CN115536855A - Preparation method and application of polyacid-based europium complex - Google Patents

Preparation method and application of polyacid-based europium complex Download PDF

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CN115536855A
CN115536855A CN202210969269.5A CN202210969269A CN115536855A CN 115536855 A CN115536855 A CN 115536855A CN 202210969269 A CN202210969269 A CN 202210969269A CN 115536855 A CN115536855 A CN 115536855A
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polyacid
europium complex
siw
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based europium
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CN115536855B (en
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于晓洋
耿嘉琦
翁小宇
吕艳欣
曲小姝
杨艳艳
金华
张强
魏庆玲
石洪飞
王嘉博
杨莹
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Jilin Institute of Chemical Technology
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Abstract

The invention discloses a preparation method and application of polyacid-based europium complex, belonging to the technical field of high molecular compounds, and the technical scheme is as follows: the polyacid-based europium complex has the chemical formula of [ Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O, organic ligand H 2 L is 2,2 '-bipyridine-6, 6' -dicarboxylic acid. Organic ligand and Eu 3+ Coordination forms a two-dimensional layered structure containing grids, polyacid anions are positioned between two-dimensional layers as objects, and a three-dimensional supramolecular network structure is formed through supramolecular acting force. The invention is mainly used for synthesizing inorganic-organic hybrid materials capable of treating organic dye wastewater, and the materials can selectively absorbAnd removing the organic dye in the wastewater.

Description

Preparation method and application of polyacid-based europium complex
Technical Field
The invention relates to the technical field of high molecular compounds, in particular to a preparation method and application of a polyacid-based europium complex.
Background
Polyoxometalates (polyacid) are a class of polyoxometalate compounds formed by oxygen bonding of early transition metal ions (V, mo, W, ta, nb, etc.). The polyacid has controllable shape, size and high negative charge, and metal ions can generate interaction through electron transfer, so that the polyacid has various physical and chemical properties and biological activities. Polyacids have been used as inorganic ligands to build POM-metal organic complexes of novel structure and diverse nature. The inorganic-organic hybrid material has the performances of acidity, high oxidation-reduction property and the like, and has potential application in the fields of electrochemistry, magnetism, catalysis, materials, medicines and energy. At present, inorganic-organic hybrid materials based on polyacid have been synthesized, wherein, since rare earth metal ions have unique electronic structure, bonding characteristics and excellent high charge property, rare earth complexes are compounded with polyacid to form rare earth organic compounds based on polyacid, which often have more excellent catalytic performance, electrochemical performance and the like, and thus, the inorganic-organic hybrid materials have become one of the hot spots of research.
As is well known, with the development of industry, organic dyes have gradually become a common pollutant in factory sewage, and are usually organic aromatic nitro compounds and aromatic amine compounds, which have high biological toxicity, carcinogenicity, mutagenicity and the like, and have serious harm to the environment, organisms and human bodies, and are one of the problems to be solved urgently in the current environmental pollution. At present, wastewater treatment agents are continuously developed and synthesized. However, in the process of treating organic dye wastewater, the prior art has the following problems and disadvantages:
(1) Organic dyes are complex in structure, often resistant to photolysis, resistant to oxidation, less susceptible to fading, and poorly degradable.
(2) The traditional treatment method for treating organic dye pollutants has the problems of poor removal rate, difficult catalyst recovery and the like.
(3) The polyacid-based inorganic-organic hybrid material is used as a solid material, has high removal rate when used for treating organic dye wastewater, is easy to recover, and is a good wastewater treatment agent. However, the rare earth organic compound with polyacid and rare earth organic compound being compounded to form polyacid group is difficult due to the problems of steric hindrance and the like, so the research on degrading organic dye by the rare earth organic compound with polyacid group is less.
In order to solve the problems, a preparation method and application of a polyacid-based europium complex are provided on the basis of the prior art.
