CN109265485A - Cobalt metal-organic framework material and preparation method and fluorescence sense rich in Louis's base identify Fe3+Application - Google Patents
Cobalt metal-organic framework material and preparation method and fluorescence sense rich in Louis's base identify Fe3+Application Download PDFInfo
- Publication number
- CN109265485A CN109265485A CN201811186783.1A CN201811186783A CN109265485A CN 109265485 A CN109265485 A CN 109265485A CN 201811186783 A CN201811186783 A CN 201811186783A CN 109265485 A CN109265485 A CN 109265485A
- Authority
- CN
- China
- Prior art keywords
- louis
- organic framework
- cobalt metal
- framework material
- base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 21
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 20
- 239000010941 cobalt Substances 0.000 title claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims abstract description 40
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 229940113088 dimethylacetamide Drugs 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 238000010791 quenching Methods 0.000 abstract description 5
- 230000000171 quenching effect Effects 0.000 abstract description 5
- 101100131043 Oryza sativa subsp. japonica MOF1 gene Proteins 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 208000033981 Hereditary haemochromatosis Diseases 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000007882 cirrhosis Effects 0.000 description 1
- 208000019425 cirrhosis of liver Diseases 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Molecular Biology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of cobalt metal-organic framework materials rich in Louis's base and preparation method thereof and fluorescence sense to identify Fe3+Application, the structural unit of the material is Co1.5(Ina)2(μ2‑O)(TPTA)0.5, an Ina represents the isonicotinic acid anion of proton on decarboxylize in formula, another Ina represents isonicotinic acid, and TPTA represents the p- terphenyl -3,3' for sloughing proton on 4 carboxyls, 5,5 "-tetracarboxylic acid acid anions；It belongs to monoclinic system, C2/c space group, and cell parameter a isB isC isα is 90 °, β is 96.016 (2) °, γ is 90.00 °, and unit cell volume isCobalt metal-organic framework material of the present invention is prepared by solvent-thermal method, can launch the fluorescence of 467nm, and there is preferable fluorescence selectivity to identify Fe3+Function, Quenching of fluorescence constant be Ksv(MOF1)For 4069.3M‑1。
Description
Technical field
The invention belongs to MOFs field of material technology, and in particular to a kind of cobalt metal organic frame rich in Louis's base
The preparation method and use material fluorescence sense identification Fe of material and the material3+Application.
Background technique
Rapidly and efficiently Selective recognition Fe3+, the movement of transport and metal ion for oxygen in life entity has heavy
The meaning wanted.A certain amount of Fe in body3+It can promote the formation of muscle and hemoglobin.Otherwise, various health problems are such as: poor
Blood, cirrhosis, hereditary hemochromatosis all can be by lacking Fe3+And cause, therefore be highly desirable to develop a kind of new detection Fe3+It is new
Material.
Currently, design synthesis has the MOFs of fluorescence sense function, there are mainly two types of modes: 1) selection synthesis lanthanide series metal
Organic frame, to improve its fluorescence indicator adsorption ability；2) introducing, there is the ligand of chromophore to have machine frame to synthesize porous metals
Frame.From the point of view of the strategy of preparation, select mixture strategy: i.e. ligand and auxiliary similar in selection length, rigidity and coordination mode are matched
Body carrys out the MOFs that controlledly synthesis has fluorescence macropore, and introduces functional group in the frame, to improve its Selective recognition
Ability.However, few work selection length mismatch, that is, it can provide frame joint, also act as the carboxyl of recognition site not
The isonicotinic acid and terphenyl tetrabasic carboxylic acid of coordination, synthesis has the metal ion of efficient selective and sensing under the conditions of solvent heat.
P- terphenyl -3,3', 5,5 "-tetrabasic carboxylic acids have advantageous advantage, have high connection rectangle building unit, various
Bridging coordination mode easily forms the metal organic frame of various structures.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of cobalt metal organic frame material rich in Louis's base
The preparation method and application of material and the material.
