CN115490869B - Method for quickly synthesizing metal organic framework material on paper chip assisted by loop furnace - Google Patents
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- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
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- B01L2300/1805—Conductive heating, heat from thermostatted solids is conducted to receptacles, e.g. heating plates, blocks
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Abstract
The invention discloses a rapid synthesis method of a metal organic framework material on a paper chip assisted by a loop furnace. The paper chip with special structure is placed on a ring furnace, a metal precursor solution and an organic ligand precursor solution are dripped in a sample injection area in the center of the paper chip, liquid is diffused to a heating area of the ring furnace due to the siphoning effect of the paper chip, the liquid is quickly changed into steam in a proper temperature environment of the area, and after quick cooling, a metal organic frame material is deposited in the heating area on the surface of the paper chip. The method realizes the synthesis of the metal organic framework material in a specific area on the paper chip, the synthesis can be completed within 1 hour, and the cost is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of material synthesis methods, and particularly relates to a rapid synthesis method of a metal organic framework material on a paper chip assisted by a loop furnace.
Background
The metal organic frame Materials (MOFs) are crystal materials which are formed by self-assembly of metal ions and organic ligands and have a periodic grid structure, and have the characteristics of large specific surface area, large porosity, diversified structures and metal unsaturated coordination, so that the metal organic frame materials have great development potential and attractive development prospects in the fields of gas adsorption, luminescence, catalysis, sensing detection and the like. In recent years, due to the requirement of MOFs device, scientific researchers load MOFs on a microchip to realize sensing application of the MOFs. Ameroot et al reported for the first time that vapor-based MOFs deposition strategies employed a combination of atomic layer deposition and vapor-assisted switching to effect conversion of metal oxide to crystalline MOFs on microchips. The method has high deposition efficiency, uniformity and controllable thickness, and can finish the deposition of MOFs in a very small size.
To further develop the application of MOFs, loading MOFs of rigid structure onto flexible substrates may confer new properties to MOFs. The paper chip has the characteristics of low cost, simplicity, easiness in operation, availability and disposability, and is widely applied to the fields of biological analysis, medical diagnosis, environmental monitoring and the like as a flexible substrate. Therefore, MOFs are loaded on the paper chip, so that the method has a certain application prospect. However, currently, the MOFs carried on the paper substrate generally adopt a direct growth method, a secondary growth method and a liquid phase epitaxy method, which generally take a long time, and contact with a solution for a long time can damage the structure of paper fibers, and especially, the MOFs are difficult to assemble at specific positions of a micro-sized substrate by a solution-based synthesis method.
The ring furnace technology was proposed by australian analytical chemist Wei Ci in 1954 for the first time, and was applied as a microanalysis method in the early stage, in which a sample to be measured was dropped into the center of a paper substrate, and was continuously radially diffused by a rinse solution, and when the sample reached a heating ring of the ring furnace, the rinse solution was rapidly evaporated under heating, and the sample was concentrated in the heating ring of the ring furnace to form a ring for detection.
Disclosure of Invention
The invention aims to solve the problems of the MOFs method for loading the paper substrate, and provides a method for synthesizing MOFs on a paper chip in situ by using a loop furnace to assist, so that the MOFs are synthesized in situ in a specific area of the paper chip at low cost and high efficiency.
Aiming at the purposes, the invention adopts the technical scheme that: spreading paper chips on a ring furnace, wherein the paper chips consist of a central sample injection area, 2-24 MOFs synthesis areas, a liquid flow channel connecting the sample injection area and the MOFs synthesis areas and an outermost waste liquid area, the diameter of the paper chips is not smaller than the outer diameter of a heating ring of the ring furnace, the diameter of the sample injection area is smaller than the inner diameter of the heating ring of the ring furnace, and the diameter of the MOFs synthesis area is not larger than the ring width of the heating ring of the ring furnace; sealing MOFs synthesis area of the paper chip with a polyethylene film, regulating the temperature to the reaction temperature by a loop furnace, sequentially dripping a metal precursor solution and an organic ligand precursor solution into a sample injection area of the paper chip for 10-60 seconds, adding an ice bag on the polyethylene film for cooling, after reacting for 10-60 minutes, pushing the paper chip downwards to enable a waste liquid area to be positioned on a loop furnace heating ring, cleaning the MOFs synthesis area by a flushing liquid, cleaning unbound sites in the waste liquid area of the paper chip, and finally drying in vacuum.
The paper chip is cut by a paper substrate, and the paper substrate is preferably Whatman No. 1 filter paper or Whatman No. 3 filter paper.
