CN110872382A - Organic calcium phosphonate coordination polymer and preparation method and application thereof - Google Patents
Organic calcium phosphonate coordination polymer and preparation method and application thereof Download PDFInfo
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- CN110872382A CN110872382A CN201911206600.2A CN201911206600A CN110872382A CN 110872382 A CN110872382 A CN 110872382A CN 201911206600 A CN201911206600 A CN 201911206600A CN 110872382 A CN110872382 A CN 110872382A
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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of coordination polymers, and particularly relates to an organic calcium phosphonate coordination polymer, a preparation method and application thereof, wherein the calcium phosphonate coordination polymer has a chemical formula of [ Ca2(hedp)H2O]nWherein n is a positive integer, hedp is hydroxyethylidene diphosphonate ion, and the molecular structure of the calcium coordination polymer is as follows. The calcium coordination polymer has good photocatalytic performance, higher water stability and thermal stability, has the degradation rate of more than 95% to Methylene Blue (MB) and basic fuchsin (PR) under the condition of illumination, and can be used for dyeing containing MB and PRAnd (4) treating wastewater of the material.
Description
Technical Field
The invention belongs to the technical field of coordination polymers, and particularly relates to an organic calcium phosphonate coordination polymer and a preparation method and application thereof.
Background
With the increasing world population and increasing human activities, the demand for clean water is increasing, while its availability is decreasing. Among them, the textile printing industry uses and pollutes a large amount of water, and nearly 100 million tons of dyes are produced every year in the world. They are structurally diverse, complex aromatic compounds with high chemical, biological and photocatalytic stability. The water pollution caused by organic dyes is extremely serious, the quality and the property of water are influenced by dye wastewater, and benzene rings and the like in the organic dyes are easy to cause cancers and harm the health of human bodies. For this reason, much research has focused on the removal of organic dyes from water.
The common physical and chemical techniques for treating dye wastewater today include coagulation, adsorption and membrane separation. During coagulation, sulfur and disperse dyes are removed from the electrostatic attraction between the relatively charged soluble dyes and the polymer molecules. Acid dyes, direct dyes, vat dyes and reactive dyes also coagulate but do not precipitate, while cationic dyes do not. However, this process produces a large amount of sludge and a high level of dissolved solids remaining in the effluent. The adsorption can well remove the dye in the wastewater. However, regeneration of the adsorbent is expensive and involves loss of the adsorbent. The use of a suitable membrane enables the removal of all types of dyes, a compact technique that does not produce sludge. However, high cost membranes and equipment, with decreasing productivity over time, are greatly limited due to membrane fouling. Therefore, an effective and cheap dye wastewater treatment method is urgently needed.
The metal organic framework material is an organic-inorganic combined hybrid functional material, has the advantages of organic matters and inorganic matters, can be used as a semiconductor catalyst, and can effectively catalyze and degrade organic dyes under the condition of illumination so as to decompose the organic dyes into pollution-free water, carbon dioxide and the like, thereby effectively treating the problem of dye pollution.
The principle of using the hydroxyethylidene diphosphonic acid as a corrosion and scale inhibitor for retarding the scaling and corrosion on the surface of a system heat exchanger is that the hydroxyethylidene diphosphonic acid is coordinated with calcium ions in water. Calcium salt is the most common and inexpensive, readily available alkaline earth metal salt and is extremely suitable for mass production. Therefore, the metal organic framework material which can catalyze and degrade organic dye is synthesized by taking hydroxy ethylidene diphosphonic acid as an organic ligand and calcium salt, and has very wide application prospect.
Disclosure of Invention
The invention mainly provides an organic calcium phosphonate coordination polymer, a preparation method and application thereof, and the calcium coordination polymer has good catalytic degradation effect on dyes in wastewater such as methylene blue, basic fuchsin and the like, and can be used for wastewater treatment. The technical scheme is as follows:
an organic calcium phosphonate coordination polymer with a chemical formula of [ Ca2(hedp)H2O]nWherein n is a positive integer, hedp is hydroxyethylidene diphosphonate ion, and the molecular structure of the calcium coordination polymer is as follows:
Preferably, the calcium coordination polymer is monoclinic, P21The/c space group, unit cell parameters are:
α＝90°，β＝109.543(4)°，γ＝90°。
the preparation method of the calcium coordination polymer comprises the following steps: dissolving a hydroxy ethylidene diphosphonic acid ligand and a calcium salt in water, uniformly mixing, adjusting the pH value to 3-5, reacting for 24-36 hours at 120-160 ℃ under a closed condition, and then cooling to room temperature to obtain the calcium coordination polymer monocrystal. The single crystal cultivation has high requirements on the water amount, pH, temperature and time of reaction. If the water amount is too much, the yield is too low, and if the water amount is too little, powder is generated; pH < 3 results in low single crystal yield or even no product formation, and pH > 5 results in the formation of large amounts of powder and impurities; the temperature is too high, the crystal grows too fast, the crystallization is not good and the powder is generated, and the temperature is too low to react; better crystals can be obtained after the reaction is carried out for 24 to 36 hours, the time is short, the crystals are small, the yield is low, and after 36 hours, the yield is not obviously changed, and the time and energy are wasted.
