阅读说明：本技术 一维镝聚合物及其制备方法 (One-dimensional dysprosium polymer and preparation method thereof ) 是由 邹华红 全汉柏 梁福沛 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种一维镝聚合物及其制备方法。所述的一维镝聚合物的分子式为：[C<Sub>6</Sub>H<Sub>10</Sub>O<Sub>11</Sub>Dy·2(H<Sub>2</Sub>O)]<Sub>n</Sub>,n为整数且n≥1；该镝聚合物属于单斜晶系,P2<Sub>1</Sub>/n空间群。所述镝聚合物的制备方法为：将六水合硝酸镝、樟脑酸或吡啶-2,6-二甲酸溶于水中,所得混合液置于敞口容器中,插入阳极和阴极,通电电解,电解结束后对所得物料过滤,收集滤液,于加热或不加热条件下反应,反应物静置,有晶体析出,收集晶体,即得；其中,阳极和阴极均采用石墨电极。本发明所述方法制备方法简单易控、安全、反应条件温和、成本低廉而且重复性好。(The invention discloses a one-dimensional dysprosium polymer and a preparation method thereof. The molecular formula of the one-dimensional dysprosium polymer is as follows: [ C ] 6 H 10 O 11 Dy·2(H 2 O)] n N is an integer and n is not less than 1; the dysprosium polymer belongs to a monoclinic system, P2 1 A/n space group. The preparation method of the dysprosium polymer comprises the following steps: dissolving dysprosium nitrate hexahydrate, camphoric acid or pyridine-2, 6-dicarboxylic acid in water, placing the obtained mixed solution in an open container, inserting an anode and a cathode, electrifying and electrolyzing, filtering the obtained material after electrolysis, collecting filtrate, reacting under heating or non-heating conditions, standing the reactant, separating out crystals, and collecting the crystals to obtain the compound; wherein, the anode and the cathode both adopt graphite electrodes. The preparation method of the invention has the advantages of simplicity, easy control, safety, mild reaction conditions, low cost and good repeatability.)

1. A one-dimensional dysprosium polymer characterized by:

the molecular formula of the one-dimensional dysprosium polymer is as follows: [ C ]₆H₁₀O₁₁Dy·2(H₂O)]_nN is an integer and n is not less than 1;

the one-dimensional dysprosium polymer belongs to a monoclinic system, P2₁The/n space group, the unit cell parameters are:

2. the method for preparing a one-dimensional dysprosium polymer according to claim 1, characterized in that: dissolving dysprosium nitrate hexahydrate, camphoric acid or pyridine-2, 6-dicarboxylic acid in water, placing the obtained mixed solution in an open container, inserting an anode and a cathode, electrifying and electrolyzing, filtering the obtained material after electrolysis, collecting filtrate, reacting under heating or non-heating conditions, standing the reactant, separating out crystals, and collecting the crystals to obtain the compound; wherein, the anode and the cathode both adopt graphite electrodes.

3. The method of claim 2, wherein: when the reaction is carried out under heating condition, the reaction temperature is less than or equal to 80 ℃.

4. The production method according to claim 3, characterized in that: the reaction is carried out at 50-65 ℃.

5. The production method according to any one of claims 2 to 4, characterized in that: the time of electrifying and electrolyzing is more than or equal to 5 hours.

6. The production method according to any one of claims 2 to 4, characterized in that: during the electrolysis by energization, the energization is stopped when the graphite electrode as the anode is stripped of the substance.

Technical Field

The invention relates to a one-dimensional dysprosium polymer and a preparation method thereof, belonging to the technical field of materials.

Background

Mellitic acid (also known as 1,2,3,4,5, 6-mellitic acid or mellitic acid) contains abundant carboxyl functional groups, has strong coordination capacity, can be used as a ligand of a metal complex, particularly an actinide complex of the metal complex, and has good fluorescence performance. However, mellitic acid salt in nature is usually present in the beeswax, and is a rare and precious organic mineral, which is very expensive, and the price is 300-And g, resulting in greater limitations in the use of the carboxylic acid ligand. In the prior art, graphite oxide and fuming nitric acid are also used for carrying out a co-thermal reaction to generate mellitic acid, but the product obtained by the method has a lot of impurities and is difficult to purify, and NO is generated₂And the like, are easy to explode and pollute the air.