The invention further preferably carries out carboxymethylation treatment on the paper chip, and the specific treatment method comprises the following steps: the paper chip is soaked in an aqueous solution containing 1 to 1.5mol/L sodium chloroacetate and 4 to 6wt.% NaOH for 40 to 60 minutes, taken out, washed and air-dried.
In the above synthesis method, the number of MOFs synthesis regions is preferably 8 to 16.
The metal precursor solution is any one of a copper nitrate solution, a copper acetate solution in ethanol-water, a zinc nitrate solution in N, N-dimethylformamide, a cobalt nitrate solution in N, N-dimethylformamide, etc., the organic ligand precursor solution is any one of a 2, 5-dihydroxyterephthalic acid solution in N, N-dimethylformamide-methanol, a 1,3, 5-tris (4-carboxyphenyl) benzene solution in N, N-dimethylformamide-nitric acid, a 1,3, 5-trimesic acid solution in N, N-dimethylformamide, a 1, 4-terephthalic acid solution in N, N-dimethylformamide, etc., and the rinse solution is a mixture solution of N, N-dimethylformamide or N, N-dimethylformamide and ethanol or a mixture solution of N, N-dimethylformamide and ethanol, water. The reaction temperature is 80-110 ℃. In addition, the invention can select corresponding metal precursors and organic ligands according to the metal organic frame materials to be synthesized, and the reaction temperature can be adjusted according to the metal organic frame materials to be synthesized.
In the above synthesis method, it is preferable to sequentially drop a metal precursor solution and an organic ligand precursor solution at a speed of 200 to 800. Mu.L/min in a sample injection region of the paper chip using a flow injection pump.
In the above synthesis method, the metal organic framework material is negative in MOFs synthesis regionThe loading is 0.1-1 mg/cm 3 。
The beneficial effects of the invention are as follows:
the invention can realize the in-situ synthesis of the metal organic frame material in the paper chip fixed-point area by utilizing the side area heating, enriching and washing functions of the ring furnace. The paper chip with special structure is placed on a ring furnace, a metal precursor solution and an organic ligand precursor solution are dripped in a sample injection area in the center of the paper chip, liquid is diffused to a heating area of the ring furnace due to the siphoning effect of the paper chip, the liquid is quickly changed into steam in a proper temperature environment of the area, and after quick cooling, a metal organic frame material is deposited in the heating area on the surface of the paper chip. The method realizes the synthesis of the metal organic frame material in a specific area on the paper chip, the synthesis dosage is controllable, the synthesis can be completed within 1 hour, the cost is greatly reduced, the operation is simple, the universality is strong, and the method is suitable for synthesizing different types of metal organic frame materials on the paper chip.
Drawings
Fig. 1 is a schematic diagram of the structure of a paper chip in the embodiment.
FIG. 2 is a schematic diagram of a loop-assisted on-chip metal-organic framework material rapid synthesis method in an embodiment.
FIG. 3 is a scanning electron microscope image of a Cu-MOF-74@paper chip prepared in example 1.
FIG. 4 is an X-ray diffraction pattern of Cu-MOF-74, paper chip, and Cu-MOF-74@paper chip prepared in example 1.
FIG. 5 is an infrared spectrum of Cu-MOF-74, paper chip, and Cu-MOF-74@paper chip prepared in example 1.
FIG. 6 is an X-ray photoelectron spectrum of a Cu-MOF-74@paper chip prepared in example 1.
FIG. 7 is a scanning electron microscope image of a Cu-BTB@paper chip prepared in example 2.
FIG. 8 is a scanning electron microscope image of a Cu-BTC@paper chip prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
The ring furnace adopted in the following embodiment is a single-hole metal ring furnace, the outside is a heat-preserving iron box, the heating body inside is a copper cylinder with the outer diameter of 60mm, the inner diameter of 22mm and the height of 35mm, the cylindrical surface of the cylinder is wound with an electric heating wire, asbestos and mica sheets are wrapped around the cylinder to preserve heat, the temperature of the heating body is controlled by a voltage-regulating transformer, and the heating range is 0-200 ℃.
The structure of the paper chip in the following embodiment is shown in fig. 1, and is cut by using Whatman No. 1 filter paper, wherein the paper chip consists of a sample injection area in the center, 12 MOFs synthesis areas, a liquid flow channel connecting the sample injection area and the MOFs synthesis areas, and an outermost waste liquid area, the diameter of the paper chip is 80mm, the diameter of the sample injection area is 10mm, the diameter of the MOFs synthesis area is 6mm, and the distance between the centers of the two MOFs synthesis areas on the same straight line is 60mm; and (3) soaking the paper chip in an aqueous solution containing 1mol/L sodium chloroacetate and 5wt.% NaOH for 1h, taking out, cleaning, and air-drying to obtain the carboxymethylation paper chip.
