CN105924460A - Metal-organic framework material good in acid and alkali stability and preparation method and application thereof - Google Patents
Metal-organic framework material good in acid and alkali stability and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 title abstract 4
- 239000003513 alkali Substances 0.000 title abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 14
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000002189 fluorescence spectrum Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 7
- 230000005284 excitation Effects 0.000 claims description 5
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 238000002050 diffraction method Methods 0.000 claims description 4
- 238000000295 emission spectrum Methods 0.000 claims description 4
- 238000000695 excitation spectrum Methods 0.000 claims description 4
- 239000013384 organic framework Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- -1 dioctyl phthalate radical ions Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 150000005837 radical ions Chemical class 0.000 abstract 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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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
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- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- 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
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Abstract
Provided are a metal-organic framework material good in acid and alkali stability and a preparation method and application thereof. A chemical formula of the product is {[Tb2(TDA)2(H2O) 4] 3H2O 0.5DMF} n, wherein TDA is 1-hydrogen-1,2,3-triazole-4,5 dimethyl acid radical ions, and DMF is N,N-dimethyl formamide. The preparation method comprises the steps that terbium chloride, 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate and 1-H-1,2,4-triazole water and DMF are added to a water and DMF mixed solution, and a target product is obtained through reaction; the product ccan be used in a Fe<3+>/Fe<2+> mixed solution for quantitative detection of Fe<3+>. The metal-organic framework material has the advantages that a product preparation process is simple, operation is easy, reaction conditions are mild, the yield is high, the costs are low, the prepared metal-organic framework material has good acid and alkali stability and has the performance of quantitative detection of Fe<3+> in the Fe<3+>/Fe<2+> mixed solution.
Description
Technical field
The present invention relates to metal-organic framework materials technical field, a kind of metal to ph stability
-organic framework materials and its preparation method and application.
Background technology
The detection of variable valency metal ions is one of key issue in life sciences and industrial process.Such as, become
Valence metal ion can participate in various biologically process, if its concentration exceedes normal value, will directly endanger
Evil organism is healthy.Fe2+/Fe3+Ion participates in many redox reaction, the quick and convenient accurate inspection of its concentration
Survey for research Fe2+/Fe3+Chemistry and biology in transport pathway etc. be significant.At present, conventional
May be used for detect Fe2+/Fe3+The method of ion pair has the chromatography of ions etc..Metal-organic framework is as glimmering
It is a kind of new trial that light probe detects ion pair.This method can be in the situation not having complicated pretreatment
Under, the Fe of detection by quantitative low concentration2+/Fe3+Ion pair, as at Fe2+/Fe3+Mixed solution in detect Fe3+。
Metal-organic framework (MOFs) be by metal ion or metal cluster with organic ligand by self assembly mode shape
Become three-dimensional coordination polymer.In recent years, MOFs enriches changeable chemical constitution and excellent property due to it
People can be received pay close attention to widely.MOFs may be used for gas storage and separates, heterogeneous catalysis, fluorescence
Sensor, magnetic material, proton conducts, the aspect such as drug delivery and bio-imaging.Based on part and metal
The multiformity of ion population, MOFs material list has revealed the multiformity of structure and regulatable physical chemistry
Energy.The size of MOFs mesopore, shape, chemical composition and inner surface environment can well be carried out chemistry tune
Control, can realize the selective absorption to guest molecule and effect based on the recognition reaction between Subjective and Objective.MOFs
The synthetic method of material mainly includes hydro-thermal method, solvent-thermal method, layering diffusion method, stirring synthetic method, diffusion
Method and the most emerging microwave method and ion full-boiled process etc..Use the impact on material of the different synthetic methods
Very big, and the proportioning of reactant, the selection of solvent and temperature, the time, pH value to the structure of crystal and
Quality also has a great impact.Solvent-thermal method is presently the most common method, and it can produce in course of reaction
A raw middle metasable state, thus control response speed, prevent crystal from quickly generating, form perfect crystal.
Summary of the invention
It is an object of the invention to for above-mentioned technical Analysis, it is provided that one is simple to operate, low cost, convenience are fast
Prompt and at Fe3+/Fe2+Mixed solution in detection by quantitative Fe3+The metal to ph stability of ion-organic
Frame material and its preparation method and application.
