CN106824100A - A kind of zinc MOF poromerics of efficient capture iodine and preparation method and application - Google Patents
A kind of zinc MOF poromerics of efficient capture iodine and preparation method and application Download PDFInfo
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- CN106824100A CN106824100A CN201710148875.XA CN201710148875A CN106824100A CN 106824100 A CN106824100 A CN 106824100A CN 201710148875 A CN201710148875 A CN 201710148875A CN 106824100 A CN106824100 A CN 106824100A
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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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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/02—Treating gases
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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Abstract
The present invention provides a kind of new, efficient capture iodine zinc MOF poromerics and preparation method and application.The zinc MOF poromerics is with Zn (OAc)2·6H2O, aminopyridine and 3,3', 5,5', terphenyl tetrabasic carboxylic acid is raw material, is prepared by solvent thermal reaction, and its chemical composition is [Zn2(tptc)(apy)2‑x(H2O)x]·H2O(0<x<2).The present invention synthesizes zinc MOF poromerics using solvent thermal process, only needs single step reaction, and raw material is cheap and easy to get, and preparation technology is simple to operate, mild condition；Parameter adjustable in course of reaction, it is easy to control crystallinity and the thing phase composition of product.Its porosity is 58.1%, and experiment proves that the material is up to 216wt% in steam and the aqueous solution to the adsorbance of iodine, and every gram of zinc MOF material can adsorb two grams of iodine, be a kind of good iodine capture material.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of zinc-MOF poromerics of efficient capture iodine and its
Preparation method and application.
Background technology
129I has caused special attention, because it has length as a kind of important radio isotope in nuke rubbish
Radioactive half-life (1.57 × 107Year), it is difficult to process, in coexisting in waste water and gas with the heavy element such as radiostrontium, barium, sternly
Heavily contaminated environment, threat human health.Therefore effectively capture radioiodine still suffers from very big challenge in nuclear waste.At this
Aspect, some iodine adsorbents have been studied, and including chalcogen aeroge, feature clay and the poroid zeolitic material of silver-based etc., bear
Carrying capacity is from 8wt% to 175wt%.However, there is high cost, limited sorption capacity or pollution in them, its application
It is restricted.Accordingly, it would be desirable to seek a kind of stabilization, the material of iodine capture ability efficient, high.
The content of the invention
It is an object of the invention to provide a kind of new, efficient capture iodine zinc-MOF poromerics and preparation method thereof with
Using.
Zinc-MOF poromerics provided by the present invention, containing Zn elements and the terphenyl tetrabasic carboxylic acid of part 3,3', 5,5'- and
Part 4-aminopyridine, its chemical composition is [Zn2(tptc)(apy)2-x(H2O)x]·H2O, wherein, 0<x<2, tptc represent 3,
3', 5,5'- terphenyl tetrabasic carboxylic acids, apy represents 4-aminopyridine, belongs to trigonal system, R-3m space groups, and cell parameter is：
18.8317(10),18.8317(10),38.5698(13),90,90,120,11845.6(13)。
Zinc-MOF poromerics provided by the present invention is that the method by comprising the steps is prepared：
With Zn (OAc)2·6H2O, 4-aminopyridine and 3,3', 5,5' ,-terphenyl tetrabasic carboxylic acid is raw material, carries out solvent heat
Reaction, obtains the system of the poromerics of-MOF containing zinc.
In the above method, Zn (OAc)2·6H2O and aminopyridine and 3,3', 5,5', the mol ratio of-terphenyl tetrabasic carboxylic acid can
It is 3~5:1:1, concretely 3:1:1.
The solvent for being used is 3~5 for DMAC N,N' dimethyl acetamide and water volume ratio:1 (concretely 5:1) mixing is molten
Agent.
The pH value of above-mentioned reaction system is 5~7, concretely 6.
The temperature of the solvent thermal reaction is 90~120 DEG C, and concretely 100 DEG C, the time is 4~7 days, concretely 5
My god.
The above method also includes the system of the poromerics of-MOF containing zinc post-process obtaining zinc-MOF micropore materials
The operation of material.The operation is specially：By the system of the poromerics of-MOF containing zinc with 5~20 DEG C per hour (concretely 5
DEG C) speed be cooled to room temperature, filter and wash and obtain white chunks crystal, as zinc-MOF poromerics.
Application of the above-mentioned zinc-MOF poromerics in iodine capture falls within protection scope of the present invention.
