CN112011063A - Cu-organic framework material based on V-type ligand and preparation method and application thereof - Google Patents
Cu-organic framework material based on V-type ligand and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000013384 organic framework Substances 0.000 title claims abstract description 48
- 239000003446 ligand Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013110 organic ligand Substances 0.000 claims abstract description 22
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 10
- 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 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims abstract description 9
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims abstract description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 14
- 239000007850 fluorescent dye Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 5
- ZKGNPQKYVKXMGJ-UHFFFAOYSA-N N,N-dimethylacetamide Chemical compound CN(C)C(C)=O.CN(C)C(C)=O ZKGNPQKYVKXMGJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010791 quenching Methods 0.000 abstract description 19
- 230000000171 quenching effect Effects 0.000 abstract description 19
- 230000004044 response Effects 0.000 abstract description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000013084 copper-based metal-organic framework Substances 0.000 description 52
- 239000000725 suspension Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 11
- 150000001450 anions Chemical class 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007900 aqueous suspension Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000010537 deprotonation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- -1 M (NO)3)n(M=Na+ Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 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"
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a Cu-organic framework material based on a V-type ligand, which has a chemical formula of [ (DMAC)2(Cu2L2)]nWherein H is2L is a V-type organic ligand, and DMAC is N, N-dimethylacetamide. The invention also discloses a preparation method of the material, which comprises the following steps: mixing copper nitrate trihydrate with 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl]Uniformly mixing-4, 4' -dicarboxylic acid, hexamethylenetetramine, N-dimethylacetamide and water, then dropwise adding a concentrated nitric acid solution into the mixed solution to enable the pH value of the mixed solution to be 3.0-4.0, and reacting under the solvothermal condition to obtain the Cu-organic framework material. The Cu-organic framework material can identify trace chromate ions in water through fluorescence quenching response, and realizes qualitative, quantitative, rapid,And (4) high-efficiency detection.
Description
Technical Field
The invention belongs to the technical field of fluorescent materials, and particularly relates to a Cu-organic framework material based on a V-type ligand, a preparation method of the Cu-organic framework material, and application of the Cu-organic framework material.
Background
Hundreds of millions of people around the world face the problem of shortage of water resources, and the water shortage is further aggravated by water pollution caused by continuous promotion of industrialization, wherein the problem of water quality deterioration caused by heavy metal ions such as chromium ions is particularly prominent. The chromium ions are usually dominated by Cr (III) and Cr (VI), the toxicity of which is about one hundred times that of Cr (III). CrO4 2-Is the most common form of Cr (VI), even with very small amounts of CrO4 2-It also damages DNA, has lethality, carcinogenicity and mutagenicity, and has great harm to human health and aquatic organisms. Therefore, trace amount of CrO can be quickly and accurately identified and quantitatively detected from polluted water body with complex chemical composition4 2-Has great significance for water safety.
Compared with the conventional chemical and complex large-scale precise instrument analysis and detection means, the high-sensitivity fluorescent probe based on the fluorescence chemical sensing can be used for detecting CrO in water4 2-Simple, low-cost, rapid and sensitive real-time monitoring is carried out, so that trace CrO in water containing complex anions and cations is prepared4 2-Fluorescent probe materials with high selective discrimination performance have been the research hotspot in the field. As a novel solid crystalline porous material, the metal-organic framework compound has adjustable spatial structure (pore size), modifiability and high internal specific surface area, so that CrO can be rapidly captured4 2-(ii) a On the other hand, the quantum dots (metal nodes) or the light-absorbing antenna (aromatic organic ligands) which are isolated and uniformly and orderly distributed can generate charge separation states on the MOFs under the action of light excitation, so that the quantum dots or the light-absorbing antenna (aromatic organic ligands) become a preferred choice for the high-sensitivity fluorescent probe.
Disclosure of Invention
The invention aims to provide a Cu-organic framework material based on a V-shaped ligand, which has good fluorescence and provides a new material for the field of fluorescent probes.
The invention also aims to provide a preparation method of the Cu-organic framework material based on the V-type ligand, which has the advantages of simple process, mild reaction conditions and high product yield.
The third purpose of the invention is to provide the application of the Cu-organic framework material in a fluorescent probe.