Preferably, the calcium salt is calcium chloride or calcium nitrate.
Preferably, the molar ratio of the ligand, the calcium salt and the water is (0.3-0.5): 1: (2000-4000).
The calcium coordination polymer can be applied to photocatalytic degradation of dyes such as methylene blue, basic fuchsin and the like.
By adopting the scheme, the invention has the following advantages:
the calcium coordination polymer has good catalytic effect and good water and heat stability, the degradation rate of methylene blue with the concentration of 5ppm in 80min is up to 97%, the degradation rate of basic fuchsin with the concentration of 5ppm in 50min is up to 96%, the repeated effect is good, and the calcium coordination polymer can be used for treating wastewater containing the methylene blue and the basic fuchsin; the preparation method of the calcium coordination polymer has the advantages of cheap and easily-obtained raw materials, low cost, mass production and capability of meeting the treatment of a large amount of wastewater; meanwhile, water is used as a solvent, so that the method is green and environment-friendly, simple in production process, mild in reaction condition, high in yield, easy for industrial production, stable in calcium coordination polymer, not easy to decompose, free of influence on the environment and free of pollution.
Drawings
FIG. 1 is a graph showing a comparison of powder XRD, single crystal simulation and recycling experimental recovery samples of the calcium coordination polymers obtained in examples 1 and 2;
FIG. 2 is a graph of the infrared spectrum (FT-IR) of the calcium coordination polymer prepared in example 1 and example 2 after mixing;
FIG. 3 is a diagram of an asymmetric unit of the calcium coordination polymer of the present invention (hydrogen atom omitted);
FIG. 4 is a diagram showing coordination environments of two calcium ions in the calcium coordination polymer of the present invention (hydrogen atoms omitted);
FIG. 5 is a graph showing the UV test results of the catalytic degradation of Methylene Blue (MB) and basic fuchsin (PR) by the calcium coordination polymer of the present invention (MB on the left and PR on the right);
FIG. 6 is a graph showing the results of three cycles of photocatalytic degradation of two dyes by the calcium coordination polymer of the present invention.
Detailed Description
The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental reagents and materials involved are conventional biochemical reagents and materials unless otherwise specified.
Example 1
Dissolving hydroxyethylidene diphosphonic acid (0.0103g, 0.05mmol) and calcium chloride (0.0147g, 0.1mmol) in 2mL of water, mixing uniformly, adding ammonia water to adjust the pH value to 3, reacting at 120 ℃ for 24 hours under a sealed condition, and naturally cooling to room temperature to obtain colorless rectangular blocky crystals of the calcium coordination polymer, wherein the yield of single crystals is 65%.
Example 2
Hydroxy ethylidene diphosphonic acid (0.0103g, 0.05mmol) and calcium nitrate tetrahydrate (0.0236g, 0.1mmol) are dissolved in 4mL of water, mixed uniformly, added with ammonia water to adjust the pH value to 5, reacted at 160 ℃ for 36 hours under a sealed condition, and then naturally cooled to room temperature to obtain colorless rectangular blocky crystals of the calcium coordination polymer, wherein the yield of single crystals is 73%.
The calcium coordination polymer prepared by the above embodiment has better water and heat stability.
X-ray single crystal diffraction was performed on the colorless rectangular bulk crystal obtained in example 1, and the measured crystallographic data are shown in Table 1.
Table 1 shows crystallographic data of single crystals of coordination polymer obtained in example 1
As can be seen from Table 1, the calcium coordination polymer crystals belong to the monoclinic system, P21The/c space group, unit cell parameters are:
α＝90°，β＝109.543(4)°，γ＝90°。
powder X-ray diffraction was performed on the calcium complex polymers and the samples recovered from the recycling experiment obtained in examples 1 and 2, and the PXRD pattern is shown in FIG. 1, from which it can be seen that the crystals, the samples recovered from examples 1 and 2 and the simulated values were the same. The results show that the products are pure phases, and the structure of the sample is unchanged after multiple experiments.
The calcium coordination polymers obtained in example 1 and example 2 were mixed and subjected to Fourier transform infrared (FT-IR) spectroscopy, and the spectra are shown in FIG. 2. Wherein 3419cm-1The peak should be the stretching vibration absorption peak of O-H bond, which is the hydroxyl on the ligand and the O-H bond in the coordination water; 1571cm-1The left and right peaks are attributed to the asymmetric stretching vibration absorption peak of the P-O bond of phosphoric acid on the ligand; 1413cm-1The peak is the absorption peak of methyl; 1178-898 cm-1The absorption peak of the region is attributed to the stretching vibration peak of P ═ O; at 649cm-1The peak at (A) is an absorption peak of a C-O bond.