Disclosure of Invention
The technical purpose of the invention is realized by the following technical scheme:
a polyacid-based europium complex, the polyacid-based europium complex has a chemical formula of [ Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O, wherein, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O is a polyoxometallate-based europium complex, L 2- Is a deprotonated organic ligand; the organic ligand is 2,2 '-bipyridine-6, 6' -dicarboxylic acid; the polyacid isThe crystal of the europium-based complex is in a pink block shape.
The invention aims to provide a preparation method and application of polyacid-based europium organic complex, wherein the inorganic-organic hybrid material for removing organic dyes in wastewater is synthesized by adopting a simple preparation process, cheap and easily-obtained synthetic raw materials and mild reaction conditions, and the material can adsorb and remove methylene blue and rhodamine B organic dyes in organic dye wastewater and selectively adsorb and remove rhodamine B organic dyes in organic dye wastewater of methyl orange and rhodamine B; the polyacid-based europium organic complex prepared by the invention has the advantages of high efficiency of removing organic dyes, catalyst stability, recoverable adsorbent and the like, and can bring qualitative leap for removing organic dye pollutants in the environment; the polyacid-based europium organic complex prepared by the invention is an inorganic-organic hybrid material with the advantages of good stability, strong oxidation capacity and the like; the polyacid-based europium complex prepared by the invention also has the advantages of water insolubility, good thermal stability, good optical property, good electrical property and wide application prospect.
Further, the polyacid-based europium complex is a tetragonal system, the polyacid-based europium complex is an I4/m space group, and the unit cell parameters are as follows:
Figure BDA0003796070010000031
Figure BDA0003796070010000032
α＝90.00°，β＝90.00°，γ＝90.00°，
Figure BDA0003796070010000033
Figure BDA0003796070010000034
the organic ligand being deprotonated L 2- The ligand is mu 3 -kO: kO ', N, N', O ": coordination mode of kO' with three Eu 3+ And (4) coordination. The Eu being 3+ Is two L 2- Simultaneous chelation coordination to form [ Eu (L) 2 ] - Unit at [ Eu (L) 2 ] - Two of the cells L 2- The planes are in mutually perpendicular positions. Said [ Eu (L) 2 ] - Two of the cells L 2- Four carboxyl oxygen atoms in (1) are replaced by four Eu 3+ Coordinated, so that adjacent [ Eu (L) 2 ] - The units being linked to form [ Eu ] 4 (L) 4 (H 2 O) 8 ] 4+ And the polyacid anions serving as objects are arranged between the two-dimensional layers and are connected with the two-dimensional layers through hydrogen bond acting force to form a three-dimensional supermolecular network structure.
Crystallographic parameters of the compounds of Table 1
Figure BDA0003796070010000035
Figure BDA0003796070010000041
The invention also provides a preparation method of the polyacid-based europium complex, which is characterized by comprising the following steps of:
s1, reacting Eu (NO) 3 ) 3 ·6H 2 O、H 2 L、H 4 SiW 12 O 40 ·H 2 Mixing and stirring O and 10mL of purified water at room temperature for 30min to obtain a first mixture;
s2, use of HNO 3 And KOH reagent to adjust the pH value of the first mixture to 1.26 to obtain suspension, adding the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing and packaging, and heating at 170 ℃ under autogenous pressure for 4 days;
s3, heating the temperature in the reaction kettle to 170 ℃, then heating the reaction kettle at a constant temperature under the autogenous pressure for 4 days, and cooling the reaction kettle to room temperature at a cooling rate of 10 ℃ per hour; obtaining pink blocky crystals, washing products in the reaction kettle by using purified water, and naturally drying the products in the air.
Further, the Eu (NO) 3 ) 3 ·6H 2 O、H 2 L and H 4 SiW 12 O 40 ·H 2 The addition ratio of the substance content of O is 5.
Further, the HNO 3 The concentration of (b) is 0.7mol/L, and the concentration of KOH is 0.2mol/L.
The invention also provides an application of the polyacid-based europium complex, and the polyacid-based europium complex is applied to a solid luminescent material.
The invention also provides application of the polyacid-based europium complex to adsorption removal of organic dyes of methylene blue in organic dye wastewater.
The invention also provides an application of the polyacid-based europium complex, which is used for adsorbing and removing the organic dye of rhodamine B in organic dye wastewater.
