CN104628710A - Metal organic skeleton material of Zn as well as preparation method and application thereof - Google Patents
Metal organic skeleton material of Zn as well as preparation method and application thereof Download PDFInfo
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- CN104628710A CN104628710A CN201510100746.4A CN201510100746A CN104628710A CN 104628710 A CN104628710 A CN 104628710A CN 201510100746 A CN201510100746 A CN 201510100746A CN 104628710 A CN104628710 A CN 104628710A
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Abstract
The invention discloses a metal organic skeleton material of Zn as well as a preparation method and application thereof, belonging to the technical field of crystalline-state materials. The chemical structural formula is [Zn2(DTYIZ)], wherein DTYIZ is an organic ligand 4,5-bis(1H-tetrazole-5-yl)-1H-imidazole. Under a closed condition, the organic ligand DTYIZ and zinc nitrate hexahydrate conduct a thermal reaction in N,N-dimethylformamide to obtain a crystal of the metal organic skeleton material, wherein the molar ratio of the organic ligand DTYIZ (4,5-bis(1H-tetrazole-5-yl)-1H-imidazole) to zinc nitrate hexahydrate is (1-2):1; and each millimole of the organic ligand DTYIZ corresponds to 3-5ml of N,N-dimethylformamide. The metal organic skeleton material carries negative charges in a solution and can be used as an adsorption material of cationic dye methylene blue.
Description
Technical field
The invention belongs to crystalline material technical field, technology relates to metal organic coordination polymer material, particularly the metal-organic framework materials of a kind of Zn, preparation method and application thereof.
Background technology
China is dye consumption state maximum in the world, and current dyestuff has been widely used in various industry, such as, print and dye, leather, the industries such as papermaking.In order to reach the requirement of environment department, these industrial effluent need could discharge through strict process.Especially need to remove the dye molecule in waste liquid.
Methylene blue belongs to a kind of cationic dyestuff common in dye substance, is often applied to timber, in silk quality and cotton industrial production.Before its waste liquid of discharge, need the methylene blue molecule removed wherein.Utilizing sorbent material to carry out dye adsorption is a kind of more common simple method.Usually these adsorbent methylene blue molecules of gac, alginate calcium particle, quadrol sporopollenin are used both at home and abroad.But, for process containing the waste liquid of a large amount of methylene blue molecule, need to seek one more efficiently, sorbent material efficiently.
Metal-organic framework materials is the class novel porous materials constructed by metal ion or ion cluster and organic ligand.Due to the adjustability of its porousness and functional group's specific surface, aperture and hole surface, metal-organic framework materials all has potential application in various fields, and its research in the fractionation by adsorption of dyestuff, has caused the extensive attention of domestic and international researcher.
Summary of the invention
The object of the present invention is to provide a kind of metal-organic framework materials, preparation method and application thereof.
A kind of metal-organic framework materials of the present invention, is characterized in that, chemical structure consists of the title complex that Zn and organic ligand DTYIZ (4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles) forms.
Chemical structural formula is [Zn
2(DTYIZ)], DTYIZ is organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles.
Metal-organic framework materials, wherein the chemical structural formula of organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles is:
n ' wherein, N ", N " ', N " " subscript just in order to distinguish the description of symbols that position is done, this material secondary building unit wherein: construct from the angle of connection, there is the zinc atom of two kinds of coordination modes, be designated as Zn1, Zn2 respectively, Zn1 is connected with from four atom N on two parts coordination, the N on Zn1 and each part " ' and N " " coordination connects and composes seven-membered ring; Zn2 is connected with from six atom N on three parts coordination, the N ' on Zn2 and each part and N " coordination connects and composes five-ring, and two kinds of coordination modes all belong to chelating ligands; By these two kinds of coordination modes, part and zinc atom define two-dimension netted structural sheet, i.e. secondary structure, misplace and be connected by hydrogen bond between two-dimensional network structure layer with two-dimensional network structure layer; Be connected by hydrogen bond between the two-dimensional layer staggered, form the metal-organic framework materials with microvoid structure.
Above-mentioned secondary building unit wherein: for crystal belongs to oblique system, spacer is I2/a, and unit cell parameters is:
γ=120 °, α=β=90 °.
The synthetic method of metal-organic framework materials of the present invention, comprises the following steps:
Under sealing condition, organic ligand DTYIZ (4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles) and zinc nitrate hexahydrate, in DMF, obtain the crystal of 3-dimensional metal organic framework material via thermal response; Wherein said organic ligand DTYIZ (4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles) be (1 ~ 2) with the mol ratio of zinc nitrate hexahydrate: 1, the DMF of the corresponding 3-5mL of organic ligand DTYIZ of every 1 mmole.
The reaction conditions of described thermal response is 60 DEG C-90 DEG C, and the reaction times is 20-30 hour, preferably 24 hours.Within 24 hours, colourless bulk crystals is obtained via thermal response.
This metal-organic framework materials, in the solution with negative charge, can be used as the absorption of cationic dyestuff methylene blue.
