CN106588951B - A kind of porous metal-organic framework compound and its preparation method and application based on zinc - Google Patents
A kind of porous metal-organic framework compound and its preparation method and application based on zinc Download PDFInfo
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- CN106588951B CN106588951B CN201710057891.8A CN201710057891A CN106588951B CN 106588951 B CN106588951 B CN 106588951B CN 201710057891 A CN201710057891 A CN 201710057891A CN 106588951 B CN106588951 B CN 106588951B
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- organic framework
- porous metal
- framework compound
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic System without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The present invention relates to a kind of porous metal-organic framework compound and its preparation method and application based on zinc.The compound is by Zn (NO3)2·6H2O, [3,2-b] 1,4-Dithiapentalene base -2,5- dicarboxylic acids, n,N-Dimethylformamide, deionized water is added to the container, and under room temperature, is stirred 20-40 minutes；It is put into baking oven after container is sealed, under temperature 368K ± 50K, is kept for 2-4 days；It is slowly cooled to room temperature, is washed, filtered with n,N-Dimethylformamide, is dry, obtaining yellow transparent bulk crystals target product.Copper ion can be separated as adsorbing base with efficient selective based on the porous metal-organic framework of zinc prepared by the present invention.
Description
Technical field
The preparation and application of the present invention relates to a kind of porous metal-organic framework compound based on zinc specifically relate to
And a kind of preparation and its application of the porous metal-organic framework compound based on zinc with selective substances adsorption function.
Background technique
In recent years, metal organic framework compound (MOFs) has been widely used different functions, metal organic frame
Compound connects into porous material by metal ion and organic ligand, itself there is a big specific surface area, adjustable orifice size, with
And hole surface can functionalization.Because of their design feature, metallic framework compound be widely used in gas separation and it is organic
Molecule separation, including organic dyestuff, organic isomers or even fullerene etc., as the product that multidisciplinary field intersects, metal has
The design of machine framework compound synthesizes and performance study has developed into very active one of the field of Recent study.However seldom
Applied to separating metal ions, transition metal ions size is very close, and relying solely on pore size cannot efficiently separate, so logical
The interaction crossed between metal ion and metal organic framework can be able to achieve the separation of different metal ions.
Heavy metal pollution, which has become, seriously threatens environmental and public health.Heavy metal ion, even if in low concentration, for work
Organism have very strong toxicity.Heavy metal be it is nondegradable, have for environment and biosystem very serious negative
It influences, copper ion is one of element necessary to human body, but copper ion excessively understands heavy metal excessively and can result in a series of minds
Through systemic disease.Therefore, copper ion is effectively removed to be very important.
Summary of the invention
The purpose of the present invention is utilize [3,2-b] 1,4-Dithiapentalene base -2,5- dicarboxylic acids using metallic zinc as metal node
As organic ligand, at a certain temperature, a kind of porous metal-organic framework based on zinc is synthesized using the method for solvent heat
Compound.
The technical solution adopted by the present invention is that:
A kind of porous metal-organic framework compound based on zinc, the preparation method is as follows:
1) by Zn (NO3) 26H2O, [3,2-b] 1,4-Dithiapentalene base -2,5- dicarboxylic acids and is gone at n,N-Dimethylformamide
Ionized water is added to the container, and under room temperature, is stirred 20-40 minutes；
2) it is put into after sealing container in baking oven, under 368K ± 50K, is kept for 2-4 days；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains crystal；
4) it is washed, is filtered with n,N-Dimethylformamide, it is dry, obtain target product.
The porous metal-organic framework compound based on zinc, the porous metal-organic framework based on zinc
The crystal for closing object belongs to cubic system, space group Fm3m.
The porous metal-organic framework compound based on zinc, Zn (NO3) 26H2O and [3,2-b] in step 1)
The mass ratio of 1,4-Dithiapentalene base -2,5- dicarboxylic acids is 5:3.
The porous metal-organic framework compound based on zinc is put into baking oven after sealing container in step 2),
Heating rate is 2-8Kmin-1.
The porous metal-organic framework compound based on zinc, the rate of temperature fall being slowly cooled to room temperature in step 3)
For 2-8Kh-1.
The porous metal-organic framework compound based on zinc described in a kind of adsorbs in transition metal as adsorbing base
The application of copper ion.
The application, the method is as follows: in organic containing the porous metals based on zinc are added in copper ion solution
Framework compound impregnates, absorption.
The application, the copper ion are Gerhardite solution.
The beneficial effects of the present invention are: a kind of porous metal-organic framework compound based on zinc prepared by the present invention can
It is applied to the rear synthesis field of host-guest chemistry as material of main part.A kind of prepared porous metal-organic framework based on zinc
It can be used as adsorbing base to adsorb copper ion, efficient selective separates copper ion.Porous gold based on zinc of the invention
It is simple to belong to organic backbone preparation method, has great application prospect.
Detailed description of the invention
Fig. 1 is the synthesis schematic diagram of the porous metal-organic framework compound the present invention is based on zinc.
Fig. 2 is the duct schematic diagram of the porous metal-organic framework compound the present invention is based on zinc.