The invention adopts the technical scheme that the Cu-organic framework material based on the V-shaped ligand has a chemical formula of [ (DMAC)2(Cu2L2)]nWherein H is2L is a V-type organic ligand, i.e. 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl]-4,4 "-dicarboxylic acid, DMAC N, N-dimethylacetamide;
the crystal structure of the Cu-organic framework material belongs to a monoclinic system, C2/C space group, and the unit cell parameters are as follows:
α＝90°，β＝98.65(2)°，γ＝90°。
the invention adopts another technical scheme that the preparation method of the Cu-organic framework material based on the V-type ligand specifically comprises the following steps:
under the closed condition, copper nitrate trihydrate and organic ligand H2L is 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl]Uniformly mixing-4, 4' -dicarboxylic acid, a template agent hexamethylenetetramine, N-dimethylacetamide and water, then dropwise adding a concentrated nitric acid solution into the mixed solution to enable the pH value of the mixed solution to be 3.0-4.0, and reacting under the solvothermal condition to obtain the Cu-organic framework material.
The present invention is also characterized in that,
the temperature of the solvothermal reaction is 60-80 ℃, and the reaction time is 60-80 hours.
Copper nitrate trihydrate, organic ligand H2The molar ratio of L to hexamethylenetetramine is 5: 5: 1; the volume ratio of the N, N-dimethylacetamide to the water is 5: 3.
the mass fraction of the concentrated nitric acid solution is 65 percent.
The third technical scheme adopted by the invention is that the Cu-organic framework material based on the V-type ligand is applied to the fluorescent probe.
The beneficial effect of the invention is that,
the preparation method of the Cu-organic framework material has the advantages of simple process, mild synthesis reaction conditions, high product yield, capability of carrying out reproducible mass synthesis, high-purity and high-crystallinity solid-state synthesis product, and easiness in industrial production. The Cu-organic framework material can identify trace chromate ions in water through fluorescence quenching response, and qualitative, quantitative, rapid and efficient detection is realized.
Drawings
FIG. 1 shows [ Cu ] of a Cu-organic framework material prepared by the present invention2(O2C-)4]Secondary structural units (central metal copper and oxygen and nitrogen atoms are labeled in the figure, and carbon atoms are not labeled);
FIG. 2 is a diagram showing the coordination environment of the Cu-organic framework material prepared by the present invention (the central metal copper (II) and oxygen, nitrogen and fluorine atoms are labeled in the figure, and carbon atoms are not labeled);
FIG. 3 is a two-dimensional plane structure diagram of a Cu-organic framework material prepared by the present invention;
FIG. 4 is a three-dimensional stacking structure diagram of a Cu-organic framework material prepared by the present invention;
FIG. 5 is a graph showing the thermal weight loss of Cu-organic framework material prepared by the present invention;
FIG. 6 is an infrared spectrum of a Cu-organic framework material prepared by the present invention;
FIG. 7 is a simulated X-ray powder diffraction pattern of a single crystal of a Cu-organic framework material prepared by the present invention and an actually tested X-ray powder diffraction pattern of a large number of crystal samples;
FIG. 8 is a graph of transient quenching response of fluorescence intensity and a graph of response persistence of a Cu-organic framework material prepared by the present invention;
FIG. 9 shows the addition of different concentrations of Cu-organic framework material to the aqueous suspension preparedCrO4 2-The fluorescence intensity map after;
FIG. 10 is a graph showing fluorescence quenching efficiency after adding different anions to the prepared suspension of the Cu-organic framework material;
FIG. 11 is a graph showing fluorescence quenching efficiency after adding different cations to a suspension of a prepared Cu-organic framework material;
FIG. 12 shows the CrO of the Cu-organic framework material prepared in 7 times of succession4 2-Fluorescence quenching and fluorescence emission profiles in the detection-regeneration-detection-regeneration cycle.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The Cu-organic framework material based on the V-shaped ligand has a chemical formula of [ (DMAC)2(Cu2L2)]nWherein H is2L is a V-type organic ligand, i.e. 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl]-4,4 "-dicarboxylic acid, DMAC N, N-dimethylacetamide, N being a natural number from 1 to plus infinity; the chemical formula of the material is C50H42Cu2F6N4O12Organic ligands H of the V type2The molecular structural formula of L is as follows:
from the construction of a space skeleton structure, the crystal structure of the Cu-organic framework material belongs to a monoclinic system, C2/C space group, and the unit cell parameters are as follows:
α＝90°，β＝98.65(2)°，γ＝90°。
in the Cu-organic framework material, 1 Cu2+Metal centre with 4H from deprotonation2L carboxyl group of organic ligand, 2Amide O atoms from DMAC molecules in organic solvents are coordinated to form [ Cu ] in the shape of a paddle2(O2C-)4(DMAC)2]And secondary structure units which are further connected by organic ligands to form a two-dimensional plane structure, and the two-dimensional layers are superposed through pi … pi stacking action and intermolecular hydrogen bonding action to be further connected and expanded into a three-dimensional structure.
