CN115181288B - Anionic metal-organic framework material, preparation method thereof and crystalline heavy metal ion probe material - Google Patents
Anionic metal-organic framework material, preparation method thereof and crystalline heavy metal ion probe material Download PDFInfo
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Abstract
The invention relates to the technical field of analytical chemistry and chemical engineering, in particular to an anionic metal-organic framework material, a preparation method thereof and a crystalline heavy metal ion probe material. The anionic metal-organic framework material comprises a compound shown in the following formula I, [ Hdma ] 0.5 (Ln) 0.5 (pdc)] n Formula I, wherein Ln is selected from at least one of the lanthanides, hdma + Represents a dimethylamine cation, pdc 2‑ Represents a deprotonated 2, 5-pyridinedicarboxylic acid; n is a positive integer greater than 2, indicating that the material is a crystalline material of periodic structure. The anionic metal-organic framework material can detect Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The equivalent weight metal ions can also efficiently adsorb Pb 2+ 、Cd 2+ And Cu 2+ And (3) an isoparaffinic metal ion.
Description
Technical Field
The invention relates to the technical field of analytical chemistry and chemical engineering, in particular to an anionic metal-organic framework material, a preparation method thereof and a crystalline heavy metal ion probe material.
Background
The reduction of available clean water resources has become an important crisis facing the world, and the main reason for this crisis is the water pollution caused by various pollutants discharged into the water body from production, life or accidents. The key to solve the water resource crisis is to treat and regenerate sewage. Various sewage treatment and regeneration methods have been developed, and among them, the adsorption method is widely used in sewage treatment due to high treatment efficiency, simple operation, and low cost.
The key to the adsorption process is the choice and application of the adsorbent. The existence of heavy metals in water not only endangers the environment, but also can reach the human body through the biological enrichment effect. Conventional adsorbents such as ion exchange resins and the like applied to the treatment of heavy metals in water cannot meet the higher standards of water pollution treatment when facing complex water environments. Therefore, the development and application of the novel heavy metal ion adsorbent become research hot spots in the adsorption field.
Meanwhile, with the development of technology and the improvement of environmental protection requirements, a heavy metal ion detection probe material with more excellent performance is required, so that under the premise of improving heavy metal ion adsorption, the research and development of the high-efficiency metal ion probe material without heavy metal, environment-friendly, good in stability and the like is an important research direction for the controllable preparation of clean water resources.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an anionic metal-organic framework material, a preparation method thereof and a crystalline heavy metal ion probe material. The anion type metal-organic framework material provided by the embodiment of the invention can detect Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The equivalent weight metal ions can also efficiently adsorb Pb 2+ 、Cd 2+ 、Cu 2+ And (3) an isoparaffinic metal ion.
The invention is realized in the following way:
in a first aspect, the present invention provides an anionic metal-organic framework material comprising a compound of formula I,
[Hdma 0.5 (Ln) 0.5 (pdc)] n the compound of the formula I,
wherein Ln is selected from at least one of trivalent metal ions of the lanthanide series, hdma + Representing a positive valence of oneIs a dimethylamine cation guest molecule, pdc 2- Represents a deprotonated 2, 5-pyridinedicarboxylic acid, which has 2 negative charges; n is a positive integer greater than 2, indicating that the material is a crystalline material of periodic structure.