The prior actinide complex using mellitic acid as ligand is usually prepared by directly reacting mellitic acid with corresponding metal salt to generate a target compound, but the method has the defects of high cost, difficult purification and the like caused by obtaining mellitic acid, and has the defects of low reaction condition because the temperature is usually above 120 ℃ during direct reaction. At present, no relevant report that mellitic acid obtained by electrolyzing camphoric acid or pyridine-2, 6-dicarboxylic acid by using a graphite electrode reacts with metal salt under mild conditions to obtain a dysprosium mellitic acid complex is found.

Disclosure of Invention

The invention aims to solve the technical problem of the prior art and provides a one-dimensional dysprosium polymer with a novel structure and a preparation method thereof.

The molecular formula of the one-dimensional dysprosium polymer is as follows: [ C ]₆H₁₀O₁₁Dy·2(H₂O)]_nN is an integer and n is not less than 1; the one-dimensional dysprosium polymer belongs to a monoclinic system, P2₁The/n space group, the unit cell parameters are:

α＝90.00°,β＝100.397(2)°,γ＝90.00°。

the repeating unit of the one-dimensional dysprosium polymer is a mononuclear dysprosium complex with the molecular formula of C₆H₁₄DyO₁₃Molecular weight is 456.67, and the ligand is 1,2,3,4,5, 6-mellitic acid.

The invention also provides a preparation method of the one-dimensional dysprosium polymer, which comprises the following steps: dissolving dysprosium nitrate hexahydrate, camphoric acid or pyridine-2, 6-dicarboxylic acid in water, placing the obtained mixed solution in an open container, inserting an anode and a cathode, electrifying and electrolyzing, filtering the obtained material after electrolysis, collecting filtrate, reacting under heating or non-heating conditions, standing the reactant, separating out crystals, and collecting the crystals to obtain the compound; wherein, the anode and the cathode both adopt graphite electrodes.

In the preparation method, the molar ratio of the dysprosium nitrate hexahydrate to the camphoric acid or the pyridine-2, 6-dicarboxylic acid is a stoichiometric ratio, specifically 2: 1. in actual practice, dysprosium nitrate hexahydrate may be in relative excess.

In the above preparation method, the amount of water is preferably such that most of the camphoric acid is dissolved but slightly precipitated. Specifically, the amount of water used for the whole raw materials participating in the reaction is usually 15 to 20mL based on 0.5mmol of camphoric acid or pyridine-2, 6-dicarboxylic acid. In the specific dissolving step, dysprosium nitrate hexahydrate and camphorate or pyridine-2, 6-dicarboxylic acid are mixed and then dissolved in distilled water, or the dysprosium nitrate hexahydrate can be added after the camphorate or the pyridine-2, 6-dicarboxylic acid is dissolved in water and stirred for a plurality of minutes.

In the preparation method, the graphite electrode is a commercial electrode, and further processing is not needed before use. The power supply for electrolysis is a direct current power supply, and is usually between 5 and 20V. The period of the electrolysis is preferably at least 5 hours or more, and it is preferable to stop the electrolysis when there is a substance falling off from the graphite electrode as the anode during the electrolysis, and the period of time required for this is generally 18 to 24 hours.

In the above production method, the time required for obtaining the target product when the reaction is carried out without heating is longer than that under heating, and it usually takes 7 to 15 days. When the reaction is carried out under heating conditions, it is preferable to control the reaction at a temperature of 80 ℃ or less, preferably 50 to 65 ℃, and the time of the reaction under the preferable conditions is usually controlled to 18 to 24 hours.

Compared with the prior art, the one-dimensional dysprosium polymer with a novel structure is obtained in a mild environment (the reaction temperature is less than or equal to 80 ℃) by taking the cheap camphoric acid or the pyridine-2, 6-dicarboxylic acid as the raw material, and compared with the prior method of directly taking the mellitic acid as the ligand and synthesizing the dysprosium complex at the temperature of more than 120 ℃, the preparation method is simple, easy to control, safe, mild in reaction condition, low in cost and good in repeatability.

Drawings

FIG. 1 shows [ C ] obtained in example 1 of the present invention₆H₁₀O₁₁Dy·2(H₂O)]_nThe metal coordination environment diagram of (1);

FIG. 2 shows [ C ] obtained in example 1 of the present invention₆H₁₀O₁₁Dy·2(H₂O)]_nThe ligand coordination environment diagram of (1);

FIG. 3 shows [ C ] obtained in example 1 of the present invention₆H₁₀O₁₁Dy·2(H₂O)]_nA one-dimensional structure diagram.

Detailed Description

The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.