The Cu-organic framework material has strong fluorescence, and can identify chromate ions in water; the recognition of chromate ions is fluorescence quenching recognition.
The preparation method of the Cu-organic framework material based on the V-type ligand specifically comprises the following steps:
under the closed condition, copper nitrate trihydrate and organic ligand H2L is 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl]Uniformly mixing-4, 4' -dicarboxylic acid, a template agent hexamethylenetetramine, N-dimethylacetamide and water, then dropwise adding a concentrated nitric acid solution into the mixed solution to enable the pH value of the mixed solution to be 3.0-4.0, reacting under a solvothermal condition, wherein the solvothermal reaction temperature is 60-80 ℃, and the required reaction time is 60-80 hours to obtain the Cu-organic framework (Cu-MOF) material.
Copper nitrate trihydrate, organic ligand H2The molar ratio of L to hexamethylenetetramine is 5: 5: 1; the volume ratio of the N, N-dimethylacetamide to the water is 5:3, the mass fraction of the concentrated nitric acid solution is 65 percent;
specifically, 5ml of N, N-dimethylacetamide and 3ml of distilled water were used for 9.66 mg of copper nitrate trihydrate, 16.68 mg of an organic ligand, 2 '-amino-5' - (trifluoromethoxy) - [1,1':3',1 '-terphenyl ] -4, 4' -dicarboxylic acid and 1.12 mg of hexamethylenetetramine;
the invention provides a method for identifying CrO through fluorescence quenching response4 2-The preparation method of the Cu-MOF material. 1mg of Cu-MOF was uniformly dispersed in 20mL of distilled water at room temperature by ultrasonic oscillation for 30min to obtain an aqueous suspension of Cu-MOF having a solid-to-liquid ratio of 50mg/L, 3mL of the aqueous suspension was taken out and put into a 4mL cuvette, and the fluorescence intensity was measured on a fluorescence spectrophotometer.
To a cuvette containing 3mL of the suspension of the prepared Cu-MOF was added 50. mu.L of 4.1X 102Mu mol/L of K2CrO4Aqueous solution, stirred well within 5 seconds and immediately tested for CrO on a fluorospectrophotometer4 2-Changes in fluorescence emission intensity at the maximum emission wavelength, with a scan every 0.06 seconds maintained for 500 seconds, to validate Cu-MOF vs CrO4 2-The transient and persistent nature of the fluorescence quenching response.
To a cuvette containing 3mL of the suspension of the prepared Cu-MOF was added potassium chromate K2CrO4Preparing an aqueous solution containing CrO with the concentration of 0.05-168 mu mol/L4 2-And separately testing the evolution of the fluorescence intensity of the Cu-MOF by a fluorescence spectrophotometer to verify the CrO causing the thorough fluorescence quenching of the Cu-MOF4 2-I.e. the sensitivity of the detection.
20mL of the solutions were prepared at a concentration of 2.4X 103Mu mol/L of aqueous solutions of potassium salts containing different anionic groups, i.e. (K)nX(X＝CrO4 2-，F-，Cl-，Br-，I-，NO2 -，NO3 -，IO3 -，CO3 2-，SO4 2-，PO4 3-，HPO4 2-，C2H5O-Or SCN-) (ii) a Or nitrate solutions containing different cations, i.e. M (NO)3)n(M＝Na+，K+，Mg2+，Ag+，Cd2+，Co2+，Cr3+Or Ni2 +). Taking 50 μ L of the above (K)nX or M (NO)3)nRespectively adding the aqueous solution into cuvettes containing 3mL of Cu-MOF suspension, uniformly mixing, and testing the fluorescence intensity on a fluorescence spectrophotometer to verify the selectivity of the Cu-MOF on the fluorescence quenching response of different anions and cations.