In an alternative embodiment, the anionic metal-organic framework material is a crystalline material;
preferably, the crystal structure of the anionic metal-organic framework material belongs to the orthorhombic system, fddd space group;
preferably, the unit cell parameters of the anionic metal-organic framework material are α＝90°，β＝90°，γ＝90°，Z＝16。
In an alternative embodiment, when Ln in formula I is Eu, the unit cell parameter of the anionic metal-organic framework material is α＝90°，β＝90°，γ＝90°，Z＝16；
Preferably, when Ln in formula I is Eu, the anionic metal-organic framework material exhibits a characteristic red emission of rare earth Eu ions;
preferably, when Ln in formula I is Eu, at [1 0.1]In one dimension, the porosity is 40.4%, and the size is
In an alternative embodiment, when Ln in formula I is Tb, the unit cell parameter of the anionic metal-organic framework material is α＝90°，β＝90°，γ＝90°，Z＝16；
Preferably, when Ln is Tb in formula I, the anionic metal-organic framework material exhibits a characteristic green emission of rare earth Tb ions;
preferably, when Ln in formula I is Tb, then it is represented by the formula [ 1.0.1]In one dimension, the porosity is 40.4%, and the size is
In a second aspect, the present invention provides a method for preparing an anionic metal-organic framework material according to any one of the preceding embodiments, comprising: 2, 5-pyridine dicarboxylic acid, N-dimethylformamide and rare earth nitrate containing lanthanide are mixed for reaction.
In an alternative embodiment, the method comprises: mixing the mixed solution of N, N-dimethylformamide containing the 2, 5-pyridine dicarboxylic acid with the rare earth nitrate, and then reacting in an environment of not lower than 70 ℃ for not lower than 24 hours;
preferably, the reaction conditions include: the feeding ratio of the 2, 5-pyridine dicarboxylic acid to the rare earth nitrate is 2-10:1-5; the reaction temperature is 70-120 ℃; the reaction time is 24-48 hours; 1-2 ml of said N, N-dimethylformamide per millimole of 2, 5-pyridinedicarboxylic acid form a saturated solution.
In a third aspect, the present invention provides a crystalline heavy metal ion probe material comprising an anionic metal-organic framework material according to any one of the preceding embodiments.
In a fourth aspect, the present invention provides a method for detecting heavy metal ions, comprising detecting heavy metal ions using an anionic metal-organic framework material as described in any one of the preceding embodiments or a crystalline heavy metal ion probe material as described in the preceding embodiments;
preferably, the heavy metal ions to be detected include Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ At least one of (a) and (b);
preferably, when Ln in formula I is Eu, the heavy metal ion Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (2) 27nM, 6.38nM, 3.01nM and 1.75nM, respectively;
when Ln in formula I is Tb, the heavy metal ion Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (2) 86nM, 1.65nM, 1.48nM and 2.23nM, respectively.
In a fifth aspect, the present invention provides an adsorbent comprising an anionic metal-organic framework material according to any one of the preceding embodiments.
In a sixth aspect, the present invention provides a method for adsorbing heavy metal ions, comprising adsorbing heavy metal ions with an anionic metal-organic framework material according to any one of the preceding embodiments or an adsorbent according to the preceding embodiments;
preferably, the heavy metal ions to be adsorbed include Pb 2+ 、Cd 2+ And Cu 2+ At least one of (a) and (b);
preferably, when Ln in formula I is Eu, the heavy metal ion Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacity of the catalyst is 196mg/g, 106mg/g and 60mg/g in sequence;
when Ln in formula I is Tb, the heavy metal ion Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacities of (C) were 187mg/g, 102mg/g and 57mg/g, respectively.