Technical scheme:
A kind of metal-organic framework materials to ph stability, chemical formula is
{[Tb2(TDA)2(H2O)4]·3H2O·0.5DMF}n, in formula: n is 1 to the most infinite natural number, wherein TDA
For 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate radical ions, DMF is DMF；This metal-
Organic framework materials is by rare-earth metal Tb3+Ion and organic ligand are by coordinate bond or intermolecular force structure
The three-dimensional net structure become, wherein organic ligand is 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate；Structure cell comprises
The Tb of two crystallography independences3+Ion, two TDA3-Part and four water of coordination molecules；Adjacent Tb3+
Ion passes through TDA3-Part bridging forms one-dimensional chain structure；Pass through TDA3-The connection formation three further of part
Dimension frame structure also has one-dimensional passage；Duct exists free object hydrone and DMF molecule.
The preparation method of a kind of described metal-organic framework materials to ph stability, comprises the following steps:
1) 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate, 1H-1,2,4-triazole, six chloride hydrate terbiums are added
In distilled water and DMF, mix homogeneously obtains mixed liquor；
2) above-mentioned mixed liquor is placed in 23mL and seals in rustless steel autoclave, at 90 DEG C, heat 72
Hour, subsequently with 1 DEG C of h-1Speed be down to room temperature, be filtrated to get crystal；
3) above-mentioned crystal distilled water and DMF mixed liquor are washed 3-5 time, can be prepared by ph stability
Metal-organic framework materials.
Described 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate, 1H-1,2,4-triazole and six chloride hydrate terbiums by mole
Ratio is 3:2:2；The amount ratio of 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate, distilled water and DMF is 0.3mmol:
2mL:0.5mL.
The application of a kind of described metal-organic framework materials to ph stability, at Fe3+/Fe2+Mixing
Detection by quantitative Fe in solution3+, method is that under room temperature, to the metal-organic framework materials of preparation, to carry out solid glimmering
The excitation and emission spectra test of light；Sample is separately immersed in 1.0 × 10-2mol·L-1Fe3+, 1.0 × 10-2
mol·L-1Fe2+, 1.0 × 10-1mol·L-1Fe3+, 1.0 × 10-1mol·L-1Fe2+3h in solution, filtration dries,
Survey its X-ray powder diffraction spectrum；The metal-organic framework materials of preparation is added separately to 4mL 1.0 ×
10-2mol·L-1Fe3+And Fe2+In aqueous solution, ultrasonic 25min forms suspension, under room temperature, it is carried out fluorescence
Character detects；The metal-organic framework materials of preparation is joined the Fe of variable concentrations3+In aqueous solution, super
Sound 25min forms suspension, and tests its fluorescence spectrum；The metal-organic framework materials of preparation is soaked
At two kinds of Fe3+/Fe2+Mixed solution is formed suspension, mixed solution comprises the Fe of different molar content3+,
Test its fluorescence spectrum.
The above two kinds of Fe3+/Fe2+The total concentration of mixed solution is respectively 1.0 × 10-2mol·L-1With 1.0 ×
10-1mol·L-1。
The invention have the advantage that 1) preparation technology of this metal-organic framework materials is simple, reaction condition temperature
, low cost high with, productivity；2) this material has preferable ph stability, in the aqueous solution of pH=2-13
Keep stable, be conducive to reality application；3) at room temperature, Fe3+This material is had the response of fluorescent quenching,
And this material can be at Fe3+/Fe2+Mixed solution in detection by quantitative Fe3+, at Fe3+Selective recognition aspect has good
Good application prospect.
Accompanying drawing explanation
Fig. 1 and Fig. 2 is the single crystal diffraction structure chart of this metal-organic framework materials, wherein: Fig. 1 (a) is for being somebody's turn to do
Tb in metal-organic framework materials3+The coordination environment figure of ion, Fig. 1 (b) is the coordination mould of Tb1 and Tb2
Formula figure.
Fig. 2 (a) is by TDA3-And Tb3+The one-dimensional chain figure that ion builds, Fig. 2 (b) Tb1 chain and Tb2 chain building
One-dimensional tubulose duct figure, Fig. 2 (c) is the three-dimensional framework figure of this compound.
Fig. 3 is the stability test figure of this metal-organic framework materials, including this metal-organic framework material
Material is immersed in the powder diagram in the aqueous solution of pH=1-14 after 3 hours.
Fig. 4 is that this metal-organic framework materials solid fluorescence at room temperature excites and launches spectrogram.
