CN108191894A - A kind of metal organic anion framework material formed based on indium and its preparation method and application - Google Patents
A kind of metal organic anion framework material formed based on indium and its preparation method and application Download PDFInfo
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- CN108191894A CN108191894A CN201810030138.4A CN201810030138A CN108191894A CN 108191894 A CN108191894 A CN 108191894A CN 201810030138 A CN201810030138 A CN 201810030138A CN 108191894 A CN108191894 A CN 108191894A
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- indium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- 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
Abstract
The present invention relates to a kind of metal organic anion framework materials formed based on indium and its preparation method and application.The technical solution adopted is that：By In (NO3)3, ligand 5,5'- (pyridyl group -2,5- bis- replaces) -1,3- phthalic acids (H4L), solvent is n,N-Dimethylformamide, adds in salpeter solution in container, is stirred 30 minutes under room temperature；It is put into baking oven after container is sealed, under temperature 358K, is kept for 3 days；It is slowly cooled to room temperature, obtains water white transparency bulk crystals；With N, the washing of N dimethylformamides, filtering, drying obtain target product.The prepared metal organic anion framework material formed based on indium of the invention can adsorb cationic organic dyestuff as adsorbing base, efficient selective separation Cationic organic dyes.
Description
Technical field
The present invention relates to it is a kind of based on indium formed metal organic anion framework material preparation and its application, specifically
Say, be related to a kind of metal organic anion skeleton formed based on indium with Cation adsorption and preparation method thereof and
Its absorption and separation application to organic dyestuff.
Background technology
In host-guest chemistry field, metal organic framework (MOFs) be used as a kind of novel molecular functional material, about it
Research span inorganic chemistry, organic chemistry, physical chemistry, materials chemistry, crystal engineering, topology, supramolecular chemistry and
Multiple ambits such as Coordinative Chemistry.As multidisciplinary field intersect product, metal-organic framework materials design synthesis and
Performance study has developed into one of very active field of Recent study.Recently, the MOFs of electrification can be induced by charge
Ion exchange process and the interest for increasingly causing researcher, this makes rear synthetic modification process simple and controllable.In these MOFs
In, the MOFs of anionic is often generated during neutral organic ligand and metal ion structure skeleton, and therefore, it is necessary to bones
Cation other than frame plays the role of charge balance.Counter cation is generally taken up in the hole of skeleton, with metal ion not
It is coordinated or has weak coordination.This material provides a uniqueness for cation receptor of the structure based on cation exchange
Chance.On the other hand, inorganic-organic hybridization MOFs has diversified internal microenvironment, can be as outstanding main body
For material for identifying and detaching cationic system, this process will depend on size, geometric shape and the binding ability in MOFs holes.
Compared with neutral backbone, the MOFs of anionic studies very limited invention content.
China has been global maximum DYE PRODUCTION state, and for annual dyestuff yield up to 150000 tons, environmental pollution phenomenon is non-
Chang Yanchong, with increasingly sophisticated, the continuous development of dyeing of dye structure, performance is increasingly stablized, these waste water from dyestuff
Processing it is more complicated.Different types of waste water from dyestuff is handled using different sewage disposal technologies, realizes sewage qualified discharge
Or the problem of recycling, being current in the urgent need to address.
Invention content
The purpose of the present invention is by the use of In as metal node, utilize 5,5'- (pyridyl group -2,5- bis- replaces) -1,3- benzene
Diacid is at a certain temperature, organic using a kind of metal formed based on indium of method synthesis of solvent heat as organic ligand
Anion frame material.
The technical solution adopted by the present invention is：A kind of preparation side of the metal organic anion framework material formed based on indium
Method includes the following steps：
1) by In (NO3)3, 5,5'- (pyridyl group -2,5- bis- replaces) -1,3- phthalic acids, n,N-Dimethylformamide, nitric acid
It adds in container, under room temperature, stirring；
2) it is put into after container is sealed in baking oven, under 353-363K, is kept for 3-4 days；Preferably, heating rate 2-6
℃·min-1。
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains colourless bulk crystals；Preferably, it is slowly cooled to room temperature
Rate of temperature fall be 4-6 DEG C of h-1, and at least 24 hours are stood at room temperature.
4) it is washed, filtered with n,N-Dimethylformamide, it is dry, obtain target product.
The beneficial effects of the invention are as follows：The metal organic anion framework material formed based on indium prepared by the present invention can
It is applied to the rear synthesis field of host-guest chemistry as material of main part.The prepared metal organic anion bone formed based on indium
Frame material can adsorb cationic organic dyestuff as adsorbing base, and efficient selective separation cation has engine dyeing
Material.The metal organic anion framework material preparation method formed based on indium of the present invention is simple, has great application prospect.
