CN115536855B - 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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CN115536855B
CN115536855B CN202210969269.5A CN202210969269A CN115536855B CN 115536855 B CN115536855 B CN 115536855B CN 202210969269 A CN202210969269 A CN 202210969269A CN 115536855 B CN115536855 B CN 115536855B
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polyacid
europium complex
siw
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organic dye
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CN115536855A (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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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide

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Abstract

The invention discloses a preparation method and application of a polyacid europium complex, which belongs to the technical field of high molecular compounds, and the technical scheme is as follows: the chemical formula of the poly-acid-based europium complex is [ 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 is carried out to form a two-dimensional layered structure containing grids, polyacid anions are used as objects to be positioned between two-dimensional layers, and a three-dimensional supermolecular network structure is formed through supermolecular acting force. The invention is mainly used for synthesizing inorganic-organic hybrid materials capable of treating organic dye wastewater, and the materials can selectively adsorb and remove 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 europium complex.
Background
Polyoxometallates (polyacids) are a class of polyoxometallate compounds formed from pre-transition metal ions (V, mo, W, ta, nb, etc.) through oxygen linkage. The polyacid has controllable shape, size and high negative charge, and the metal ions can generate interaction through electron transfer, so that the polyacid presents various physical and chemical properties and biological activities. Polyacids have been used as inorganic ligands to build novel structured, diverse POM-metal organic complexes. The inorganic-organic hybrid material often has the properties of acidity, high redox performance and the like, and has potential application in the fields of electrochemistry, magnetism, catalysis, materials, medicines and energy sources. At present, inorganic-organic hybrid materials based on polyacids have been synthesized, wherein rare earth metal ions have unique electronic structures, bonding characteristics and excellent high-charge properties, rare earth complexes are compounded with the polyacids to form rare earth organic compounds based on the polyacids, so that the rare earth organic compounds often have more excellent catalytic performance, electrochemical performance and the like, and the rare earth organic compounds have become one of hot spots for research.
As is well known, with the development of industry, organic dyes are gradually a common pollutant in factory sewage, and the organic dyes are usually organic aromatic nitro compounds and aromatic amine compounds, have large biotoxicity, have cancerogenicity, mutagenicity and the like, have serious harm to environment, biology and human bodies, and are one of the problems to be solved urgently for environmental pollution at present. 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) The organic dye has a complex structure and is often resistant to photolysis, oxidation and fading and poor in degradability.
(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 treating organic dye wastewater, is easy to recycle, and is a good wastewater treatment agent. However, the polyacid and the rare earth organic compound are difficult to form the multi-acid-base rare earth organic compound due to the problems of steric hindrance and the like, so that the research on the degradation of the multi-acid-base rare earth organic compound into organic dye is less.
In order to solve the problems, a preparation method and application of the polyacid-based europium complex are provided on the basis of the prior art.
Disclosure of Invention
The technical aim of the invention is realized by the following technical scheme:
a polyacid-based europium complex with 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 europium complex based on polyoxometallate, L 2- An organic ligand that is deprotonated; the organic ligand is 2,2 '-bipyridine-6, 6' -dicarboxylic acid; the crystal of the polyacid europium complex is pink blocky.
The invention aims to provide a preparation method and application of a polyacid-based europium organic complex, and the inorganic-organic hybrid material with the function of removing organic dyes in wastewater is synthesized by adopting a simple preparation process, low-cost and easily-obtained synthetic raw materials and mild reaction conditions, and can adsorb and remove methylene blue and rhodamine B organic dyes in the organic dye wastewater, and selectively adsorb and remove rhodamine B organic dyes in the organic dye wastewater of methyl orange and rhodamine B; the polyacid-based europium organic complex prepared by the method has the advantages of high efficiency in removing organic dye, stability of catalyst, recoverable adsorbent and the like, and can be a 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 oxidizing 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 performance and good electrical performance, and has wide application prospect.
