CN111019150A - Two-dimensional interpenetrating formed three-dimensional cadmium coordination polymer and preparation method and application thereof - Google Patents
Two-dimensional interpenetrating formed three-dimensional cadmium coordination polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a three-dimensional cadmium coordination polymer formed by two-dimensional interpenetrating, and the chemical general formula of the three-dimensional cadmium coordination polymer is { [ Cd ]2(etc)(pyan)1.5(H2O)3](H2O)2}nBelonging to the monoclinic system, space group is P21N, unit cell parameter
In the chemical general formula, the component etc4‑Is a quaternary organic carboxylic acid H4etc. 4 protons are eliminated, the H4The structure of etc is shown as formula I; the structure of the component pyan is shown as a formula II,
the polymer has mild preparation conditions, the yield can reach 45 percent, and the thermal stability is higher; in a space structure, the structure has a pillared porous 2D coordination polymerization structure, and a three-dimensional metal-organic framework structure is formed by triple interpenetrating of a 2D network; under 365nm ultraviolet irradiation, the crystal sample presents bright green fluorescence; in addition, the cadmium coordination polymer can be used for NO in aqueous solution2 ‑And for the preparation of photosensitive composites and devices.
Description
Technical Field
The invention belongs to the field of advanced luminescent materials, and particularly relates to a three-dimensional cadmium coordination polymer formed by two-dimensional interpenetrating, and a preparation method and application thereof.
Background
A novel coordination polymer is constructed by taking an electron-rich organic ligand and a common transition metal salt as raw materials through coordination bonds, and the coordination polymer becomes a leading problem in the field of new luminescent materials. Practice proves that in the process of preparing the coordination polymer, the microscopic reaction process, the topological structure and the performance are difficult to predict. Therefore, the preparation of coordination polymers with novel topological structure, excellent performance and practicability is a challenging subject, and particularly, the three-dimensional coordination polymers have higher difficulty.
Nitrite, widely found in the human environment, is one of the most common nitrogen-containing compounds in nature, the most common salt being sodium nitrite (NaNO)2)，NaNO2Is white to light yellow powder or granular, has slightly salty taste, is easy to dissolve in water, is widely used in industry and construction industry, and is allowed to be used as a color former in limited quantity in meat products. Because the appearance of nitrite is similar to that of common salt, the nation prohibits the catering industry from purchasing, storing and using nitrite (sodium nitrite, potassium nitrite and the like), and prevents the nitrite from being used as common salt by mistake. Nitrite can be converted into nitrosamine in the acid environment of human gastrointestinal tract, and nitrosamine has strong carcinogenic effect, and mainly causes esophageal cancer, gastric cancer, liver cancer, colorectal cancer and the like, and in food inspection, nitrite (mainly sodium nitrite) is an important index. Therefore, the development of a new method for rapidly detecting nitrite is undoubtedly of great practical significance.
Disclosure of Invention
In view of the above-mentioned disadvantages in the prior art, the present invention provides a two-dimensional interpenetrating three-dimensional cadmium coordinationPolymers, the novel substances being useful for nitrite NO2 -Fast fluorescence detection of ions and preparation of fluorescent doped organic glass.
