CN114181399A - Metal organic framework material, preparation thereof and application thereof in quick response of hydrogen chloride gas - Google Patents
Metal organic framework material, preparation thereof and application thereof in quick response of hydrogen chloride gas Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 41
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 32
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000007789 gas Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 230000004044 response Effects 0.000 title abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 44
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 2-tetraphenyl Chemical group 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- 229910001429 cobalt ion Chemical group 0.000 claims abstract description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical group [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 11
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002902 ferrimagnetic material Substances 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 239000011540 sensing material Substances 0.000 claims description 2
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 13
- 239000011701 zinc Substances 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 230000005389 magnetism Effects 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 18
- 239000002178 crystalline material Substances 0.000 description 11
- 239000000523 sample Substances 0.000 description 7
- 230000006399 behavior Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 230000005291 magnetic effect Effects 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000005290 antiferromagnetic effect Effects 0.000 description 3
- 230000005293 ferrimagnetic effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013259 porous coordination polymer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/72—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating magnetic variables
- G01N27/74—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating magnetic variables of fluids
- G01N27/76—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating magnetic variables of fluids by investigating susceptibility
Abstract
The invention belongs to the technical field of metal organic framework materials, and discloses a metal organic framework material, and preparation and application thereof in quick response of hydrogen chloride gas. The structure of the material is [ M ]7(L)5(NO3)2(H2O)6]xSolv, M is zinc or cobalt ion; l is 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenecarboxylic acid; solv is solvent molecules adsorbed in the pore channels. The method comprises the following steps: 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenyl formic acid and nitrate are put into a solvent to react to obtain the metal organic framework material. The material of the present invention responds to hydrogen chloride gas quickly and sensitively. In the material, M is zinc and has strong blue solid fluorescence, and M is cobalt and has ferrimagnetismA behavior; the change of solid state fluorescence or the change of magnetism is shown after HCl is absorbed. The material of the invention is used for detecting hydrogen chloride gas.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials, and particularly relates to a metal organic framework material constructed by TPE derivatives, and a preparation method and application thereof. The metal organic framework material is used for preparing a sensor, in particular a sensor for quickly responding to hydrogen chloride gas. The material of the invention can generate fluorescence or magnetic change after contacting with hydrogen chloride gas.
Background
At present, sensors are increasingly applied to various fields of social development and human life, such as industrial automation, agricultural modernization, aerospace technology, robotics, environmental monitoring, medical diagnosis, transportation, smart home, wearable devices, and the like. The intelligent sensor is attracting high attention from the electronic information world at home and abroad. Metal Organic Frameworks (MOFs), also known as Porous Coordination Polymers (PCPs), are a class of crystalline Porous materials with periodic network structures, which have been widely used as intelligent response probes in sensing and detecting analytes such as Metal ions, small organic molecules, and aromatic explosives. However, the progress of MOFs in smart response to acidic gases with strong polarity, corrosivity, and volatility has remained elusive due to the lower stability and poor solid-state fluorescence of conventional MOFs.
In recent years, with the intensive study of the mechanism of Aggregation Induced Emission (AIE), compounds having AIE properties are increasingly being applied to various fields. TPE derivatives (TPEs) have received a great deal of attention as one of the most common compounds having AIE properties. The TPE derivative is used as an organic linker for constructing and synthesizing MOFs which have precise crystal structures and are arranged periodically, so that the improvement of solid-state fluorescence performance can be realized, and the research on the light-emitting mechanism of the MOFs is further promoted. However, MOFs constructed using TPE derivatives have high symmetry, and are difficult to stably exist under strongly acidic conditions. In addition, the high symmetry makes it difficult to achieve a uniform distribution of charges for a stimulus response of an acid gas having a strong dipole effect.
Disclosure of Invention
To overcome the disadvantages and drawbacks of the prior art, it is an object of the present invention to provide a metal organic framework material. The metal organic framework material is a porous crystalline material, and when metal ions are different, the metal organic framework material has strong blue solid fluorescence and no fluorescence. The metal organic framework material can realize quick response to hydrogen chloride through the change of fluorescence or the change of magnetism.
It is another object of the present invention to provide a method for preparing the above metal-organic framework material (porous crystalline material).
