CN103588809B - Preparation method of two types of metal-organic frame materials containing Pb ions - Google Patents
Preparation method of two types of metal-organic frame materials containing Pb ions Download PDFInfo
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Abstract
The invention discloses a preparation method of two types of metal-organic frame materials containing Pb ions, belonging to the technical field of environment-friendly materials. The preparation method comprises the steps of putting a certain amount of metal salt and organic ligand into an appropriate amount of distilled water for dissolving, wherein the metal salt is nitrate or carbonate of a divalent transition metal, and the organic ligand is a polydentate organic ligand containing two or more ligand functional groups; adjusting the pH value of the mixed solution obtained in the step (1) to be 7 by using NaOH of which the mass percentage is 10%, and transferring the mixed solution to a corresponding reaction kettle; reacting at 180 DEG C for 72 hours, and naturally cooling to the room temperature at an ambient temperature to obtain faint yellow bulk crystals; filtering the crystal product obtained in the step (3), washing the crystals by using distilled water and anhydrous ethanol in sequence, and naturally drying to obtain the final product. The preparation method disclosed by the invention is simple, low in cost, strong in controllability, good in product crystallinity, high in yield and environment-friendly.
Description
Technical field
The present invention relates to hydro-thermal method synthesizes two kinds of new metal-organic framework compounds comprising Pb ion, two kinds new
The metal-organic framework compound of type has certain photocatalytic activity, the synthesis of metal organic framework compound, belongs to environment
Friendly field of material technology.
Background technology
Metal organic framework compound (Metal-Organic Framworks, MOFs) is Coordinative Chemistry in recent ten years
Develop to obtain the fastest a direction, be one and be related to the multi-disciplinary brand-new scientific research such as inorganic chemistry, organic chemistry and Coordinative Chemistry
Problem.MOFs is different from the material such as general composite high-molecular and complex, and it shows the property of many uniquenesses, such as ties
The features such as diversified, the unusual electronic effect of structure, spendable numerous transition metal atoms, in nonlinear optics material
All many-sides such as material, magnetic material, superconductor, catalysis and biologically active have potential using value, cause people's
Great interest and the great attention of scientific and technological circle and industrial circle.
Hydro-thermal method（hydrothermal method）It is that geologist simulates nature mineralization and opens in the middle of the 19th century
Beginning research.It belongs to the category of liquid phase chemical, usually in the sealed reactor of inner liner polytetrafluoroethylene, with water for being situated between
Matter, is 120-200 DEG C in reaction temperature（Spontaneous vapour pressure is usually 10-30atm）Under conditions of, make usual indissoluble or insoluble
Material carry out in the solution dissolving, self assembly and a kind of method of recrystallizing.Due to viscosity and the table of water under hydrothermal condition
Face tension force step-down and the change of the thermal diffusion coefficient high physical property of change, enhance the life that diffusion process is beneficial to crystal in solution
Long, and hydro-thermal method has potential advantage for indissoluble or insoluble material long crystal, and therefore, it is widely used in recent years
Preparation has the coordination polymer of novel structure and special nature, especially relates to the crystal life of the complex of original position part synthesis
Long.
In recent years, construct the MOFs of various structures by different organic ligands, so how to select a kind of multi-functional
The part of property becomes the problem that we must solve building new MOFs material.Our seminars are in flexible polycarboxylic acid part
Build MOFs compound aspect and make a few thing.Why this patent adopts quinoline -2,3- dicarboxylic acids and 1,10- Phen
Report relatively mainly due to the metal-organic framework compound being part with regard to quinoline -2,3- dicarboxylic acids so far for part
Few, quinoline -2,3- dicarboxylic acids, as a kind of multifunctionality part, can be formed multiple by carboxylic acid oxygen and nitrogen-atoms connection metal
The metal organic framework compound of coordination mode.A lot of reports are super with regard to being built with 1,10- Phen growth for part
Molecular framework compound, has good coordination activity and larger conjugated system mainly due to it, so being easily formed π-π
Effect.Metallic lead, as the heavy metal of P race, is lived because it has large radius, multiple coordination environment and variable spatial chemistry
Property, so being easily formed the fully connected topology with fine property.Due to metallic lead 6s2Electron configuration, spatial chemistry,
The field such as photocatalysis and photochemistry causes the concern of chemists.Live so finding a kind of method synthesis and there is certain photocatalysis
The metal organic framework compound of property is necessary and challenging.WangMing-Fang etc.（Dalton
Transactions, 2012,41,11,898 11906）It is that close at different temperatures by hydro-thermal method for part with quinoline -2,3- dicarboxylic acids
Become M (2,3-Hqldc)2(H2O)2(M=Co, Zn and Cd), [M (3-qlc)2(H2O)2]n(M=Co, Zn and Cd), M (2-qldc-
3-OCH3)2(CH3OH)2(M=Co and Zn) and [Cd (2,3-qldc-OCH3)(μ2-Cl)]2n, wherein 3-Hqlc is quinoline -3- carboxylic
Acid, 2-qldc-3-OCH3It is 3-（Methoxyl group）Quinaldic acid and 2,3-Hqldc are nine kinds of differences of quinoline -2,3- dicarboxylic acids
The MOFs of structure.Du Jing-jing etc.（Journal of Hazardous Materials, 2011,190,945 951）Close
Become new MIL-53（Fe）, and degradating organic dye methylene blue under the irradiation of visible ray and ultraviolet-visible light respectively.