In order to achieve the purpose, the invention provides the following technical scheme: a two-dimensional interpenetrating three-dimensional cadmium coordination polymer is characterized in that the chemical general formula is { [ Cd ]2(etc)(pyan)1.5(H2O)3](H2O)2}n(Cd-MOF) belongs to monoclinic system, and the space group is P21N, unit cell parameter
In the chemical general formula, the component etc4-Is a quaternary organic carboxylic acid H4etc. 4 protons are eliminated, the H4The structure of etc is shown as formula I; the structure of the component pyan is shown as a formula II,
furthermore, the three-dimensional cadmium coordination polymer contains 2 Cd in crystallographically independent asymmetric structure2+Ion, 1 etc4-And 1.5 pyan components; each of the etc4-And 4 Cd2+The ion coordination mode is shown as formula III, and the components pyan and Cd2+There are two coordination modes, pyan-A as shown in formula IV and pyan-B as shown in formula V; the Cd2+The coordination modes of the ions are respectively shown as a formula VI and a formula VII; wherein the atom number designations in formulae III to VII denote the source;
in the space structure of Cd-MOF, metal ion Cd2+With the organic component etc4-And pyan-A to form a two-dimensional (2D) coordination polymerization layer, further comprising a pyan-B bondAlloy Cd2+Ions form a pillared porous 2D coordination polymerization structure, the structure can be simplified into a rare 3,4, 4-connected porous 2D topological network, the porous 2D topological network forms a three-dimensional metal-organic framework (MOF) structure through triple interpenetrating, the stability of the whole structure can be further improved through triple interpenetrating, meanwhile, the porosity of the structure is also reduced, and the theoretical porosity of the Cd-MOF is calculated by a Platon program to be 8.5%.
The three-dimensional cadmium coordination polymer formed by two-dimensional interpenetrating adopts the following preparation method: with H4etc、pyan、Cd(NO3)2·4H2O and HBF4The raw material is prepared by a solvent thermal synthesis method by using a mixed solution of acetonitrile and water as a solvent.
Further, the preparation method specifically comprises the following steps:
(1) mixing the raw materials and a solvent to form a reaction system, and placing the reaction system in a closed container; the raw material H4etc、pyan、Cd(NO3)2·4H2O and HBF4The mass ratio of (1): 1: 2: 2.5-8; the volume ratio of the solvents acetonitrile and water is 3: 7;
(2) and (3) stirring the reaction system at room temperature for 0.5h, then heating the reaction system to 140-160 ℃, reacting for 4-6 days, and then naturally cooling, filtering and drying to obtain blocky crystals.
Further, said H in step (1)4etc：pyan：Cd(NO3)2·4H2O：HBF4The mass ratio of (1): 1: 2: 5.
further, H in the reaction system4The starting material of etc or pyan is present in a concentration of 5 mmol/L.
Further, the reaction temperature in step (2) was 140 ℃, and the drying means that the crystals were naturally dried in the air at room temperature after being washed with distilled water.
The three-dimensional cadmium coordination polymer formed by two-dimensional interpenetrating prepared by the preparation method is applied to ion detection and identification and preparation of photosensitive composite materials and devices.
Compared with the prior art, the invention has the following beneficial effects:
(1) the two-dimensional interpenetrating three-dimensional cadmium coordination polymer Cd-MOF provided by the invention has high thermal stability and stably exists in solvents such as water, acetonitrile and the like; at room temperature, the crystal material emits green fluorescence at 525nm under the excitation of 418 nm; under 365nm ultraviolet irradiation, the crystal sample presents bright green fluorescence; meanwhile, the solution prepared by the Cd-MOF sample can be used as an ion detector, and the fluorescence emission spectrogram shows that the Cd-MOF solution can be used for identifying NO in an aqueous solution2 -Ions.
(2) The yield of the Cd-MOF prepared by the method provided by the invention can reach 45%. The Cd-MOF provided by the invention can be used for preparing photosensitive composite materials and devices.
Drawings
FIG. 1 is a coordination pattern of an organic ligand and a metal ion of a three-dimensional cadmium coordination polymer according to the present invention;
FIG. 2 is a schematic diagram of a three-dimensional cadmium coordination polymer according to the present invention, wherein (a) is etc4-、Cd2+A two-dimensional (2D) coordination polymerization layer constructed by a pyan-A component, (B) a porous two-dimensional coordination polymer layer supported by a pyan-B column, (c) a 3,4, 4-connection topological diagram, and (D) a three-dimensional metal-organic framework structure formed by three-dimensional interpenetrating;
FIG. 3 is a graph of the X-ray powder diffraction pattern of a three-dimensional cadmium coordination polymer of the present invention;
FIG. 4 is an infrared spectrum of a three-dimensional cadmium coordination polymer of the present invention;
FIG. 5 is a thermogravimetric plot of a three-dimensional cadmium coordination polymer of the present invention;
FIG. 6 is a photograph of a bright green color of a three-dimensional cadmium coordination polymer of the present invention under 365nm UV light;
FIG. 7 is a graph of room temperature solid state fluorescence spectra of a three-dimensional cadmium coordination polymer in accordance with the present invention;
FIG. 8 is a fluorescence spectrum of the three-dimensional cadmium coordination polymer of the present invention for detecting anions in an aqueous solution;
FIG. 9 is a photograph of a three-dimensional cadmium coordination polymer doped organic glass composite of the present invention under UV light at 365 nm.