It is a further object of the present invention to provide the use of the above metal organic framework material (porous crystalline material). The porous crystalline material of the present invention is useful in sensors, particularly as sensors that intelligently respond to hydrogen chloride gas. The porous crystalline material of the present invention has high selectivity to hydrogen chloride gas.
The purpose of the invention is realized by the following technical scheme:
a metal organic frame material (porous crystalline material) has a structure
[M7(L)5(NO3)2(H2O)6]·xSolv
Wherein M is zinc ion (Zn)2+) Or cobalt ion (Co)2+)；
L is TPE derivative 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenylcarboxylic acid
Solv is solvent molecule adsorbed in pore canal (such as water (H)2O) and N, N-Diethylformamide (DEF)), x being the number of solvent molecules adsorbed.
The solvent molecule is one or more of water, N-Diethylformamide (DEF), N-dimethylformamide, and N, N-diethylacetamide, preferably a mixture of water and one or more of N, N-Diethylformamide (DEF), N-dimethylformamide, and N, N-diethylacetamide, and more preferably water (H)2O) and N, N-Diethylformamide (DEF).
The crystalline porous material is M7(L)5(NO3)2(H2O)7xSolv, which crystallizes in the monoclinic system, C2/C space group, with unit cell parameters of
α＝90(deg)，β＝111.188(3)(deg)，γ＝90(deg)。
The preparation method of the metal organic framework material (porous crystalline material) comprises the following steps:
4, 4' - (ethylene-1, 1, 2, 2-tetra-phenyl) tetraphenyl formic acid and nitrate are placed in a solvent and are heated to react to obtain a metal organic framework material; the nitrate is more than one of zinc nitrate containing crystal water or cobalt nitrate containing crystal water, and preferably more than one of zinc nitrate hexahydrate or cobalt nitrate hexahydrate.
The temperature of the heating reaction is 70-100 ℃, and preferably 80-100 ℃; the heating reaction time is more than or equal to 24 hours, preferably more than or equal to 48 hours. The reaction is a solvothermal reaction. And after the heating reaction is finished, cooling. The cooling rate is 5-10 ℃/h.
The molar ratio of the 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenyl formic acid to the nitrate is 1: 10-10: 1, preferably 1: 10-1: 1, and more preferably 1: 6-4.
The solvent is one or more of water, N-Diethylformamide (DEF), N-dimethylformamide, and N, N-diethylacetamide, preferably a mixture of water and one or more of N, N-Diethylformamide (DEF), N-dimethylformamide, and N, N-diethylacetamide, and more preferably water (H)2O) and N, N-Diethylformamide (DEF).
The solvent is water (H)2O) and N, N-Diethylformamide (DEF), water (H)2O) and N, N-Diethylformamide (DEF) in a volume ratio of 1: 3 to 0.5, preferably 1: 3 to 1.
The application of the metal organic framework material (porous crystalline material) in detecting hydrogen chloride gas.
The porous crystalline material of the present invention is useful in sensors, particularly as sensors that intelligently respond to hydrogen chloride gas.
A sensing material responding to hydrogen chloride gas comprises the metal organic framework material.
The individual units of the ZnMOF of the invention comprise three coordination mode ligands L and three Second Building Units (SBUs) consisting of zinc clusters. The three different SBUs have different valence states, namely positive valence, zero valence and negative valence;
the porous crystalline material ZnMOF has strong blue solid-state fluorescence (445nm, intensity of 1.3 x 10)7(a.u.)) and stronger than solid state fluorescence of the ligand (445nm, intensity 9.5X 106(a.u.))。
ZnMOF absorbs hydrochloric acid solution in a closed environment (20 ℃, C)HCl223.7ppm) and then the volatilized hydrogen chloride gas was able to red-shift the fluorescence and the intensity was reduced (510nm, intensity 2.1 × 10)5(a.u.)). Furthermore, the solid-state fluorescence wavelength and intensity of the ZnMOF responding to the hydrogen chloride gas show a linear relationship with the response time or concentration (the linear relationship y of the wavelength with the response time is 3.98x + 440; the linear relationship y of the wavelength with the hydrochloric acid concentration is 12.6x + 445; the concentration here refers to the concentration of the hydrochloric acid solution). The limit of detection of ZnMOF on hydrogen chloride gas was 2.63 ppm.