Solve the structural unit of the cobalt metal-organic framework material used by above-mentioned technical problem rich in Louis's base
For Co1.5(Ina)2(μ2-O)(TPTA)0.5, an Ina represents the isonicotinic acid anion of proton on decarboxylize in formula, another
Ina represents isonicotinic acid, and TPTA represents the p- terphenyl -3,3' for sloughing proton on 4 carboxyls, 5,5 "-tetracarboxylic acid acid anions；It belongs to
In monoclinic system, C2/c space group, cell parameter a isB is C is
α is 90 °, β is 96.016 (2) °, γ is 90.00 °, and unit cell volume is
The above-mentioned cobalt metal-organic framework material rich in Louis's base the preparation method comprises the following steps: by Cobalt diacetate tetrahydrate, different cigarette
Acid and p- terphenyl -3,3', 5,5 "-tetrabasic carboxylic acids are added N in molar ratio, N'- dimethyl acetamide, ethyl alcohol and deionized water it is mixed
It closes in liquid, 90~120 DEG C of constant temperature stand reaction 3~6 days in confined conditions, and it is organic to obtain the cobalt metal rich in Louis's base
Frame material.
Above-mentioned Cobalt diacetate tetrahydrate, isonicotinic acid, p- terphenyl -3,3', the molar ratio (2.9~3.1) of 5,5 "-tetrabasic carboxylic acids:
(4.9~5.1): (1.9~2.1).
Above-mentioned N, N'- dimethyl acetamide, ethyl alcohol, deionized water volume ratio be (3.9~4.1): (0.9~1.1):
(0.9~1.1).
In above-mentioned preparation method, preferably 100~110 DEG C of constant temperature stand reaction 4~5 days in confined conditions.
Cobalt metal-organic framework material (hereinafter referred to as MOF1) of the present invention rich in Louis's base is identified in fluorescence sense
Fe3+In application, the specific detection method is as follows:
1, with N, N'- dimethyl acetamide (DMF) is solvent, and compound concentration is the MOF1 suspension of 1mg/mL；To MOF1
Fe is added in suspension3+Standard sample measures various concentration Fe with Fluorescence Spectrometer3+The fluorescence intensity of corresponding system, draws I0/
I-1 value is with Fe3+The standard curve of concentration variation.
2, Fe to be measured is measured according to the method for step 13+The fluorescence intensity of sample, according to the I of sample to be tested0/ I-1 value, knot
The linear equation of standardization curve can highly selective identification Fe3+And determine Fe in sample to be tested3+Concentration.
Beneficial effects of the present invention are as follows:
The present invention uses solvent structure cobalt metal-organic framework material, and synthetic method is simple, which can launch
The fluorescence of 467nm, and Fe is identified with high fluorescence selectivity3+Performance, fluorescent quenching constant be Ksv(MOF1)For
4069.3M-1。
Detailed description of the invention
Fig. 1 is the coordination structure figure of MOF1 of the present invention.
Fig. 2 is the three core Co cluster figures of MOF1 of the present invention.
Fig. 3 is the two-dimensional structure figure of MOF1 of the present invention.
Fig. 4 is the 1-dimention nano duct figure of MOF1 of the present invention.
Fig. 5 is the three-dimensional framework figure of MOF1 of the present invention.
Fig. 6 is the fluorescence spectra of MOF1 of the present invention.
Fig. 7 is MOF1 of the present invention to Fe3+Fluorescence quenching spectrum figure.