Detailed Description
The process of the present invention will be described in detail with reference to specific examples. The three-dimensional cadmium coordination polymer formed by two-dimensional interpenetrating provided by the invention can be abbreviated as Cd-MOF. The method carries out X-ray single crystal diffraction test on the final product, and analyzes to obtain the accurate electronic structure of the final product; and performing a series of characterizations such as infrared, fluorescence, X-ray powder diffraction, thermogravimetry and the like on the final product to determine that the chemical composition general formula is { [ Cd ]2(etc)(pyan)1.5(H2O)3](H2O)2}n. Calculating the yield according to the pyan dosage, namely calculating the mass of the complex to be obtained theoretically according to the ratio of the pyan dosage in the product Cd-MOF composition, wherein the ratio of the actually obtained product mass to the former is the yield. In the invention H4The mesocultural name of etc is 3,5,9, 11-tetracarboxyl-diphenyl ether and the mesogenic name of the component pyan is 9, 10-bis (4-pyridyl) anthracene.
Firstly, preparation of three-dimensional cadmium coordination polymer
Example 1
Taking the following materials according to the specific mass or volume: h4etc(17.3mg,0.05mmol)，pyan(16.6mg,0.05mmol)，Cd(NO3)2·4H2O(30.8mg，0.1mmol)，CH3CN(3mL)，H2O(7mL)，40％HBF4Solution (40uL,1.39g/mL,0.25 mmol). Placing the materials in a 25mL polytetrafluoroethylene lining, stirring for about 0.5h, sealing in a stainless steel reaction kettle, placing the reaction kettle in an electric heating air blowing oven, heating to 140 ℃, reacting for 4 days, naturally cooling to room temperature to obtain a blocky crystal sample, filtering the blocky crystal sample from mother liquor, washing with distilled water, and naturally drying in the air at room temperature.
The crystal sample of the prepared three-dimensional cadmium coordination polymer is subjected to powder diffraction test by adopting an Shimadzu XRD-6100X-ray diffractometer (see figure 3, abscissa-angle; ordinate-diffraction intensity), and the peak of the test pattern can be well matched with the peak of a crystal structure simulation pattern (software Mercury), so that the structure of the obtained crystal sample is the same as that of single crystal data, and the purity of the sample is high.
In the crystal sample, a suitable single crystal was selected and subjected to X-ray single crystal diffraction analysis to analyze the crystal structure (see fig. 1 and 2). Wherein, in the crystallographically independent asymmetric structure, as shown in FIG. 1, 2 Cd are contained2+1 etc4-And 1.5 pyan components; each etc4-And 4 Cd2+Ion coordination, namely two coordination modes exist in pyan, and the pyan is respectively coordinated with two Cd2+And (4) ion coordination. FIG. 2 shows the spatial structure of Cd-MOF, from which it can be seen that the metal ion Cd2+With the organic component etc4-And pyan-A to form a two-dimensional (2D) coordination polymerization layer, and further bonding Cd by pyan-B2+Ions form a pillared porous 2D coordination polymerization structure, the structure can be simplified into a rare 3,4, 4-connected porous 2D topological network, importantly, the porous 2D topological network forms a three-dimensional metal-organic framework (MOF) structure through triple interpenetrating, the stability of the whole structure can be further improved through the triple interpenetrating, meanwhile, the spatial void ratio is also reduced, and the theoretical void ratio of the Cd-MOF is calculated to be 8.5% by a Platon program. Generally speaking, the stability of the porous MOF is poor, and the thermal stability of the Cd-MOF is high as shown in the following thermogravimetric curve map, and the Cd-MOF is related to the structure interpenetrating property, which is also the basis for the application and development of the polymer.