A crystalline porous material CoMOF, which has too weak diffraction peak due to its very small crystal, can not obtain its single crystal structure, but shows that CoMOF is isomorphic (homolog) with ZnMOF by powder X-ray diffraction (PXRD) test.
The original sample of CoMOF exhibited ferrimagnetic behavior while the sample after a period of smoking (e.g., 2 hours) exhibited antiferromagnetic behavior. The higher the concentration of hydrochloric acid, the faster the CoMOF response.
A ferrimagnetic material comprising coffe. The CoMOF is prepared by the following method: 4, 4' - (ethylene-1, 1, 2, 2-tetra-phenyl) tetraphenyl formic acid and cobalt nitrate are put into a solvent and heated to react to obtain the metal organic framework material. The cobalt nitrate is cobalt nitrate hexahydrate.
The temperature of the heating reaction is 70-100 ℃, and preferably 80-100 ℃; the heating reaction time is more than or equal to 24 hours, preferably more than or equal to 48 hours. And after the heating reaction is finished, cooling. The cooling rate is 5-10 ℃/h.
The molar ratio of the 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenyl formic acid to the nitrate is 1: 10-10: 1, preferably 1: 10-1: 1, and more preferably 1: 6-4.
The solvent is one or more of water, N-Diethylformamide (DEF), N-dimethylformamide, and N, N-diethylacetamide, preferably a mixture of water and one or more of N, N-Diethylformamide (DEF), N-dimethylformamide, and N, N-diethylacetamide, and more preferably water (H)2O) and N, N-Diethylformamide (DEF).
The solvent is water (H)2O) and N, N-Diethylformamide (DEF), water (H)2O) and N, N-Diethylformamide (DEF) in a volume ratio of 1: 3 to 0.5, preferably 1: 3 to 1.
The application of the ferrimagnetic material in detecting hydrogen chloride gas.
Compared with the prior art, the invention has the advantages that:
the synthetic method of the crystalline porous material (metal organic framework material) constructed based on TPE derivative 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenyl formic acid is simple and convenient, and the yield is high; the ZnMOF has strong blue solid fluorescence, and can rapidly show the change of the solid fluorescence in the HCl vapor environment volatilized from a hydrochloric acid solution; the CoMOF of the invention exhibits ferrimagnetic behavior and, upon absorption of hydrogen chloride gas, exhibits antiferromagnetic behavior. The metal organic framework material has high selectivity to hydrogen chloride gas.
Drawings
FIG. 1 is a schematic diagram of the structure of a porous material ZnMOF prepared in example 1;
FIG. 2 is a schematic diagram of the cluster structures of three different valences in the individual units of the porous material ZnMOF prepared in example 1;
FIG. 3 is a powder diffraction (PXRD) pattern of ZnMOF, a porous material prepared in example 1;
FIG. 4 is an SEM image of the porous material ZnMOF prepared in example 1; the three figures are respectively figures with different magnification;
FIG. 5 is a thermogravimetric plot of the porous material ZnMOF prepared in example 1;
FIG. 6 is a powder diffraction pattern of the porous material CoMOF prepared in example 2;
FIG. 7 is an SEM image of a porous material CoMOF prepared in example 2;
FIG. 8 is a thermogravimetric plot of the porous material CoMOF prepared in example 2;
FIG. 9 is a graph comparing solid state fluorescence of the porous material ZnMOF prepared in example 1 and ligand L; in the figure, L1 represents ligand L;
FIG. 10 is a graph comparing solid state fluorescence of porous materials ZnMOF and CoMOF prepared in examples 1 and 2, respectively;
FIG. 11 is a graph showing the solid-state fluorescence response of the porous material ZnMOF prepared in example 1 to hydrogen chloride gas volatilized from a 20% hydrochloric acid solution in a closed environment;
FIG. 12 is a magnetic diagram of the porous material CoMOF prepared in example 2 before and after absorbing hydrogen chloride gas.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1:
crystalline porous material [ Zn ]7(L)5(NO3)2(H2O)6]·(H2O)21(DEF)6Synthesis of (ZnMOF):
0.02mmol of 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenecarboxylic acid (H)4L, 10.2mg) was added to a teflon reaction kettle, then 0.1mmol of zinc nitrate hexahydrate (29.7mg) was added, finally 1mL of water and 1mL of N, N-Diethylformamide (DEF) were added respectively, dissolved under ultrasonic conditions and then sealed, placed in an oven at 85 ℃ for insulation for 48h, and then slowly cooled to give colorless transparent bulk crystals (roughly 10h to room temperature) with a yield of about 75.3% (calculated on the amount of ligand). Cell parameters of
α＝90(deg)，β＝111.188(3)(deg)，γ＝90(deg)。
FIG. 1 is a structural representation of the porous material ZnMOF prepared in example 1Intention is. As shown in fig. 1, the individual units of ZnMOF contain three coordination mode ligands L and three Second Building Units (SBUs) consisting of zinc clusters. Three zinc cluster SBUS units appear alternately to form a pore diameter of
Of (3) a three-dimensional ZnMOF. The zinc ions which are not coordinated and saturated and the oxygen atoms which do not participate in coordination are exposed in the pore channels of the porous material ZnMOF.