The iodine can be radioiodine129I。
Application of the above-mentioned zinc-MOF poromerics in the nuclear waste disposal containing iodine falls within protection scope of the present invention.
The present invention also provides a kind of using above-mentioned zinc-MOF poromerics nuke rubbish method of the treatment containing iodine.
Methods described is：By zinc-MOF poromerics activation, by the zinc-MOF poromerics after activation with containing iodine
Nuke rubbish is contacted, and 0-50 hours (endpoint value 0 does not take) is kept at 50-100 DEG C, you can.
Wherein, the operation of the activation is：Zinc-MOF poromerics the methyl alcohol is soaked and is heated to remove wherein
Guest molecule.Wherein, guest molecule is hydrone, [Zn in molecular composition2(tptc)(apy)2-x(H2O)x]·H2O brackets
The part of outside.
The nuke rubbish containing iodine can be alternatively core waste gas for nuclear waste.
The present invention synthesizes zinc-MOF poromerics using solvent thermal process, only needs single step reaction, and raw material is cheap and easy to get, system
Standby technological operation is simple, mild condition；Parameter adjustable in course of reaction, it is easy to control crystallinity and the thing phase composition of product.
Its chemical composition is [Zn2(tptc)(apy)2-x(H2O)x]·H2O(0<x<2), porosity is 58.1%, and experiment proves the material
Be up to 216wt% to the adsorbance of iodine in steam and solution, every gram of zinc-MOF material can adsorb two grams of iodine, be it is a kind of very well
Iodine capture material.This material is to the strong affinity of iodine mainly due to the halogen bond effect between iodine molecule, iodine molecule and skeleton
Electric charge transfer effect, electron supplying capacity of amino between phenyl ring etc..
Brief description of the drawings
Fig. 1 is the structure chart of zinc-MOF poromerics prepared by embodiment 1, wherein, a is coordination context diagram, and b isHole, c isShuttle hole long, d is three-dimensional structure, and e is NbO topological networks.
The figure that color is gradually changed after the zinc-MOF poromerics absorption iodine that Fig. 2 is prepared for embodiment 1.
Fig. 3 is the zinc-MOF poromerics of the preparation of embodiment 1 to I2Adsorbance changes over time figure.
Fig. 4 is I after being put into the zinc-MOF materials of the preparation of embodiment 12The figure that gradually changes of cyclohexane solution color.
Fig. 5 is the I in zinc-MOF materials absorption cyclohexane solution prepared by embodiment 12Front and rear photo.
Specific embodiment
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
Experimental technique used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., unless otherwise specified, commercially obtain.
Embodiment 1, using solvent thermal process synthesize zinc-MOF poromerics
By Zn (OAc)2·6H2O, 4-aminopyridine and 3,3', 5,5', (mol ratio is the mixture of-terphenyl tetrabasic carboxylic acid
3:1:1) it is 5 to be dissolved in DMAC N,N' dimethyl acetamide and water volume ratio:It is added dropwise 6mol/L's in 1 mixed solvent, in whipping process
It is 6 that salpeter solution adjusts pH value；Be transferred to mixed liquor in the reactor with polytetrafluoroethylsubstrate substrate after 30 minutes by stirring, is placed in
Heating is kept for 5 days in 100 DEG C of baking ovens；Room temperature is cooled to 5 DEG C per hour of speed again, filters and wash that to obtain final product white chunks brilliant
Body (complex 1, i.e. zinc-MOF poromerics).
Complex 1 is crystallized in tripartite's space group R-3m, and cell parameter is：18.8317(10),18.8317(10),
38.5698(13),90,90,120,11845.6(13).As shown in figure 1, two Zn2+Ion forms double by four carboxyl oxygen bridgings
Core [Zn2(COO)4] wheel paddle type secondary structure unit, 4-aminopyridine molecule is in the coordination of direction of principal axis end group.The secondary knot of each double-core
Structure unit is connected by four terphenyl Carboxylic acid ligand bridgings, and each part with four two core clusters, forms a NbO for three-dimensional
Topological classification framework (Fig. 1-e).Two kinds of D3The hole of symmetry replaces accumulation and forms three-dimensional framework, and PLATON softwares are calculated and show hole
Gap rate is 58.1%.Fig. 1 is to parse real structure chart by single crystal data, and provable structure is exactly such.
Therefore, complex 1 has good porous and stability.
