CN109232918B - Supramolecular coordination polymer metallogel based on oxydiacetic acid and azide and preparation method thereof - Google Patents
Supramolecular coordination polymer metallogel based on oxydiacetic acid and azide and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种基于氧二乙酸和叠氮酸根的超分子配位聚合物金属凝胶及其制备方法，属于凝胶纳米材料领域，所述金属凝胶以氧二乙酸和叠氮酸根为原料，将其溶入DMF/H2O混合溶剂中；再在加热搅拌下，加入钴盐，得紫红色溶液；调节所述紫红色溶液的pH=5~6，继续加热搅拌，回流得反应液Ⅰ；加入可溶性稀土盐，继续加热搅拌，回流得反应液Ⅱ；趁热过滤，得澄清滤液；将所得滤液密封静置，得所述凝胶。本发明采用上述方法制备出一种超分子d‑f双金属配位聚合物金属凝胶；所用原料简单易得，工艺流程简单易控，便于工业化生产；性能优良，是较理想的软物质纳米材料。
The invention relates to a supramolecular coordination polymer metal gel based on oxydiacetic acid and azide and a preparation method thereof, and belongs to the field of gel nanomaterials. The metal gel uses oxydiacetic acid and azide as raw materials , dissolve it into the DMF/H 2 O mixed solvent; then add cobalt salt under heating and stirring to obtain a purple-red solution; adjust the pH of the purple-red solution=5~6, continue heating and stirring, and reflux to obtain a reaction solution Ⅰ; add soluble rare earth salt, continue to heat and stir, and reflux to obtain reaction solution Ⅱ; filter while hot to obtain clear filtrate; seal the obtained filtrate and stand to obtain the gel. The invention adopts the above method to prepare a supramolecular d-f bimetallic coordination polymer metal gel; the raw materials used are simple and easy to obtain, the technological process is simple and easy to control, and the industrial production is convenient; the performance is excellent, and it is an ideal soft matter nanometer Material.
Description
Technical Field
The invention belongs to the technical field of supermolecule gel soft matter nano materials, and particularly relates to supermolecule coordination polymer metal gel based on oxyacetic acid and azide acid radicals and a preparation method thereof.
Background
In recent years, supermolecule gel has gained wide attention of researchers at home and abroad as an intelligent/functional soft substance nano material with wide application prospect, and has gained encouraging results. In a supramolecular gel system, the supramolecular coordination polymer metal gel has attracted great interest of researchers due to unique gelation modes, chemical stimulation response mechanisms, new performances of light, electricity, magnetism, catalysis, oxidation reduction and the like. However, due to the complexity of the gelation mechanism of the supramolecular coordination polymer metal gel, the selection limitation of raw materials and the uncontrollable property of the gelation process, the research and the application of the supramolecular coordination polymer metal gel are greatly limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a supermolecular coordination polymer metal gel based on oxodiacetic acid and azide acid radicals and a preparation method thereof.
In order to achieve the purpose, the invention adopts the specific scheme that:
a preparation method of supermolecular coordination polymer metal gel based on oxygen diacetic acid and azide radical comprises the following steps:
step one, respectively weighing 6-8 parts of oxydiethanoic acid and 0.3-0.4 part of azide acid salt according to the parts by weight, and sequentially adding 6-8 parts of DMF/H2Glass container of O mixed solventStirring in a container until the mixture is dissolved to obtain a mixed solution;
step two, weighing 8-10 parts of cobalt salt according to the parts by weight, and adding the cobalt salt into the mixed solution obtained in the step one under the condition of heating and stirring to obtain a mauve solution;
step three, weighing sodium hydroxide or potassium hydroxide, and dissolving the sodium hydroxide or potassium hydroxide in DMF/H2Preparing alkali liquor from the O mixed solvent;
step four, under the heating and stirring conditions, adjusting the pH = 5-6 of the mauve solution obtained in the step two by using the alkali liquor prepared in the step three, continuing heating and stirring, and refluxing for 15-20 minutes to obtain a reaction solution I;
step five, weighing 1-2 parts of soluble rare earth salt according to the parts by weight, adding the soluble rare earth salt into the reaction liquid I obtained in the step four, continuously heating and stirring, and refluxing for 20-25 minutes to obtain a reaction liquid II; after the reflux is finished, quickly filtering the reaction solution II while the reaction solution is hot to obtain clear filtrate;
and step six, standing the clear filtrate obtained in the step five for 2-3 days in a sealed state to obtain the supermolecule coordination polymer metal gel.
