CN105037283A - Metal organic framework based on Cu(II) ion, synthetic method therefor and application thereof - Google Patents
Metal organic framework based on Cu(II) ion, synthetic method therefor and application thereof Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 title abstract description 15
- -1 Cu(II) ion Chemical class 0.000 title abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 33
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 150000003852 triazoles Chemical group 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 abstract description 12
- 230000004044 response Effects 0.000 abstract description 10
- 239000003086 colorant Substances 0.000 abstract description 4
- 230000000007 visual effect Effects 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 22
- 239000000243 solution Substances 0.000 description 15
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 *c1cccc(Cc2cccc(C(F)(F)F)c2)c1 Chemical compound *c1cccc(Cc2cccc(C(F)(F)F)c2)c1 0.000 description 1
- XKVLZBNEPALHIO-UHFFFAOYSA-N 1-bromo-2-methylbutane Chemical compound CCC(C)CBr XKVLZBNEPALHIO-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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Abstract
The invention discloses a metal organic framework based on a Cu(II) ion, a synthetic method therefor and an application thereof. A structural formula is [Cu(C27H32N6)2(CF3SO3)2]n, wherein n is a nonzero natural number; Cu(II)-MOF-1 is crystallized to an orthorhombic system which belongs to a pbcn space group; a node Cu(II) metal center is positioned in a coordination environment of a deformed octahedron; an octahedron coordination plane is occupied by four triazole N atoms (Cu(1)-N(1)=2.001(3) angstrom and Cu(1)-N(6)=2.011(3) angstrom) from a ligand L; and two trifluorosulfonate radicals take part in coordination in an axial direction: (Cu(1)-O(1)=2.452(2) angstrom. Cu(II)-MOF-1 is applied in ion exchange and regeneration. Cu(II)-MOF-1 is applied in ion selective recognition. Cu(II) ion is highly exposed because of weak coordination properties of an anion CF3SO3-, so that the metal organic framework can display different colors by changing the Cu(II) central coordination environment through exchange of different anions, thereby realizing visual response of anions with different concentrations and different types, and selective recognition on anions with different coordination capacities, and realizing reuse through reversed exchange of anions.
Description
Technical field
The present invention relates to a kind of metal organic frame based on Cu (II) ion and synthetic method thereof and application.
Background technology
The application of super-molecule assembling body is the most important study hotspot of current supramolecular chemistry, and the super molecular complex of the discrete type or porous with balance anion can carry out anion exchange reaction, thus makes MOFs material derive novel ion identification character.Negatively charged ion in vivo, ubiquity and playing an important role in environmental pollutant and chemical reaction process, to negatively charged ion simple and quick be identified in biochemical field and environmental protection research field has important meaning.The detection method of current negatively charged ion mainly contains ion selective electrode, ion chromatography and chemical titration etc., these methods generally need complicated process or large-scale instrument, detection of complex or cost are comparatively large, so, the requirement that simple and quick identification becomes urgent is carried out to negatively charged ion.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of metal organic frame based on Cu (II) ion and synthetic method thereof and application, this metal organic frame achieves visual response and the Selective recognition of different concns and different classes of negatively charged ion and repeats regeneration and use.
For realizing above technical problem, the technical solution used in the present invention is as follows:
For the synthesis of an organic ligand L for metal organic frame, its chemical name is 2,7-bis-(1-hydrogen-1,2,4-triazole)-9,9-diisoamyl fluorenes, and its chemical structural formula is:
A kind of metal organic frame Cu (II)-MOF-1 structural formula is [Cu (C
27h
32n
6)
2(CF
3sO
3)
2]
nn is the natural number of non-zero, and Cu (II)-MOF-1 crystallization, in rhombic system, belongs to pbcn spacer, node Cu (II) metal center is in the octahedral coordination environment of distortion, and octahedral coordination plane is by four triazole atom N from ligand L
occupying, is axially that two trifluoromethane sulfonic acid roots participate in coordination:
The synthetic method of described metal organic frame Cu (II)-MOF-1, comprises the steps:
Ligand L be dissolved in methylene dichloride, be dissolved in by copper triflate in methyl alcohol, through diffusion crystallisation method, obtained Cu (II)-MOF, heats 1-2h by Cu (II)-MOF, obtains Cu (II)-MOF-1 at 100-120 DEG C.
Preferably, the concentration of described ligand L in methylene dichloride is 1.0 × 10
﹣ 3-1.2 × 10
﹣ 3g/ml.
Preferably, the concentration of described copper triflate in methyl alcohol is 1.8 × 10
﹣ 3-2.0 × 10
﹣ 3g/ml.