Metal-organic framework materials novel structure of the present invention, has the duct of suitable dimension, with negative charge, can carry out active adsorption to methylene blue dye, can be used as the dye adsorption material in waste liquid; Preparation method's technique of the present invention is simple, easy to implement, and productive rate is high, is conducive to large-scale promotion application.
Accompanying drawing explanation
Fig. 1 is the structural representation of the asymmetric cell of this metal-organic framework materials;
Fig. 2 is the structural representation of this metal-organic framework materials.
Fig. 3 is the absorption test pattern of this metal-organic framework materials to methylene blue dye.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles (1 mmole) and zinc nitrate hexahydrate (0.5 mmole) are stirred in the DMF of 3mL, encloses in bottle.Within 30 hours, obtain the crystal of metal-organic framework materials via thermal response at 60 DEG C.
Embodiment 2
Organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles (1 mmole) and zinc nitrate hexahydrate (1 mmole) are stirred in the DMF of 3mL, encloses in bottle.Within 24 hours, obtain the crystal of metal-organic framework materials via thermal response at 80 DEG C.
Embodiment 3
Organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles (1 mmole) and zinc nitrate hexahydrate (1 mmole) are stirred in the DMF of 4mL, encloses in bottle.Within 24 hours, obtain the crystal of metal-organic framework materials via thermal response at 80 DEG C.
Embodiment 4
Organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles (1 mmole) and zinc nitrate hexahydrate (1 mmole) are stirred in the DMF of 5mL, encloses in bottle.Within 20 hours, obtain the crystal of metal-organic framework materials via thermal response at 90 DEG C.
The test result of the product of above-described embodiment gained is identical, specifically sees following:
(1) crystal structure determination:
Choose the monocrystalline of suitable size under the microscope, visit on diffractometer in Bruker SMART 1000CCD face under room temperature, with the Mo-K alpha-ray through graphite monochromator monochromatization, collect diffraction data in ω-φ mode.All diffraction datas use SADABS program to carry out absorption correction.Unit cell parameters uses method of least squares to determine.Reduction of data and structure elucidation use SAINT and SHELXTL program to complete respectively.First determine whole non-hydrogen atom coordinate by difference functions method and method of least squares, and obtain hydrogen atom position with theoretical hydrogenation method, then with SHELXTL, refine is carried out to crystalline structure.Fig. 1 and Fig. 2 be shown in by structure iron.Crystallographic data is in table 1.
The crystallographic data of table 1 title complex
The structure iron of Fig. 1 shows: this obtained framework material has the zinc atom of two kinds of coordination modes, is designated as Zn1, Zn2 respectively.Zn1 is connected with from four atom N on two parts coordination, and Zn2 is connected with from six atom N on three parts coordination, and two kinds of coordination modes all belong to chelating ligands.
The structure iron of Fig. 2 shows: by these two kinds of coordination modes, part and zinc atom define two-dimension netted structure.Be connected by hydrogen bond between layers.Be connected by hydrogen bond between the two-dimensional layer staggered, form the metal-organic framework materials with microvoid structure.
(2) dye adsorption performance characterization:
Fig. 3 is that material of the present invention is to methylene blue dye Characterization of Adsorption.In Fig. 3, curve from top to bottom represents absorption 0 minute respectively, 1 minute, 3 minutes, 5 minutes, 8 minutes, 13 minutes, 18 minutes, 23 minutes, methanol solution Methylene Blue uv-absorbing peak intensity when 28 minutes.In test, metal-organic framework materials is 30 milligrams of corresponding 100ml methylene blue methanol solutions, and in methylene blue methanol solution, initial methylene blue mass concentration is 50 mg/litre.Along with the increase of time, methylene blue uv-absorbing peak intensity in methanol solution is reduced to gradually does not have absorption peak to occur, namely methanol solution Methylene Blue concentration is constantly reducing until be zero, illustrates that material of the present invention has good absorption property to methylene blue dye.
Claims (7)
1. a metal-organic framework materials, is characterized in that, chemical structural formula is [Zn
2(DTYIZ)], DTYIZ is organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles.
2. according to a kind of metal-organic framework materials of claim 1, it is characterized in that, wherein the chemical structural formula of organic ligand 4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles is:
n ' wherein, N ", N " ', N " " subscript just in order to distinguish the description of symbols that position is done, this material secondary building unit wherein: construct from the angle of connection, there is the zinc atom of two kinds of coordination modes, be designated as Zn1, Zn2 respectively, Zn1 is connected with from four atom N on two parts coordination, the N on Zn1 and each part " ' and N " " coordination connects and composes seven-membered ring; Zn2 is connected with from six atom N on three parts coordination, the N ' on Zn2 and each part and N " coordination connects and composes five-ring, and two kinds of coordination modes all belong to chelating ligands; By these two kinds of coordination modes, part and zinc atom define two-dimension netted structural sheet, i.e. secondary structure, misplace and be connected by hydrogen bond between two-dimensional network structure layer with two-dimensional network structure layer; Be connected by hydrogen bond between the two-dimensional layer staggered, form the metal-organic framework materials with microvoid structure.