The absorption of embodiment 2, zinc-MOF poromerics to iodine molecule
Zinc-MOF poromerics activation processs：In order to remove the guest molecule in material structure, (the i.e. embodiment 1 of complex 1
Zinc-MOF the poromerics of preparation) soak three days in methyl alcohol, three new methyl alcohol are changed daily.Material is in 100 DEG C of vacuum drying oven
A whole night is heated, for the research of iodine adsorption experiment.
Crystal after activation is placed in a vial weighed in advance, a closing system containing iodine molecule is placed on
System, in the lower 75 DEG C of baking ovens of normal pressure.The color of crystal is gradually changed into black (such as Fig. 2) from colourless, and different time claims its crystal mass
Change.In initial 20 hours, the adsorption capacity of complex 1 is very fast；Crystal is to I after 50 hours2Load capacity does not substantially become
Change, show that adsorbance has basically reached saturation, to I2Uptake is up to 206wt% (such as Fig. 3), and this is all holes of hitherto reported
(including zeolite, activated carbon and POF) is to I in shape adsorbent2The maximum of adsorbance.
This zinc-MOF materials are to I2Strong absorption affinity be attributable to big porosity, abundant phenyl ring conjugated electrons fragrance
Halogen bond effect between framework, strong electron donor amino and iodine molecule etc..Specific explanations are as follows：(1) iodine molecule can utilize I-
I ... N and I-I ... π halogen bond effects, are adsorbed in hole；(2) I-I ... I-I halogen keys can be formed between iodine molecule, is acted on stronger.Three
Kind halogen key collective effect is greatly facilitated the adsorption capacity to iodine molecule.Meanwhile, electric charge is easily formed between phenyl ring and iodine molecule
Transfer complex, further increases adsorbance of the MOF materials to iodine molecule.
Zinc-MOF materials prepared by embodiment 1 are put into I2Cyclohexane solution in, find growth over time, solution
Color gradually becomes shallower as (Fig. 4), and after finally filtering, zinc-MOF materials become dark red (Fig. 5) by white crystal.Experimental result table
It is bright, the I that zinc-MOF materials of the invention also can be in adsorbent solution2。
Claims (9)
1. a kind of zinc-MOF poromerics, contains Zn elements and the terphenyl tetrabasic carboxylic acid of part 3,3', 5,5'- and part 4- amino pyrroles
Pyridine, its chemical composition is [Zn2(tptc)(apy)2-x(H2O)x]·H2O, wherein, x=0<x<2, tptc represent 3,3', 5,5'-
Terphenyl tetrabasic carboxylic acid, apy represents 4-aminopyridine, belongs to trigonal system, R-3m space groups, and cell parameter is：18.8317
(10),18.8317(10),38.5698(13),90,90,120,11845.6(13)。
2. the method for preparing the zinc-MOF poromerics described in claim 1, including：With Zn (OAc)2·6H2O, 4-aminopyridine
With 3,3', 5,5' ,-terphenyl tetrabasic carboxylic acid is raw material, carries out solvent thermal reaction, obtains the system of the poromerics of-MOF containing zinc.
3. method according to claim 2, it is characterised in that：
Zn(OAc)2·6H2O is 3~5 with the mol ratio of aminopyridine and the phenyl ring tetrabasic carboxylic acid of 3,3', 5,5' ,-three:1:1；
The solvent for being used is 3~5 for DMAC N,N' dimethyl acetamide and water volume ratio:1 mixed solvent；
The pH value of reaction system is 5~7；
The temperature of the solvent thermal reaction is 90~120 DEG C, and the time is 4~7 days.
4. according to the method in claim 2 or 3, it is characterised in that：Methods described also includes to the micropores of-MOF containing zinc
The system of material carries out post-processing the operation for obtaining zinc-MOF poromerics；
The operation is：The system of the poromerics of-MOF containing zinc is cooled to room temperature, mistake with 5~20 DEG C per hour of speed
Filter and wash and obtain white chunks crystal, as zinc-MOF poromerics.
5. application of the zinc-MOF poromerics described in claim 1 in iodine capture.
6. application according to claim 5, it is characterised in that：The iodine is radioiodine129I。
7. application of the zinc-MOF poromerics described in claim 1 in nuclear waste disposal containing iodine.
8. a kind of processing method of the nuke rubbish containing iodine, including：Zinc-MOF poromerics activation described in claim 1, will
Zinc-MOF poromerics after activation is contacted with the nuke rubbish containing iodine, is kept for 0-50 hours at 50-100 DEG C, you can.