Fig. 3 is that the present invention is based on the porous metal-organic framework compound chromatographic columns of zinc to select separation copper ion and cobalt ions
Solution picture.
Fig. 4 is that the present invention is based on the histograms of the porous metal-organic framework compound of zinc absorption transition metal ions.
Fig. 5 is the histogram of the porous metal-organic framework compound Selective Separation copper ion the present invention is based on zinc.
Specific embodiment
A kind of porous metal-organic framework compound based on zinc of embodiment 1
The preparation method is as follows:
1) by the Zn (NO of 10mg3)2·6H2[3,2-b] 1,4-Dithiapentalene base -2,5- dicarboxylic acids of O, 6mg, the N of 1ml, N- bis-
Methylformamide, the deionized water of 1ml is added in the vial that volume is 5ml, and normal temperature condition stirs 30 minutes.
2) vial is sealed and is put into baking oven.Heating makes the temperature of baking oven reach 368K from room temperature, and heating rate is
5K·min-1, and maintain the temperature at and keep the temperature 72 hours under this condition.
3) with 5Kh-1Rate of temperature fall be slowly cooled to room temperature, obtain yellow transparent bulk crystals；
4) it washed, filter and is dried in air with n,N-Dimethylformamide (DMF) solution, as target product is based on
The porous metal-organic framework of zinc, yield 68%.
The present invention is based on the synthesis of the porous metal-organic framework compound of zinc as shown in Figure 1, its structure as shown in Fig. 2,
The crystal structure belongs to monoclinic system, and space group is cube Fm3m.The compound is matched as node by dicarboxylic acids by four core zinc clusters
Three-dimensional structure made of body bridging.Cation [(CH3)2NH2]+It is located in the duct of the MOF as counter ion counterionsl gegenions.Each [3,2-
B] 1,4-Dithiapentalene base -2,5- dicarboxylic acids and two zinc clusters are coordinated.
A kind of porous metal-organic framework compound based on zinc of embodiment 2 adsorbs the selection of copper ion
Method: using embodiment 1 preparation based on zinc porous metal-organic framework compound as adsorbing base to copper ion into
Row absorption.
1) Cu (NO is taken3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cd(NO3)2·6H2O、Pb(NO3)2·
6H2O is dissolved in DMF solution respectively, obtains M (NO3)2·nH2O (M=Cu2+、Co2+、Ni2+、Cd2+、Pb2+) concentration be respectively 1
×10-4The metallic solution of M.
Metallic solution 3ml is taken, the porous metal-organic framework crystal 30mg based on rare earth is added, impregnates at room temperature.4h
Afterwards, filtering is taken out, and after processing, tests tenor by ICP.It as a result as shown in table 1 and Fig. 4, is M/Er (M=Cu in table2+、
Co2+、Ni2+、Cd2+、Pb2+) contain numerical quantity.By table 1 and Fig. 4 as it can be seen that content of copper ion is very high, and Pb2+、Co2+、Ni2+、Cd2+
Content it is very low.This illustrates that the porous metal-organic framework compound of the invention based on zinc has selection well to copper ion
Property absorption.
Table 1 is the ICP test gold the present invention is based on the porous metal-organic framework compound of zinc absorption transition metal ions
Belong to content table.
2) Cu (NO has been taken3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O is dissolved in DMF, obtains Cu2+,Co2 +,Ni2+Concentration is respectively 1 × 10-4The mixed metal solution of M.
Mixed metal solution 3ml is taken, the porous metal-organic framework crystal 30mg based on zinc is added, soaks 4h at room temperature
Afterwards, filtering is taken out, and after processing, tests tenor by ICP.It as a result is M/Er (M=Cu in table as shown in table 2 and Fig. 52+、
Co2+、Ni2+).By table 2 and Fig. 5 as it can be seen that the content of copper ion is very high, and Co2+、Ni2+Content it is very low, this illustrates base of the present invention
There is good selective absorption to copper ion in the crystal structure of the porous metal-organic framework of zinc.Table 2 be the present invention is based on
The ICP of the porous metal-organic framework Selective Separation copper ion of zinc tests tenor table.
| Metal ions(M) | M/Er Mass(experimental) | M/Zn Mol ratio(calculation) |
| Cu2+ | 58.16/70.71 | 0.91 |
| Co2+ | 7.37/70.71 | 0.12 |
| Ni2+ | 4.13/70.71 | 0.07 |
3) the organic machine skeleton crystal of metal based on zinc is studied by ion chromatographic column to Cu2+And Co2+High efficiency selected
Property.
Take Cu (NO3)2·6H2O、Co(NO3)2·6H2O is dissolved in DMF, is obtained containing Cu2+And Co2+Concentration is 0.2mol/
The solution of L.