In the above step, the DMF/H2DMF and H in O mixed solvent2The volume ratio of O is 1: 0.5-1: 1.
As a further optimization of the scheme, the concentration of the alkali liquor in the third step is 5mol.L-1。
As a further optimization of the above solution, the cobalt salt in step two includes, but is not limited to, any one of cobalt acetate, cobalt chloride or cobalt nitrate.
As a further optimization of the above scheme, in step five, the soluble rare earth salt is europium salt, dysprosium salt, ytterbium salt or holmium salt.
As a further optimization of the above solution: the soluble rare earth salts include, but are not limited to, rare earth chlorides, rare earth nitrates, or rare earth acetates.
As a further optimization of the scheme, the heating temperature of the heating and stirring is 60-80 ℃.
The invention further protects the supermolecular coordination polymer metal gel prepared by the preparation method.
The invention also protects the application of the supermolecule coordination polymer metal gel in the research of soft substance nano materials.
Has the advantages that:
the invention provides a supermolecule d-f bimetal coordination polymer metal gel and a preparation method thereof, wherein the supermolecule d-f bimetal coordination polymer metal gel is prepared by a one-pot method; the raw materials are simple and easy to obtain, the process flow is simple and easy to control, and the industrial production is facilitated; the supermolecule coordination polymer metal gel prepared by the invention is pure and transparent, has good chemical stimulation response and optical and magnetic properties, and is an ideal soft substance nano material.
Drawings
FIG. 1 is a comparative diagram of beaker inversion of supramolecular coordination polymer metal gels prepared separately in examples 1-4; wherein, a refers to example 1; b refers to example 2; c refers to example 3; d refers to example 4;
FIG. 2 is an infrared spectrum of the supramolecular coordination polymer metal gel prepared in example 1;
FIG. 3 is an infrared spectrum of the supramolecular coordination polymer metal gel prepared in example 2;
FIG. 4 is an infrared spectrum of the supramolecular coordination polymer metal gel prepared in example 3;
FIG. 5 is an infrared spectrum of the supramolecular coordination polymer metal gel prepared in example 4.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
A supermolecule coordination polymer metal gel based on oxygen diacetic acid and azide acid radicals and a preparation method thereof comprise the following steps:
step one, respectively weighing the oxygen diacetic acid and the azide, and sequentially adding the oxygen diacetic acid and the azide into DMF/H2Stirring and dissolving the O mixed solvent in a glass container to obtain a mixed solution;
step two, weighing a certain amount of cobalt salt under heating and stirring, and adding the cobalt salt into the mixed solution obtained in the step one to obtain a mauve solution;
step three, weighing a certain amount of sodium hydroxide or potassium hydroxide, and dissolving the sodium hydroxide or potassium hydroxide in DMF/H2Preparing 5mol of O mixed solvent.L-1Alkali liquor of (4);
step four, under heating and stirring, adjusting the pH value of the mauve solution obtained in the step two by using the alkali liquor prepared in the step three to ensure that the pH value is = 5-6, continuing heating and stirring, and refluxing for minutes to obtain a reaction solution I;
step five, weighing a certain amount of soluble rare earth salt, adding the soluble rare earth salt into the reaction liquid I obtained in the step four, continuously heating and stirring, and refluxing for 20-25 minutes to obtain a reaction liquid II;
sixthly, filtering the reaction solution II into a beaker while the reaction solution II is hot to obtain clear filtrate;
and step seven, covering the opening of the beaker filled with the filtrate obtained in the step six with a preservative film, and standing for 2-3 days to obtain pink transparent gel.