In recent years, the new catalyst of exploitation had critically important theoretical and practical significance, and utilized new MOF material, exploitation
Catalyst efficient and that cycle performance is good, more has far-reaching scientific research prospect and actual application prospect.
Content of the invention
It is an object of the invention to provide the side of two kinds of new metal-organic framework compounds containing lead ion of synthesis
Method, and have studied property in terms of photocatalysis for this compound.
To achieve these goals, the technical solution used in the present invention is：Two kinds of metal-organic framework materials containing Pb ion
The preparation method of material, is carried out as steps described below：
（1）A certain amount of slaine and organic ligand is taken to put into dissolving in appropriate distilled water, described slaine is divalence mistake
Cross nitrate or the carbonate of metal, organic ligand is the multiple tooth organic ligand containing two or more co-ordinating functionality；
（2）By step（1）Resulting solution weight/mass percentage composition is that 10% NaOH adjusts mixed solution pH value to 7, shifts
To corresponding reactor；
（3）After with temperature for 180 DEG C of reaction 72h, naturally cool to room temperature at ambient temperature, obtain faint yellow block brilliant
Body.
（4）By step（3）The crystal product obtaining filters, and successively uses distilled water and absolute ethanol washing crystal respectively, from
Product is obtained final product after being so dried.
Wherein step（1）The nitrate of described solution is Pb (NO3)2·6H2O, described carbonate is PbCO3, described
Organic ligand 1 is quinoline -2,3- dicarboxylic acids, and described organic ligand 2 is 1,10- Phen.
Wherein step（1）The mol ratio of described solution metal salt and two kinds of organic ligands is 0.15:0.15:0.15.
The technological merit of the present invention：Preparation method is simple, with low cost, controllability strong, product good crystallinity, yield are high,
Environmental protection.
Brief description
Fig. 1 is compound 1 and the coordination context diagram of compound 2 central metal atom Pb, and it is former that not specified atom is C
Son.It can be seen that compound 1 and 2 is all 6 coordinations, in compound 1, metal Pb connects two from quinoline -2,3- dicarboxylic acids
Oxygen and four nitrogen being derived from 1.10- Phen；In compound 2, metal Pb connects four oxygen being derived from quinoline -2,3- dicarboxylic acids
The nitrogen being derived from 1.10- Phen with two.
Fig. 2 is that compound 1 is self-assembly of two-dimentional oversubscription sublayer and Magnetic Properties of Three-Dimensional Supramolecular Complex structure by 4 kinds of π-π effects.
Fig. 3 is that compound 2 is self-assembly of two-dimentional oversubscription sublayer structure by 3 kinds of π-π effects.
Fig. 4 is the XRD of compound 1 and 2.It can be seen that the experimental patterns of compound 1 and 2 and the simulation basic phase of collection of illustrative plates
Seemingly, illustrate that we have synthesized more pure crystal.But compared with simulation collection of illustrative plates, different this of intensity at peak be due to
The anisotropy of two kinds of compounds causes.
Fig. 5 is the thermogravimetric analysis figure of compound 1 and 2.It can be seen that the weightless trend of two kinds of compounds is identical, work as temperature
When degree rises to 1000 DEG C, product is PbO.
Fig. 6 is the research of photoluminescent property under compound 1 and 2 solid-states.It can be seen that compound 1 and 2 is in 590nm (λex
=369nm) and 622nm (λex=467nm) all have very strong luminous, and part quinoline -2,3- dicarboxylic acids light compared very big
Red shift.
Fig. 7 is compound 1 and the research of 2 UV-vis DRS spectrum.It can be seen that compound 1 is in Uv and visible light
Qu Douyou absorbs, so we select tungsten lamp as the light source of light-catalyzed reaction in photocatalysis test below；Compound 2 is in purple
There is absorption in Wai Guang area, so we select uviol lamp as the light source of light-catalyzed reaction.