The invention also provides an application of the polyacid-based europium complex, which is used for selectively adsorbing and removing the rhodamine B organic dye in the organic dye wastewater containing methyl orange and rhodamine B.
In conclusion, the invention has the following beneficial effects:
1. the invention adopts simple preparation process, cheap and easily available synthetic raw materials and mild reaction conditions to synthesize the inorganic-organic hybrid material capable of degrading organic dye pollutants, and the material can adsorb and remove methylene blue organic dye in organic dye wastewater; the material can adsorb and remove rhodamine B organic dye in organic dye wastewater; the material can selectively adsorb and remove the rhodamine B organic dye in the organic dye wastewater containing methyl orange and rhodamine B.
2. The polyacid-based europium organic complex prepared by the invention is an inorganic-organic hybrid material with the advantages of good stability, strong oxidizing capability and the like;
3. the polyacid-based europium complex prepared by the invention has high efficiency and stability and can be recycled.
4. The polyacid-based europium complex prepared by the invention has the advantages of insolubility in water, good thermal stability, good optical performance and wide application prospect.
Drawings
FIG. 1 shows Eu according to example 1 of the present invention 3+ Schematic diagrams of two coordination modes of (a);
FIG. 2 is a schematic diagram showing the coordination pattern of an organic ligand in example 1 of the present invention;
FIG. 3 shows Eu according to example 1 of the present invention 3+ And L 2- A schematic diagram of the formed two-dimensional layered structure;
FIG. 4 is a topological diagram of a two-dimensional layered structure according to embodiment 1 of the present invention;
FIG. 5 shows the polyacid anion and [ Eu ] of example 1 of the present invention 4 (L) 4 (H 2 O) 8 ] 4+ The two-dimensional layer forms a schematic diagram of a three-dimensional supramolecular structure through supramolecular acting force;
FIG. 6 shows [ Eu ] in example 1 of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 An infrared spectrum of O;
FIG. 7 shows [ Eu ] in example 1 of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Thermogravimetric curve of O;
FIG. 8 shows [ Eu ] in example 1 of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 PXRD simulation and experimental plot of O;
FIG. 9 shows [ Eu ] in example 1 of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Solid fluorescence spectrum of O;
FIG. 10 shows [ Eu ] according to an embodiment of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 A performance diagram of removing methylene blue organic dye wastewater by using O as an adsorbent;
FIG. 11 shows [ Eu ] in examples of the present invention and comparative examples 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 A performance diagram of removing methyl orange organic dye wastewater by using O as an adsorbent;
FIG. 12 shows an embodiment of the present inventionOf [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Removing the performance diagram of the rhodamine B organic dye wastewater by using O as an adsorbent;
FIG. 13 shows [ Eu ] according to an embodiment of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O selectively adsorbs and removes a performance diagram of rhodamine B in the mixed organic dye of methyl orange and rhodamine B;
FIG. 14 shows [ Eu ] according to an embodiment of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Cyclic voltammograms of O-CPE at different scan rates in 0.1mol of sulfuric acid and 0.5mol of aqueous sodium sulfate;
Detailed Description
The invention is described in further detail below with reference to the following figures and embodiments:
example 1: a polyacid-based europium complex, wherein the polyacid-based europium complex has a chemical formula of [ Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O, wherein, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiMo 12 O 40 ]·4H 2 O is a polyoxometallate-based europium functional complex, L 2- Is a deprotonated organic ligand; the organic ligand is 2,2 '-bipyridine-6, 6' -dicarboxylic acid (abbreviated as H) 2 L); the crystal of the polyacid-based europium complex is in a pink block shape.