Description of the drawings
Fig. 1 is that the present invention is based on the synthesis schematic diagrames of metal organic anion framework material that indium is formed.
Fig. 2 is that the present invention is based on the XRD diagram of metal organic anion framework material that indium is formed.
Fig. 3 is the structure chart of metal organic anion framework material basic unit formed based on indium prepared by embodiment 1.
Fig. 4 is the metal organic anion framework material a axis direction schematic diagrames formed based on indium prepared by embodiment 1.
Fig. 5 is the metal organic anion framework material Selective Separation methyl orange and methine formed the present invention is based on indium
The ultraviolet-visible spectrogram of blue organic dyestuff.
Fig. 6 is the metal organic anion framework material Selective Separation tonyred and methine formed the present invention is based on indium
The ultraviolet-visible spectrogram of blue organic dyestuff.
Fig. 7 is the metal organic anion framework material Selective Separation crystal violet and methine formed the present invention is based on indium
The ultraviolet-visible spectrogram of blue organic dyestuff.
Specific embodiment
A kind of metal organic anion skeleton formed based on indium of embodiment 1
By the In (NO of 0.016mmol3)3, 0.015mmol's, 5,5'- (pyridyl group -2,5- bis- replaces) -1,3- phthalic acids
(H4L), the n,N-Dimethylformamide (DMF) of 2ml, the nitric acid of 0.15ml are added in the vial that volume is 5ml, and room temperature
Condition stirs 30 minutes.Vial is sealed and is put into baking oven.Heating makes the temperature of baking oven reach 358K, heating speed from room temperature
Rate is 5 DEG C of min-1, and maintain the temperature under the conditions of this and keep the temperature 72 hours.With 5 DEG C of h-1Rate of temperature fall progressively cool to room
Temperature obtains water white transparency bulk crystals；It washed, filter and is dried in air with n,N-Dimethylformamide (DMF) solution, i.e.,
For target product, based on the metal organic anion skeleton that indium is formed, yield 45%.
The structure of metal organic anion skeleton that the present invention synthesized formed based on indium as Figure 1-Figure 4, the crystal
Structure belongs to tetragonal crystal system, space group P42/mmc.Molecular formula is：(Me2NH2)[In(L)].The compound is by monokaryon
[In(O2CR)4] three-dimensional structure that is formed as node by tetracarboxylic acid ylidene ligands bridging.Each indium center is several using eight-coordinate
What structure forms the tetrahedral structure of four nodes by four carboxylic acid groups.In four independent indiums of each ligand binding
A square two dimensional surface is formed centrally, and has the structure there are one complete PtS types.Along c-axis direction, between rectangular duct
By being connected by four indium centers with the square that four ligands form, can be observed in a, b axis direction.It is molten in duct
Agent molecule is high degree of dispersion, and voidage reaches 63.6% by PLATON/SOLV estimations.
A kind of metal organic anion framework material selective absorption organic dyestuff formed based on indium of embodiment 2
Method：Using the metal organic anion framework material based on indium formation prepared by embodiment 1 as adsorbing base pair
Mixing organic dyestuff is adsorbed.
1st, organic anionic dyes methyl orange and organic cation dye methylene blue is taken to be dissolved in DMF solution, obtains first
The concentration of base orange and methylene blue is respectively 5 × 10-5The mixed dye solution of M.
Mixed dye solution 5ml is taken, adds in the metal organic anion skeleton crystal formed based on indium prepared by embodiment 1
20mg impregnates at room temperature.The variation of dye strength in mixed dye solution is detected with uv-vis spectra.As a result such as Fig. 5 institutes
Show, peak value is followed successively by 0min, 2min, 4min, 6min, 8min, 10min from top to bottom in figure.As seen from Figure 5, mixed dye is molten
Methylene blue is gradually reduced in the feature peak intensity of 650nm in liquid, and feature peak intensity of the methyl orange in 420nm is constant.This says
A kind of crystal structure of metal organic anion skeleton formed based on indium of the bright present invention has methylene blue choosing well
Selecting property is adsorbed.
Metal organic anion skeleton the present invention is based on indium formation reaches the adsorption rate of methylene blue in 6min
75%, in 10min, adsorption rate has reached 98%.
2nd, organic zeroth order dyestuff tonyred and organic cation dye methylene blue is taken to be dissolved in DMF solution, obtains the Sudan
Red and methylene blue concentration is respectively 5 × 10-5The mixed dye solution of M.