The invention has the following beneficial effects: the anionic metal-organic framework material provided by the embodiment of the invention has good thermal stability and water stability, and the synthetic process is environment-friendly and has the advantages of Pb 2+ 、Cd 2+ And Cu 2+ The equal heavy metal ion has good adsorption effect, the adsorption effect is higher than that of the current commercial metal ion adsorbent (such as ion exchange resin), the defect of high industrial energy consumption in the traditional heavy metal ion adsorbent is overcome, and the equal heavy metal ion adsorbent has important commercial application value in the field of heavy metal ion adsorbents. At the same time, can be used for detecting Pb 2+ 、Cd 2+ And Cu 2+ And (3) an isoparaffinic metal ion.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows UM-1 provided in Experimental example 1 of the present invention # And UM-2 # A schematic representation of the crystal structure (without hydrogen atoms);
FIG. 2 shows UM-1 provided in Experimental example 1 of the present invention # And UM-2 # Is a schematic diagram of the pore structure;
FIG. 3 shows UM-1 provided in Experimental example 1 of the present invention # And UM-2 # Fourier infrared spectra of (a);
FIG. 4 shows UM-1 provided in Experimental example 1 of the present invention # And UM-2 # X-ray powder diffraction phase analysis of (2);
FIGS. 5 to 6 show UM-1 according to Experimental example 2 of the present invention # And UM-2 # An experimental result diagram of the thermal stability test experiment of (a);
FIG. 7 shows UM-1 provided in Experimental example 3 of the present invention # And UM-2 # Is a photoluminescence experimental spectrum;
FIG. 8 shows UM-1 provided in Experimental example 4 of the present invention # For Pb 2+ 、Cd 2+ 、Cu 2+ 、Cr 3+ Is limited by the detection limit of (2);
FIG. 9 shows UM-2 provided in Experimental example 4 of the present invention # For Pb 2+ 、Cd 2+ 、Cu 2+ 、Cr 3+ Is a detection limit of (2).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides an anionic metal-organic framework material, which comprises a compound shown in the following formula I,
[Hdma 0.5 (Ln) 0.5 (pdc)] n the compound of the formula I,
wherein Ln is selected from at least one of trivalent metal ions of the lanthanide series, hdma + Dimethylamine cation guest molecule, pdc, representing positive monovalent 2- Represents a deprotonated 2, 5-pyridinedicarboxylic acid, which has 2 negative charges; n is a positive integer greater than 2, indicating that the material is a crystalline material of periodic structure.
Hdma in the anionic metal-organic framework material is a dimethylamine counter cation, and aims at balancing the system charge. Ln is at least one element selected from lanthanoid elements (atomic number 57-71), is trivalent and has 9 coordination.
The anionic metal-organic framework material is crystalline material, and the material can be blocky millimeter-level single crystals or micro-nano-level crystal powder. The crystal structure belongs to orthorhombic system, fddd space group; specifically, the unit cell parameters are α＝90°，β＝90°，γ＝90°，Z＝16。
The anionic metal-organic framework material has good water stability, and maintains good crystallinity after being soaked in water phase for 30 days. Meanwhile, it has excellent thermal stability, for example, when Ln in formula I is Tb, its thermal decomposition temperature may reach 343 ℃, and when Ln in formula I is Eu, its thermal decomposition temperature may reach 323 ℃.
Further, when Ln in formula I is Eu, the unit cell parameter of the anionic metal-organic framework material is α=90°, β=90°, γ=90°, z=16; the anionic metal-organic framework material exhibits characteristic red emission of rare earth Eu ions; at [ 1.0.1]The orientation is one-dimensional structure, the porosity is 40.4%, and the size is +.>
Further, when Ln is Tb, the unit cell parameter of the anionic metal-organic framework material isα=90°, β=90°, γ=90°, z=16; the anionic metal-organic framework material exhibits characteristic green emission of rare earth Tb ions; at [ 1.0.1]The orientation is one-dimensional structure, the porosity is 40.4%, and the size is +.>
The anionic metal-organic framework material provided by the embodiment of the invention has good thermal stability and water stability, and the synthetic process is environment-friendly and has the advantages of Pb 2+ 、Cd 2+ And Cu 2+ The equal heavy metal ion has good adsorption effect, the adsorption effect is higher than that of the current commercial metal ion adsorbent (such as ion exchange resin), the defect of high industrial energy consumption in the traditional heavy metal ion adsorbent is overcome, and the equal heavy metal ion adsorbent has important commercial application value in the field of heavy metal ion adsorbents. The anion type metal-organic framework material is applied to environmental protection, resident water and quality management of traditional Chinese medicine decoction pieces as detection and adsorption removal of heavy metal cations. At the same time, can be used for detecting Pb 2+ 、Cd 2+ And Cu 2+ And (3) an isoparaffinic metal ion.
Further, an embodiment of the present invention provides a method for preparing the above-mentioned anionic metal-organic framework material, including:
2, 5-pyridine dicarboxylic acid, N-dimethylformamide and rare earth nitrate containing lanthanide are mixed for reaction.