The DMF mentioned above is dimethylformamide;
in the above step, the DMF/H2DMF and H in O mixed solvent2The volume ratio of O is 1: 0.5-1: 1;
in the preparation steps, the oxygen diacetic acid, the azide salt, the cobalt salt and the soluble rare earth salt are added in sequence; weighing 6-8 parts of oxydiacetic acid and 0.3-0.4 part of azide acid salt in the step one according to the mass parts, and respectively and sequentially adding the oxydiacetic acid and the azide acid salt into 6-8 parts of DMF/H2O mixed solvent; 8-10 parts of cobalt salt and 1-2 parts of soluble rare earth salt; wherein the cobalt salt is cobalt acetate, cobalt chloride or cobalt nitrate; the soluble rare earth salt is chloride, nitrate or acetate of rare earth metals europium, dysprosium, ytterbium or holmium.
Example 1
A supermolecule coordination polymer metal gel based on oxygen diacetic acid and azide acid radicals and a preparation method thereof comprise the following steps:
step one, respectively weighing 0.67g of oxydiethanoic acid and 0.038g of sodium azide, and putting the oxydiethanoic acid and the sodium azide into a container containing 6mL of DMF/H2Stirring and dissolving the O mixed solvent in a flask to obtain a mixed solution;
step two, weighing 0.89g of cobalt acetate under the heating of water bath at the temperature of 80 ℃, adding the cobalt acetate into the mixed solution obtained in the step one, and stirring to obtain a purple red reactant solution;
step three, weighing 0.06g of sodium hydroxide, and dissolving the sodium hydroxide in DMF/H2In O mixed solvent, the concentration is 5mol.L-1Sodium hydroxide solution of (a);
step four, under heating and stirring, adjusting the pH value of the reactant solution in the step two by using the sodium hydroxide solution in the step three to enable the pH value to be =5, continuing heating and stirring, and refluxing for 15 minutes to obtain a reaction solution I;
step five, weighing 0.175g of europium acetate, adding the europium acetate into the reaction liquid I obtained in the step four, continuously heating and stirring, and refluxing for 25 minutes to obtain a reaction liquid II;
sixthly, taking down the flask, and filtering the reaction solution II into a small beaker while the reaction solution is hot to obtain pink clear filtrate;
and step seven, covering the opening of the beaker filled with the filtrate obtained in the step six with a preservative film, and standing for 3 days to obtain pink transparent gel (see figure 1 a).
In the above step, the DMF/H2DMF and H in O mixed solvent2The volume ratio of O is 1: 0.5.
Example 2
A supermolecule coordination polymer metal gel based on oxygen diacetic acid and azide acid radicals and a preparation method thereof comprise the following steps:
step one, respectively weighing 0.67g of oxydiethanoic acid and 0.038g of sodium azide, and putting the oxydiethanoic acid and the sodium azide into a container containing 7mL of DMF/H2Stirring and dissolving the O mixed solvent in a round-bottom flask to obtain a mixed solution;
step two, weighing 0.89g of cobalt acetate under the heating of water bath at the temperature of 80 ℃, adding the cobalt acetate into the mixed solution obtained in the step one, and stirring to obtain a purple red reactant solution;
step three, weighing 0.056g of potassium hydroxide, and dissolving the potassium hydroxide in DMF/H2In O mixed solvent, the concentration is 5mol.L-1Potassium hydroxide solution of (a);
step four, under heating and stirring, regulating the pH value of the reactant solution obtained in the step two by using the potassium hydroxide solution obtained in the step three to enable the pH value to be =6, continuing heating and stirring, and refluxing for 15 minutes to obtain a reaction solution I;
step five, weighing 0.19g of dysprosium chloride, adding the dysprosium chloride into the reaction liquid I obtained in the step four, continuously heating and stirring, and refluxing for 25 minutes to obtain a reaction liquid II;
sixthly, taking down the flask, and filtering the reaction solution II into a small beaker while the reaction solution is hot to obtain pink clear filtrate;
and step seven, covering the beaker containing the filtrate obtained in the step six with a preservative film, and standing for 2 days to obtain pink transparent gel (see figure 1 b).