Preferably, described diffusion crystallisation method be methyl alcohol is layered on be dissolved with ligand L dichloromethane solution above, as buffer layer, then will be dissolved with copper triflate methanol solution paving on the buffer layer, utilize the diffusion of methyl alcohol, make copper triflate and ligand L contact reacts.
Preferred further, the volume ratio of the methanol solution being dissolved with the dichloromethane solution of ligand L, methyl alcohol and being dissolved with copper triflate is 7-9:0.8-1.2:7-9.
Preferably, the time of described standing and reacting is 3-7 days, and the temperature of reaction is 20-25 DEG C.
The application of described Cu (II)-MOF-1 in ion-exchange and regeneration.
The described application of Cu (II)-MOF-1 in ion selectivity identification.
The application of Cu (II)-MOF-1 in ion-exchange and regeneration, experiment skeleton symbol is as follows:
Above-mentioned Cu (II)-MOF-1 is in the application of ion selectivity identification.Experiment skeleton symbol is as follows:
Advantageous Effects of the present invention is:
1, by the growth of design part No. nine position carbochains, the extension in metal organic frame duct, thus the thermostability adding Cu (II)-MOF-1;
2, the normal temperature solvent diffusion method that Cu (II)-MOF-1 adopts is synthesized, mild condition, economical and practical, and normal temperature diffusion process synthesis method required time is short.
3, due to negatively charged ion CF
3sO
3 -weak binding property make Cu (II) ion height exposed, this is made metal organic frame can be exchanged by different anions and makes the coordination environment change of Cu (II) center, thus show distinct colors, achieve like this different concns and the visual response of different classes of negatively charged ion and the anion-selective identification of different coordination ability and exchange realization by negatively charged ion inverse and repeat regeneration and use.
4, diffusion crystallisation method is adopted to obtain Cu (II)-MOF, relative to directly mixing advantage can obtain the crystalline structure of Cu (II)-MOF, thus the coordination environment and structure iron of BrukerSmartApexCCD single crystal diffractometer being resolved Cu (II)-MOF can be placed in.
Accompanying drawing explanation
The coordination environment figure of Fig. 1 Cu of the present invention (II)-MOF-1;
The two-dimentional packed structures figure of Fig. 2 Cu of the present invention (II)-MOF-1;
The infrared spectrum of Fig. 3 ligand L of the present invention;
The infrared spectrum of Fig. 4 Cu of the present invention (II)-MOF-1;
The TGA spectrogram of Fig. 5 Cu of the present invention (II)-MOF-1;
Fig. 6 Cu of the present invention (II)-MOF-1 is for the color corresponding figures of different anions;
Fig. 7 Cu of the present invention (II)-MOF-1 is based on the solid-state UV-Vis spectrogram of the compound after ion-exchange;
Fig. 8 Cu of the present invention (II)-MOF-1 is based on the infrared spectrum of the compound after ion-exchange;
The XPS figure of F in Fig. 9 (a) compound 2; The F of (b) compound 2
-chromatography of ions figure; C (peak position corresponding in standard specimen is F to () compound 2 chromatography of ions full figure according to this
-, Cl
-, Br
-, SO
4 2-);
The XPS figure of Cl in Figure 10 (a) compound 3; The Cl of (b) compound 3
-chromatography of ions figure; C (peak position corresponding in standard specimen is F to () compound 3 chromatography of ions full figure according to this
-, Cl
-, Br
-, SO
4 2-);
The XPS figure of Br in Figure 11 (a) compound 4; The Br of (b) compound 4
-chromatography of ions figure; C (peak position corresponding in standard specimen is F to () compound 4 chromatography of ions full figure according to this
-, Cl
-, Br
-, SO
4 2-);
The XPS figure of I in Figure 12 compound 5;
SO in Figure 13 (a) compound 6
4 2-chromatography of ions figure; B (peak position corresponding in standard specimen is F to () compound 6 intermediate ion chromatogram full figure according to this
-, Cl
-, Br
-, SO
4 2-);
The XPS figure at Cu center in Figure 14 compound 2-7;
The XPRD of Figure 15 compound 2'-7' and Compound C u (II)-MOF-1 schemes;
Figure 16 Cu of the present invention (II)-MOF-1 based on regenerate after ion-exchange infrared spectrum;
Figure 17 Cu of the present invention (II)-MOF-1 is at SCN
-with N
3 -selective recognition N in system
3 -infrared spectrum;
Figure 18 Cu of the present invention (II)-MOF-1 limits and the time of response for the Concentration Testing of negatively charged ion sensing.