The invention develops 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl based on a V-type organic ligand]-4,The Cu metal-based organic framework material of 4' -dicarboxylic acid is a solid crystalline porous material, and the Cu-MOF is an A-B-A-B type superposed three-dimensional stacking structure. In particular crystallographically independent Cu2+With H from 4 deprotonations2The carboxyl of the L ligand and the O atom of the N, N-dimethylacetamide molecule form a [ Cu ] with a typical paddle structure2(O2C-)4]Secondary structural unit, V-type H in which secondary structural unit is deprotonated2The L ligands are further connected to form a two-dimensional plane latticed framework, and independent two-dimensional layers are overlapped through pi-pi stacking effect and intermolecular hydrogen bonding effect and further connected and expanded to form a three-dimensional stacking structure. The technical scheme of the invention proves that the prepared Cu-MOF material has excellent photoluminescence and luminescence characteristics and can be used as a fluorescent probe for identifying and detecting chromate ions in water.
Infrared spectroscopy tests related to the present invention: the solid of Cu-MOF and potassium bromide powder are uniformly mixed and ground according to the mass ratio of 1:100, pressed into a sheet and tested on an infrared spectrometer.
The invention relates to a test of a thermal weight loss curve: weighing 8-20 mg of naturally dried solid of Cu-MOF, putting the solid into an alumina crucible, and testing on a thermal weight loss analyzer.
The fluorescence emission test to which the present invention relates: the suspension of the solid of Cu-MOF after being dispersed in distilled water for 30min by ultrasound was placed in a cuvette and tested on a fluorescence photometer.
Example 1
Organic ligand H2L(0.05mmol)、Cu(NO3)2·3H2O (0.05mmol) and hexamethylenetetramine (0.01mmol) were uniformly mixed in 4.0mL of a mixed solution of N, N-dimethylacetamide and water (volume ratio: 5:3), 10. mu.L of 65% concentrated nitric acid was added, and the mixture was sealed in a 25mL glass vial. And carrying out solvothermal reaction at 65 ℃ for 80 hours, and naturally cooling to room temperature to obtain the dark green strip Cu-organic framework material.
Example 2
Organic ligand H2L(0.1mmol)、Cu(NO3)2·3H2O (0.1mmol) and hexamethylenetetramine (0.02mmol) were uniformly mixed in 8.0mL of a mixed solution of N, N-dimethylacetamide and water (volume ratio: 5:3), 20. mu.L of 65% concentrated nitric acid was added, and the mixture was sealed in a 25mL glass vial. And carrying out solvothermal reaction at 75 ℃ for 72 hours, and naturally cooling to room temperature to obtain the dark green strip Cu-organic framework material.
The crystal structure test method and structure of the Cu-MOF obtained in the above embodiment are the same, and the specific points are as follows:
determination of crystal structure:
single crystals of clear, crack-free Cu-MOF were selected, single crystal structure testing and diffraction data collection were performed at room temperature (about 296K) using a Bruker Aper II CCD model single crystal X-ray diffractometer from Bruker, Inc. of Germany, Mo-Ka α monochromated using a graphite monochromator
The crystal cell parameters obtained by least square correction are analyzed by adopting SHELXS-97 software package, and the absorption correction of the collected data is completed by adopting SADABS program. The crystallographic data are shown in table 1, and the crystal structures are shown in fig. 1 to 4.
TABLE 1 crystallographic parameters
The structure of FIG. 1 shows that Cu2+With H from 4 deprotonations2The carboxyl oxygen atom of the L ligand is coordinated with the amide oxygen atom of the N, N-dimethylacetamide molecule to construct [ Cu ] with a typical paddle-shaped structure2(O2C-)4]A secondary building block.
The structure of FIG. 2 shows that in the asymmetric structural unit of Cu-MOF, there is one deprotonated coordinated H2L ligand, 4 coordinated Cu2+And 1 of the coordinated N,a molecule of N-dimethylacetamide.