In the above step, the DMF/H2DMF and H in O mixed solvent2The volume ratio of O is 1: 0.5.
Example 3
A supermolecule coordination polymer metal gel based on oxygen diacetic acid and azide acid radicals and a preparation method thereof comprise the following steps:
step one, respectively weighing 0.67g of oxydiethanoic acid and 0.038g of sodium azide, and putting the oxydiethanoic acid and the sodium azide into a container containing 8mL of DMF/H2Stirring and dissolving the O mixed solvent in a round-bottom flask to obtain a mixed solution;
step two, weighing 0.89g of cobalt acetate under the condition of heating and stirring in a water bath at the temperature of 80 ℃, and adding the cobalt acetate into the mixed solution obtained in the step one to obtain a mauve reactant solution;
step three, weighing 0.06g of sodium hydroxide, and dissolving the sodium hydroxide in DMF/H2In O mixed solvent, the concentration is 5mol.L-1Sodium hydroxide solution of (a);
step four, under heating and stirring, adjusting the pH value of the reactant solution obtained in the step two by using the sodium hydroxide solution obtained in the step three to enable the pH value to be =6, continuing heating and stirring, and refluxing for 20 minutes to obtain a reaction solution I;
step five, weighing 0.18g of ytterbium acetate, adding the ytterbium acetate into the reaction liquid I obtained in the step four, continuously heating and stirring, and refluxing for 25 minutes to obtain a reaction liquid II;
sixthly, taking down the flask, and filtering the reaction solution II into the beaker while the reaction solution is hot to obtain pink clear filtrate;
and step seven, covering the opening of the beaker filled with the filtrate obtained in the step six with a preservative film, and standing for 3 days to obtain pink transparent gel (see figure 1 c).
In the above step, the DMF/H2DMF and H in O mixed solvent2The volume ratio of O is 1: 1.
Example 4
A supermolecule coordination polymer metal gel based on oxygen diacetic acid and azide acid radicals and a preparation method thereof comprise the following steps:
step one, respectively weighing 0.67g of oxydiethanoic acid and 0.038g of sodium azide, and putting the oxydiethanoic acid and the sodium azide into a container containing 8mL of DMF/H2Stirring and dissolving the O mixed solvent in a round-bottom flask to obtain a mixed solution;
step two, weighing 0.89g of cobalt acetate under the condition of heating and stirring in a water bath at 70 ℃, and adding the cobalt acetate into the mixed solution obtained in the step one to obtain a mauve reactant solution;
step three, weighing 0.06g of sodium hydroxide, and dissolving the sodium hydroxide in DMF/H2In O mixed solvent, the concentration is 5mol.L-1Sodium hydroxide solution of (a);
step four, under heating and stirring, adjusting the pH value of the reactant solution obtained in the step two by using the sodium hydroxide solution obtained in the step three to enable the pH value to be =6, continuing heating and stirring, and refluxing for 20 minutes to obtain a reaction solution I;
step five, weighing 0.16g of holmium nitrate, adding the holmium nitrate into the reaction liquid I obtained in the step four, continuously heating and stirring, and refluxing for 25 minutes to obtain a reaction liquid II;
sixthly, taking down the flask, and filtering the reaction solution II into the beaker while the reaction solution is hot to obtain a light pink clear filtrate;
and step seven, covering the opening of the beaker filled with the filtrate obtained in the step six with a preservative film, and standing for 2 days to obtain light pink transparent gel (see figure 1 d).
In the above step, the DMF/H2DMF and H in O mixed solvent2The volume ratio of O is 1: 0.5.
In the preparation method of the embodiments 1-4 of the present invention, the oxygen diacetic acid and the azide are used as raw materials, and the cobalt salt and the rare earth salt are added at different stages during the preparation, so as to prepare the supermolecule d-f bimetal coordination polymer metal gel, because the rare earth ions and the transition metal ions have respective unique coordination characteristics, especially because the rare earth ions have the characteristics of the electronic shell layer thereof, the rare earth ions have high coordination numbers and flexible and changeable coordination modes, so that the structure of the formed coordination compound is also rich and varied, and the supermolecule coordination polymer metal gel has wide application prospects in many aspects such as light, electricity, magnetism, etc.