Embodiment
Mode by the following examples further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally selects with condition.
Embodiment 1
The synthetic route of Cu (the II)-MOF-1 of the present invention's synthesis is as follows:
1, the preparation of ligand L:
Under normal temperature, 2,7-dibromo fluorenes (9.72g, 30mmol), Tetrabutyl amonium bromide (0.08g, 0.25mmol), the bromo-2-methylbutane of 1-(10.33g, 90mmol), the NaOH solution 10mL of 50% joins in the DMSO of 130mL, ultrasonic reaction (100W) 5 hours, pours in 500mL water after reaction terminates, 1 hour is left standstill after stirring 20mins, suction filtration, filter cake with 1% NaCl solution washing, dry, obtain the violet solid 11.90g of intermediate A, productive rate 90.9%.
N
2under protection, intermediate A (3.52g, 10mmol) 1,2; 4-triazole (1,93g, 28mmol), cesium carbonate (13.03g; 40mmmol, cuprous iodide (0.762g, 4mmol) is placed in 100ml there-necked flask; 20mlDMF makes solvent, is heated to 120 DEG C, and TLC follows the tracks of; pour in 300ml water after reaction terminates, leave standstill, suction filtration; after solid dries, silica gel column chromatography (methylene dichloride: ethyl acetate=1:1), obtains yellow solid 2.3g, productive rate 70%.The IR of ligand L as shown in Figure 3.
2, the synthesis of Cu (II)-MOF-1
In test tube, 1ml methyl alcohol is slowly layered on the 8mlCH being dissolved with L (8.8mg)
2cl
2on as buffer layer, then will be dissolved with Cu (OTf)
2(15.0mg) 8mL methyl alcohol slowly spreads on the buffer layer, room temperature leaves standstill three days and obtains green bulk crystals 12.0mg, i.e. Cu (II)-MOF, heats 1.5h by Cu (II)-MOF at 110 DEG C, namely obtains Cu (the II)-MOF-1 that we need.
Or, in test tube, 0.9ml methyl alcohol is slowly layered on the 7.5mlCH being dissolved with L (8.5mg)
2cl
2on as buffer layer, then will be dissolved with Cu (OTf)
2(14.5mg) 7.8mL methyl alcohol slowly spreads on the buffer layer, 20 DEG C leave standstill 7 days and obtain green bulk crystals 11mg, i.e. Cu (II)-MOF, heats 1h by Cu (II)-MOF at 120 DEG C, namely obtains Cu (the II)-MOF-1 that we need.
Or, in test tube, 1.2ml methyl alcohol is slowly layered on the 7mlCH being dissolved with L (8.2mg)
2cl
2on as buffer layer, then will be dissolved with Cu (OTf)
2(14mg) 7.5mL methyl alcohol slowly spreads on the buffer layer, room temperature leaves standstill 5 days and obtains green bulk crystals 10mg, i.e. Cu (II)-MOF, heats 2h by Cu (II)-MOF at 100 DEG C, namely obtains Cu (the II)-MOF-1 that we need.
Obtained Cu-MOF-1 is placed on BrukerSmartApexCCD single crystal diffractometer, with MoK α radiation
with ω/θ scan mode, collect diffraction data under low temperature (123K), structural analysis is completed by ShelxtlV6.12 software package, and the first structure of title complex solves by directly sending out, and then passes through complete matrix method of least squares to F
2carry out revising the coordinate and anisotropic parameters that obtain whole non-hydrogen atom.We characterize the structure of this compound by IR and TGA, and result is shown in accompanying drawing 4 and Fig. 5 respectively.
Cu (II)-MOF-1 coordination environment as shown in Figure 1.Cu (II)-MOF-1 is in rhombic system as shown in Figure 1, belongs to pbcn spacer, takes the mode of two dimension accumulation as shown in Figure 2.Node Cu (II) metal center is in the octahedral coordination environment of distortion, and octahedral coordination plane is by four triazole atom N from ligand L
occupying, is axially that two trifluoro sulfonate radicals participate in coordination
actual crystal data are shown in Table1.
The crystallographic data of Table1Cu (II)-MOF-1
The color response of experimental example 2 pairs of different anions and sign
The each 50mg of crystal (0.0403mmol) taking Cu (the II)-MOF-1 after 6 parts of grindings is immersed in 5mL0.2MMX (KF, KCl, KBr, KI, KSCN and NaN respectively
3) solution in, Cu-MOF-1 fast response can present different colours.The sample of variable color is taken out centrifugation solvent wash respectively and drying obtains compound 2,3,4,5,6,7 under infrared lamp.The metachromasia time is respectively immediately, 5min, 1min, 1min, 3s, immediately.We have carried out the test of solid-state UV, infrared, XPS and chromatography of ions to above-mentioned 5 kinds of compounds.