Fig. 8 is MOF1 of the present invention to Fe3+Selective recognition linear relationship chart.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
By 0.037g (0.15mmol) Cobalt diacetate tetrahydrate, 0.025g (0.20mmol) isonicotinic acid, 0.041g (0.1mmol) p-
Terphenyl -3,3', 5,5 "-tetrabasic carboxylic acids, 4mLN, N'- dimethyl acetamide (DMA), 1mL ethyl alcohol and 1mL deionized water are added
It in 25mL vial, stirs evenly, 100 DEG C isothermal reaction 4 days, obtain bulk-shaped monocrystal in confined conditions after having reacted, i.e., rich
The cobalt metal-organic framework material (MOF1) of the base containing Louis.The structural unit of the material is [Co1.5(Ina)2(μ2-O)
(TPTA)0.5], an Ina represents the isonicotinic acid anion of proton on decarboxylize in formula, another Ina represents isonicotinic acid,
TPTA represents the p- terphenyl -3,3' for sloughing proton on 4 carboxyls, 5,5 "-tetracarboxylic acid acid anions；It belongs to monoclinic system, C2/
C space group, cell parameter a are B isC isα is 90 °, β is
96.016 (2) °, γ are 90.00 °, unit cell volumeAs shown in Figure 1, containing in the asymmetric cell of MOF1
1.5 crystallography independent Co (II) ions, 1 p- terphenyl -3,3', 5,5 "-tetrabasic carboxylic acid ligands, 2 isonicotinic acid ligands.No
Co (II) in symmetrical structure unit is hexa-coordinate, takes the octahedral geometric configuration of deformation.With the carboxyl 4 of Co (1) coordination
A oxygen atom, respectively from two carboxyl oxygen atoms and 2 p- terphenyls -3,3' in 1 isonicotinic acid ligand, 5,5 "-tetracarboxylic acids
Carboxyl oxygen in sour ligand, 2 N atoms come from 2 isonicotinic acid ligands；With the carboxyl oxygen atom of Co (2) Atomic coordinate, 2 are come from
A isonicotinic acid ligand, in addition 4 carboxyl oxygens are respectively from two different p- terphenyls -3,3', 5,5 "-tetrabasic carboxylic acids.Wherein Co-O
Bond distance's range isBond distance's range of Co-N is
As shown in Fig. 2, two Co (1) and 1 Co (2) pass through 4 carboxyls and two μ2- O and form three core cluster [Co3(μ2-O)2
(COO)4]。
If Fig. 3 is along b axis direction, two three core cluster [Co3(μ2-O)2(COO)4] pass through p- terphenyl -3,3', 5,5 "-tetracarboxylic acids
Pyridine ring in phenyl ring and isonicotinic acid in acid forms one-dimensional chain, in ac plane, passes through terphenyl -3 p- between one-dimensional chain,
3', 5,5 "-tetrabasic carboxylic acids are expanded into two-dimensional surface, wherein four three core cluster [Co3(μ2-O)2(COO)4] between pass through two p- tri-
Biphenyl -3,3', 5,5 "-tetrabasic carboxylic acid ligands and 2 isonicotinic acid ligands form the big ring of 44 atoms, and there are two groups of " faces in ring
The isonicotinic acid that the terminal carboxyl group oxygen on opposite " is not coordinated.As seen in Figure 4, in ab plane, four three core clusters pass through 4 phenyl ring and 4
Isonicotinic acid head and the tail are formed by connecting 1-dimention nano duct, there is the isonicotinic acid that 4 carboxyls are not coordinated on hole wall, golden for orientation identification
Belong to ion and potential active site is provided.As seen from Figure 5, in bc plane, four one-dimensional nano pores pass through pyridine ring and benzene
Ring is expanded into three-dimensional porous structure.As seen from Figure 6, MOF1 can use the excitation wavelength of 425nm, launch the fluorescence of 467nm.
Embodiment 2
Cobalt metal-organic framework material (MOF1) rich in Louis's base prepared by embodiment 1 is identified in fluorescence sense
Fe3+In application, the specific method is as follows:
Using DMA as solvent, compound concentration is the MOF1 suspension of 1mg/mL；1mL MOF1 suspension is taken respectively, is then divided
The 0.01mol/L FeCl of 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L, 70 μ L, 100 μ L are not added dropwise3DMA solution, using fluorescence
Measurement launch wavelength is the fluorescence intensity at 467nm under spectrophotometer is 425nm in maximum excitation wavelength, as a result sees Fig. 7.By
Fig. 7 as it can be seen that the fluorescence intensity of the system with Fe in system3+The increase of concentration gradually weakens, and 100 μ L Fe are added3+After solution,
The fluorescent quenching rate of 1 suspension of MOF is 80%.