The macroscopic results of the metal gels prepared in examples 1 to 4 are that the whole system loses fluidity, and the gels will not collapse or be damaged even if the beaker containing the gel is inverted, as shown in fig. 1, mainly because various physical or chemical effects are assembled inside the gel to form rigorous and variously sized nanostructures during the preparation process, and it is these nanostructures which make the system lose fluidity. In addition, the present invention further performed infrared spectroscopy analysis on the supramolecular coordination polymer metal gel prepared in examples 1 to 4, and the infrared spectrum is shown in fig. 2 to 5. The metal gels prepared in the embodiments 1 to 4 have small structural difference and excellent performances in all aspects, and are relatively ideal soft matter nano materials.
It should be noted that the above-mentioned embodiments are only preferred examples of the present invention under experimental conditions, and are not intended to limit the present invention, and the present invention may be variously modified and changed. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of supermolecular coordination polymer metal gel based on oxodiacetic acid and azide radical is characterized in that: the method comprises the following steps:
step one, respectively weighing 6-8 parts of oxydiethanoic acid and 0.3-0.4 part of azide acid salt according to the parts by weight, and sequentially adding 6-8 parts of DMF/H2Stirring the O mixed solvent in a glass container until the O mixed solvent is dissolved to obtain a mixed solution;
step two, weighing 8-10 parts of cobalt salt according to the parts by weight, and adding the cobalt salt into the mixed solution obtained in the step one under the condition of heating and stirring to obtain a mauve solution;
step three, weighing sodium hydroxide or potassium hydroxide, and dissolving the sodium hydroxide or potassium hydroxide in DMF/H2Preparing alkali liquor from the O mixed solvent;
step four, under the heating and stirring conditions, adjusting the pH = 5-6 of the mauve solution obtained in the step two by using the alkali liquor prepared in the step three, continuing heating and stirring, and refluxing for 15-20 minutes to obtain a reaction solution I;
step five, weighing 1-2 parts of soluble rare earth salt according to the parts by weight, adding the soluble rare earth salt into the reaction liquid I obtained in the step four, continuously heating and stirring, and refluxing for 20-25 minutes to obtain a reaction liquid II; after the reflux is finished, quickly filtering the reaction solution II while the reaction solution is hot to obtain clear filtrate;
step six, standing the clear filtrate obtained in the step five for 2-3 days in a sealed state to obtain supermolecular coordination polymer metal gel;
in the above step, the DMF/H2DMF and H in O mixed solvent2The volume ratio of O is 1: 0.5-1: 1.
2. The method for preparing the supramolecular coordination polymer metal gel based on the oxodiacetic acid and the azide radical as claimed in claim 1, wherein the method comprises the following steps: the concentration of the alkali liquor in the third step is 5mol.L-1。
3. The method for preparing the supramolecular coordination polymer metal gel based on the oxodiacetic acid and the azide radical as claimed in claim 1, wherein the method comprises the following steps: and the cobalt salt in the second step is any one of cobalt acetate, cobalt chloride or cobalt nitrate.
4. The method for preparing the supramolecular coordination polymer metal gel based on the oxodiacetic acid and the azide radical as claimed in claim 1, wherein the method comprises the following steps: and fifthly, the soluble rare earth salt is europium salt, dysprosium salt, ytterbium salt or holmium salt.
5. The method of claim 4, wherein the preparation method of the supramolecular coordination polymer metal gel based on the oxodiacetic acid and the azide radical is as follows: the soluble rare earth salt is rare earth chloride, rare earth nitrate or rare earth acetate.
6. The method for preparing the supramolecular coordination polymer metal gel based on the oxodiacetic acid and the azide radical as claimed in claim 1, wherein the method comprises the following steps: the heating temperature of the heating and stirring is 60-80 ℃.
7. The supramolecular coordination polymer metal gel prepared by the preparation method of any one of claims 1 to 6.
8. Use of the supramolecular coordination polymer metal gel as claimed in claim 7 in the study of soft-matter nanomaterials.
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