FIG. 2 is a schematic diagram of cluster structures of three different valence states in the individual units of the porous material ZnMOF prepared in example 1. As shown in FIG. 2, the ligands L of the three different coordination modes coordinate with zinc ions to form zinc clusters with positive valence, zero valence and negative valence respectively. The positive valence zinc cluster consists of two four-coordinated zinc ions, two ligands L, two water molecules coordinated with end groups and one nitrate ion coordinated with bidentate chelate, and the molecular formula is Zn2(L)2(H2O)2(NO3). The zero-valent zinc cluster SBU comprises a penta-coordinated zinc ion (pyramid coordination configuration), a tetra-coordinated zinc ion (triangular cone coordination configuration), three ligands L, a terminal group coordinated water molecule and a chelate coordinated nitrate ion, and the molecular formula of the zero-valent zinc cluster SBU is Zn2(L)3(H2O)(NO3). Five ligands L, three water molecules coordinated by end groups, a triple-bridged oxygen anion, two zinc ions coordinated by four (triangular pyramid coordination configuration) and zinc ions coordinated by six (double-quadrangular pyramid coordination configuration) form a zinc cluster SBU with negative valence and single valence, and the molecular formula of the SBU is Zn3(O)(L)5(H2O)3。
Fig. 3 is a powder diffraction Pattern (PXRD) of a crystalline porous material, ZnMOF. Through the comparison of the experimental value and the fitting value of powder diffraction, the crystalline porous material ZnMOF synthesized by the method is pure phase.
Fig. 4 is a Scanning Electron Microscope (SEM) image of a crystalline porous material ZnMOF. It can be seen from the SEM images of ZnMOF of different magnifications that it is a columnar crystal (about 53 microns long and about 3 microns wide) and the surface is very clean.
FIG. 5 is a thermogravimetric analysis (thermogravimetric curve) of a crystalline porous material ZnMOF, controlled at a temperature ranging from room temperature to 800 ℃ and at a flow rate of 15cm3ZnMOF thermal stability tests were performed at a temperature ramp rate of 5 ℃/min under nitrogen conditions/min. The thermogravimetric results of ZnMOF showed that it had two weight loss processes before 300 ℃, corresponding to the loss of twenty-one water molecules (9.55%) and six N, N-diethylformamide molecules (15.24%) free in its pore channels, respectively. As the temperature is further increased above 400 ℃, the framework of ZnMOF rapidly decomposes.
Example 2:
synthesis of crystalline porous material coffe:
0.02mmol of 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenecarboxylic acid (L, 10.2mg) was added to a 25 mL-capacity polytetrafluoroethylene reaction kettle, then 0.1mmol of cobalt nitrate hexahydrate (29.1mg) was added, finally 1mL of water and 1mL of N, N-Diethylformamide (DEF) were added, respectively, dissolved under ultrasonic conditions, sealed, placed in an 85 ℃ oven for 48h, and then slowly cooled to give purple transparent fine bulk crystals (roughly 10h down to room temperature), with a yield of about 73.2% (based on the amount of ligand). Since the diffraction peak is too weak due to the very small crystals of the CoMOF, its single crystal structure cannot be obtained.
FIG. 6 is a powder diffraction Pattern (PXRD) of crystalline porous material CoMOF. The structure of the CoMOF is consistent with that of the ZnMOF as can be seen by comparing the powder diffraction theoretical value of the ZnMOF, and in addition, the crystalline porous material CoMOF synthesized by the method is also pure phase.