Using DMA as solvent, compound concentration is the MOF1 suspension of 1mg/mL；1mL MOF1 suspension is taken respectively, is then divided
The 0.01mol/LFeCl of 0 μ L, 5 μ L, 10 μ L, 15 μ L, 20 μ L, 25 μ L, 30 μ L are not added dropwise3DMA solution, Fe3+Concentration is about
For 0.000,0.0497,0.0990,0.147,0.196,0.243,0.291mmol/L, using sepectrophotofluorometer in maximum
Excitation wavelength is the fluorescence intensity that measurement launch wavelength is at 467nm under 425nm, draws I0/ I-1 value is with Fe3+Concentration variation
Standard curve, and with formula (I0/ I)=1+KSV[C] carries out linear fit, fluorescent quenching constant K to itsv(MOF1)For
4069.3M-1.As shown in figure 8, I0/ I-1 value and Fe3+Concentration is in a linear relationship, linear equation are as follows:
Y=0.0006+0.007x
Y is I in formula0/ I-1 value, x Fe3+Concentration, coefficient R2It is 0.9913, by related coefficient as it can be seen that I0/ I-1 value
With Fe3+The linear relationship of concentration is fine.
Claims (6)
1. a kind of cobalt metal-organic framework material rich in Louis's base, it is characterised in that: the structural unit of the material is
Co1.5(Ina)2(μ2-O)(TPTA)0.5, an Ina represents the isonicotinic acid anion of proton on decarboxylize, another Ina in formula
Isonicotinic acid is represented, TPTA represents the p- terphenyl -3,3' for sloughing proton on 4 carboxyls, 5,5 "-tetracarboxylic acid acid anions；It belongs to
Monoclinic system, C2/c space group, cell parameter a areB isC is
α is 90 °, β is 96.016 (2) °, γ is 90.00 °, and unit cell volume is
2. a kind of preparation method of the cobalt metal-organic framework material described in claim 1 rich in Louis's base, feature
Be: by Cobalt diacetate tetrahydrate, isonicotinic acid and p- terphenyl -3,3', N, N'- dimethyl second is added in 5,5 "-tetrabasic carboxylic acids in molar ratio
In the mixed liquor of amide, ethyl alcohol and deionized water, 90~120 DEG C of constant temperature stand reaction 3~6 days in confined conditions, obtain richness
The cobalt metal-organic framework material of the base containing Louis.
3. the preparation method of the cobalt metal-organic framework material according to claim 2 rich in Louis's base, feature
It is: the Cobalt diacetate tetrahydrate, isonicotinic acid, p- terphenyl -3,3', the molar ratio (2.9~3.1) of 5,5 "-tetrabasic carboxylic acids: (4.9
~5.1): (1.9~2.1).
4. the preparation method of the cobalt metal-organic framework material according to claim 2 rich in Louis's base, feature
Be: the N, N'- dimethyl acetamide, ethyl alcohol, deionized water volume ratio be (3.9~4.1): (0.9~1.1):
(0.9~1.1).
5. the preparation method of the cobalt metal-organic framework material according to claim 2 rich in Louis's base, feature
Be: 100~110 DEG C of constant temperature stand reaction 4~5 days in confined conditions.
6. the cobalt metal-organic framework material described in claim 1 rich in Louis's base identifies Fe in fluorescence sense3+In
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811186783.1A CN109265485B (en) | 2018-10-12 | 2018-10-12 | Cobalt metal organic framework material rich in Lewis base, preparation method and fluorescent sensing recognition Fe3+Application of |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811186783.1A CN109265485B (en) | 2018-10-12 | 2018-10-12 | Cobalt metal organic framework material rich in Lewis base, preparation method and fluorescent sensing recognition Fe3+Application of |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109265485A true CN109265485A (en) | 2019-01-25 |
| CN109265485B CN109265485B (en) | 2020-11-27 |
Family
ID=65196622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811186783.1A Expired - Fee Related CN109265485B (en) | 2018-10-12 | 2018-10-12 | Cobalt metal organic framework material rich in Lewis base, preparation method and fluorescent sensing recognition Fe3+Application of |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109265485B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483588A (en) * | 2019-08-26 | 2019-11-22 | 皖西学院 | A kind of preparation method and applications of the organic micropore cobalt compound of metal- |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967219A (en) * | 2017-03-23 | 2017-07-21 | 山西师范大学 | Cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application |
-
2018