The asymmetric unit diagram of the calcium coordination polymer of the invention is shown in figure 3, wherein O1W is coordinated water, the asymmetric unit of the calcium coordination polymer comprises two calcium ions of Ca1 and Ca2 respectively, and an organic ligand hedp4-Ion, one coordinating water.
FIG. 4 shows the coordination environment diagram of two calcium ions in the calcium coordination polymerization of the present invention, and it can be seen from the diagram that Ca1 coordinates with eight phosphonic acid oxygen atoms and one hydroxyl oxygen atom of four hedp ligands to form a square antiprism configuration; ca2 coordinated to the five phosphonic acid oxygen atoms and one water molecule of the five hedp ligands, forming a distorted octahedral configuration.
The calcium coordination polymers prepared in inventive examples 1 and 2 were mixed and ground into powder using a mortar as a catalyst to conduct an experiment. Mixing and stirring an MB/PR aqueous solution with the concentration of 5ppm and a catalyst, carrying out dark reaction for about 30min, enabling the catalyst to achieve the adsorption-desorption balance of the dye, enabling the dye concentration in the solution to be almost unchanged, starting illumination by using a xenon lamp as a visible light source (filtering light with a wave band below 420 nm), taking 1mL of dye stock solution, finishing the dark reaction, sampling for 1mL, then sampling for one time every 20min by using MB, sampling for one time every 10min by using PR, and finishing the reaction by illuminating for 120 min. The reaction is nearly complete after MB illumination for about 80min, and the reaction is nearly complete after PR illumination for about 50min, so that the data of 0-80min and 0-50min are respectively selected for drawing 5, the degradation rate of the catalyst for catalyzing the MB reaction for about 80min reaches 97%, and the degradation rate of the catalyst for catalyzing the PR reaction for about 50min reaches 96%.
Fig. 6 is a graph of the results of three cycles of the two dyes degraded by the catalyst, and it can be seen from the graph that the degradation rate of three cycles is not changed much, and the repeatability of the catalyst in photocatalytic degradation of the dyes is better.
The synthesis method adopted by the invention is green and environment-friendly, has mild reaction process, simple production process, cheap raw materials and high yield, is suitable for large-scale production, and can be used for treating dye wastewater containing MB and PR.
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (7)
1. An organic calcium phosphonate coordination polymer characterized by: the chemical formula of the calcium coordination polymer is [ Ca2(hedp)H2O]nWherein n is a positive integer, hedp is hydroxyethylidene diphosphonate ion, and the molecular structure of the calcium coordination polymer is as follows:
2. the calcium organophosphate coordination polymer according to claim 1, characterized in that: the calcium coordination polymer is monoclinic system, P21Crystal of/c space groupThe cell parameters are:
α＝90°，β＝109.543(4)°，γ＝90°。
3. a method for preparing the organic calcium phosphonate coordination polymer of claim 1, wherein: dissolving a hydroxy ethylidene diphosphonic acid ligand and a calcium salt in water, uniformly mixing, adjusting the pH value to 3-5, reacting for 24-36 hours at 120-160 ℃ under a closed condition, and then cooling to room temperature to obtain the calcium coordination polymer monocrystal.
4. The method for preparing the organic calcium phosphonate coordination polymer according to claim 3, wherein: the calcium salt is calcium chloride or calcium nitrate.
5. The method for preparing the organic calcium phosphonate coordination polymer according to claim 3, wherein: the molar ratio of the ligand, the calcium salt and the water is (0.3-0.5): 1: (2000-4000).
6. Use of the calcium organophosphate coordination polymer of claim 1 to photocatalytically degrade dyes.
7. Use according to claim 6, characterized in that: the dye is methylene blue or basic fuchsin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105646185A (en) * | 2016-01-12 | 2016-06-08 | 中国石油大学(华东) | Calcium metal-organic coordination polymer and preparation method thereof |
| CN110218333A (en) * | 2019-06-24 | 2019-09-10 | 江苏理工学院 | A kind of pyridine methylene phosphonic acids nickel coordination polymer and its preparation method and application |
| CN110229346A (en) * | 2019-06-13 | 2019-09-13 | 江苏理工学院 | A kind of strontium coordination polymer and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646185A (en) * | 2016-01-12 | 2016-06-08 | 中国石油大学(华东) | Calcium metal-organic coordination polymer and preparation method thereof |
| CN110229346A (en) * | 2019-06-13 | 2019-09-13 | 江苏理工学院 | A kind of strontium coordination polymer and its preparation method and application |
| CN110218333A (en) * | 2019-06-24 | 2019-09-10 | 江苏理工学院 | A kind of pyridine methylene phosphonic acids nickel coordination polymer and its preparation method and application |
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| I. CUKROWSKI等: "Modeling and spectroscopic studies of bisphosphonate–bone interactions.", 《BONE》 * |
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