CN108144326A - A kind of method that organic dyestuff is efficiently separated based on anionic metal-organic framework materials - Google Patents
A kind of method that organic dyestuff is efficiently separated based on anionic metal-organic framework materials Download PDFInfo
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- CN108144326A CN108144326A CN201810141426.7A CN201810141426A CN108144326A CN 108144326 A CN108144326 A CN 108144326A CN 201810141426 A CN201810141426 A CN 201810141426A CN 108144326 A CN108144326 A CN 108144326A
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- anionic metal
- organic framework
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/362—Cation-exchange
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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]
Abstract
The present invention relates to a kind of methods that organic dyestuff is efficiently separated based on anionic metal-organic framework materials.The technical solution adopted is that：In the N containing organic dyestuff, N dimethyl formamide solutions, anionic metal-organic framework materials are added in, are impregnated, absorption；The anionic metal-organic framework materials are [Me2NH2][In(tptc)](DMF)2(H2O)4, wherein tptc is [1,1 ':4 ', 1 " terphenyl] 3,3 ", 5,5 " tetracarboxylic acid hydrochlorates.Anionic metal-organic framework materials material prepared by the present invention can detach cationic organic dyestuff as adsorbing base with efficient selective.
Description
Technical field
The present invention relates to a kind of anionic metal-organic framework materials for efficiently separating organic dyestuff, specifically,
It is related to a kind of anionic metal-organic framework materials with cation exchange to be applied to efficiently separate organic dyestuff.
Background technology
In recent years, multifunctional material pushed the development of new high-tech industry, with bio-pharmaceuticals, electronic information, the energy, ring
Border protection etc. is the high-technology field of representative, by the concern of domestic and international scientist.Metal organic frame (MOFs) material has
There are the aesthetic structures of novel and unique, and in gas absorption separation, catalysis, chemical sensitisation, optics and energy stores etc.
With potential application value, therefore cause enthusiasm of the scientist to metal organic frame (MOFs) investigation of materials.At these
In, gas absorption, drug delivery and release depend primarily on the size in hole and the type of MOFs；And luminescence generated by light and sensing
Composition depending on MOFs materials.Therefore, it synthesizes porous MOFs and changes their functional character to respond host-guest interactions
It is the work of an important and great challenge.In the ionic MOFs materials reported, porous ionic frame MOFs materials
Material is since its is commutative and detaches dyestuff and is concerned.Dyestuff is widely used in the industrial production, is particularly weaved, is made
In the industrial productions such as paper, cosmetics, plastic products, pharmacy.Therefore, it before natural cycle system is entered, removes in separation waste
Dyes on Environment protection it is of crucial importance.
Invention content
The purpose of the present invention is synthesizing a kind of anionic metal-organic framework materials using the method for solvent heat, for height
Effect separation organic dyestuff.
The technical solution adopted by the present invention is：One kind has efficiently separated engine dyeing based on anionic metal-organic framework materials
The method of material, method are as follows：In the n,N-Dimethylformamide solution containing organic dyestuff, it is organic to add in anionic metal
Framework material impregnates, absorption；The anionic metal-organic framework materials are [Me2NH2][In(tptc)](DMF)2
(H2O)4, wherein tptc is [1,1 ':4 ', 1 "-terphenyl] -3,3 ", 5,5 "-tetracarboxylic acid hydrochlorate.
The above-mentioned method that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, the anion
Type metal-organic framework materials are three-dimensional anion frame materials, belong to tetragonal crystal system, space group P42/ mmc, counter ion counterionsl gegenions
For dimethylamine cation, there is square duct, channel diameterPore volume is 65-73%.
The above-mentioned method that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, the anion
The preparation method of type metal-organic framework materials includes the following steps：By In (NO3)3, [1,1 ':4 ', 1 "-terphenyl] -3,3 ",
5,5 "-tetrabasic carboxylic acid, n,N-Dimethylformamide and acetonitrile are added in vial, and stirred 30 minutes under normal temperature condition, by glass
Glass bottle, which is sealed, to be put into baking oven, and heating makes the temperature of baking oven reach 363K from room temperature, and heating rate is 5K min-1, and keep
Temperature keeps the temperature 36 hours on this condition, with 5Kh-1Rate of temperature fall be slowly cooled to room temperature, stand 2 days after, use DMF solution
Washing is filtered and is dried in air, as target product anionic metal-organic framework materials.