Example 1
As shown in fig. 2, carboxymethylated paper chips are tiled on a loop furnace, MOFs synthesis regions of the paper chips are sealed with polyethylene film, and the loop furnace is adjusted to 100 ℃; 0.0299g of copper nitrate trihydrate was weighed and dissolved in 10mL of N, N-dimethylformamide to give a 15mmol/L copper nitrate solution; 0.0731g of 2, 5-dihydroxyterephthalic acid is weighed and dissolved in 10mL of mixed solution of N, N-dimethylformamide and methanol in a volume ratio of 9:1, and 30mmol/L of 2, 5-dihydroxyterephthalic acid solution is obtained; and (3) dropwise adding a copper nitrate solution for 30s at a speed of 400 mu L/min in a sample injection area at the center of the paper chip by using a flow injection pump, dropwise adding a 2, 5-dihydroxyterephthalic acid solution for 30s, adding an ice bag on a polyethylene film, cooling, pushing the paper chip downwards to enable a waste liquid area to be positioned on a ring furnace heating ring after the reaction is carried out for 30min, cleaning a MOFs synthesis area by using N, N-dimethylformamide, cleaning an unbound site in the waste liquid area at the outermost ring of the paper chip, and finally carrying out vacuum drying at 50 ℃ to obtain the Cu-MOF-74@paper chip.
As can be seen from FIG. 3, the morphology of Cu-MOF-74 on the paper chip is in the shape of unidirectional flower bundles, and Cu-MOF-74 is shared along the fibersValence bonds to the paper-based surface. As can be seen from fig. 4, the X-ray diffraction pattern of Cu-MOF-74 on the paper chip simultaneously has characteristic diffraction peaks of the paper chip at 2θ=24.5° and characteristic diffraction peaks of Cu-MOF-74 at 2θ=6.7° and 11.8° corresponding to (210) and (300) crystal planes, respectively. As can be seen from FIG. 5, the infrared spectrum of Cu-MOF-74 on the paper chip has Cu-MOF-74 at 1558cm -1 、1430cm -1 、1250cm -1 、1191cm -1 、1043cm -1 、598cm -1 Absorption peak at 2870cm for paper chip -1 、3325cm -1 the-OH stretching vibration peak at the position. As can be seen from FIG. 6, the presence of C, O and Cu elements is also clearly shown in the broad scanning spectrum of the X-ray photoelectron spectrum of Cu-MOF-74 on a paper chip, wherein the characteristic peaks of Cu elements appear mainly at binding energies 954.9 and 935.0, corresponding to Cu 2p 1/2 、Cu 2p 3/2 。
Example 2
As shown in fig. 2, carboxymethylated paper chips are tiled on a loop furnace, MOFs synthesis regions of the paper chips are sealed with polyethylene film, and the loop furnace is adjusted to 100 ℃; 0.0241g of copper nitrate trihydrate is weighed and dissolved in 10mL of N, N-dimethylformamide to obtain 10mmol/L copper nitrate solution; 0.0246g of 1,3, 5-tris (4-carboxyphenyl) benzene is weighed and dissolved in 10mL of mixed solution of N, N-dimethylformamide and nitric acid in a volume ratio of 3:1, so as to obtain 5mmol/L of 1,3, 5-tris (4-carboxyphenyl) benzene solution; firstly dripping copper nitrate solution for 30s, then dripping 1,3, 5-tris (4-carboxyphenyl) benzene solution for 30s in a sample injection area at the center of a paper chip by using a flow injection pump at the speed of 400 mu L/min, adding an ice bag on a polyethylene film for cooling, pushing the paper chip downwards to enable a waste liquid area to be positioned on a ring furnace heating ring after the reaction of the polyethylene film for 30min, cleaning a MOFs synthesis area by using N, N-dimethylformamide, cleaning an unbound site in the waste liquid area at the outermost ring of the paper chip, and finally carrying out vacuum drying at 50 ℃ to obtain the Cu-BTB@paper chip. As can be seen from fig. 7, the Cu-BTB morphology on the paper chip is hexahedral, and the Cu-BTB is covalently bonded to the paper chip surface along the fibers.