Fig. 5 is that this metal-organic framework materials is immersed in 1.0 × 10-2mol·L-1Fe3+, 1.0 × 10-2mol·L-1
Fe2+, 1.0 × 10-1mol·L-1Fe3+, 1.0 × 10-1mol·L-1Fe2+Powder diagram after 3h in solution.
Fig. 6 is that this metal-organic framework materials is separately immersed in 1.0 × 10-2mol·L-1Fe3+, 1.0 × 10-2
mol·L-1Fe2+The fluorescence spectrum figure of solution.
Fig. 7 is the Fe that this metal-organic framework materials is immersed in variable concentrations3+The fluorescence spectrum figure of aqueous solution,
Illustration is I0/Ivs.Fe3+Concentration map.
Fig. 8 (a) is that this metal-organic framework materials is immersed in and comprises different molar content Fe3+, total concentration is
1.0×10-2mol·L-1Fe3+/Fe2+The fluorescence spectrum figure of mixed solution, Fig. 8 (b) is this metal-organic framework material
Material is immersed in and comprises different molar content Fe3+, total concentration is 1.0 × 10-1mol·L-1Fe3+/Fe2+Mixed solution
Fluorescence spectrum figure.
Detailed description of the invention
Embodiment:
A kind of metal-organic framework materials to ph stability, chemical formula is
{[Tb2(TDA)2(H2O)4]·3H2O·0.5DMF}n, in formula: n is 1 to the most infinite natural number, wherein TDA
For 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate radical ions, DMF is DMF；This metal-
Organic framework materials is by rare-earth metal Tb3+Ion and organic ligand are by coordinate bond or intermolecular force structure
The three-dimensional net structure become, wherein organic ligand is 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate；Structure cell comprises
The Tb of two crystallography independences3+Ion, two TDA3-Part and four water of coordination molecules；Adjacent Tb3+
Ion passes through TDA3-Part bridging forms one-dimensional chain structure；Pass through TDA3-The connection formation three further of part
Dimension frame structure also has one-dimensional passage；Duct exists free object hydrone and DMF molecule.
The preparation method of the described metal-organic framework materials to ph stability, comprises the following steps:
1) by 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate of 0.3mmol, 1H-1,2,4-tri-nitrogen of 0.2mmol
Azoles and the six chloride hydrate terbiums of 0.2mmol, add in 2 milliliters of distilled water and 0.5 milliliter of DMF, and mixing is all
Even obtain mixed liquor；
2) above-mentioned mixed liquor is placed in 23mL seal in rustless steel autoclave, is placed at 90 DEG C and adds
Heat 72 hours, subsequently with 1 DEG C of h-1Speed be down to room temperature, be filtrated to get crystal；
3) above-mentioned crystal distilled water and DMF mixed liquor are washed 4 times, can be prepared by ph stability
Metal-organic framework materials, product is colourless bulk crystals, is 59% based on Tb productivity.
Measure crystal structure by Supernova type X-ray single crystal diffractometer, use through graphite monochromator
The Mo-K of monochromatizationαRayFor Incident Irradiation Source, withScan mode collects point diffraction,
Through their coordinate of least square refinement and anisotropic parameters thereof, the position of hydrogen atom is hydrogenated with by theory
Obtaining, all of calculating uses SHELXL-97 and SHELXL-97 program bag to carry out.In conjunction with elementary analysis,
Thermogravimetric analysis, and Advances in crystal X-ray diffraction data determine the final molecular formula of this compound.Result shows:
The structural formula of this metal-organic framework materials is { [Tb2(TDA)2(H2O)4]·3H2O·0.5DMF}n, belong to
Rhombic system, space group P212121, cell parameter is α=β=γ=90 °, unit cell volume isZ=4, Dc=2.215g/cm3。
The mono-crystalline structures figure of the metal-organic framework materials of preparation is shown in Fig. 1 and Fig. 2, wherein: Fig. 1 (a) is this metal
Tb in-organic framework materials3+The coordination environment figure of ion, Fig. 1 (b) is the coordination mode figure of Tb1 and Tb2.