Further, the polyacid-based europium complex is tetragonal, the polyacid-based europium complex is an I4/m space group, and the unit cell parameters are as follows: α＝90.00°，β＝90.00°，γ＝90.00°，/> the organic ligand being deprotonated L 2- Mu is adopted as ligand 3 -kO：kO′，N，N ', O': coordination mode of kO' "and three Eu 3+ Coordination. The Eu 3+ Is formed by two L 2- At the same time chelate coordination to form [ Eu (L) 2 ] - Unit, in [ Eu (L) 2 ] - Two L in a cell 2- The planes are positioned at mutually perpendicular positions. Said [ Eu (L) 2 ] - Two L in a cell 2- Four carboxyl oxygen atoms of (a) are replaced by four Eu atoms 3+ Coordination, thus adjacent [ Eu (L) 2 ] - Units are connected to form [ Eu ] 4 (L) 4 (H 2 O) 8 ] 4+ The polyacid anions are used as objects between 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
The invention also provides a preparation method of the polyacid-based europium complex, which is characterized by comprising the following steps:
s1, reactant 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 mixture I;
s2, using HNO 3 And KOH reagent to regulate the pH value of the first mixture to 1.26, obtaining a suspension, adding the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing and packaging, and heating at 170 ℃ for 4 days under autogenous pressure;
s3, heating the temperature in the reaction kettle to 170 ℃, then heating the reaction kettle at constant temperature for 4 days under autogenous pressure, and cooling the reaction kettle to room temperature at a cooling rate of 10 ℃ per hour; and (3) obtaining pink blocky crystals, washing the products in the reaction kettle with purified water, and naturally airing 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 amount of O was 5:1:1.
Further, the HNO 3 The concentration of KOH was 0.7mol/L and the concentration of KOH was 0.2mol/L.
The invention also provides 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, which is applied to organic dye for removing methylene blue in organic dye wastewater by adsorption.
The invention also provides application of the polyacid-based europium complex, which is applied to organic dye for removing rhodamine B in organic dye wastewater by adsorption.
The invention also provides application of the polyacid-based europium complex, which is applied to selective adsorption removal of rhodamine B organic dye in organic dye wastewater containing methyl orange and rhodamine B.
In summary, the invention has the following beneficial effects:
1. the invention adopts a simple preparation process, is low in cost and easy to obtain synthetic raw materials and mild in 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 the organic dye wastewater; the material can selectively adsorb and remove rhodamine B organic dye in 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 capacity and the like;
3. the polyacid-based europium complex prepared by the invention has high efficiency, stability and recyclability.
4. The polyacid-based europium complex prepared by the invention also has the advantages of water insolubility, good thermal stability and good optical performance, and has wide application prospect.
Drawings
FIG. 1 shows Eu according to example 1 of the present invention 3+ Is a schematic diagram of two coordination modes;
FIG. 2 is a schematic diagram showing the coordination mode of the 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 formed two-dimensional layered structure schematic diagram;
FIG. 4 is a topology of a two-dimensional layered structure of example 1 of the present invention;
FIG. 5 shows polyacid anions of example 1 of the present invention [ Eu ] 4 (L) 4 (H 2 O) 8 ] 4+ The two-dimensional layer forms a schematic diagram of a three-dimensional supermolecular structure through supermolecular acting force;
FIG. 6 shows [ Eu ] of example 1 of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Infrared spectrogram of O;
FIG. 7 shows [ Eu ] of example 1 of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Thermal weight curve of O;
FIG. 8 shows [ Eu ] of example 1 of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 PXRD simulations and experimental patterns for O;
FIG. 9 shows [ Eu ] of 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 ] of the embodiment of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The performance diagram of removing methylene blue organic dye wastewater by using O as an adsorbent;
FIG. 11 shows Eu of the present invention and the comparative example 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The performance diagram of removing methyl orange organic dye wastewater by using O as an adsorbent;
FIG. 12 shows [ Eu ] of the embodiment of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The performance diagram of removing rhodamine B organic dye wastewater by using O as an adsorbent;
FIG. 13 shows [ Eu ] of the embodiment of the present invention 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O selectively adsorbs and removes rhodamine B performance diagram in methyl orange and rhodamine B mixed organic dye;
FIG. 14 shows [ Eu ] of the 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 aqueous solutions of 0.1mol sulfuric acid and 0.5mol sodium sulfate;
Detailed Description
The invention is described in further detail below with reference to the attached drawings and embodiments:
example 1: a polyacid-based europium complex with 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 europium functional complex based on polyoxometallate, L 2- An organic ligand that is deprotonated; the organic ligand is 2,2 '-bipyridine-6, 6' -dicarboxylic acid (abbreviated as H) 2 L); the crystal of the polyacid europium complex is pink blocky.
The polyacid europium complex is tetragonal, and the polyacid europium complex is I4/m space group, and the unit cell parameters are as follows: α＝90.00°，β＝90.00°，γ＝90.00°，/>the organic ligand being deprotonated L 2- Mu is adopted as ligand 3 -kO: kO ', N, N ', O ': coordination mode of kO' "and three Eu 3+ Coordination. The Eu 3+ Is formed by two L 2- At the same time chelate coordination to form [ Eu (L) 2 ] - Unit, in [ Eu (L) 2 ] - Two L in a cell 2- The planes are positioned at mutually perpendicular positions. Said [ Eu (L) 2 ] - Two L in a cell 2- Four carboxyl oxygen atoms of (a) are replaced by four Eu atoms 3+ Coordination, thus adjacent [ Eu (L) 2 ] - Units are connected to form [ Eu ] 4 (L) 4 (H 2 O) 8 ] 4+ The polyacid anions are used as objects between two-dimensional layers, and are connected with the two-dimensional layers through hydrogen bond acting force to form a three-dimensional supermolecular network structure.