Fig. 8 be by degradation of methylene blue to compound 1 and 2 the photocatalytic Quality Research under different light sources.Can
It is respectively 53% and 45.5% with the degradation rate finding out compound 1 and 2 pairs of methylene blues.
Specific embodiment
Below by the drawings and specific embodiments, the invention will be further described.
Embodiment 1：[Pb(qlc)(phen)2(NO3)]2·H2The synthesis of O
（1）Weigh 0.0326g quinoline -2,3- dicarboxylic acids with electronic balance respectively（Hqlc）, 1,10- neighbour's Féraud of 0.027g
Quinoline（phen）It is dissolved in the deionized water of 10ml with the plumbi nitras of 0.0497g, stirred with glass bar；
（2）The pH of mixed liquor is adjusted to 7 by the NaOH solution being 10% with mass percent, and solution is transferred to 15ml's
In ptfe autoclave；
（3）Reactor is placed in the baking oven that temperature is 180 DEG C, naturally cools at ambient temperature after reaction 72h
Room temperature, finally gives faint yellow bulk crystals.
（4）Collect MOF crystal, and use the crystal in distilled water and absolute ethanol washing solution respectively, natural drying obtains
Product.
[Pb(qlc)(phen)2(NO3)]2·H2O belong to monoclinic system,C 2/cSpace group, belong to zero-dimension structural.As Fig. 1
（1）Shown, each dissymmetrical structure unit includes Pb (II) ion, a qlc-Ion, two phen molecules, one
NO3 2-Ion and half H2O molecule.Central metal Pb is derived from the oxygen of Hqlc respectively with four nitrogen-atoms from phen and two
Atom forms the pattern of hexa-coordinate.Fig. 2 illustrates compound 1 and passes through the Magnetic Properties of Three-Dimensional Supramolecular Complex structure that four kinds of pi-pi accumulation effects are formed,
Between wherein three kinds phen pi-pi accumulation effect by zero-dimension structural be self-assembled into two dimension supramolecular structure, a kind of phen with
Structure is self-assembled into Magnetic Properties of Three-Dimensional Supramolecular Complex structure by pi-pi accumulation effect between Hqlc further.As Fig. 4（1）Shown, compound 1
The diffraction maximum position tested in spectrogram and analogue spectrums of X-ray powder diffraction substantially identical, this shows the purity of compound 1 very
High.But experiment spectrogram compared with analogue spectrums, some difference of their peak intensity, this be likely due to sample powder crystal each to
Caused by the opposite sex.Fig. 5（1）It is the thermogravimetric curve of compound 1, weightless process is broadly divided into two stages, first stage exists
50-400 DEG C of weightlessness 30.88%, in 400-630 DEG C of weightlessness 43.90%, final product is PbO to second stage.The room of compound 1
Warm solid state fluorescence spectrum is listed in Fig. 6, and under excitation wavelength 369nm, maximum emission peak is at 586nm, owing to central ligand
Fluorescent emission.Fig. 7 in 200-800nm sweep limits, with barium sulfate as background, inhale by the UV, visible light determining complex 1
Receive spectrum.The absorption to light of compound 1 is concentrated mainly on ultraviolet region as shown in the figure.Therefore, by the irradiation in uviol lamp
Decline solution methyl blue the photocatalytic activity of compound 1 to be tested, as shown in figure 8, the photocatalytic activity of compound 1 reaches
53%.
Embodiment 2：[Pb(qlc)2(phen)]·3H2The synthesis of O
（1）Weigh 0.0326g quinoline -2,3- dicarboxylic acids with electronic balance respectively（Hqlc）, 1,10- neighbour's Féraud of 0.027g
Quinoline（phen）It is dissolved in the deionized water of 10ml with the ceruse of 0.04g, stirred with glass bar；
（2）PH need not be adjusted, directly the solution mixing is transferred in the ptfe autoclave of 15ml；
（3）Reactor is placed in the baking oven that temperature is 180 DEG C, naturally cools at ambient temperature after reaction 72h
Room temperature, finally gives faint yellow bulk crystals.
（4）Collect MOF crystal, and use the crystal in distilled water and absolute ethanol washing solution respectively, natural drying obtains
Product.
[Pb(qlc)2(phen)]·3H2O belong to anorthic system,P-1Space group, belong to zero-dimension structural.As Fig. 1（2）Institute
Show, each dissymmetrical structure unit includes Pb (II) ion, two qlc-Ion, a phen molecule and three H2O divides
Son.The nitrogen-atoms that central metal Pb is derived from phen with four oxygen atoms from HL and two respectively forms the pattern of hexa-coordinate.