The polyacid-based europium complex is a tetragonal crystal system, the polyacid-based europium complex is an I4/m space group, and the unit cell parameters are as follows:
Figure BDA0003796070010000081
Figure BDA0003796070010000082
α＝90.00°，β＝90.00°，γ＝90.00°，
Figure BDA0003796070010000083
organic ligandsIs deprotonated L 2- The ligand is mu 3 -kO: kO ', N, N', O ": coordination mode of kO' with three Eu 3+ And (4) coordination. The Eu being 3+ Is divided into two L 2- Simultaneous chelate coordination to form [ Eu (L) 2 ] - Unit at [ Eu (L) 2 ] - Two of the cells L 2- The planes are in mutually perpendicular positions. Said [ Eu (L) 2 ] - Two of the cells L 2- In which four carboxyl oxygen atoms are replaced by four Eu atoms 3+ Coordinated, so that adjacent [ Eu (L) 2 ] - The units being linked to form [ Eu ] 4 (L) 4 (H 2 O) 8 ] 4+ And the polyacid anions serving as objects are arranged between the two-dimensional layers and are connected with the two-dimensional layers through hydrogen bond acting force to form a three-dimensional supermolecular network structure.
Inventive para [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The characterization results for O are as follows:
(1)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 structure of O
Eu 3+ The coordination pattern of (A) is shown in FIG. 1, in which Eu1 is simultaneously bound by two L groups in FIG. 1 (a) 2- Two pyridine nitrogens and two carboxyl groups each provide an oxygen chelating coordination, the two ligands being in mutually perpendicular positions; eu2 is four L 2- Bridging coordination, each L 2- Each providing a carboxyl oxygen, the coordination mode of which is shown in fig. 1 (b).
In FIG. 2, ligand L 2- By using mu 3 -kO: kO ', N, N', O ": coordination mode of kO' with three Eu 3+ And (4) coordination.
FIG. 3 shows Eu 3+ And L 2- Coordination extends along an ab plane to form a two-dimensional layered structure; eu1 and L 2- Form [ Eu (L) 2 ] - The cells, in turn, are connected by Eu2 to form a two-dimensional layered structure with lattices.
Fig. 4 is a topological diagram of the two-dimensional layered structure of fig. 3, in which metal europium is used as a node of the topological structure and an organic ligand is used as a connector, thereby forming a "grid" state as shown in the figure.
Fig. 5 is a schematic diagram of a polyacid anion situated between two-dimensional layers, forming a three-dimensional supramolecular structure with the layers through hydrogen bonding forces.
(2)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Infrared spectrogram of O
FIG. 6 is [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Infrared spectrum of O at 968, 910, 796, 763cm -1 The peak should belong to the characteristic absorption peak of vSi-Oa, vW-Od, vW-Oc-W and vW-Od-W in the polyacid anion; at 1623, 1594, 1444cm -1 The peak should be attributed to the characteristic absorption peak of carboxyl in the organic ligand; 3403cm -1 The peaks at (a) are characteristic absorption peaks corresponding to crystal water and coordinated water.
(3)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Thermogravimetric analysis of O
As shown in FIG. 7, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The thermogravimetric curve of O shows the trend of two-step weight loss, and the weight loss rate is 4.7 percent in the temperature range of 25-262 ℃, and is consistent with the weight loss rate (calculated value is 4.6 percent) of coordinated water and crystal water. The organic framework of the material is kept unchanged in the temperature range of 262-563 ℃, and the result proves that [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has good thermal stability.
(4)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 PXRD simulation diagram and experimental diagram of O
As shown in FIG. 8, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The PXRD experimental result of O is consistent with the simulated PXRD spectrum, and the product has higher phase purity. The difference in strength may be due to the preferred orientation of the powder sample.
(5)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Solid state fluorescence spectrum of O
As shown in FIG. 9, [ Eu ] is excited by light having an excitation wavelength of 375nm 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has emission peaks at 423nm, 469nm and 539nm, wherein the peak at 423nm can be assigned as ligand luminescence, and the peaks at 469nm and 539nm can correspond to metal Eu 3+ Is/are as follows 5 D 0 - 7 F 1 Characteristic emission of the transition;
(6)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 performance diagram for removing organic dye in wastewater of O
1) As shown in FIG. 10, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 And (3) removing the methylene blue organic dye in the dye wastewater by adsorbing the O.
2) As shown in FIG. 11, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 And (3) removing the methyl orange organic dye in the dye wastewater by adsorbing the O.