The organic machine skeleton crystal of metal based on zinc is put into chromatographic column, ion chromatographic column (80mm × 5mm) is obtained, takes
The Cu of 2ml2+And Co2+Mixed liquor injection the organic machine skeleton crystal of metal based on zinc be put into chromatographic column, as a result as shown in figure 3,
Cu2+Retain in the chromatography column, Co2+It is filtered out with DMF.This illustrates of the invention organic based on the porous metals containing thiophene
The crystal structure of skeleton has good selective absorption to copper ion.This illustrates that the porous metals of the invention based on zinc are organic
Framework compound has good selective absorption to copper ion.
Claims (7)
1. a kind of porous metal-organic framework compound based on zinc, which is characterized in that the porous metals based on zinc have
The crystal of machine framework compound belongs to cubic system, space group Fm3m, and preparation method is as follows:
1) by Zn (NO3)2·6H2O, [3,2-b] 1,4-Dithiapentalene base -2,5- dicarboxylic acids, n,N-Dimethylformamide and deionization
Water is added to the container, and under room temperature, is stirred 20-40 minutes；
2) it is put into after sealing container in baking oven, under 368K ± 50K, is kept for 2-4 days；
3) it is slowly cooled to room temperature, after standing at least 1 day, obtains crystal；
4) it is washed, is filtered with n,N-Dimethylformamide, it is dry, obtain target product.
2. the porous metal-organic framework compound according to claim 1 based on zinc, it is characterised in that: Zn in step 1)
(NO3)2·6H2The mass ratio of O and [3,2-b] 1,4-Dithiapentalene base -2,5- dicarboxylic acids is 5:3.
3. the porous metal-organic framework compound according to claim 1 based on zinc, it is characterised in that: will in step 2)
It is put into baking oven after container sealing, heating rate 2-8Kmin-1。
4. the porous metal-organic framework compound according to claim 1 based on zinc, it is characterised in that: delay in step 3)
The rate of temperature fall of slow cool down to room temperature is 2-8Kh-1。
5. a kind of porous metal-organic framework compound based on zinc as described in claim 1 is as adsorbing base in transition gold
The application of copper ion is adsorbed in category.
6. application according to claim 5, it is characterised in that method is as follows: in containing described in addition in copper ion solution
Porous metal-organic framework compound based on zinc impregnates, absorption.
7. application according to claim 5, it is characterised in that: the copper ion is Gerhardite solution.
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| CN107177038B (en) * | 2017-04-21 | 2020-04-21 | 辽宁师范大学 | Moisture-resistant MOF-5-like compound, preparation method and application |
| CN107759802B (en) * | 2017-10-25 | 2020-05-01 | 中国科学技术大学 | Preparation method of high-molecular organic ligand, preparation method of high-molecular metal organic framework, ion separation membrane and preparation method of ion separation membrane |
| CN109046255A (en) * | 2018-08-30 | 2018-12-21 | 东北师范大学 | A kind of metal-organic framework desulfuration adsorbent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009042802A1 (en) * | 2007-09-25 | 2009-04-02 | The Regents Of The University Of California | Edible and biocompatible metal-organic frameworks |
| CN102895953A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Method for synthesizing hierarchical pore zeolitic imidazolate framework 8 (ZIF-8) and application thereof in deep desulfurization of gasoline |
| CN105175295A (en) * | 2015-09-24 | 2015-12-23 | 南昌航空大学 | Preparation for thiol-functionalization MOFs material and application thereof in adsorption and removal of heavy metal ions in water |
| CN105254901A (en) * | 2015-11-04 | 2016-01-20 | 中国科学院化学研究所 | Metal organic framework material as well as preparation method and application thereof |
| CN105457614A (en) * | 2015-11-23 | 2016-04-06 | 扬州大学 | Preparation method of copper ion adsorbent based on metal-organic framework material |
| US20160361702A1 (en) * | 2015-06-09 | 2016-12-15 | The Regents Of The University Of California | Polymer-metal organic framework materials and methods of using the same |
-
2017
- 2017-01-23 CN CN201710057891.8A patent/CN106588951B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009042802A1 (en) * | 2007-09-25 | 2009-04-02 | The Regents Of The University Of California | Edible and biocompatible metal-organic frameworks |
| CN102895953A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Method for synthesizing hierarchical pore zeolitic imidazolate framework 8 (ZIF-8) and application thereof in deep desulfurization of gasoline |
| US20160361702A1 (en) * | 2015-06-09 | 2016-12-15 | The Regents Of The University Of California | Polymer-metal organic framework materials and methods of using the same |
| CN105175295A (en) * | 2015-09-24 | 2015-12-23 | 南昌航空大学 | Preparation for thiol-functionalization MOFs material and application thereof in adsorption and removal of heavy metal ions in water |
| CN105254901A (en) * | 2015-11-04 | 2016-01-20 | 中国科学院化学研究所 | Metal organic framework material as well as preparation method and application thereof |
| CN105457614A (en) * | 2015-11-23 | 2016-04-06 | 扬州大学 | Preparation method of copper ion adsorbent based on metal-organic framework material |
Non-Patent Citations (1)
| Title |
|---|
| Control of interpenetration in S-containing metal-organic frameworks for selective separation of transition metal ions;Guang-Sheng Yang,等;《Chem. Commun.》;20121210;第49卷(第11期);1088-1090以及Supporting information |
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