The above-mentioned method that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, described has engine dyeing
Material is cationic organic dyestuff.
The above-mentioned method that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, the cation
Type organic dyestuff is methylene blue.
The beneficial effects of the invention are as follows：Anionic metal-organic framework materials prepared by the present invention can be used as main body material
Rear synthesis field of the material applied to host-guest chemistry.Prepared anionic metal-organic framework materials can be used as absorption base
Confrontation cationic organic dyestuff is adsorbed, efficient selective separation Cationic organic dyes.The anionic gold of the present invention
It is simple to belong to organic framework material preparation method, the method has universality, has great application prospect.
Description of the drawings
Fig. 1 is the structure diagram of anionic metal-organic framework materials of the present invention.
Fig. 2 is the test XRD spectra of anionic metal-organic framework materials of the present invention and the XRD spectra of simulation.
Fig. 3 is the UV, visible light that anionic metal-organic framework materials of the present invention are used to adsorb methylene blue organic dyestuff
Spectrogram.
Fig. 4 is anionic metal-organic framework materials Selective Separation crystal violet of the present invention and methylene blue organic dyestuff
Ultraviolet-visible spectrogram.
Fig. 5 is anionic metal-organic framework materials Selective Separation methyl orange of the present invention and methylene blue organic dyestuff
Ultraviolet-visible spectrogram.
Fig. 6 is anionic metal-organic framework materials Selective Separation tonyred of the present invention and methylene blue organic dyestuff
Ultraviolet-visible spectrogram.
Fig. 7 is anionic metal-organic framework materials packing chromatography post separation methylene blue of the present invention, crystal violet, the Sudan
Red and methyl orange organic dyestuff.
Specific embodiment
Embodiment 1
(1) preparation of anionic metal-organic framework materials
By the In (NO of 0.037mmol3)3, [1, the 1 ' of 0.037mmol:4 ', 1 "-terphenyl] -3,3 ", 5,5 "-tetrabasic carboxylic acid,
The n,N-Dimethylformamide (DMF) of 2mL, the acetonitrile of 1mL are added in the vial that volume is 5mL, and normal temperature condition stirs
30 minutes.Vial is sealed and is put into baking oven.Heating makes the temperature of baking oven reach 363K, heating rate 5K from room temperature
min-1, and maintain the temperature under the conditions of this and keep the temperature 36 hours.With 5K h-1Rate of temperature fall be slowly cooled to room temperature, stand 2 days
Afterwards, water white transparency octahedral crystal is obtained；It is washed, filtered with DMF solution and dried in air, as target product anion
Type metal-organic framework materials, yield 79%.
The structure of anionic metal-organic framework materials that the present invention synthesizes is as shown in Figure 1, the crystal structure belongs to four
Prismatic crystal system, space group P42/mmc.Molecular formula is：[Me2NH2][In(tptc)](DMF)2(H2O)4.The compound is by monokaryon
[In(O2CR)4] as node, the three-dimensional structure formed by tetrabasic carboxylic acid ligand bridging.Cation [(CH3)2NH2]+As contend with from
Son is in the duct of the MOF.Each [1,1 ':4 ', 1 "-terphenyl] -3,3 ", 5,5 "-tetrabasic carboxylic acid ligand and four In3+Ion
Coordination, each In3+Ion and four come from [1,1 ':4 ', 1 "-terphenyl] -3,3 ", eight oxygen atoms of 5,5 "-tetrabasic carboxylic acid
Coordination.Along c- axis directions, which has square duct, and channel diameter is aboutCounter cation and solvent molecule are removed, it should
The pore volume of framework material is 65-73%.
It, can by Fig. 2 such as the test XRD spectra and the XRD spectra of simulation that Fig. 2 is anionic metal-organic framework materials
See, test XRD spectra and theoretical modeling XRD spectra result is coincide substantially, the object phase purity that can be proved is very high.
(2) anionic metal-organic framework materials are used to efficiently separate organic dyestuff
Organic dyestuff is adsorbed as adsorbing base using the anionic metal-organic framework materials of preparation.