FIG. 7 is a Scanning Electron Microscope (SEM) image of a crystalline porous material, CoMOF. From SEM photographs of CoMOF at different magnifications, it can be seen that it is a cone-shaped crystal (about 61 microns long and about 12 microns wide) and the surface is very clean.
FIG. 8 is a thermogravimetric analysis (thermogravimetric curve) of crystalline porous material CoMOF, with the same test conditions as ZnMOF. The thermogravimetric results of the coffe show that it has two weight loss processes before 300 ℃, corresponding to the loss of twenty-one water molecules (9.55%) and six N, N-diethylformamide molecules (15.24%) free in its pore channels, respectively. As the temperature was further increased above 400 ℃, the framework of the coffe rapidly decomposed.
Example 3:
solid state fluorescence of ligands 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenecarboxylic acid, ZnMOF and CoMOF
Solid state fluorescence of ligands 4, 4 ', 4 ", 4'" - (ethylene-1, 1, 2, 2-tetra-yl) tetraphenylcarboxylic acid (ligand L), ZnMOF and cofef was tested using a high sensitivity integrated fluorescence spectrometer model HORIBA FluoroMax-4, manufactured by HORIBA Scientific, usa at room temperature using an excitation slit width of 0.5 nm, an emission slit width of 0.5 nm, an excitation wavelength of 365nm, and collected data ranged from 380 to 700 nm.
FIG. 9 is a solid state fluorescence comparison of the porous material ZnMOF prepared in example 1 and ligand L. As shown in fig. 9, under the 365nm excitation condition, the emission peak values of the ligand L and the ZnMOF are 445nm, but the emission peak intensity of the ZnMOF is higher than that of the ligand L.
FIG. 10 is a graph comparing solid state fluorescence of porous materials ZnMOF and CoMOF prepared in examples 1 and 2, respectively. As shown in fig. 10, ZnMOF has a strong emission broad peak under 365nm excitation and a peak value of 445nm, but the emission peak intensity of the comf is almost zero. The ligand L undergoes efficient ligand-to-metal energy transfer (LMCT) with the cobalt ion resulting in no emission of the comf.
Example 4:
fluorescence or magnetic change of porous materials ZnMOF and CoMOF after absorbing hydrogen chloride gas
To a closed, large glass vial having a volume of about 100mL, 2mL of a dodecahydric acid solution (20 ℃, CHCl ═ 6.32 × 10) was added-3mol/L), about 5mg of crystalline porous materials ZnMOF and CoMOF are respectively filled into an open glass bottle with the volume of about 5mL and are placed inside the large closed glass bottle for smoking and taken out at different times.
FIG. 11 is a graph showing the solid-state fluorescence response of the porous material ZnMOF prepared in example 1 to hydrogen chloride gas volatilized from a 20% hydrochloric acid solution in a closed environment. As shown in fig. 11, smokingZnMOF samples were prepared at different times and separately subjected to solid state fluorescence measurements (excitation wavelength 365 nm). The test results showed that the emission peak wavelength of ZnMOF was gradually red-shifted from 445nm to 510nm and the intensity was gradually red-shifted from 8.5X 10 with the smoking time gradually increased5(a.u.) to 2.1X 105(a.u.)。
FIG. 12 is a magnetic diagram of the porous material CoMOF prepared in example 2 before and after absorbing hydrogen chloride gas. As shown in fig. 12, alternating magnetic susceptibility testing was performed on both the 2 hour fumigated coff sample and the raw unfermented coff sample, and the results showed that the raw coff sample exhibited ferrimagnetic behavior and the sample after fumigation exhibited antiferromagnetic behavior.
The porous crystalline material provided by the invention is found to have high selectivity to the hydrogen chloride through a series of screens (comprising the hydrogen chloride, the hydrogen sulfide, the hydrogen bromide, the oxynitride and the ammonia gas).
Claims (10)
1. A metal organic framework material, characterized by: the structure is as follows
[M7(L)5(NO3)2(H2O)6]·xSolv
Wherein M is zinc ion or cobalt ion; l is 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenecarboxylic acid;
solv is solvent molecules adsorbed in the pore channels, and x is the number of the adsorbed solvent molecules.