- 2018-10-12 CN CN201811186783.1A patent/CN109265485B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967219A (en) * | 2017-03-23 | 2017-07-21 | 山西师范大学 | Cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| CHUN-HUI CHEN ET AL.: "Highly selective sensing of Fe3+ by an anionic metal–organic framework containing uncoordinated nitrogen and carboxylate oxygen sites", 《DALTON TRANS.》 * |
| WEI SUN ET AL.: "A luminescent terbium MOF containing uncoordinated carboxyl groups exhibits highly selective sensing for Fe3+ ions", 《RSC ADV.》 * |
| WEN-JUAN JI ET AL.: "Decoration of bare carboxyl group on the pore surface of metal-organic frameworks for high selective fluorescence Fe3+ detection", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483588A (en) * | 2019-08-26 | 2019-11-22 | 皖西学院 | A kind of preparation method and applications of the organic micropore cobalt compound of metal- |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109265485B (en) | 2020-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kruger et al. | Stabilization of trivalent nickel in tetragonal NiS4N2 and NiN6 environments: synthesis, structures, redox potentials and observations related to [NiFe]-hydrogenases | |
| CN104804027B (en) | A kind of rare earth metal organic framework materials and preparation method and application | |
| CN102827175B (en) | N-(2,4-dinitrophenyl)-rhodamine B hydrazide and preparation method and application thereof | |
| CN111690150B (en) | Rare earth europium (III) coordination polymer with network structure and preparation method and application thereof | |
| CN106084247A (en) | A kind of Rare Earth Europium base organic crystalline material, preparation and application thereof | |
| Sakiyama et al. | Dinuclear manganese (II) complexes of 2, 6-Bis [2-(dialkylamino) ethyliminomethyl]-4-methylphenolate (1–): synthesis, structure, and magnetism | |
| CN107987282B (en) | Water-stable lanthanide metal-organic framework material, preparation and application thereof | |
| Zhong et al. | Turn-on fluorescent sensor based on curcumin@ MOF-5 for the sensitive detection of Al 3+ | |
| Li et al. | A lanthanide metal–organic framework as ratio fluorescence probe to detect pesticides in water | |
| CN109265485A (en) | Cobalt metal-organic framework material and preparation method and fluorescence sense rich in Louis's base identify Fe3+Application | |
| Guo et al. | A multifunctional Cd (ii)-based metal–organic framework with amide groups exhibiting luminescence sensing towards multiple substances | |
| CN114891045A (en) | Metal organic coordination compound containing acid-base ligand and flow chemistry preparation method and application thereof | |
| CN108931505B (en) | Method for detecting nitrite ions based on rare earth metal organic framework material | |
| Yang et al. | Hollow terbium metal–organic-framework spheres: preparation and their performance in Fe 3+ detection | |
| CN109912633B (en) | Eu-complex fluorescent probe and preparation method and application thereof | |
| CN109283163B (en) | Method for detecting L-cysteine based on calcium-metal organic framework material as fluorescent probe | |
| CN111848655A (en) | Synthesis of three-dimensional cadmium complex and application of three-dimensional cadmium complex as fluorescent probe | |
| CN111763330B (en) | Chain-structured rare earth europium (III) coordination polymer and preparation method and application thereof | |
| CN104262351A (en) | A preparing method of N-(2,4-dinitrophenyl)rhodamine B-hydrazide and an application of the N-(2,4-dinitrophenyl)rhodamine B-hydrazide for detection of Cu(II) | |
| CN106397466A (en) | Metal-organic framework capable of selectively identifying Cr < 3+ > and preparation method thereof | |
| Wu et al. | Two stable cobalt (II) coordination polymers as dual-functional fluorescent sensors for efficient detection of Zn2+/Cu2+ ions and norfloxacin | |
| Jubert et al. | Structural effects of potentially hexadentate N 4 O 2, N 4 S 2 or N 6 ligands involving pyridine, amine and ether or thioether donors: crystal structure of copper (II) and zinc (II) complexes | |
| CN107384373B (en) | One kind having selectivity detection Fe3+Luminescent crystal material of ion and preparation method thereof | |
| Guo et al. | An unprecedented antimonato-polyoxovanadate (SbPOV) based on both α-[V 14 Sb 8 O 42] 4− and β-[V 14 Sb 8 O 42] 4− isomers | |
| CN106006753A (en) | Preparation method of zinc ferrite nanocrystalline assemblies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201127 |