The structure of FIG. 3 shows that the [ Cu ] of the paddle structure2(O2C-)4]Secondary structural unit, deprotonated H of V-type2The L ligands are further linked to form a two-dimensional, planar, lattice-like framework.
The structure of fig. 4 shows that the individual two-dimensional layers are further connected and expanded into a three-dimensional stacked structure by superposition of pi … pi stacking and intermolecular hydrogen bonding.
The thermogravimetric plot of fig. 5 shows that Cu-MOF undergoes 3 weight loss stages in the range of 30-850 ℃ with temperature increase at 10 ℃/min under flowing nitrogen. A weight loss rate of about 16.08% between 30-230 ℃ from the leaving of guest small molecules and coordinated DMAC molecules within the Cu-MOF cavity; between 231 ℃ and 380 ℃, 36.17% of the weight loss rate is from partial collapse of the skeleton and decomposition of the organic ligand; between 381 and 682 ℃, 33.29 percent of weight loss rate is from complete collapse and decomposition of the skeleton; the remaining 14.46% by mass is ash and Cu oxides. This curve shows that Cu-MOF has good thermal stability below 230 ℃.
FIG. 6 shows the spectrum showing that asymmetric stretching vibration peaks of carboxyl groups on organic ligands in Cu-MOF framework appear at 1686 and 3475cm-1And at 639, 712 and 784cm-1The characteristic peak of (A) should be attributed to the flexural vibration of the C-H bond on the benzene ring in the organic ligand.
The spectrum of fig. 7 shows that the actual value (i.e. 2 theta angle value) of the diffraction peak of the X-ray powder diffraction spectrum of the Cu-MOF sample is basically consistent with the theoretical value obtained by single crystal diffraction test, which indicates that the structure of a large amount of synthesized Cu-MOF is consistent with that of a single crystal used by single crystal test. The difference in the intensity of the individual diffraction peaks is related to the preferred orientation of the Cu-MOF sample.
FIG. 8 shows the addition of 50. mu.L of 4.1X 10 to 3mL of aqueous Cu-MOF suspension (solid-to-liquid ratio: 50mg/L)2Mu mol/L of K2CrO4Transient quenching response of fluorescence intensity (intensity drops instantaneously from 923 to 780) and persistence of response (within 500 seconds) of Cu-MOF after aqueous solution. The spectrum of FIG. 8 shows 6.0X 10 with 50. mu.L2Mu mol/L of K2CrO4Dropping the aqueous solution into the aqueous suspension of Cu-MOFIn the suspension and mixed rapidly, the fluorescence emission intensity of Cu-MOF decreased instantaneously from 947.06 to about 725a.u., and the intensity remained essentially unchanged for the next 500 seconds (every 0.06 second scan). This demonstrates that Cu-MOF is specific to CrO in water4 2-And the persistence of the response.
Respectively adding 3mL of Cu-MOF suspension with solid-to-liquid ratio of 50mg/L into different four-side light-transmitting cuvettes, and respectively adding CrO with different concentrations into each cuvette4 2-Ions (0-168. mu. mol) were mixed homogeneously with the suspension of Cu-MOF and the fluorescence intensity of the Cu-MOF suspension was measured separately on a fluorescence spectrophotometer. As shown in FIG. 9, the fluorescence emission band of the Cu-MOF suspension decayed rapidly and finally disappeared, and the corresponding 371nm fluorescence emission intensity dropped from 923.05 to 0.085a.u., obtaining the Cu-MOF material for different concentrations of CrO4 2-Fluorescence quenching of the ions and fluorescence emission.
3mL of Cu-MOF suspension with a solid-to-liquid ratio of 50mg/L are respectively added into different four-side light-transmitting cuvettes, and 50 mu L of 2.4X 103Mu mol/L of an anion (CrO)4 2-，F-，Cl-，Br-，I-，NO2 -，NO3 -，IO3 -，CO3 2-，SO4 2-，PO4 3-，HPO4 2-，C2H5O-Or SCN-) And respectively and uniformly mixing, and respectively testing the fluorescence intensity of the Cu-MOF suspension on a fluorescence spectrophotometer. As shown in FIG. 10, Cu-MOF suspension vs. CrO4 2-The anions undergo almost complete fluorescence quenching, and the calculated fluorescence quenching efficiency is 97.2%; in contrast, when the Cu-MOF meets other anions, the fluorescence emission intensity of the Cu-MOF is almost kept unchanged, and the fluorescence quenching and fluorescence emission conditions of the Cu-MOF material on different anions are obtained.