1) organic cation dye methylene blue is taken in DMF solution, obtains methylene blue (MB) a concentration of 1 × 10-4M's
Methylene blue dye solution.
Methylene blue dye solution 5mL is taken, anionic metal-organic framework materials 30mg is added in, impregnates at room temperature.
The variation of dye strength in dye solution is detected with uv-vis spectra.The results are shown in Figure 3, and as seen from Figure 3, methylene blue exists
The feature peak intensity of 650nm is gradually reduced with the growth of adsorption time, illustrates the anionic metal organic framework material of the present invention
Material has methylene blue good absorption property.
2) 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 (CV) and methylene blue is respectively 1 × 10-4The mixed dye solution of M.
Mixed dye solution 5mL is taken, anionic metal-organic framework materials 30mg is added in, impregnates at room temperature.With purple
The variation of dye strength in outer visible spectrum detection mixed dye solution.The results are shown in Figure 4, and peak value is from top to bottom successively in figure
For 0min, 5min, 15min, 30min, 1h, 2h, 3h and 4h.From fig. 4, it can be seen that mixed dye solution Methylene Blue is in 650nm
Feature peak intensity be gradually reduced with the growth of adsorption time, and feature peak intensity of the crystal violet in 600nm is constant.This illustrates this
The anionic metal-organic framework materials of invention have good selective absorption to methylene blue.
The anionic metal-organic framework materials of the present invention have reached 75% in 3h to the adsorption rate of methylene blue,
In 5h, adsorption rate has reached 98%.
3) organic anionic dyes methyl orange and organic cation methylene blue is taken to be dissolved in DMF solution, obtains methyl orange
(MO) and the concentration of methylene blue is all 1 × 10-4The mixed dye solution of M.
Mixed dye solution 5mL is taken, anionic metal-organic framework materials 30mg is added in, impregnates at room temperature.With purple
The variation of dye strength in outer visible spectrum detection mixed dye solution.The results are shown in Figure 5, and peak value is from top to bottom successively in figure
For 0min, 5min, 15min, 30min, 1h, 2h, 3h and 4h.As seen from Figure 5, mixed dye solution Methylene Blue is in 650nm
Feature peak intensity be gradually reduced with the growth of adsorption time, and feature peak intensity of the methyl orange in 420nm is constant.This illustrates this
The anionic metal-organic framework materials of invention have good selective absorption to methylene blue.
4) organic zeroth order dyestuff tonyred (SD) and organic cation methylene blue is taken to be dissolved in DMF solution, obtains the Sudan
Red and methylene blue concentration is respectively 1 × 10-4The mixed dye solution of M.
Mixed dye solution 5mL is taken, anionic metal-organic framework materials 30mg is added in, impregnates at room temperature.With purple
The variation of dye strength in outer visible spectrum detection mixed dye solution.The results are shown in Figure 6, and peak value is from top to bottom successively in figure
For 0min, 5min, 15min, 30min, 1h, 2h, 3h and 4h.As seen from Figure 6, mixed dye solution Methylene Blue is in 650nm
Feature peak intensity be gradually reduced with the growth of adsorption time, and feature peak intensity of the tonyred in 480nm is constant.This illustrates this
The anionic metal-organic framework materials of invention have good selective absorption performance to methylene blue.
5) chromatography column packing chromatography post separation methylene blue organic dyestuff.
The freshly prepd anionic metal-organic framework materials chromatography columns of 100mg are taken, take 5mL respectively, a concentration of 1 ×
10-4The dye solution MB of M+；MB+/MO-；MB+/CV+；MB+/SD0, it is added dropwise in 4 groups of chromatographic columns.The results are shown in Figure 7, Fig. 7
In, (a) pure anionic metal-organic framework materials；(b)MB+；(c)MB+/MO-；(d)MB+/CV+；(e)MB+/SD0.By
Fig. 7 as it can be seen that this present invention anionic metal-organic framework materials filling chromatographic column can efficiently adsorb methylene blue, and
With good selectivity.