Specifically, the mixed solution of N, N-dimethylformamide containing the 2, 5-pyridine dicarboxylic acid is placed on a magnetic stirrer of not lower than 400rpm and stirred at room temperature (about 25 ℃) for 20 to 30 minutes; after adding rare earth nitrate Ln (NO) 3 ) 3 ·6H 2 The water solution of O is continuously stirred for 5 to 15 minutes to obtain clear, colorless and transparent solution; transferring the mixture into a reaction kettle, and reacting in an environment of not lower than 70 ℃ for not lower than 24 hours.
The reaction time and reaction temperature are based on the reaction being sufficiently carried out, but in order to promote the formation of the above-mentioned anionic metal-organic framework material and the performance thereof, the feeding ratio of the 2, 5-pyridinedicarboxylic acid to the rare earth nitrate is preferably 2 to 10:1-5; examples are: 2:1, 10:5, 4:2, 1:0.5, 8:4, etc. 2-10: any number between 1 and 5. The reaction temperature is any value between 70 and 120 ℃ such as 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ and the like; the reaction time is 24-48 hours; for example, 1-2 ml of said N, N-dimethylformamide per millimole of 2, 5-pyridinedicarboxylic acid.
The preparation method has simple operation steps, and the obtained anionic metal-organic framework material has high purity, good crystallinity and high yield, and is suitable for large-scale industrial production.
Further, the invention provides a crystalline heavy metal ion probe material comprising an anionic metal-organic framework material according to any one of the preceding embodiments.
Further, the present invention provides a method for detecting heavy metal ions, comprising detecting heavy metal ions using the anionic metal-organic framework material of any one of the preceding embodiments or the crystalline heavy metal ion probe material of the preceding embodiments;
preferably, the heavy metal ions to be detected include Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ At least one of (a) and (b);
for example, when Ln in formula I is Eu, the heavy metal ion Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (2) 27nM, 6.38nM, 3.01nM and 1.75nM, respectively; when Ln is Tb in formula I, the heavy metal ion Pb is functionalized 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (2) 86nM, 1.65nM, 1.48nM and 2.23nM, respectively.
Further, the present invention provides an adsorbent comprising the anionic metal-organic framework material of any one of the preceding embodiments.
Further, the present invention provides a method for adsorbing heavy metal ions, comprising adsorbing heavy metal ions using the anionic metal-organic framework material according to any one of the preceding embodiments or the adsorbent according to the preceding embodiments;
preferably, the heavy metal ions to be adsorbed include Pb 2+ 、Cd 2+ And Cu 2+ At least one of (a) and (b);
preferably, when Ln in formula I is Eu, the heavy metal ion Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacity of the catalyst is 196mg/g, 106mg/g and 60mg/g in sequence;
when Ln in formula I is Tb, the heavy metal ion Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacities of (C) were 187mg/g, 102mg/g and 57mg/g, respectively. It can be seen that the adsorption effect of the adsorbent provided by the embodiment of the invention is higher than that of the current commercial metal ion adsorbent (such as ion exchange resin), and the defect of high industrial energy consumption in the traditional heavy metal ion adsorbent is overcome, so that the adsorbent has important commercial application value in the field of heavy metal ion adsorbents.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of an anionic metal-organic framework material, which comprises the following steps:
taking a 25mL clean small beaker, accurately weighing 160mg of 2, 5-pyridine dicarboxylic acid, placing the 2, 5-pyridine dicarboxylic acid in the clean small beaker, adding 8mL of N, N-dimethylformamide and small magnetons, setting the rotating speed of a magnetic stirrer to be 800rpm, and stirring the mixture at room temperature for 30 minutes;
a25 mL clean small beaker was taken and 120mg of nitrate Ln (NO) 3 ) 3 ·6H 2 O (Ln=Eu), the anionic metal-organic framework material formed is denoted UM-1 # When ln=tb, the anionic metal-organic framework material formed is denoted UM-2 # ) Placing the mixture in the reactor, adding 2mL of deionized water, and stirring to obtain a clear colorless transparent solution;
mixing the two beakers, and continuing stirring for 10 minutes to obtain a uniform mixed phase; and transferring the mixed solution into a reaction kettle, and reacting for 36 hours in an environment of 100 ℃ to obtain the corresponding anionic metal-organic framework material.