Example 3
As shown in fig. 2, carboxymethylated paper chips are tiled on a loop furnace, MOFs synthesis regions of the paper chips are sealed with polyethylene film, and the loop furnace is adjusted to 100 ℃; 0.0241g of copper acetate is weighed and dissolved in 10mL of mixed solution with the volume ratio of ethanol to water being 1:1, and 10mmol/L copper acetate solution is obtained; 0.0630g of 1,3, 5-trimesic acid was weighed and dissolved in 5mL of N, N-dimethylformamide to obtain 30mmol/L of 1,3, 5-trimesic acid solution; and (3) dropwise adding a copper acetate solution for 30s at a speed of 400 mu L/min in a sample injection area at the center of the paper chip by using a flow injection pump, dropwise adding a 1,3, 5-trimellitic acid solution for 30s, adding an ice bag on a polyethylene film for cooling, pushing the paper chip downwards after the reaction for 30min to enable a waste liquid area to be positioned on a ring furnace heating ring, cleaning a MOFs synthesis area by using a mixed solution of N, N-dimethylformamide, ethanol and water in a water volume ratio of 1:1:1, cleaning an unbound site in the waste liquid area at the outermost ring of the paper chip, and finally performing vacuum drying at 50 ℃ to obtain the Cu-BTC@paper chip. As can be seen from fig. 5, the Cu-BTC morphology on the paper chip is in the shape of a regular octahedron, with Cu-BTC covalently bonded to the paper-based surface along the fibers.
Example 4
As shown in fig. 2, carboxymethylated paper chips are tiled on a loop furnace, MOFs synthesis regions of the paper chips are sealed with polyethylene film, and the loop furnace is adjusted to 110 ℃; 0.0297g of zinc nitrate hexahydrate was weighed and dissolved in 10mL of N, N-dimethylformamide to obtain a copper nitrate solution of 10 mmol/L; 0.0630g of 1, 4-terephthalic acid was weighed and dissolved in 10mL of N, N-dimethylformamide to obtain a 5 mmol/L1, 4-terephthalic acid solution; and (3) dropwise adding zinc nitrate solution for 30s at a speed of 400 mu L/min in a sample injection area in the center of the paper chip by using a flow injection pump, dropwise adding 1, 4-terephthalic acid solution for 30s, adding an ice bag on a polyethylene film, cooling, pushing the paper chip downwards to enable a waste liquid area to be positioned on a ring furnace heating ring after the reaction is carried out for 30min, cleaning a MOFs synthesis area by using a mixed solution of N, N-dimethylformamide and ethanol with a volume ratio of 1:1, cleaning an unbound site in the waste liquid area at the outermost ring of the paper chip, and finally carrying out vacuum drying at 50 ℃ to obtain the MOF-5@paper chip.
Claims (4)
1. A rapid synthesis method of a metal organic framework material on a paper chip assisted by a loop furnace is characterized by comprising the following steps of: spreading paper chips on a ring furnace, wherein the paper chips consist of a central sample injection area, 2-24 MOFs synthesis areas, a liquid flow channel connecting the sample injection area and the MOFs synthesis areas and an outermost waste liquid area, the diameter of the paper chips is not smaller than the outer diameter of a heating ring of the ring furnace, the diameter of the sample injection area is smaller than the inner diameter of the heating ring of the ring furnace, and the diameter of the MOFs synthesis area is not larger than the ring width of the heating ring of the ring furnace; sealing MOFs synthesis area of the paper chip by using a polyethylene film, regulating the temperature to 80-110 ℃ by using a loop furnace, sequentially dripping metal precursor solution and organic ligand precursor solution into the sample injection area of the paper chip at the speed of 200-800 mu L/min for 10-60 seconds by using a flow injection pump, adding an ice bag on the polyethylene film for cooling, reacting for 10-60 minutes, pushing the paper chip downwards to enable a waste liquid area to be positioned on a loop furnace heating ring, cleaning the MOFs synthesis area by using flushing liquid, cleaning unbound sites into the waste liquid area of the paper chip, and finally drying in vacuum;
the paper chip is formed by cutting a paper substrate and is subjected to carboxymethylation treatment, and the specific treatment method comprises the following steps: soaking the paper chip in an aqueous solution containing 1-1.5 mol/L sodium chloroacetate and 4-6 wt percent NaOH for 40-60 minutes, taking out, cleaning and air-drying; the paper substrate is Whatman No. 1 filter paper or Whatman No. 3 filter paper;
the metal precursor solution is any one of an N, N-dimethylformamide solution of copper nitrate, an ethanol-water solution of copper acetate, an N, N-dimethylformamide solution of zinc nitrate and an N, N-dimethylformamide solution of cobalt nitrate, and the organic ligand precursor solution is any one of an N, N-dimethylformamide-methanol solution of 2, 5-dihydroxyterephthalic acid, an N, N-dimethylformamide-nitric acid solution of 1,3, 5-tris (4-carboxyphenyl) benzene and an N, N-dimethylformamide solution of 1,3, 5-trimesic acid.