It is to form two-dimentional supramolecular structure, the pi-pi accumulation between wherein phen by two kinds of pi-pi accumulation effects that Fig. 3 illustrates compound 2
Zero-dimension structural is self-assembled into one-dimensional chain supramolecular structure, a kind of Hqlc by the pi-pi accumulation effect between effect and phen and Hqlc
Between pi-pi accumulation effect further structure is linked to be two-dimentional supramolecular structure.As Fig. 4（2）Shown, the X-ray powder of compound 2
Diffraction maximum position in last diffraction experiment spectrogram and analogue spectrums is substantially identical, and this shows that the purity of compound 2 is very high.But it is real
Test spectrogram compared with analogue spectrums, some difference of their peak intensity, the anisotropy that this is likely due to sample powder crystal is drawn
Rise.Fig. 5（2）It is the thermogravimetric curve of compound 2, weightless process is broadly divided into three phases, and first stage is at 50-155 DEG C
Weightless 7.10%, second stage weightlessness 43.82%, in 480-645 DEG C of weightlessness 23.15%, final product is PbO to three phases.
The room temperature solid fluorescence spectrum of compound 2 is listed in Fig. 6, and under excitation wavelength 467nm, maximum emission peak is at 622nm, attribution
Fluorescent emission in central ligand.Fig. 7, in 200-800nm sweep limits, with barium sulfate as background, determines complex 2
Ultraviolet-visible absorption spectroscopy.The absorption to light of compound 2 is concentrated mainly on ultraviolet and visibility region as shown in the figure.Therefore, lead to
Cross the decline solution methyl blue that irradiates in tungsten lamp the photocatalytic activity of compound 2 is tested, as shown in figure 8, compound 2
Photocatalytic activity has reached 45.5%.
Embodiment 3
Weigh [the Pb (qlc) (phen) of preparation in embodiment 1 and 22(NO3)]2·H2O and [Pb (qlc)2(phen)]·
3H2The each 25mg of O, is added in the methylene blue solution that 100ml initial concentration is 10mg/L, dark reaction 1.5h, after photocatalysis 5h,
As shown in figure 8, compound 1 and compound 2 have respectively reached 53% and 45.5% to the total removal rate of methylene blue.Two kinds of compounds
The reason be not very high to the degradation rate of methylene blue is likely due to it and has high fluorescence and zero-dimension structural at room temperature
Lead to.But, the present invention still has certain photocatalytic activity, has good environmental benefit to improving environment.
Claims (1)
1. a kind of preparation method of the metal-organic framework materials containing Pb ion is it is characterised in that carry out as steps described below：
（1）A certain amount of slaine and organic ligand is taken to put into dissolving in appropriate distilled water, described slaine is divalent transitional gold
The nitrate belonging to, organic ligand 1 is quinoline -2,3- dicarboxylic acids, and organic ligand 2 is 1,10- Phen；Nitrate is Pb
(NO3)2·6H2O, the mol ratio of solution metal salt and two kinds of organic ligands is 0.15:0.15:0.15；
（2）By step（1）Resulting solution weight/mass percentage composition be 10% NaOH adjust mixed solution pH value to 7, be transferred to phase
In the reactor answered；
（3）After with temperature for 180 DEG C of reaction 72h, naturally cool to room temperature at ambient temperature, obtain faint yellow bulk crystals；
（4）By step（3）The crystal product obtaining filters, and successively uses distilled water and absolute ethanol washing crystal respectively, naturally does
Product is obtained final product after dry；
The described metal-organic framework materials containing Pb ion are [Pb (quinoline -2,3- dicarboxylic acid radical) (1,10- Phen)2
(NO3)]2·H2O, its belong to monoclinic system,C 2/cSpace group, belong to zero-dimension structural, each dissymmetrical structure unit includes one
Individual Pb (II) ion, quinoline -2,3- dicarboxylic acids single anion, two 1,10- Phen molecules, NO3 2-Ion and
Half H2O molecule；Central metal Pb is derived from quinoline -2,3- with four nitrogen-atoms from 1,10- Phen and two respectively
The oxygen atom of dicarboxylic acids forms the pattern of hexa-coordinate.
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| CN105566380B (en) * | 2016-01-28 | 2018-06-29 | 中国石油大学(华东) | A kind of double-core lead metal-organic coordination polymer and preparation method thereof |
| CN109503851A (en) * | 2018-10-17 | 2019-03-22 | 东营峰谷源新能源科技有限公司 | A kind of metal organic framework compound and preparation method and application |
| CN116262247A (en) * | 2021-12-14 | 2023-06-16 | 鲁东大学 | Chain Pb (II) coordination polymer visible light catalyst containing mixed organic ligand and preparation method thereof |
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| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
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