Fig. 2 (a) is by TDA3-And Tb3+The one-dimensional chain figure that ion builds, Fig. 2 (b) is Tb1 chain and Tb2 chain building
One-dimensional tubulose duct figure, Fig. 2 (c) is the three-dimensional framework figure of this compound.In the structure cell of this metal-organic framework
Comprise the Tb of two crystallography independences3+Ion, two TDA3-Part and four water of coordination molecules.Tb1 and
Tb2 has distorted octahedra coordination environment { TbO6N2, four oxygen atoms and two nitrogen-atoms come from TDA3-
Part, remaining two oxygen atoms come from two hydrones.Adjacent Tb1 and Tb2 ion passes through TDA3-
Part bridging forms one-dimensional chain structure；Pass through TDA3-Connecting further of part forms three-dimensional frame structure and has
There is one-dimensional passage.The orifice size calculation value of one-dimensional distortion tubular conduit isDuct exist free
Object hydrone and DMF molecule.
Performance detects:
The metal-organic framework of acquisition is separately immersed in the aqueous solution of pH=1-14, after 3 hours, by crystalline substance
After body filters, it is dried in atmosphere, and carries out the test of powder X-ray RD respectively.As shown in Figure 3: pH 2-13
The peak of the diffraction spectrogram that the peak position of the diffraction spectrogram of the sample that solution soaking is crossed and peak type are simulated with single crystal data
It is the best that position and peak type coincide, and shows that the frame structure of material keeps constant, the metal of the present invention-organic
Frame material has preferable stability in acid-base solution.
The application of a kind of described metal-organic framework materials to ph stability, at Fe3+/Fe2+Mixing
Detection by quantitative Fe in solution3+, method is: under room temperature, carries out solid to the metal-organic framework materials of preparation
The excitation and emission spectra test of body fluorescence；Sample is separately immersed in 1.0 × 10-2mol·L-1Fe3+, 1.0 ×
10-2mol·L-1Fe2+, 1.0 × 10-1mol·L-1Fe3+, 1.0 × 10-1mol·L-1Fe2+3h in solution, filters
Dry, survey its X-ray powder diffraction spectrum；The metal-organic framework materials of preparation is added separately to 4mL
1.0×10-2mol·L-1Fe3+And Fe2+In aqueous solution, ultrasonic 25min forms suspension, under room temperature enters it
Row photoluminescent property detects；The metal-organic framework materials of preparation is joined the Fe of variable concentrations3+Aqueous solution
In, ultrasonic 25min forms suspension, and tests its fluorescence spectrum；Metal-organic framework material by preparation
Material is immersed in two kinds of Fe3+/Fe2+(total concentration of solution is respectively 1.0 × 10 to form suspension in mixed solution-2
mol·L-1With 1.0 × 10-1mol·L-1), mixed solution comprises the Fe of different molar content3+, test its fluorescence
Spectrum.
Fig. 4 is the excitation and emission spectra test that this metal-organic framework materials carries out solid fluorescence,
The excitation wavelength of 280nm excites down, presents four main emission peaks, respectively 487nm, 544nm,
585nm, 621nm, corresponding to Tb3+Ion5D4→7FJ(J=6-3) transition.Fig. 5 is this metal
XRD spectra before and after-organic framework materials soaking solution, shows in figure: after immersion, XRD figure spectrum is with logical
Crossing the XRD figure spectrum that single crystal data simulates to fit like a glove, illustrative material has higher stablizing in above-mentioned solution
Property, the research of fluorescent probe can be carried out.Fig. 6 is that the immersion of this metal-organic framework materials is separately immersed in
Fe3+And Fe2+The fluorescence spectrum of aqueous solution gained, shows in figure: Fe3+Introducing to can result in fluorescence the most sudden
Go out, and Fe2+Introducing fluorescence intensity be substantially not changed in.Fig. 7 is that this metal-organic framework materials soaks
Fe at variable concentrations3+The fluorescence spectrum of aqueous solution gained, shows in figure: along with Fe3+The increase of ion concentration,
The fluorescence intensity of this emission peak reduces, and in order to probe into its kinetics relation further, depicts I0/ I is to Fe3+
The curve of ion concentration, I0/ I and Fe3+Ion concentration meets relational expression I0/ I=0.988+KSV[Fe3+]([Fe3+]
Represent Fe3+The molar concentration of ion), wherein KSVIt is 8.230 × 103M-1.Fig. 8 (a) is this metal-organic
Frame material is immersed in the Fe of different molar content3+, total concentration is 1.0 × 10-2mol·L-1Fe3+With
Fe2+The fluorescence spectrum of mixed aqueous solution gained, shows in figure, along with Fe3+Being continuously increased of ion concentration, glimmering
Light intensity is gradually lowered.When its molar content is 10%, fluorescent emission spectrogram shows that its quencher percentage ratio is high
Reach 90%.Fig. 8 (b) is the Fe that this metal-organic framework materials is immersed in different molar content3+, always
Concentration is 1.0 × 10-1mol·L-1Fe3+And Fe2+The fluorescence spectrum of mixed aqueous solution gained, indicates in figure,
Along with Fe3+Addition, fluorescence intensity substantially reduces, at Fe3+Molar content when being 2%, almost all is sudden
Go out.These experimental results show, at mixing Fe3+/Fe2+In aqueous solution, this metal-organic framework materials can be used
In detection by quantitative Fe3+Concentration.