3mL of Cu-MOF suspension with the solid-to-liquid ratio of 50mg/L are respectively added into different four-side light-transmitting cuvettes and then divided into the cuvettesAdding 50 μ L of 2.4 × 103μ mol/L cation (Na)+，K+，Mg2+，Ag+，Cd2+，Co2+，Cr3+Or Ni2+) The Cu-MOF suspensions were mixed well and tested for fluorescence intensity separately on a fluorescence spectrophotometer. As shown in FIG. 11, when Cu-MOF meets the above cations in water, the change of fluorescence emission intensity is little or almost unchanged, and the fluorescence quenching and fluorescence emission of Cu-MOF material to different cations are obtained, and the fluorescence emission is compared with that of 2.4X 10 added with 50 μ L3Mu mol/L CrO4 2-The fluorescence intensity of the ionic Cu-MOF suspensions was compared.
3mL of a suspension of Cu-MOF at a solid-to-liquid ratio of 50mg/L was added to the cuvette followed by CrO4 2-Ions and mixed uniformly to obtain a concentration of 1.5X 102Mu mol of the mixed solution, and testing the fluorescence intensity of the Cu-MOF suspension on a fluorescence spectrophotometer; then pouring the mixed solution into a centrifuge tube, pouring out supernatant after high-speed centrifugation, separating out solid of Cu-MOF, circularly and repeatedly washing for 5 times by distilled water, adding 3mL of distilled water, ultrasonically dispersing for 30 minutes again, and adding CrO4 2-The ions are mixed uniformly, and the fluorescence quenching and fluorescence emission conditions of the Cu-MOF suspension are tested repeatedly. As shown in FIG. 12, the fluorescence emission intensity at 7 detection cycles was still as high as 888.20a.u., corresponding to a percent intensity decay of only about 9.2%, compared to the initial fluorescence emission intensity (978.21a.u.) of the Cu-MOF suspension, resulting in 7 consecutive CrO cycles4 2-Fluorescence quenching and fluorescence emission of Cu-MOF in the detection-regeneration-detection-regeneration cycle.
Claims (6)
1. Cu-organic framework material based on V-type ligand, characterized in that the chemical formula is [ (DMAC)2(Cu2L2)]nWherein H is2L is a V-type organic ligand, i.e. 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl]-4,4 "-dicarboxylic acid, DMAC N, N-dimethylacetamide;
the crystal structure of the Cu-organic framework material belongs to a monoclinic system, C2/C space groupThe unit cell parameters are:
α＝90°，β＝98.65(2)°，γ＝90°。
2. the V-ligand based Cu-organic framework material of claim 1, wherein the Cu-organic framework material is used in a fluorescent probe.
3. The preparation method of the Cu-organic framework material based on the V-type ligand is characterized by comprising the following steps:
under the closed condition, copper nitrate trihydrate and organic ligand H2L is 2' -amino-5 ' - (trifluoromethoxy) - [1,1':3', 1' -terphenyl]Uniformly mixing-4, 4' -dicarboxylic acid, a template agent hexamethylenetetramine, N-dimethylacetamide and water, then dropwise adding a concentrated nitric acid solution into the mixed solution to enable the pH value of the mixed solution to be 3.0-4.0, and reacting under the solvothermal condition to obtain the Cu-organic framework material.
4. The method for preparing a Cu-organic framework material based on V-type ligand of claim 3, wherein the temperature of the solvothermal reaction is 60-80 ℃ and the reaction time is 60-80 hours.
5. The method for preparing a Cu-organic framework material based on V-type ligand of claim 3, wherein the copper nitrate trihydrate and organic ligand H2The molar ratio of L to hexamethylenetetramine is 5: 5: 1; the volume ratio of the N, N-dimethylacetamide to the water is 5: 3.
6. the method for preparing a Cu-organic framework material based on V-type ligand of claim 3, wherein the mass fraction of the concentrated nitric acid solution is 65%.
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