Determination of the Single Crystal Structure: selecting proper three-dimensional cadmium coordination polymer single crystals, and performing diffraction on the three-dimensional cadmium coordination polymer single crystals on a SMARTAPEXII CZN single crystal diffractometer (Mo-Ka,
graphite monochromator) were collected at room temperature and X-ray diffraction data were corrected for Lp factor. The crystal structure is solved by direct method, the analysis and refinement of the structure are completed by SHELXTL-97 program package, and then the full matrix least square method F is used2All non-hydrogen atoms are anisotropically refined. The hydrogen atom coordinates of the organic ligand are obtained by theoretical hydrogenation. The main crystallographic data are shown in table 1; the length of the coordination bond is shown in Table 2.
Table 1 main crystallographic data
*R1＝Σ||Fo|-|Fc||/Σ|Fo|,wR2＝[Σw(Fo 2-Fc 2)2/Σw(Fo 2)2]1/2
TABLE 2 length of coordination bond
Symmetric conversion #1x-1, y-1, z; #2x, y-1, z
Cd-MOF is of formula C52H40N3O14Cd2The formula weight is 1155.72, wherein C, H, N element analysis, calculated (%): c54.04, H3.49, N3.64; actually measured (%): c54.08, H3.52, N3.59. FIG. 4 shows an infrared spectrum (abscissa-wavenumber; ordinate-transmittance) of a three-dimensional cadmium coordination polymer according to the present invention. FT-IR (KBr, cm)-1): 3360(m),3075(w),1611(vs),1553(vs),1372(vs),1233(m),1066(w),988(m),816(m),772(m),737(s),655 (m). Description of the drawings: the elemental analysis value is measured by a Perkin-Elmer2400 elemental analyzer; infrared spectrum was measured by a PerkinElmerFT-IRSpectrometer Two spectrometer with KBr as the base at 400-4000cm-1Measured within the range.
Thermogravimetric data analysis of the obtained crystal sample shows (see fig. 5, nitrogen atmosphere, abscissa-temperature, ordinate-residue), and it can be seen from the figure that Cd-MOF loses about 4.0% weight at about 200 ℃, can be attributed to the separation of guest water molecules (calculated value is 3.1%) and part of coordination water molecules, and the framework is decomposed after 320 ℃. This shows that the three-dimensional cadmium coordination polymer of the invention has higher thermal stability, and is consistent with the result of the Cd-MOF space structure analysis.
The crystal sample showed yellow-green color under natural light and bright green fluorescence under 365nm ultraviolet light (see fig. 6). The solid state fluorescence spectrum of the crystal samples was measured at room temperature (see FIG. 7, abscissa-wavelength; ordinate-fluorescence intensity), and data analysis showed: under the excitation at 418nm, the coordination polymer Cd-MOF generates a green fluorescence emission peak at 525nm, and is a more typical green fluorescent substance. It can be seen that the spectral data and the crystal uv photograph are mutually supported.
The embodiment is repeated for many times, the mass of the actually obtained Cd-MOF is kept at 13.5-17.4 mg, and the yield is 35.0% -45.1% based on pyan calculation.
Example 2
Taking the following materials according to the specific mass or volume: h4etc(17.3mg,0.05mmol)，pyan(16.6mg,0.05mmol)，Cd(NO3)2·4H2O(30.8mg，0.1mmol)，CH3CN(3mL)，H2O(7mL)，40％HBF4Solution (63uL,1.39g/mL, 0.4 mmol). Placing the materials in a 25mL polytetrafluoroethylene lining, stirring for about 0.5h, sealing in a stainless steel reaction kettle, placing the reaction kettle in an electric heating blast oven, heating to 160 ℃, reacting for 5 days, naturally cooling to room temperature to obtain a blocky crystal sample, filtering the blocky crystal sample from mother liquor, washing with distilled water, and naturally drying in the air at room temperature.