3) As shown in FIG. 12, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 And removing the rhodamine B organic dye in the dye wastewater by adsorbing the O.
4) As shown in FIG. 13, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 And removing the rhodamine B performance diagram in the mixed organic dye wastewater containing the methyl orange and the rhodamine B by selective adsorption of O.
(7)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Electrochemical behavior of O
As shown in FIG. 14, electrochemical behavior at different potential ranges and scan rates was studied using a three-electrode system. When the scanning speed is 40-400mv/s, the cathode peak potential gradually moves to the positive direction and the anode peak potential gradually moves to the negative direction along with the increase of the scanning speed. The peak current is proportional to the scan rate, indicating [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The redox process of O is surface controlled.
Example 2: a preparation method of polyacid europium complex comprises the following steps:
s1, reacting Eu (NO) 3 ) 3 ·6H 2 O、H 2 L、H 4 SiW 12 O 40 ·H 2 O and 10mL of purified water are mixed and stirred at room temperature for 30min to obtain a first mixture;
s2, 0.7mol/L HNO is used 3 Adjusting the pH value of the first mixture to 1.26 by using 0.2mol/L KOH reagent to obtain suspension, adding the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing, packaging, and heating at 170 ℃ under autogenous pressure for 4 days;
s3, heating the temperature in the reaction kettle to 170 ℃, then heating the reaction kettle at a constant temperature under the autogenous pressure for 4 days, and cooling the reaction kettle to room temperature at a cooling rate of 10 ℃ per hour; obtaining pink transparent blocky crystals, washing products in the reaction kettle with purified water, and placing the products in the air for natural air drying.
Preparation of [ Eu ] by the method 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The yield of O was 13.05% (based on Eu).
[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Elemental analysis (C) of O 48 H 40 N 8 O 68 Eu 4 SiW 12 Molecular weight 4666.63): 12.35 percent of C; 1.04 percent of H; 2.40 percent of N. Actually: 12.29 percent of C; 1.01 percent of H; 2.46 percent of N.
Example 3: an application of polyacid-based europium complex, which is used for adsorbing and removing methylene blue organic dye wastewater.
Shown in FIG. 10 as [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has adsorption property on methylene blue organic dye, and [ Eu ] is added into 40ppm methylene blue solution in dark 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 After O,15min, the removal rate of the methylene blue solution reaches 100 percent, which indicates that [ Eu ] is 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has the ability to rapidly adsorb methylene blue. And within three hours, the ultraviolet-visible spectrum test result of the solution is continuously taken, so that the adsorbed solution is stable and the desorption phenomenon does not occur. The experimental results show that [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O is a good adsorbent for the organic dye methylene blue.
Example 4: an application of polyacid-based europium complex, which is used for adsorbing and removing rhodamine B organic dye in wastewater.
Shown in FIG. 12 as [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has adsorption performance on rhodamine B organic dye, and [ Eu ] is added into 40ppm rhodamine B solution in the dark 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 After 15min of O, the removal rate of the rhodamine B solution reaches 100 percent, which indicates that [ Eu ] is 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has the ability to rapidly adsorb rhodamine B. And within three hours, the ultraviolet-visible spectrum test result of the solution is continuously taken, so that the adsorbed solution is stable and the desorption phenomenon does not occur. The experimental result shows that [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O is a good adsorbent for organic dye rhodamine B.
Example 5: the application of the polyacid europium complex to adsorption removal of waste water contains mixed organic dye of methyl orange and rhodamine B, and the mixed organic dye has the effect of selective adsorption removal of rhodamine B.
As shown in FIG. 13, [ Eu ] was added to a 40ppm solution containing a mixed organic dye of methyl orange and rhodamine B in the dark 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 After 15min of O, the removal rate of rhodamine B organic dye can reach 78%, and the removal rate of methyl orange is only 2%, which indicates that [ Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The O has the function of selectively adsorbing the rhodamine B organic dye by using the mixed organic dye simultaneously containing methyl orange and rhodamine B in the wastewater.
Comparative example 1: an application of polyacid-based europium complex, which is used for adsorbing organic dye for removing methyl orange in wastewater.