3. according to a kind of metal-organic framework materials of claim 2, it is characterized in that, secondary building unit wherein: for crystal belongs to oblique system, spacer is I2/a, and unit cell parameters is:
γ=120 °, α=β=90 °.
4. prepare the method for material according to claim 1, it is characterized in that, comprise the following steps: under sealing condition, organic ligand DTYIZ (4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles) with zinc nitrate hexahydrate at N, in dinethylformamide, obtain the crystal of metal-organic framework materials via thermal response; Wherein said organic ligand DTYIZ (4,5-bis-(1H-TETRAZOLE-5-base)-1H-imidazoles) be (1 ~ 2) with the mol ratio of zinc nitrate hexahydrate: 1, the DMF of the corresponding 3-5mL of organic ligand DTYIZ of every 1 mmole.
5. prepare method according to claim 4, it is characterized in that, the reaction conditions of described thermal response is 60 DEG C-90 DEG C, and the reaction times is 20-30 hour.
6. prepare method according to claim 5, it is characterized in that, the reaction times is 24 hours.
7. a kind of metal-organic framework materials according to claim 1 is used as the methylene blue dye sorbing material of crystalline state.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001245A (en) * | 2015-07-15 | 2015-10-28 | 北京工业大学 | Metal organic framework material of Zn and preparation method and application of metal organic framework material of Zn |
| CN105153207A (en) * | 2015-09-23 | 2015-12-16 | 辽宁大学 | Porous rare-earth-cluster metal organic anion framework and preparation method and application thereof |
| CN105218832A (en) * | 2015-09-16 | 2016-01-06 | 北京工业大学 | A kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu and preparation method thereof |
| CN105503734A (en) * | 2016-01-22 | 2016-04-20 | 辽宁大学 | Coordination polymer constructed based on nitrogenous ligand and synthesis method and application thereof |
| CN105693750A (en) * | 2016-03-01 | 2016-06-22 | 青岛大学 | Rapid preparation method of environment-friendly metal-organic framework material |
| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN108355611A (en) * | 2018-01-22 | 2018-08-03 | 西北师范大学 | A kind of MOF complexs and its synthesis and application in absorption organic dyestuff in wastewater |
| CN109317104A (en) * | 2018-11-02 | 2019-02-12 | 北京工业大学 | A kind of mercapto-functionalized metal-organic framework materials, preparation and its application |
| CN111097386A (en) * | 2019-12-26 | 2020-05-05 | 江苏大学 | Two-dimensional layered water-stable dye adsorbent and preparation method thereof |
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| CN101069836A (en) * | 2007-02-16 | 2007-11-14 | 南开大学 | Microporous zinc coordination polymer material and preparing method and use |
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| CN101069836A (en) * | 2007-02-16 | 2007-11-14 | 南开大学 | Microporous zinc coordination polymer material and preparing method and use |
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| HONGMING HE ET AL.: ""Three novel zinc(II) metal-organic frameworks based on three tetrazolate ligands: synthesis, structures and photoluminescence"", 《RSC ADV.》 * |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001245A (en) * | 2015-07-15 | 2015-10-28 | 北京工业大学 | Metal organic framework material of Zn and preparation method and application of metal organic framework material of Zn |
| CN105218832B (en) * | 2015-09-16 | 2017-12-15 | 北京工业大学 | A kind of metal-organic framework materials based on low symmetrical four teeth Carboxylic acid ligand Cu and preparation method thereof |
| CN105218832A (en) * | 2015-09-16 | 2016-01-06 | 北京工业大学 | A kind of metal-organic framework materials based on low symmetrical four tooth Carboxylic acid ligand Cu and preparation method thereof |
| CN105153207A (en) * | 2015-09-23 | 2015-12-16 | 辽宁大学 | Porous rare-earth-cluster metal organic anion framework and preparation method and application thereof |
| CN105503734A (en) * | 2016-01-22 | 2016-04-20 | 辽宁大学 | Coordination polymer constructed based on nitrogenous ligand and synthesis method and application thereof |
| CN105693750A (en) * | 2016-03-01 | 2016-06-22 | 青岛大学 | Rapid preparation method of environment-friendly metal-organic framework material |
| CN105693750B (en) * | 2016-03-01 | 2018-04-06 | 青岛大学 | A kind of quick preparation of environment protection metal organic framework material |
| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN107011525B (en) * | 2017-03-08 | 2020-03-31 | 宁波大学 | Zinc metal organic framework material and preparation method and application thereof |
| CN108355611A (en) * | 2018-01-22 | 2018-08-03 | 西北师范大学 | A kind of MOF complexs and its synthesis and application in absorption organic dyestuff in wastewater |
| CN109317104A (en) * | 2018-11-02 | 2019-02-12 | 北京工业大学 | A kind of mercapto-functionalized metal-organic framework materials, preparation and its application |
| CN111097386A (en) * | 2019-12-26 | 2020-05-05 | 江苏大学 | Two-dimensional layered water-stable dye adsorbent and preparation method thereof |
| CN111097386B (en) * | 2019-12-26 | 2022-01-11 | 江苏大学 | Two-dimensional layered water-stable dye adsorbent and preparation method thereof |
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Application publication date: 20150520 |