Mixed dye solution 5ml is taken, adds in the metal organic anion skeleton crystal that indium prepared by embodiment 1 is formed
20mg impregnates at room temperature.The variation of dye strength in mixed dye solution is detected with uv-vis spectra.As a result such as Fig. 6 institutes
Show, peak value is followed successively by 0min, 2min, 4min, 6min, 8min, 10min from top to bottom in Fig. 6.As seen from Figure 6, mixed dye is molten
Methylene blue is gradually reduced in the feature peak intensity of 650nm in liquid, and feature peak intensity of the tonyred in 480nm is constant.This says
The crystal structure for the metal organic anion skeleton that the indium of the bright present invention is formed has good selective absorption to methylene blue.
3rd, organic cation dye crystal violet and organic cation dye methylene blue is taken to be dissolved in DMF solution, is tied
The concentration of crystalviolet and methylene blue is respectively 5 × 10-5The mixed dye solution of M.
Mixed dye solution 5ml is taken, adds in the metal organic anion skeleton crystal that indium prepared by embodiment 1 is formed
20mg impregnates at room temperature.The variation of dye strength in mixed dye solution is detected with uv-vis spectra.As a result such as Fig. 7 institutes
Show, peak value is followed successively by 0min, 2min, 4min, 6min, 8min, 10min from top to bottom in Fig. 7.As seen from Figure 7, mixed dye is molten
Methylene blue is gradually reduced in the feature peak intensity of 650nm in liquid, and feature peak intensity of the crystal violet in 600nm is constant.This says
The bright present invention's has good selective absorption based on the metal organic anion framework material that indium is formed to methylene blue.
Claims (7)
1. a kind of metal organic anion framework material formed based on indium, it is characterised in that：The gold formed based on indium
Belong to organic anion framework material, which belongs to tetragonal crystal system, space group P42/ mmc, molecular formula are：(Me2NH2)[In
(L)]；
The compound is by monokaryon [In (O2CR)4] three-dimensional structure that is formed as node by tetracarboxylic acid ylidene ligands bridging, it is each
A indium center uses the geometry of eight-coordinate, the tetrahedral structure of four nodes is formed by four carboxylic acid groups, each
Four independent indiums of ligand binding are centrally formed a square two dimensional surface, and have the structure there are one complete PtS types,
Along c-axis direction, by being connected by four indium centers with the square that four ligands form between rectangular duct.
2. a kind of preparation method of metal organic anion framework material formed based on indium described in claim 1, feature
It is：
Preparation method includes the following steps：
1) by In (NO3)3, 5,5'- (pyridyl group -2,5- bis- replaces) -1,3- phthalic acids (H4L), n,N-Dimethylformamide, nitre
Acid is added in container, under room temperature, stirring；
2) it is put into after container is sealed in baking oven, under 353-363K, is kept for 3 days；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains bulk crystals；
4) it is washed, filtered with n,N-Dimethylformamide, it is dry, obtain target product.
3. a kind of preparation method of metal organic anion framework material formed based on indium according to claim 2,
It is characterized in that：It in step 2), is put into after container is sealed in baking oven, heating rate is 2-6 DEG C of min-1。
4. a kind of preparation method of metal organic anion framework material formed based on indium according to claim 2,
It is characterized in that：The rate of temperature fall being slowly cooled to room temperature is 4-6 DEG C of h-1, and at least 24 hours are stood at room temperature.
5. it is described in claim 1 based on the metal organic anion framework material that indium is formed as adsorbing base absorption it is positive from
Application in subtype organic dyestuff.
6. application according to claim 5, which is characterized in that method is as follows：In the N containing cationic organic dyestuff,
In dinethylformamide solution, the metal organic anion framework material described in claim 1 formed based on indium, leaching are added in
Bubble, absorption.
7. application according to claim 5 or 6, it is characterised in that：The cationic organic dyestuff is methylene blue.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603177A (en) * | 2021-02-07 | 2021-11-05 | 北京航空航天大学 | Reconfigurable and regenerative azo dye adsorption method and application thereof |
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| CN103041778A (en) * | 2012-12-28 | 2013-04-17 | 浙江大学 | Metal-organic frame material for absorbing and storing acetylene and preparation method thereof |
| CN104650125A (en) * | 2015-03-13 | 2015-05-27 | 辽宁大学 | InIII-based metal organic anion framework and application thereof |
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| CN113603177A (en) * | 2021-02-07 | 2021-11-05 | 北京航空航天大学 | Reconfigurable and regenerative azo dye adsorption method and application thereof |
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Application publication date: 20180622 |