Claims (5)
- A kind of 1. method that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, which is characterized in that method It is as follows：In the n,N-Dimethylformamide solution containing organic dyestuff, anionic metal-organic framework materials, leaching are added in Bubble, absorption；The anionic metal-organic framework materials are [Me2NH2][In(tptc)](DMF)2(H2O)4, wherein tptc It is [1,1 ':4 ', 1 "-terphenyl] -3,3 ", 5,5 "-tetracarboxylic acid hydrochlorate.
- 2. the method according to claim 1 that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, It is characterized in that, the anionic metal-organic framework materials are three-dimensional anion frame materials, belong to tetragonal crystal system, it is empty Between group be P42/ mmc, counter ion counterionsl gegenions are dimethylamine cation, have square duct, channel diameterPore volume is 65- 73%.
- 3. the method according to claim 1 that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, It is characterized in that, the preparation method of the anionic metal-organic framework materials includes the following steps：By In (NO3)3, [1, 1’:4 ', 1 "-terphenyl] -3,3 ", 5,5 "-tetrabasic carboxylic acid, n,N-Dimethylformamide and acetonitrile are added in vial, and room temperature Under the conditions of stir 30 minutes, vial is sealed and is put into baking oven, heating the temperature of baking oven is made to reach 363K from room temperature, heat up Rate is 5Kmin-1, and maintain the temperature under the conditions of this and keep the temperature 36 hours, with 5Kh-1Rate of temperature fall progressively cool to room Temperature after standing 2 days, is washed with DMF solution, is filtered and is dried in air, as the organic bone of target product anionic metal Frame material.
- 4. the method according to claim 1 that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, It is characterized in that, the organic dyestuff is cationic organic dyestuff.
- 5. the method according to claim 4 that organic dyestuff is efficiently separated based on anionic metal-organic framework materials, It is characterized in that, the cationic organic dyestuff is methylene blue.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942417A (en) * | 2019-03-13 | 2019-06-28 | 西北大学 | Prepare the method with the indium metal organic frame compound and cotton spinning knitted fabric of anti-ultraviolet function |
| CN110575818A (en) * | 2019-08-06 | 2019-12-17 | 杭州电子科技大学 | Carboxyl modified ionic metal organic framework material capable of rapidly, efficiently and selectively adsorbing trace pollutants as well as preparation method and application thereof |
| CN114276552A (en) * | 2020-09-28 | 2022-04-05 | 中国科学院福建物质结构研究所 | Carboxylic acid monomer based anionic hydrogen bond organic frame material, preparation method and application thereof |
| CN114870807A (en) * | 2022-04-25 | 2022-08-09 | 天津国科医工科技发展有限公司 | Ionized magnetic microsphere material |
-
2018
- 2018-02-11 CN CN201810141426.7A patent/CN108144326A/en active Pending
Non-Patent Citations (1)
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| 曹小漫: "多齿羧酸配体构筑的金属有机框架材料的合成及其性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942417A (en) * | 2019-03-13 | 2019-06-28 | 西北大学 | Prepare the method with the indium metal organic frame compound and cotton spinning knitted fabric of anti-ultraviolet function |
| CN109942417B (en) * | 2019-03-13 | 2021-07-06 | 西北大学 | Method for preparing indium metal organic framework compound with ultraviolet resistance function and cotton textile fabric |
| CN110575818A (en) * | 2019-08-06 | 2019-12-17 | 杭州电子科技大学 | Carboxyl modified ionic metal organic framework material capable of rapidly, efficiently and selectively adsorbing trace pollutants as well as preparation method and application thereof |
| CN110575818B (en) * | 2019-08-06 | 2022-08-23 | 杭州电子科技大学 | Carboxyl modified ionic metal organic framework material capable of rapidly, efficiently and selectively adsorbing trace pollutants as well as preparation method and application thereof |
| CN114276552A (en) * | 2020-09-28 | 2022-04-05 | 中国科学院福建物质结构研究所 | Carboxylic acid monomer based anionic hydrogen bond organic frame material, preparation method and application thereof |
| CN114276552B (en) * | 2020-09-28 | 2023-03-28 | 中国科学院福建物质结构研究所 | Carboxylic acid monomer based anionic hydrogen bond organic frame material, preparation method and application thereof |
| CN114870807A (en) * | 2022-04-25 | 2022-08-09 | 天津国科医工科技发展有限公司 | Ionized magnetic microsphere material |
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Application publication date: 20180612 |