Experimental example 1
UM-1 prepared in example 1 # And UM-2 # Characterization of Structure
Specifically UM-1 # And UM-2 # X-ray single crystal diffraction of (C) is carried out on a Mercury CCD single crystal diffractometer, mo target and K alpha radiation sourceThe test temperature was 100K. And structural analysis was performed by the Olex 2.1.2 pair. The test results are shown in FIG. 1, wherein a is a crystal structure diagram of UM-1#; b is a crystal structure diagram of UM-2#.
UM-1 was analyzed by PLATON software # And UM-2 # Has a pore structure, in [1 0.1 ]]In one dimension, the porosity is 40.4%, and the size isThe results are shown in FIG. 2, wherein a is UM-1# at [ 1.0.1 ]]A one-dimensional duct schematic diagram in the direction; b is UM-2# # in [ 1.0.1]A schematic diagram of a one-dimensional duct in the direction. And at [ 1.0.1]The direction shows good cation adsorption capacity.
UM-1 was measured on a VERTEX 70 IR spectrometer # And UM-2 # Characterization after KBr tabletting, the graph is 3500cm –1 Has higher broad peak nearby, indicating that the sample can beNeutral water molecules in the adsorption column; on the other hand, at 1500cm –1 There is a stronger spike in the vicinity, indicating that the sample contains a dimethylamine counter cation. The test results are shown in FIG. 3, wherein a is the Fourier-infrared spectrum of UM-1# and b is the Fourier-infrared spectrum of UM-2#.
UM- 1# And UM-2 # X-ray powder diffraction phase analysis (XRD) after milling was performed on a MiniFlex 600X-ray diffractometer from Rigaku, cu target, K.alpha.radiation source The test results are shown in FIG. 4, wherein a is the X-ray powder diffraction pattern of UM-1#; b is an X-ray powder diffraction pattern of UM-2#.
As shown in figure 3, the XRD diffraction pattern obtained by fitting the single crystal data is highly consistent with the XRD diffraction pattern obtained by the experiment, and the obtained sample is proved to be a sample with high purity and high crystallinity. Likewise, the XRD diffractogram and theoretical values for 30 days immersed in water are highly consistent, indicating that they are stable in the aqueous phase.
The X-ray powder diffraction and single crystal diffraction results show that:
UM-1# and UM-2# (chemical formula [ Hdma0.5 (Ln) 0.5 (pdc))]n) all belong to Fddd space group of orthorhombic system. For UM-1#, the unit cell parameters are α=90°, β=90°, γ=90°, z=16; for UM-2#, the unit cell parameter isα＝90°，β＝90°，γ＝90°，Z＝16。
Experimental example 2
Thermal stability test experiment
UM-1 # And UM-2 # Can be thermally stable in TGA&DSC METTLER TOLEDOT thermogravimetric analyzer under nitrogen atmosphere. The results are shown in FIGS. 5 and 6, wherein FIG. 5 is a thermogravimetric analysis map of UM-1# and FIG. 6 is a thermogravimetric analysis map of UM-2#. As shown in FIGS. 5-6, sample UM-1 # And UM-2 # Has good thermal stability and still maintains structural integrity at 320 ℃.
Experimental example 3
Photoluminescence performance test experiments
UM-1 # And UM-2 # And (5) performing photoluminescence performance test experiments. The photoluminescence experimental spectrum is shown in figure 7, wherein a is the photoluminescence spectrum of UM-1#; b is UM-2# photoluminescence spectrum, which shows that the fluorescent probe can be used as a fluorescent probe for efficiently detecting heavy metal ions.
Specifically UM-1 # Characteristic emission of Eu (III) is typical at 365nm, and is red light emission. UM-2 # Characteristic emissions of Tb (III), which are typical under 365nm excitation, are green emissions.