The product was characterized by powder X-ray diffraction and data similar to example 1 were obtained. It is shown that the crystal structure obtained in example 2 is unchanged and the product purity is higher.
The method is repeated for multiple times, the mass of the actually obtained Cd-MOF is kept at 10.2-15.3 mg, and the yield is 26.5% -39.7% based on pyan calculation.
Example 3
Taking the following materials according to the specific mass or volume: h4etc(17.3mg,0.05mmol)，pyan(16.6mg,0.05mmol)，Cd(NO3)2·4H2O(30.8mg，0.1mmol)，CH3CN(3mL)，H2O(7mL)，40％HBF4Solution (20uL,1.39g/mL,0.127 mmol). Placing the above materials at 25mStirring for about 0.5h in an L polytetrafluoroethylene lining, sealing in a stainless steel reaction kettle, placing the reaction kettle in an electric heating blast oven, heating to 150 ℃, reacting for 6 days, naturally cooling to room temperature to obtain a blocky crystal sample, filtering the blocky crystal sample from mother liquor, washing with distilled water, and naturally drying in the air at room temperature.
Second, application of three-dimensional cadmium coordination polymer of the invention
Example 4 fluorescent detection of anions by three-dimensional cadmium coordination Polymer solution
Preparing a detection solution of a cadmium coordination polymer in a 150mL conical flask, dissolving the ground crystal powder in 100mL water, shaking, ultrasonically dispersing for 10min to obtain a suspension, aging the suspension for 60 hours, and respectively taking 4.5mL of an upper clear solution as a detection solution in a numbered glass bottle when the solution is stable.
Respectively measuring 0.5mLHCO2 -(formate radical), CH3CO2 -、CO3 2-、NO2 -、Cl-、Br-、I-、WO4 2-And MoO4 2-Sodium salt aqueous solution (concentration: 0.01 mol. L)-1) Adding the mixture into the detection solution, and uniformly mixing to obtain a solution to be detected.
The fluorescence spectra of the above solutions were measured separately by a Perkin-Elmer LS55 type fluorescence spectrometer under excitation at a wavelength of 400nm (FIG. 8). Data analysis shows that the complex Cd-MOF aqueous solution has the strongest fluorescence emission at 490 nm; containing NO2 -The fluorescence intensity of the nitrite mixture solution is enhanced compared with the intensity of the Cd-MOF aqueous solution, while the fluorescence intensity of other anion sodium salt solutions is weakened, and the weakening of the fluorescence intensity is obvious when the CO is contained3 2-A mixture solution of anions. Thus, solutions prepared from the novel cadmium coordination polymers can be used for NO2 -And CO3 2-The ion identification is more green and convenient than the traditional method.
Example 5 preparation of fluorescent doped organic glass composite (doped-PMMA)
Taking 10mg of Cd-MOF coordination polymer, and fully grinding for later use. In a 20mL clean dry tube, 1.5mL of Methyl Methacrylate (MMA), 0.025g of dibenzoyl peroxide (BPO, free radical excited) and 0.5mL of dibutyl phthalate (DBP, plasticizer) were added, respectively. Shaking, placing in water bath, heating in water bath to 65 deg.C, stopping heating when the liquid is viscous, and cooling to 40 deg.C. Carefully adding fully ground Cd-MOF into the test tube in batches, fully shaking up, putting the test tube in a water bath for heating again, continuously shaking up to keep the Cd-MOF powder crystals in a uniform dispersion state, continuously heating to about 85 ℃, keeping the temperature for about 20 minutes, finishing the polymerization reaction, and cooling to room temperature to obtain the organic glass composite material (coped-PMMA) doped with the coordination polymer, wherein the reaction process is shown in the formula. The composite material obtained by the preparation exhibited a greenish fluorescence (a cyan color in a place where the polymer content is small locally) under the irradiation of ultraviolet light at 365nm (see fig. 9).