The conclusion of experimental example 2 is:
Fig. 6 shows, relative to Cu (II)-MOF-1, the color of compound 2-7 there occurs change, is respectively cream-coloured, blue-greenish colour, deep green, yellow, and grass green is blackish green.Fig. 8 shows CF in compound 2-7
3sO
3 -(1251cm
-1and 1031cm
-1) peak disappearance, this anion exchange procedures of qualitative explanation is complete.There is thiocyanate ion SCN in compound 6 and compound 7 simultaneously respectively
-ion is at 2071.46cm
-1with azide anion N
3 -at 2036.74cm
-1characteristic peak, SCN is described
-and N
3 -exchange in the framework of Cu-MOF-1.
(2) show that the ion exchange ratio having exchanged rear above-claimed cpd 2-7 is all more than 95% by the calculating of Fig. 9, Figure 10, Figure 11, Figure 12, Figure 13 XPS coupled ion chromatographic data, the anion exchange procedures that quantitative analysis obtains Cu (II)-MOF-1 is more complete.
(3) Figure 14 shows relative to Cu (II)-MOF-1 and other compound in ion exchange process, and the valence state at the Cu center of compound 5 becomes+1 valency from+divalent.
Can be drawn by conclusions: Cu (the II)-MOF-1 of this invention can realize visual F
-, Cl
-, Br
-, I
-, SCN
-and N
3 -anionresin, exchange rate can reach more than 95%.
Experimental example 3 is studied based on the recycling of the negatively charged ion sensing material of anionresin
Cu (II)-MOF-1 sample 50mg (0.0403mmol) taken after 6 parts of grindings is immersed in volume 5mL respectively, concentration is that below 0.2M is containing in the solution of different anions (1mmol), the sample of variable color is taken out centrifugation solvent wash respectively and drying obtains compound 2 under infrared lamp, 3,4,5,6,7.All transfer to 2 of gained, 3,4,5,6,7 respectively in 6 small beakers, use volume 5mL, concentration is that 0.2M contains CF
3sO
3 -the solution soaking 12h of negatively charged ion (1mmol), period changes once this solution every 1-2h.By dry under infrared lamp through the compound centrifugation solvent wash of above-mentioned process, obtain compound 2 ＇, 3 ＇, 4 ＇, 5 ＇, 6 ＇, 7 ＇.And compound 2 ＇, 3 ＇, 4 ＇, 6 ＇, the solid colour of the color of 7 ＇ and Cu (II)-MOF-1.
The conclusion of experimental example 3:
Figure 15 and Figure 16 shows that, except compound 5 ＇, other several compound can be regenerated as Cu (II)-MOF-1, thus can reuse.
Experimental example 4 is about the research of Anion separation
Take the Cu after grinding (II)-MOF-1 sample 50mg (0.0403mmol) and be immersed in volume 10mL respectively, concentration is the N of 0.1M
3 -, SCN
-mixing methanol aqueous solution (N
3 -: SCN
-=1:1) mixing solutions in, soak after 6h, the sample of variable color taken out centrifugation solvent wash and drying obtains compound 8 under infrared lamp.The color of compound 8 more levels off to the blackish green of compound 7.The infrared figure of Figure 17 shows and only has N
3 -(2037cm
-1) peak, without CF
3sO
3 -(1251cm
-1and 1031cm
-1) peak and SCN
-(2052cm
-1) peak.The content that ultimate analysis records C, H, N, S in compound 8 is respectively 63.07., and 6.21,23.89,0.70, record Theoretical molecular formula CuL
2(SCN)
0.2(N
3)
1.8, thus can illustrate that Cu (II)-MOF-1 is to N
3 -and SCN
-selectivity be: N
3 ->SCN
-, and the separating effect of color response can be realized.