Experimental example 4
The samples um#1 and um#2 prepared in the examples were tested for liquid photoluminescence performance, and the specific steps were as follows:
irradiating the red light-emitting fluorescent probe crystalline material with Xe of Edinburgh FL920 40W, and dispersing 2mg of the ground fluorescent probe crystalline material sample 1# in 2.5mL of deionized water; 365nm is selected as excitation wavelength, 380-780 nm is selected as emission monitoring range; pb (NO) was disposed at a concentration of 1. Mu.M 3 ) 2 、Cd(NO 3 ) 3 、Cu(NO 3 ) 2 And Cr (NO) 3 ) 3 Dropwise adding the aqueous solution to the aqueous solutions of the fluorescent probe crystalline materials emitting the liquid phases UM#1 and UM#2; the test results are shown in FIGS. 8 to 9, and the abscissa indicates the content of heavy metal ions (ng) added dropwise.
As can be seen from FIGS. 8 to 9, the crystalline material of the red light-emitting fluorescent probe emits red light when excited at 365nmThe aqueous solution of the crystalline material exhibits a ratio-type decrease in fluorescence emission intensity at 618nm for 1 μm of metal ion fluorescence quenching, i.e., the red light-emitting fluorescent probe crystalline material is capable of quenching Pb 2+ 、Cd 2+ 、Cu 2+ Cr 3+ The ratio detection is carried out, which proves that the fluorescent probe material prepared in the embodiment of the invention can be used for Pb 2+ 、Cd 2+ 、Cu 2+ Cr 3+ And detecting the equivalent weight metal ions. In particular, the linear slope of the curve represents the detection sensitivity of the red light emitting fluorescent probe crystalline material to metal ions in aqueous solution, |k (Pb) |= 43.979, |k (Cd) |= 15.664, |k (Cu) |= 33.258, |k (Cr) |= 57.149, which indicates that the red light emitting fluorescent probe crystalline material has a certain selective detection capability to metal ions, and the detection capability to metal ions is Cr 3+ >Pb 2+ >Cu 2+ >Cd 2+ 。
According to the international union of pure chemistry and applied chemistry, the detection limit of metal ion is 3 sigma, and sigma is the ratio of instrument noise standard deviation and fluorescence detection curve slope |k|, so that the crystalline material UM-1# of the red light emitting fluorescent probe can be respectively obtained for heavy metal ion Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (2) 27nM, 6.38nM, 3.01nM and 1.75nM, respectively.
Similarly, for UM-2 # The aqueous solution thereof fluorescence-quenches 1 mu M metal ions, the fluorescence emission intensity at 543nm is reduced in a ratio, namely, the green light-emitting fluorescent probe crystalline material can perform fluorescence quenching on Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ Make ratio detection to heavy metal ion Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (2) 86nM, 1.65nM, 1.48nM and 2.23nM, respectively.
This indicates UM-1 # And UM-2 # Has sensitive heavy metal ion detection capability.
Experimental example 5
Theoretical calculation of adsorption of heavy metal ions
All calculations occur under ideal conditions, i.e. the default 1 molar equivalent cation exchange occurrence probability is 100%. The results are shown in Table 1.
TABLE 1
Theoretical calculation shows that UM-1 # For Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacities of (2) are 196mg/g, 106mg/g and 60mg/g; UM-2 # For Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacities of (2) were 187mg/g, 102mg/g and 57mg/g. This indicates UM-1 # And UM-2 # Has sensitive heavy metal ion adsorption and removal capacity.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. An anionic metal-organic framework material, characterized in that it comprises a compound represented by the following formula I,
[Hdma 0.5 (Ln) 0.5 (pdc)] n the compound of the formula I,
wherein Ln is selected from at least one of trivalent metal ions of the lanthanide series, hdma + Dimethylamine cation guest molecule, pdc, representing positive monovalent 2- Represents a deprotonated 2, 5-pyridinedicarboxylic acid, which has 2 negative charges; n is a positive integer greater than 2, indicating that the material is a crystalline material of periodic structure;
when Ln is Eu ion in formula I, the unit cell parameters of the anionic metal-organic framework material are a=17.710-17.720 a, b=17.857-17.867 a, c=26.828-26.838 a, α=90 °, β=90 °, γ=90 °, z=16;
when Ln is Tb ion in formula I, the unit cell parameter of the anionic metal-organic framework material is a=17.593-17.603 a, b=17.891-17.901 a, c=26.676-26.686 a, α=90°, β=90°, γ=90°, z=16.