The invention is to [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 The characterization result of O is as follows:
(1)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 o structure
Eu 3+ As shown in FIG. 1, eu1 in FIG. 1 (a) is simultaneously bonded to two L' s 2- Two pyridine nitrogen and two carboxyl groups respectively provide one oxygen chelate coordination, and two ligands are positioned at mutually perpendicular positions; eu2 is covered with four L 2- Bridging coordination, each L 2- Each of the two carboxyl groups is provided with a coordination pattern shown in FIG. 1 (b).
In FIG. 2, ligand L 2- Mu is adopted 3 -kO: kO ', N, N ', O ': coordination mode of kO' "and three Eu 3+ Coordination.
FIG. 3 is Eu 3+ And L 2- A two-dimensional layered structure formed by extending coordination along an ab plane; eu1 and L 2- Formation of [ Eu (L) 2 ] - Unit, relayAnd are connected by Eu2 to form a two-dimensional layered structure with grids.
Fig. 4 is a topological diagram of the two-dimensional layered structure of fig. 3, with europium metal as a node of the topological structure and an organic ligand as a linker, forming a "grid" state as shown.
FIG. 5 is a schematic representation of polyacid anions 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 O infrared spectrum, at 968, 910, 796, 763cm -1 The peaks at the positions are attributed to characteristic absorption peaks of vSi-Oa, vW-Od, vW-Oc-W and vW-Od-W in polyacid anions; at 1623, 1594, 1444cm -1 The peak at the position is the characteristic absorption peak of carboxyl in the organic ligand; 3403cm -1 The peak at this point is a characteristic absorption peak corresponding to the crystal water and the 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 thermal weight curve of O shows the trend of two-step weight loss, the weight loss rate is 4.7% in the temperature range of 25-262 ℃, and the weight loss rate is consistent with the weight loss rate (calculated value is 4.6%) of coordination water and crystallization water. The organic framework of the catalyst is kept unchanged within the temperature range of 262-563 ℃, which 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 and experimental diagrams 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, which shows that the product has higher phase purity. The intensity differences may be due to the preferred direction of the powder sample.
(5)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 Solid fluorescence spectrum of O
As shown in FIG. 9, [ Eu ] under excitation 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, 539nm, wherein the peak at 423nm can be attributed to ligand luminescence, and the peak at 469nm, 539nm can correspond to metal Eu 3+ A kind of electronic device 5 D 0 - 7 F 1 Characteristic emission of transitions;
(6)[Eu 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 performance graph of O for removing organic dye from waste water
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 adsorption of 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 adsorption of O.
3) As shown in FIG. 12, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 And (3) removing the rhodamine B organic dye in the dye wastewater by adsorbing O.
4) As shown in FIG. 13, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 And (3) removing the rhodamine B 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 rate is 40-400mv/s, the cathode peak potential gradually moves towards the positive direction and the anode peak potential gradually moves towards the negative direction along with the increase of the scanning rate. The peak current is proportional to the scan rate, indicating that [ 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 a polyacid europium complex comprises the following steps:
s1, reactant 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 mixture I;
s2, 0.7mol/L HNO is used 3 And 0.2mol/L KOH reagent to adjust the pH value of the first mixture to 1.26, obtaining a suspension, adding the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing and packaging, and heating for 4 days at 170 ℃ under autogenous pressure;
s3, heating the temperature in the reaction kettle to 170 ℃, then heating the reaction kettle at constant temperature for 4 days under autogenous pressure, and cooling the reaction kettle to room temperature at a cooling rate of 10 ℃ per hour; and (3) obtaining pink transparent blocky crystals, washing the products in the reaction kettle with purified water, and naturally airing in the air.
The method prepares [ Eu ] 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) 48 H 40 N 8 O 68 Eu 4 SiW 12 Molecular weight 4666.63): 12.35 percent of C; h is 1.04%; n is 2.40%. Actual: 12.29 percent of C; h is 1.01%; n (N):2.46％。
Example 3: the application of the polyacid europium complex applies the polyacid europium complex to organic dye wastewater for removing methylene blue by adsorption.
As shown in FIG. 10, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has adsorption property to methylene blue organic dye, and [ Eu ] is added to 40ppm methylene blue solution in darkness 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 After 15min, the removal rate of the methylene blue solution reaches 100%, which indicates [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has the ability to adsorb methylene blue rapidly. And in three hours, the solution is continuously taken for ultraviolet-visible spectrum test results, so that the adsorbed solution is stable and no desorption phenomenon occurs. 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: the application of the polyacid europium complex applies the polyacid europium complex to adsorption removal of rhodamine B organic dye in wastewater.