Experimental example 5 is based on the Concentration Testing limit research of the negatively charged ion sensing material of anionresin
Taking 10mgCu (II)-MOF-1 grinding is respectively placed in easy elution device, does drip washing test respectively, guarantee constantly to change salts solution record color transition point with the salts solution of different concns.Strength of solution is respectively 2 × 10
-1m, 2 × 10
-2m, 2 × 10
-3m, 2 × 10
-4m, 2 × 10
-5m, 2 × 10
-6m finds that Cu (II)-MOF-1 is to different negatively charged ion distinct colors response (Figure 18), within the scope of higher concentration, the time of response is very rapid, but along with the reduction of concentration, color transition point progressively postpones, the response color of same solion there will not be too big difference.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. for the synthesis of an organic ligand L for metal organic frame, it is characterized in that: its chemical name is 2,7-bis-(1-hydrogen-1,2,4-triazole)-9,9-diisoamyl fluorenes, and its chemical structural formula is:
2. metal organic frame Cu (II)-MOF-1, is characterized in that: structural formula is [Cu (C
27h
32n
6)
2(CF
3sO
3)
2]
nn is the natural number of non-zero, and Cu (II)-MOF-1 crystallization, in rhombic system, belongs to pbcn spacer, node Cu (II) metal center is in the octahedral coordination environment of distortion, and octahedral coordination plane is by four triazole atom N from ligand L
occupying, is axially that two trifluoro sulfonate radicals participate in coordination:
3. the synthetic method of metal organic frame Cu (II)-MOF-1 according to claim 2, is characterized in that: comprise the steps:
Ligand L is dissolved in methylene dichloride, copper triflate is dissolved in methyl alcohol, be obtained by reacting Cu (II)-MOF through diffusion crystallisation method, Cu (II)-MOF is heated 1-2h at 100-120 DEG C, obtain Cu (II)-MOF-1.
4. synthetic method according to claim 3, is characterized in that: the concentration of described ligand L in methylene dichloride is 1.0 × 10
﹣ 3-1.2 × 10
﹣ 3g/ml.
5. synthetic method according to claim 3, is characterized in that: the concentration of described copper triflate in methyl alcohol is 1.8 × 10
﹣ 3-2.0 × 10
﹣ 3g/ml.
6. synthetic method according to claim 3, it is characterized in that: described diffusion crystallisation method be methyl alcohol is layered on be dissolved with ligand L dichloromethane solution above, as buffer layer, then the methanol solution paving of copper triflate will be dissolved with on the buffer layer, utilize the diffusion of methyl alcohol, make copper triflate and ligand L contact reacts.
7. according to the synthetic method that claim 6 is stated, it is characterized in that: the volume ratio of the methanol solution being dissolved with the dichloromethane solution of ligand L, methyl alcohol and being dissolved with copper triflate is 7-9:0.8-1.2:7-9.
8. synthetic method according to claim 3, is characterized in that: the time of described reaction is 3-7 days, and the temperature of reaction is 20-25 DEG C.
9. the application of Cu according to claim 2 (II)-MOF-1 in ion-exchange and regeneration.
10. the application of Cu according to claim 2 (II)-MOF-1 in ion selectivity identification.
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| CN110227456A (en) * | 2019-06-05 | 2019-09-13 | 华南理工大学 | MOFs derives two-dimensional multistage hole Cu/C composite material and preparation method |
| CN111992185A (en) * | 2020-09-21 | 2020-11-27 | 桂林理工大学 | Cu-MOF, modified adsorption material thereof and preparation method |
| CN113671005A (en) * | 2021-07-01 | 2021-11-19 | 广州大学 | Copper ion selective electrode based on MOF, and preparation method and application thereof |
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|---|---|---|---|---|
| CN107664630A (en) * | 2016-07-30 | 2018-02-06 | 天津师范大学 | Dopamine detection method based on metal-organic framework materials |
| CN107664630B (en) * | 2016-07-30 | 2020-01-07 | 天津师范大学 | Dopamine detection method based on metal organic framework material |
| CN110128451A (en) * | 2019-05-14 | 2019-08-16 | 安徽理工大学 | Copper metal organic coordination compound and its preparation method and application based on diphenyl ether ligand |
| CN110128451B (en) * | 2019-05-14 | 2022-03-18 | 安徽理工大学 | Copper metal organic complex based on diphenyl ether ligand and preparation method and application thereof |
| CN110227456A (en) * | 2019-06-05 | 2019-09-13 | 华南理工大学 | MOFs derives two-dimensional multistage hole Cu/C composite material and preparation method |
| CN111992185A (en) * | 2020-09-21 | 2020-11-27 | 桂林理工大学 | Cu-MOF, modified adsorption material thereof and preparation method |
| CN111992185B (en) * | 2020-09-21 | 2022-04-29 | 桂林理工大学 | Cu-MOF, modified adsorption material thereof and preparation method |
| CN113671005A (en) * | 2021-07-01 | 2021-11-19 | 广州大学 | Copper ion selective electrode based on MOF, and preparation method and application thereof |
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