2. The anionic metal-organic framework material of claim 1 wherein the crystalline structure of the anionic metal-organic framework material belongs to an orthorhombic system,Fdddspace group.
3. The anionic metal-organic framework material of claim 1 wherein,
when Ln is Eu ion in formula I, the anionic metal-organic framework material exhibits characteristic red emission of rare earth Eu ion;
at [ 1.0.1]In one dimension, the porosity is 40.4%, and the size is 3426.0A 3 。
4. The anionic metal-organic framework material of claim 1 wherein,
when Ln is a Tb ion in formula I, the anionic metal-organic framework material exhibits a characteristic green emission of rare earth Tb ions;
at [ 1.0.1]In one dimension, the porosity is 40.4%, and the size is 3426.0A 3 。
5. A method of preparing an anionic metal-organic framework material according to any one of claims 1-4, comprising: 2, 5-pyridine dicarboxylic acid, N-dimethylformamide and rare earth nitrate containing lanthanide are mixed for reaction.
6. The method according to claim 5, comprising: mixing the mixed solution of N, N-dimethylformamide containing the 2, 5-pyridine dicarboxylic acid with rare earth nitrate containing lanthanide, and then reacting in an environment of not lower than 70 ℃ for not lower than 24 hours.
7. The method of claim 6, wherein the reaction conditions include: the feeding ratio of the 2, 5-pyridine dicarboxylic acid to the rare earth nitrate containing the lanthanide is 2-10:1-5; the reaction temperature is 70-120 ℃; the reaction time is 24-48 hours; 1-2 ml of said N, N-dimethylformamide per millimole of 2, 5-pyridinedicarboxylic acid form a saturated solution.
8. A crystalline heavy metal ion fluorescent probe material, characterized in that it comprises an anionic metal-organic framework material according to any one of claims 1-4.
9. A method for detecting heavy metal ions, comprising detecting heavy metal ions using the anionic metal-organic framework material of any one of claims 1 to 4 or the crystalline heavy metal ion fluorescent probe material of claim 8.
10. The method for detecting heavy metal ions according to claim 9, wherein the heavy metal ions to be detected include Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ At least one of them.
11. The method for detecting heavy metal ions according to claim 9, wherein when Ln is Eu ion in formula I, the heavy metal ion Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (1) are 2.27nM, 6.38nM, 3.01nM and 1.75nM, respectively;
when Ln in formula I is Tb ion, the heavy metal ion Pb 2+ 、Cd 2+ 、Cu 2+ And Cr (V) 3+ The detection limits of (a) are 2.86nM, 1.65nM, 1.48nM and 2.23nM, respectively.
12. An adsorbent comprising an anionic metal-organic framework material according to any one of claims 1-4.
13. A method of adsorbing heavy metal ions, comprising adsorbing heavy metal ions using the anionic metal-organic framework material of any one of claims 1 to 4 or the adsorbent of claim 12.
14. The method of claim 13, wherein the heavy metal ions to be adsorbed include Pb 2+ 、Cd 2+ And Cu 2+ At least one of them.
15. The method of claim 13, wherein when Ln is Eu ion in formula I, the heavy metal ion Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacities of 196mg/g, 106mg/g and 60mg/g in this order;
when Ln in formula I is Tb ion, the heavy metal ion Pb 2+ 、Cd 2+ And Cu 2+ The adsorption capacities of (2) were 187mg/g, 102mg/g and 57mg/g, respectively.
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