2. The metal-organic framework material of claim 1, wherein: the solvent molecules are more than one of water, N-diethylformamide, N-dimethylformamide and N, N-diethylacetamide;
the metal organic framework material is a crystalline porous material; the crystalline porous material is M7(L)5(NO3)2(H2O)6xSolv, which crystallizes in the monoclinic system, C2/C space group, with unit cell parameters of
α＝90(deg)，β＝111.188(3)(deg)，γ＝90(deg)。
3. The metal-organic framework material of claim 2, wherein: the solvent molecule is a mixture of more than one of N, N-diethylformamide, N-dimethylformamide and N, N-diethylacetamide and water.
4. The method for preparing a metal organic framework material according to any one of claims 1 to 3, wherein: the method comprises the following steps:
4, 4' - (ethylene-1, 1, 2, 2-tetra-phenyl) tetraphenyl formic acid and nitrate are placed in a solvent and are heated to react to obtain a metal organic framework material; the nitrate is more than one of zinc nitrate containing crystal water or cobalt nitrate containing crystal water.
5. The method for preparing a metal organic framework material according to claim 4, wherein:
the nitrate is more than one of zinc nitrate hexahydrate or cobalt nitrate hexahydrate;
the temperature of the heating reaction is 70-100 ℃; the heating reaction time is more than or equal to 24 hours; the reaction is a solvothermal reaction; after the heating reaction is finished, cooling;
the molar ratio of the 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenyl formic acid to the nitrate is 1: 10-10: 1;
the solvent is more than one of water, N-diethylformamide, N-dimethylformamide and N, N-diethylacetamide;
when the solvent is a mixture of water and N, N-diethylformamide, the volume ratio of the water to the N, N-diethylformamide is 1: 3-0.5.
6. The method for preparing a metal organic framework material according to claim 5, wherein: the temperature of the heating reaction is 80-100 ℃; the heating reaction time is more than or equal to 48 hours; the cooling rate is 5-10 ℃/h;
the molar ratio of the 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenecarboxylic acid to the nitrate is 1: 10-1: 1;
the solvent is a mixture of more than one of N, N-diethylformamide, N-dimethylformamide and N, N-diethylacetamide and water.
7. Use of the metal organic framework material according to any one of claims 1 to 3 for detecting hydrogen chloride gas.
8. Use of a metal organic framework material according to any of claims 1 to 3 for the preparation of a sensor that responds intelligently to hydrogen chloride gas.
9. A sensing material responsive to hydrogen chloride gas, comprising: comprising the metal organic framework material according to any of claims 1 to 3.
10. A ferrimagnetic material, characterized by: comprising a metal organic framework material; the metal organic framework material is prepared by the following method: putting 4, 4' - (ethylene-1, 1, 2, 2-tetra-radical) tetraphenyl formic acid and cobalt nitrate into a solvent, and heating to react to obtain a metal organic framework material; the cobalt nitrate is cobalt nitrate hexahydrate;
the temperature of the heating reaction is 70-100 ℃; the heating reaction time is more than or equal to 24 hours; the reaction is a solvothermal reaction; after the heating reaction is finished, cooling;
the molar ratio of the 4, 4' - (ethylene-1, 1, 2, 2-tetraphenyl) tetraphenecarboxylic acid to the nitrate is 1: 10-10: 1;
the solvent is more than one of water, N-diethylformamide, N-dimethylformamide and N, N-diethylacetamide.
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| CN106459095A (en) * | 2014-04-25 | 2017-02-22 | 新泽西鲁特格斯州立大学 | Metal organic framework (MOF) yellow phosphors and their applications in white light emitting devices |
| CN109651126A (en) * | 2019-01-17 | 2019-04-19 | 杭州师范大学 | A kind of preparation method of tetraphenyl ethylene yl carboxylic acid organic ligand and its complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459095A (en) * | 2014-04-25 | 2017-02-22 | 新泽西鲁特格斯州立大学 | Metal organic framework (MOF) yellow phosphors and their applications in white light emitting devices |
| CN109651126A (en) * | 2019-01-17 | 2019-04-19 | 杭州师范大学 | A kind of preparation method of tetraphenyl ethylene yl carboxylic acid organic ligand and its complex |
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