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. A two-dimensional interpenetrating three-dimensional cadmium coordination polymer is characterized in that the chemical general formula is { [ Cd ]2(etc)(pyan)1.5(H2O)3](H2O)2}nBelonging to the monoclinic system, space group is P21N, unit cell parameter
In the chemical general formula, the component etc4-Is a quaternary organic carboxylic acid H4etc. 4 protons are eliminated, the H4The structure of etc is shown as formula I; the structure of the component pyan is shown as a formula II,
2. the two-dimensional interpenetrating three-dimensional cadmium coordination polymer of claim 1, wherein said three-dimensional cadmium coordination polymer comprises 2 Cd's in a crystallographically independent asymmetric structure2+Ion, 1 etc4-And 1.5 pyan components; each of the etc4-And 4 Cd2+The ion coordination mode is shown as formula III, and the components pyan and Cd2+There are two coordination modes, pyan-A as shown in formula IV and pyan-B as shown in formula V; the Cd2+The coordination modes of the ions are respectively shown as a formula VI and a formula VII; wherein the atom numbers in the formulas III to VII represent the sources,
3. a method of preparing the two-dimensional interpenetrating three-dimensional cadmium coordination polymer of claim 1 or 2, wherein said two-dimensional interpenetrating three-dimensional cadmium coordination polymer is formed as H4etc、pyan、Cd(NO3)2·4H2O and HBF4The raw material is prepared by a solvent thermal synthesis method by using a mixed solution of acetonitrile and water as a solvent.
4. The method of preparing the two-dimensional interpenetrating three-dimensional cadmium coordination polymer of claim 3, wherein said method of preparing specifically comprises the steps of:
(1) mixing the above raw materials and solvent to form a reaction system, and placing in a sealed containerIn the device; the raw material H4etc、pyan、Cd(NO3)2·4H2O and HBF4The mass ratio of (1): 1: 2: 2.5-8; the volume ratio of the solvents acetonitrile and water is 3: 7;
(2) and (3) stirring the reaction system at room temperature for 0.5h, then heating the reaction system to 140-160 ℃, reacting for 4-6 days, and then naturally cooling, filtering and drying to obtain blocky crystals.
5. The method of preparing a three-dimensional cadmium coordination polymer formed by two-dimensional interpenetration of claim 4, wherein said H in step (1)4etc：pyan：Cd(NO3)2·4H2O：HBF4The mass ratio of (1): 1: 2: 5.
6. the method of preparing the two-dimensional interpenetrating three-dimensional cadmium coordination polymer of claim 4 wherein H is present in the reaction system4The starting material of etc or pyan is present in a concentration of 5 mmol/L.
7. The method for preparing the three-dimensional cadmium coordination polymer formed by two-dimensional interpenetration according to claim 4, wherein the reaction temperature in the step (2) is 140 ℃, and the drying refers to natural drying in the air at room temperature after the crystal is washed by distilled water.
8. The application of the three-dimensional cadmium coordination polymer formed by two-dimensional interpenetrating is characterized in that the three-dimensional cadmium coordination polymer formed by two-dimensional interpenetrating and prepared by the method of any one of claims 3 to 7 is applied to ion detection and identification and the preparation of photosensitive composite materials and devices.
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| CN116120577A (en) * | 2023-02-01 | 2023-05-16 | 重庆师范大学 | Double-core multi-hole light conversion material, preparation method thereof and application thereof in preparation of warm yellow light LED device |
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| CN116120577B (en) * | 2023-02-01 | 2024-05-28 | 重庆师范大学 | Double-core multi-hole light conversion material, preparation method thereof and application thereof in preparation of warm yellow light LED device |
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