9. the processing method of the nuke rubbish containing iodine according to claim 8, it is characterised in that：The nuke rubbish containing iodine is
Nuclear waste or core waste gas.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400896A (en) * | 2018-10-25 | 2019-03-01 | 陕西科技大学 | A kind of zinc coordination polymer iodine vapor support materials and its preparation method and application |
| CN110152734A (en) * | 2019-05-15 | 2019-08-23 | 山西师范大学 | A kind of application of Hemin@Zn-MOF material in terms of catalysis oxidation |
| CN110544544A (en) * | 2019-09-25 | 2019-12-06 | 中国原子能科学研究院 | Device and method for continuously generating iodine steam |
| CN111535033A (en) * | 2020-04-30 | 2020-08-14 | 江阴苏达汇诚复合材料有限公司 | Preparation method and application of iodine-based antimicrobial microporous fiber material |
| CN112479835A (en) * | 2020-11-20 | 2021-03-12 | 上海应用技术大学 | Pentabiphenyl macrocyclic compound and preparation and application thereof |
| CN114405482A (en) * | 2022-01-27 | 2022-04-29 | 陕西科技大学 | MOF porous adsorption material and preparation method and application thereof |
| CN114409918A (en) * | 2022-01-27 | 2022-04-29 | 陕西科技大学 | Lead-based microporous adsorption material and preparation method and application thereof |
| CN115286790A (en) * | 2022-07-12 | 2022-11-04 | 太原理工大学 | Iodine capture material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402914A (en) * | 2014-10-16 | 2015-03-11 | 东北师范大学 | Zinc metal organic framework material for catalysis degradation of organic dye under visible light |
| CN105503912A (en) * | 2016-01-04 | 2016-04-20 | 辽宁大学 | Novel Zn (II) metal organic framework and synthetic method and application thereof |
-
2017
- 2017-03-14 CN CN201710148875.XA patent/CN106824100A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402914A (en) * | 2014-10-16 | 2015-03-11 | 东北师范大学 | Zinc metal organic framework material for catalysis degradation of organic dye under visible light |
| CN105503912A (en) * | 2016-01-04 | 2016-04-20 | 辽宁大学 | Novel Zn (II) metal organic framework and synthetic method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| RU-XIN YAO ET AL.: "A Luminescent Zinc(II) Metal−Organic Framework (MOF) with Conjugated π‑Electron Ligand for High Iodine Capture and Nitro-Explosive Detection", 《INORGANIC CHEMISTRY》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400896A (en) * | 2018-10-25 | 2019-03-01 | 陕西科技大学 | A kind of zinc coordination polymer iodine vapor support materials and its preparation method and application |
| CN110152734A (en) * | 2019-05-15 | 2019-08-23 | 山西师范大学 | A kind of application of Hemin@Zn-MOF material in terms of catalysis oxidation |
| CN110544544A (en) * | 2019-09-25 | 2019-12-06 | 中国原子能科学研究院 | Device and method for continuously generating iodine steam |
| CN110544544B (en) * | 2019-09-25 | 2021-07-30 | 中国原子能科学研究院 | Device and method for continuously generating iodine steam |
| CN111535033A (en) * | 2020-04-30 | 2020-08-14 | 江阴苏达汇诚复合材料有限公司 | Preparation method and application of iodine-based antimicrobial microporous fiber material |
| CN111535033B (en) * | 2020-04-30 | 2023-06-23 | 江阴苏达汇诚复合材料有限公司 | Preparation method and application of iodine antimicrobial microporous fiber material |
| CN112479835B (en) * | 2020-11-20 | 2022-10-14 | 上海应用技术大学 | Pentabiphenyl macrocyclic compound and preparation and application thereof |
| CN112479835A (en) * | 2020-11-20 | 2021-03-12 | 上海应用技术大学 | Pentabiphenyl macrocyclic compound and preparation and application thereof |
| CN114405482A (en) * | 2022-01-27 | 2022-04-29 | 陕西科技大学 | MOF porous adsorption material and preparation method and application thereof |
| CN114409918B (en) * | 2022-01-27 | 2023-06-23 | 陕西科技大学 | Lead-based microporous adsorption material and preparation method and application thereof |
| CN114409918A (en) * | 2022-01-27 | 2022-04-29 | 陕西科技大学 | Lead-based microporous adsorption material and preparation method and application thereof |
| CN115286790A (en) * | 2022-07-12 | 2022-11-04 | 太原理工大学 | Iodine capture material and preparation method and application thereof |
| CN115286790B (en) * | 2022-07-12 | 2023-05-23 | 太原理工大学 | Iodine capturing material and preparation method and application thereof |
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