Claims (5)
1. the metal-organic framework materials to ph stability, it is characterised in that chemical formula is
{[Tb2(TDA)2(H2O)4]·3H2O·0.5DMF}n, in formula: n is 1 to the most infinite natural number, wherein TDA
For 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate radical ions, DMF is DMF；This metal-
Organic framework materials is by rare-earth metal Tb3+Ion and organic ligand are by coordinate bond or intermolecular force structure
The three-dimensional net structure become, wherein organic ligand is 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate；Structure cell comprises
The Tb of two crystallography independences3+Ion, two TDA3-Part and four water of coordination molecules；Adjacent Tb3+
Ion passes through TDA3-Part bridging forms one-dimensional chain structure；Pass through TDA3-The connection formation three further of part
Dimension frame structure also has one-dimensional passage；Duct exists free object hydrone and DMF molecule.
2. a preparation method for the metal-organic framework materials to ph stability as claimed in claim 1, its
It is characterised by comprising the following steps:
1) 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate, 1H-1,2,4-triazole, six chloride hydrate terbiums are added
In distilled water and DMF, mix homogeneously obtains mixed liquor；
2) above-mentioned mixed liquor is placed in 23mL and seals in rustless steel autoclave, at 90 DEG C, heat 72
Hour, subsequently with 1 DEG C of h-1Speed be down to room temperature, be filtrated to get crystal；
3) above-mentioned crystal distilled water and DMF mixed liquor are washed 3-5 time, can be prepared by ph stability
Metal-organic framework materials.
The most according to claim 2, the preparation method to the metal-organic framework materials of ph stability, it is special
Levy and be: described 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate, 1H-1,2,4-triazole and six chloride hydrate terbiums are pressed
Mol ratio is 3:2:2；The amount ratio of 1-hydrogen-1,2,3-triazole-4,5 dioctyl phthalate, distilled water and DMF is 0.3
Mmol:2mL:0.5mL.
4. an application for the metal-organic framework materials to ph stability as claimed in claim 1, its feature
It is: at Fe3+/Fe2+Mixed solution in detection by quantitative Fe3+, method is the metal under room temperature to preparation
-organic framework materials carries out the excitation and emission spectra test of solid fluorescence；Sample is separately immersed in 1.0 ×
10-2mol·L-1Fe3+, 1.0 × 10-2mol·L-1Fe2+, 1.0 × 10-1mol·L-1Fe3+, 1.0 × 10-1mol·L-1
Fe2+3h in solution, filtration is dried, and surveys its X-ray powder diffraction spectrum；By the metal of preparation-have machine frame
Frame material is added separately to 4mL 1.0 × 10-2mol·L-1Fe3+And Fe2+In aqueous solution, ultrasonic 25min is formed
Suspension, carries out photoluminescent property detection to it under room temperature；The metal-organic framework materials of preparation is joined
The Fe of variable concentrations3+In aqueous solution, ultrasonic 25min forms suspension, and tests its fluorescence spectrum；Will system
Standby metal-organic framework materials is immersed in two kinds of Fe3+/Fe2+Mixed solution is formed suspension, mixed solution
In comprise the Fe of different molar content3+, test its fluorescence spectrum.
The application of the metal-organic framework materials to ph stability the most according to claim 4, its feature
It is: the two Fe3+/Fe2+The total concentration of mixed solution is respectively 1.0 × 10-2mol·L-1With 1.0 × 10-1
mol·L-1。
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| CN114672038B (en) * | 2022-04-22 | 2023-03-10 | 山西大学 | Two-dimensional binuclear terbium coordination polymer and preparation method and application thereof |
| CN114805839A (en) * | 2022-05-13 | 2022-07-29 | 南开大学 | Coordination polymer-based ultraviolet wavelength detection material and application thereof |
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