2. The rapid synthesis method of metal organic framework materials on a paper chip assisted by a loop furnace according to claim 1, wherein the rapid synthesis method comprises the following steps: the number of MOFs synthesis regions is 8-16.
3. The rapid synthesis method of metal organic framework materials on a paper chip assisted by a loop furnace according to claim 1, wherein the rapid synthesis method comprises the following steps: the flushing liquid is N, N-dimethylformamide or a mixed solution of N, N-dimethylformamide and ethanol or a mixed solution of N, N-dimethylformamide, ethanol and water.
4. The rapid synthesis method of metal organic framework materials on a paper chip assisted by a loop furnace according to claim 1, wherein the rapid synthesis method comprises the following steps: the loading capacity of the metal organic framework material in the MOFs synthesis region is 0.1-1 mg/cm 3 。
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3719490A (en) * | 1967-07-13 | 1973-03-06 | Eastman Kodak Co | Photosensitive element containing a photoreducible palladium compound and the use thereof in physical development |
| JP2016052620A (en) * | 2014-09-03 | 2016-04-14 | 日本製紙株式会社 | Composite of metal-organic framework and cellulose nanofiber |
| CN105924478A (en) * | 2016-05-24 | 2016-09-07 | 济南大学 | Preparation method of three-dimensional paper-based metal organic framework |
| CN107478701A (en) * | 2017-08-24 | 2017-12-15 | 济南大学 | A kind of metal-organic framework material signal amplifies electrochemical analysis paper chip sensor |
| CN108593610A (en) * | 2018-04-17 | 2018-09-28 | 武汉大学 | A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF |
| CN108816064A (en) * | 2018-06-26 | 2018-11-16 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material |
| CN110095454A (en) * | 2019-05-28 | 2019-08-06 | 陕西师范大学 | With the paper chip for extending chemiluminescence function |
| CN110511392A (en) * | 2019-08-22 | 2019-11-29 | 浙江大学 | A kind of preparation method of gamma-cyclodextrin metal organic frame@cellulose fiber composite material and products thereof and application |
| CN110596085A (en) * | 2019-09-03 | 2019-12-20 | 中山大学 | Distance measurement-based non-consumable paper chip and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014115177A2 (en) * | 2013-01-28 | 2014-07-31 | Council Of Scientific & Industrial Research | A process for the preparation of mofs-porous polymeric membrane composites |
| JP7170410B2 (en) * | 2018-03-29 | 2022-11-14 | 大阪瓦斯株式会社 | Humidity control element |
| WO2019210159A1 (en) * | 2018-04-26 | 2019-10-31 | Texas A&M University | In situ fabrication of metal-organic framework films and mixed-matrix membranes |
-
2021
- 2021-06-18 CN CN202110679838.8A patent/CN115490869B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3719490A (en) * | 1967-07-13 | 1973-03-06 | Eastman Kodak Co | Photosensitive element containing a photoreducible palladium compound and the use thereof in physical development |
| JP2016052620A (en) * | 2014-09-03 | 2016-04-14 | 日本製紙株式会社 | Composite of metal-organic framework and cellulose nanofiber |
| CN105924478A (en) * | 2016-05-24 | 2016-09-07 | 济南大学 | Preparation method of three-dimensional paper-based metal organic framework |
| CN107478701A (en) * | 2017-08-24 | 2017-12-15 | 济南大学 | A kind of metal-organic framework material signal amplifies electrochemical analysis paper chip sensor |
| CN108593610A (en) * | 2018-04-17 | 2018-09-28 | 武汉大学 | A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF |
| CN108816064A (en) * | 2018-06-26 | 2018-11-16 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of the chitosan nano fiber membrane of growth in situ metal-organic framework material |
| CN110095454A (en) * | 2019-05-28 | 2019-08-06 | 陕西师范大学 | With the paper chip for extending chemiluminescence function |
| CN110511392A (en) * | 2019-08-22 | 2019-11-29 | 浙江大学 | A kind of preparation method of gamma-cyclodextrin metal organic frame@cellulose fiber composite material and products thereof and application |
| CN110596085A (en) * | 2019-09-03 | 2019-12-20 | 中山大学 | Distance measurement-based non-consumable paper chip and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Ring-Oven Washing Technique Integrated Paper-based Immunodevice for Sensitive Detection of Cancer Biomarker》;Wei Liu et al;《Anal. Chem.》(第87期);第7951−7957页 * |
| 用环炉技术监测大气中微量汞;耿信笃;周曼君;张秀云;刘燃;;分析化学(第02期);第140-141页 * |
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