As shown in FIG. 11, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has adsorption property on methyl orange organic dye, and [ Eu ] is added into 40ppm methyl orange solution in dark 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 And O, after 15min, no obvious change exists, and within three hours, the solution is continuously taken for ultraviolet visible spectrum, and no obvious change exists all the time. The experimental result shows that [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has no adsorption effect on the organic dye methyl orange.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (9)

1. A polyacid europium complex is characterized in that: the polyacid europium complex has a chemical formula of[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O, wherein [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O is a polyoxometallate-based europium complex, L 2- Is a deprotonated organic ligand; the organic ligand is 2,2 '-bipyridine-6, 6' -dicarboxylic acid; the crystal of the polyacid-based europium complex is in a pink block shape.
2. The polyacid-based europium complex of claim 1, which is characterized by: the polyacid-based europium complex is a tetragonal crystal system, the polyacid-based europium complex is an I4/m space group, and the unit cell parameters are as follows:
Figure FDA0003796070000000011
α＝90.00°，β＝90.00°，γ＝90.00°，
Figure FDA0003796070000000012
the organic ligand being deprotonated L 2- The ligand is mu 3 -kO: kO ', N, N', O ": coordination mode of kO' with three Eu 3+ And (4) coordination. The Eu 3+ Is two L 2- Simultaneous chelate coordination to form [ Eu (L) 2 ] - Unit at [ Eu (L) 2 ] - Two of the units L 2- The planes are in mutually perpendicular positions. Said [ Eu (L) 2 ] - Two of the cells L 2- Four carboxyl oxygen atoms in (1) are replaced by four Eu 3+ Coordinated, so that adjacent [ Eu (L) 2 ] - The units being linked to form [ Eu ] 4 (L) 4 (H 2 O) 8 ] 4+ And the polyacid anions serving as objects are arranged between the two-dimensional layers and are connected with the two-dimensional layers through hydrogen bond acting force to form a three-dimensional supermolecular network structure.
3. The method for preparing polyacid-based europium complex according to claim 1, which comprises the following steps:
s1, reacting Eu (NO) 3 ) 3 ·6H 2 O、H 2 L、H 4 SiW 12 O 40 ·H 2 O and 10mL of purified water are mixed and stirred at room temperature for 30min to obtain a first mixture;
s2, use of HNO 3 And KOH reagent to adjust the pH value of the first mixture to 1.26 to obtain suspension, adding the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing and packaging, and heating at 170 ℃ under autogenous pressure for 4 days;
s3, heating the temperature in the reaction kettle to 170 ℃, then heating the reaction kettle at a constant temperature under the autogenous pressure for 4 days, and cooling the reaction kettle to room temperature at a cooling rate of 10 ℃ per hour; obtaining pink blocky crystals, washing products in the reaction kettle by using purified water, and naturally drying the products in the air.
4. The method of claim 3, wherein the europium complex polyacid comprises: in step S1, the Eu (NO) 3 ) 3 ·6H 2 O、H 2 L and H 4 SiW 12 O 40 ·H 2 The addition ratio of the amount of O is 5.
5. The method of claim 3, wherein the europium complex polyacid comprises: the HNO 3 The concentration of (3) is 0.7mol/L, and the concentration of the KOH is 0.2mol/L.
6. Use of a polyacid-based europium complex according to any one of claims 1 or 2, characterized in that: the polyacid-based europium complex is applied to a solid luminescent material.
7. Use of a polyacid-based europium complex according to any one of claims 1 or 2, characterized in that: the polyacid-based europium complex is applied to adsorption removal of methylene blue organic dye in dye wastewater.
8. Use of a polyacid-based europium complex according to any one of claims 1 or 2, characterized by: the polyacid-based europium complex is applied to adsorption removal of rhodamine B organic dye in dye wastewater.
9. Use of a polyacid-based europium complex according to any one of claims 1 or 2, characterized by: the polyacid-based europium complex is applied to selective adsorption to remove rhodamine B in organic dye wastewater containing methyl orange and rhodamine B.
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