As shown in FIG. 12, [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has adsorption property to rhodamine B organic dye, and [ Eu ] is added into 40ppm rhodamine B solution in dark 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 After O for 15min, the removal rate of rhodamine B solution reaches 100%, which indicates [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has the capacity of rapidly adsorbing rhodamine B. And in three hours, the solution is continuously taken for ultraviolet-visible spectrum test results, so that the adsorbed solution is stable and no desorption phenomenon occurs. 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 rhodamine B.
Example 5: the polyacid-based europium complex is applied to adsorption removal of wastewater, and meanwhile, mixed organic dye containing methyl orange and rhodamine B has the effect of selectively adsorbing and removing rhodamine B.
As shown in FIG. 13, to 40ppm of a mixed organic dye containing methyl orange and rhodamine B, eu was added in the dark 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 After O and 15min, the removal rate of rhodamine B organic dye can reach 78%, and the removal rate of methyl orange is only 2%, which indicates [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O has the function of selectively adsorbing rhodamine B organic dye by mixing methyl orange and rhodamine B organic dye in the wastewater.
Comparative example 1: the application of the polyacid europium complex applies the polyacid europium complex to the adsorption of 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 to 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 O, after 15min, the solution is continuously taken for ultraviolet visible spectrum within three hours, and no obvious change exists all the time. Experimental results show that [ Eu ] 4 (L) 4 (H 2 O) 8 ][SiW 12 O 40 ]·4H 2 O is methyl orange which has no adsorption effect on organic dye.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.

Claims (5)

1. An application of a polyacid europium complex is characterized in that: the chemical formula of the polyacid-based europium complex is [ 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 europium complex based on polyoxometallate, L 2- An organic ligand that is deprotonated; the organic ligand is 2,2 '-bipyridine-6, 6' -dicarboxylic acid; the crystal of the polyacid europium complex is pink blocky;
the polyacid europium complex is applied to adsorption removal of methylene blue organic dye and rhodamine B organic dye in dye wastewater or selective adsorption removal of rhodamine B in organic dye wastewater containing methyl orange and rhodamine B.
2. The use of a polyacid-based europium complex according to claim 1, characterized in that: the polyacid europium complex is tetragonal, the polyacid europium complex is I4/m space group, and the unit cell parameters are as follows:a = 11.6253(3) Å，b = 11.6253(3) Å，c = 32.5840(8) Å，α = 90.00°，β = 90.00°，γ = 90.00°，V = 4403.65(19)Å 3 the organic ligand being deprotonated L 2- Ligand adoptsμ 3 -kO：kO΄，N，N΄，O΄΄：kCoordination mode of O ΄ ΄ ΄ and three Eu 3+ Coordination of the Eu 3+ Is formed by two L 2- At the same time chelate coordination to form [ Eu (L) 2 ] - Unit, in [ Eu (L) 2 ] - Two L in a cell 2- The planes are positioned at mutually perpendicular positions, the [ Eu (L) 2 ] - Two L in a cell 2- Four carboxyl oxygen atoms of (a) are replaced by four Eu atoms 3+ Coordination, thus adjacent [ Eu (L) 2 ] - Units are connected to form [ Eu ] 4 (L) 4 (H 2 O) 8 ] 4+ Two-dimensional lattice knotThe polyacid anions serve as objects between 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 use of a polyacid-based europium complex according to claim 1, characterized in that the preparation method of the polyacid-based europium complex comprises the following steps:
s1, reactant Eu (NO) 3 ) 3 ·6H 2 O、H 2 L、H 4 SiW 12 O 40 ·H 2 Mixing O and 10mL purified water at room temperature, and stirring for 30min to obtain a first mixture;
s2, using HNO 3 And KOH reagent to regulate the pH value of the first mixture to 1.26, obtaining a suspension, adding the suspension into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing and packaging, and heating at 170 ℃ for 4 days under autogenous pressure;
s3, heating the temperature in the reaction kettle to 170 ℃, then heating the reaction kettle at constant temperature for 4 days under autogenous pressure, and cooling the reaction kettle to room temperature at a cooling rate of 10 ℃ per hour; and (3) obtaining pink blocky crystals, washing the products in the reaction kettle with purified water, and naturally airing in the air.
4. The use of a polyacid-based europium complex according to claim 3, characterized in that: 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 was 5:1:1.
5. The use of a polyacid-based europium complex according to claim 3, characterized in that: the HNO is 3 The concentration of KOH was 0.7mol/L and the concentration of KOH was 0.2mol/L.
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