal obtained by detection and the volume fraction of the crystal obtained in the step (1);
wherein, the solid-to-liquid ratio of the metal-organic framework material and the ethanol-water solution in the step (1) and the step (2) is the same;
the preparation method of the metal-organic framework material comprises the following steps:
(1) Mixing metal salt with water to obtain a metal ion aqueous solution;
(2) Mixing an organic ligand with water to obtain an organic ligand aqueous solution;
(3) Mixing a metal ion aqueous solution and an organic ligand aqueous solution for reaction to obtain a metal-organic framework material;
wherein the metal salt is cobalt salt, and the organic ligand is N, N-carbonyl diimidazole;
the molar ratio of cobalt ions to organic ligands in step (3) was 0.15:1.
2. The method of claim 1, wherein the cobalt salt is cobalt nitrate hexahydrate or cobalt chloride hexahydrate.
3. The method according to claim 1 or 2, wherein in step (3), the reaction conditions include: the temperature is 5-35 ℃ and the time is 1-2h.
4. The method of claim 1, wherein the metal-organic framework material to ethanol-water solution solid to liquid ratio in step (1) and step (2) is 1mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210673029.0A CN114907574B (en) | 2022-06-14 | 2022-06-14 | Metal-organic framework material with controllable morphology and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210673029.0A CN114907574B (en) | 2022-06-14 | 2022-06-14 | Metal-organic framework material with controllable morphology and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114907574A CN114907574A (en) | 2022-08-16 |
| CN114907574B true CN114907574B (en) | 2023-07-28 |
Family
ID=82770983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210673029.0A Active CN114907574B (en) | 2022-06-14 | 2022-06-14 | Metal-organic framework material with controllable morphology and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114907574B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044913B (en) * | 2021-10-25 | 2023-05-30 | 广东美的白色家电技术创新中心有限公司 | Metal-organic framework material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109835937B (en) * | 2017-11-29 | 2021-09-17 | 中国科学院大连化学物理研究所 | Metal sulfide nanosheet derived from metal organic framework compound and preparation method thereof |
| FR3104457B1 (en) * | 2019-12-17 | 2023-04-21 | Centre Nat Rech Scient | Composite material combining MOF nanoparticles and metallic nanoparticles |
| CN112837943A (en) * | 2021-04-22 | 2021-05-25 | 中国科学院过程工程研究所 | Ultrathin two-dimensional nanosheet layer NiCo-MOF material, and preparation method and application thereof |
| CN113248725A (en) * | 2021-05-13 | 2021-08-13 | 青岛理工大学 | Preparation method of electromagnetic wave absorbing material based on MOF derivation and electromagnetic wave absorbing material |
| CN114106352B (en) * | 2021-11-25 | 2023-05-12 | 浙江理工大学 | Cobalt-based metal-hydrogen bond-organic framework material and preparation method and application thereof |
-
2022
- 2022-06-14 CN CN202210673029.0A patent/CN114907574B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114907574A (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiao et al. | Facile synthesis of ultrathin Ni-MOF nanobelts for high-efficiency determination of glucose in human serum | |
| CN114907574B (en) | Metal-organic framework material with controllable morphology and preparation method and application thereof | |
| CN107764788B (en) | Synthesis method of carbon quantum dots, carbon quantum dots and Fe detection3+Method (2) | |
| CN107576714B (en) | A kind of preparation method and application of graphite phase carbon nitride@MOF nanocrystal | |
| CN111205470B (en) | Azole functionalized divalent copper frame coordination material, preparation method and application thereof, and p-nitrophenol detection method | |
| CN105061482B (en) | A kind of method utilizing trimesic acid to be directly synthesized metal-organic framework materials MIL-100A1 | |
| CN101334365B (en) | Determination method for chloride ion content of temper rolling liquor for steel plate rolling | |
| CN106866988A (en) | A kind of layer column type metal-organic framework material as well as preparation method and application thereof | |
| CN107987282B (en) | Water-stable lanthanide metal-organic framework material, preparation and application thereof | |
| CN110885451A (en) | In metal-organic framework material based on tricarboxylic acid ligand, preparation method and application thereof | |
| CN104151366B (en) | A kind of 3d-4f heterometallocenes-organic framework materials and preparation method thereof | |
| CN108931505B (en) | Method for detecting nitrite ions based on rare earth metal organic framework material | |
| CN110726790A (en) | Method for measuring chloride ions in fluorine-containing lithium salt | |
| CN101735798A (en) | Rare earth organic framework material having sensing function to acetone, preparation method and application thereof | |
| CN108384027A (en) | A kind of zinc-organic frame and preparation method with acetylacetone,2,4-pentanedione fluorescence response | |
| CN106188155A (en) | A kind of four core Iron clusters and crystal structure thereof and preparation method | |
| CN108424527B (en) | Synthetic method of Zn (II) complex of three-dimensional mixed ligand and application of fluorescent probe | |
| NL2030557B1 (en) | Europium—based metal-organic framework material for fluorescence recognition of antibiotics and preparation method thereof | |
| Wang et al. | Synthesis, structure, fluorescence and electrochemical properties of a new Zn (ii)–organic framework constructed by a tricarboxylic acid ligand | |
| CN112500582A (en) | Multinuclear cobalt cluster metal organic framework material based on four-head pyrazole ligand, preparation and application | |
| CN111103336A (en) | Preparation method and application of electrochemical deposition modified glassy carbon electrode | |
| CN115015362B (en) | Electrochemical method for detecting myricetin | |
| CN110879223A (en) | Rapid detection reagent and detection method for formaldehyde in beer | |
| CN109759019A (en) | A kind of MOF-Zr-EDTA material, preparation method and the application in cigarette | |
| CN111394090A (en) | Three-layer coated copper cluster ratio fluorescent probe and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |