WO2023108809A1 - 一种高效绿色的二价铕化合物的制备方法 - Google Patents

一种高效绿色的二价铕化合物的制备方法 Download PDF

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WO2023108809A1
WO2023108809A1 PCT/CN2021/141534 CN2021141534W WO2023108809A1 WO 2023108809 A1 WO2023108809 A1 WO 2023108809A1 CN 2021141534 W CN2021141534 W CN 2021141534W WO 2023108809 A1 WO2023108809 A1 WO 2023108809A1
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divalent europium
europium compound
preparation
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王殳凹
张明星
陈俊畅
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Suzhou University
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    • B01J19/085—Electron beams only
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    • C01F17/00—Compounds of rare earth metals
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    • C01—INORGANIC CHEMISTRY
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    • C01F17/00—Compounds of rare earth metals
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  • the invention relates to the technical field of rare earth europium, in particular to a preparation method of an efficient green divalent europium compound.
  • europium compounds are widely used in the fields of optical and magnetic functional materials, and their synthesis, structural characterization and performance research have always attracted the attention of chemistry and materials researchers.
  • the common valence state of rare earth element ions is +3, while the outer electron structure of element europium is 4f 7 6s 2 , indicating that the valence of europium ions also has a +2 valence in addition to the normal +3 valence.
  • many pure trivalent europium compounds and compounds doped with a small amount of divalent europium have been synthesized and reported, but there are relatively few studies on pure divalent europium compounds.
  • divalent europium compounds Compared with trivalent europium compounds, divalent europium compounds have more advantages in fluorescent and magnetic semiconductor materials. Since the standard redox potential between divalent and trivalent europium (E 0 Eu(III)/Eu(II) ) is -0.35V, which is relatively low, divalent europium compounds are easily oxidized by oxygen in the air or Oxidation of hydrogen ions in aqueous solution. Therefore, stable divalent europium compounds are difficult to synthesize.
  • the reported methods for synthesizing divalent europium compounds are mainly conventional chemical methods, including high temperature and high pressure reduction method, reducing agent reduction method and electrochemical reduction method.
  • the high-temperature and high-pressure reduction method mainly generates reducing species in situ by decomposing other compounds in a high-temperature and high-pressure environment, and reduces trivalent europium to divalent europium to prepare divalent europium compounds. risk, and have high requirements for the reaction device.
  • the reducing agent reduction method is to convert trivalent europium into divalent europium by additionally adding a certain amount of reducing agent to the reaction system to synthesize divalent europium compounds.
  • Commonly used reducing agents include zinc powder, zinc amalgam and sodium amalgam, etc. These reducing agents are dangerous to operate, toxic and harmful, and the subsequent treatment process is cumbersome.
  • the electrochemical reduction method is to generate active electrons on the electrode surface by applying an external voltage, so that the trivalent europium can be reduced to divalent europium by electrons, and the divalent europium compound can be obtained. High, it is difficult to achieve large-scale industrial production. Therefore, there is still an urgent need for an efficient, green and extremely low-cost method for preparing divalent europium compounds.
  • the present invention provides a method for preparing an efficient green divalent europium compound.
  • An object of the present invention is to provide a method for preparing a divalent europium compound, comprising the following steps: performing ionizing radiation on an organic solution of a trivalent europium compound under a protective atmosphere to obtain the divalent europium compound.
  • the organic solvent in the organic solution of the trivalent europium compound is ethanol.
  • Divalent europium is insoluble in ethanol and can be precipitated after reaction, which is safe and green.
  • the trivalent europium compound is one or more of europium trichloride, europium nitrate and europium acetate.
  • the radiation source of the ionizing radiation is one or more of electron beams, gamma rays and X-rays.
  • the irradiation dose of ionizing radiation is 10-1000 kGy; the irradiation time of ionizing radiation is 27 minutes-17 hours.
  • the gas in the protective atmosphere is nitrogen and/or argon.
  • it also includes washing and drying the crystalline compound produced after irradiation to obtain the divalent europium compound.
  • the washing is 2-3 times with ethanol.
  • the drying temperature is 50-70°C.
  • the drying time is 30-60 minutes.
  • the preparation method described in the present invention is a brand-new preparation method proposed on the basis of radiation synthesis chemistry.
  • the material Under the reasonable control of the reaction system, the material is excited, ionized, etc. under the irradiation of high-energy rays, resulting in a large amount of Reductive active species to realize efficient green conversion of trivalent europium compounds into divalent europium compounds.
  • From the perspective of energy supply, using radiant energy to replace traditional thermal energy is a simple and extremely low-cost way.
  • the invention can reduce or avoid the disadvantages of the prior art, and realize the high-efficiency, green and extremely low-cost synthesis of divalent europium compounds.
  • the preparation method of the present invention can efficiently and greenly synthesize divalent europium compounds.
  • the divalent europium compound can be synthesized at room temperature and normal pressure, avoiding high-temperature and high-pressure systems, and reducing the requirements for reaction equipment; the synthesis cycle is greatly shortened to within 30 minutes; the solvent used in the synthesis process of this method is non-toxic, environmentally friendly, and low in price.
  • the method can be recycled to reduce production cost and waste discharge; the method can completely convert the starting material into the target product, reaching a conversion rate of 100%.
  • the technical means required by the preparation method of the present invention are simple, and it is a high-efficiency, green and extremely low-cost synthesis method. Under the irradiation of high-energy rays, divalent europium compounds can be rapidly synthesized at room temperature and normal pressure, and the risk factor in the synthesis process is low, and the high-energy rays can realize continuous operation, which is suitable for industrial batch production.
  • FIG. 1 is a crystal structure diagram of Eu(H 2 O)Cl 2 prepared in Example 1 of the present invention.
  • Fig. 2 is a powder diffraction pattern of Eu(H 2 O)Cl 2 prepared in Example 1 of the present invention.
  • Fig. 3 is an ultraviolet-visible light absorption spectrum diagram of Eu(H 2 O)Cl 2 prepared in Example 1 of the present invention.
  • Fig. 4 is a fluorescence emission spectrum of Eu(H 2 O)Cl 2 prepared in Example 1 of the present invention.
  • Figure 5 is a schematic diagram of the compounds of the examples of the present invention.
  • each Eu atom is connected to 7 Cl atoms and 1 H 2 O
  • each Cl atom is connected to 2 Eu atoms
  • each H 2 O connects two Eu atoms to form a three-dimensional ordered structure, and the most simplified chemical structure after analysis is Eu(H 2 O)Cl 2 .
  • the purity of the product is determined by a polycrystalline powder diffractometer, as shown in Figure 2, the experimentally measured powder diffraction pattern is consistent with the theoretically simulated powder diffraction pattern, indicating that the prepared product is of high purity.
  • the ultraviolet-visible light absorption properties and fluorescence emission properties of the product are studied by a solid-state spectrometer. As shown in Figure 3, the product has an ultraviolet-visible light absorption peak at 300-400nm, and the maximum absorption wavelength is 368nm; as shown in Figure 4, the product is in There is a fluorescence emission peak at 410-460nm, and the maximum emission wavelength is 427nm.
  • Electron beam irradiation the above-mentioned sealed EuCl 3 ethanol solution was irradiated under an electron accelerator, the absorbed dose was 1000 kGy, and the irradiation time was 27 minutes.
  • the crystalline compound produced after irradiation was washed three times with absolute ethanol, and the final solid product was dried in an oven at 60°C.
  • Figure 5 is a schematic diagram of the compounds of the examples of the present invention.
  • Eu(H 2 O)Cl 2 is obtained under the irradiation of high-energy rays in EuCl 3 ⁇ 6H 2 O.

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Abstract

一种二价铕化合物的制备方法。在保护气氛下，对三价铕化合物的有机溶液进行电离辐射，得到所述二价铕化合物。在高能射线照射下，二价铕化合物可在室温常压下快速合成，合成过程的风险系数低，且高能射线能够实现连续化操作，适合工业化批量生产。

Description

一种高效绿色的二价铕化合物的制备方法 技术领域
本发明涉及稀土铕技术领域，尤其涉及一种高效绿色的二价铕化合物的制备方法。
背景技术
铕化合物因其独特的荧光和磁性，在光学和磁性等功能材料领域具有广泛应用，其合成、结构表征和性能研究一直备受化学和材料研究学者关注。稀土元素离子的常见价态为+3价，而元素铕的外层电子结构为4f 76s 2，表明铕离子的化合价除了正常的+3价外，还存在+2价形式。目前，已合成并报道了许多具有特殊性能的纯的三价铕化合物和以微量二价铕掺杂的化合物，而对纯的二价铕化合物研究相对较少。相比于三价铕化合物，二价铕化合物在荧光和磁性半导体材料更具优势。由于二价和三价铕之间的标准氧化还原电势(E 0 Eu(III)/Eu(II))为-0.35V，相对较低，导致二价铕化合物易被空气中的氧气氧化或被水溶液中的氢离子氧化。因此，稳定的二价铕化合物很难合成。已报道的合成二价铕化合物的方法主要为常规的化学法，包括高温高压还原法、还原剂还原法和电化学还原法。高温高压还原法主要通过在高温高压环境下，通过分解其它化合物原位产生还原物种，将三价铕还原成二价铕，制备二价铕化合物，但反应过程需要高温高压密封体系，存在较高的风险，且对反应装置要求高。还原剂还原法是通过额外向反应体系加入一定量的还原剂，实现三价铕转化为二价铕，合成二价铕化合物。通常使用的还原剂有锌粉、锌汞齐和钠汞齐等，这些还原剂操作危险，有毒有害，且后续处理过程繁琐。电化学还原法是通过外加电压在电极表面产生活性电子，促使三价铕得到电子还原成二价铕，获得二价铕化合物，但整个过程对反应装置要求高，且生产能力弱，生产成本也高，很难实现规模化的工业生产。因此，高效绿色极低成本制备二价铕化合物的方法仍亟待需求。
与本发明相关的现有技术主要为常规化学法合成二价铕化合物，包括高温高压还原法、还原剂还原法和电化学还原法。常规化学法通常借助外界的苛刻条件，营造还原性体系，实现将三价铕化合物还原成二价铕化合物。然而，现有制备二价铕化合物的技术需要高温高压的密封体系，使用有毒有害的有机溶剂和还原剂，存在较高的风险，且生产能力弱，导致生产成本高，很难实现工业化批量生产。已报道的技术存在许多缺点，包括无水无氧体系、高温高压体系、有毒有害的反应溶剂和还原剂、弱的生产能力等，导致二价铕化合物的生产成本高、合成过程存在高风险和反应路径不环保等。
发明内容
为解决上述技术问题，本发明提供了一种高效绿色的二价铕化合物的制备方法。
本发明的一个目的是提供一种二价铕化合物的制备方法，包括如下步骤：保护气氛下，对三价铕化合物的有机溶液进行电离辐射，得到所述二价铕化合物。
在本发明的一个实施例中，所述三价铕化合物的有机溶液中的有机溶剂为乙醇。二价铕不溶于乙醇，反应后可以析出，安全绿色。
在本发明的一个实施例中，所述三价铕化合物为三氯化铕、硝酸铕和醋酸铕中的一种或多种。
在本发明的一个实施例中，所述电离辐射的辐射源为电子束、伽玛射线和X-射线中的一种或多种。
在本发明的一个实施例中，所述电离辐射的照射剂量为10-1000kGy；电离辐射的照射时间为27min-17h。
在本发明的一个实施例中，所述保护气氛中的气体为氮气和/或氩气。
在本发明的一个实施例中，还包括对照射后产生的结晶化合物进行洗涤、干燥，得到所述的二价铕化合物。
在本发明的一个实施例中，所述洗涤为用乙醇洗涤2-3次。
在本发明的一个实施例中，所述干燥的温度为50-70℃。
在本发明的一个实施例中，所述干燥的时间为30-60min。
本发明的技术方案相比现有技术具有以下优点：
(1)本发明所述的制备方法是建立在辐射合成化学的基础上提出的全新制备方法，在对反应体系的合理调控，物质在高能射线照射下，发生激发、电离等作用，产生大量的还原性活性物种，实现三价铕化合物高效绿色转化为二价铕化合物。从供能角度来说，利用辐射能代替传统的热能是一种简便的、成本极低的方式。本发明能够降低或规避现有技术存在的缺点，实现高效绿色极低成本地合成二价铕化合物。
(2)本发明所述的制备方法能够高效绿色地合成二价铕化合物。能够室温常压下合成二价铕化合物，避免高温高压系统，降低对反应设备的要求；合成周期大大缩短至30分钟以内；本方法合成过程中使用的溶剂无毒，绿色环保，价格低廉，可循环使用，从而降低生产成本，减少废物排放；本方法能够将起始物完全转化目标产物，达到100％的转化率。
(3)本发明所述的制备方法所需技术手段简单，是一种高效绿色极低成本的合成方法。在高能射线照射下，二价铕化合物可在室温常压下快速合成，合成过程中存在风险系数低，且高能射线能够实现连续化操作，适合工业化批量生产。
附图说明
为了使本发明的内容更容易被清楚地理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中：
图1为本发明实施例1制备的Eu(H 2O)Cl 2的晶体结构图。
图2为本发明实施例1制备的Eu(H 2O)Cl 2的粉末衍射图。
图3为本发明实施例1制备的Eu(H 2O)Cl 2的紫外-可见光吸收光谱图。
图4为本发明实施例1制备的Eu(H 2O)Cl 2荧光发射光谱图。
图5为本发明实施例的化合物的示意图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例1
伽玛射线辐射制备二价铕化合物(Eu(H 2O)Cl 2)，具体步骤如下：
(1)EuCl 3乙醇溶液的配制：称取0.2g的EuCl 3·6H 2O到20mL的玻璃瓶中，再加入5mL无水乙醇。将上述混合物超声3min左右，得到无色澄清的EuCl 3乙醇溶液。
(2)鼓入氮气：将所配制EuCl 3乙醇溶液鼓入氮气，鼓入氮气3min后密封，保证EuCl 3乙醇溶液处在氮气氛围下。
(3)伽玛射线照射：将上述密封好的EuCl 3乙醇溶液置于伽玛源下照射，吸收剂量为200kGy，照射时间为17h。照射后产生的结晶化合物用无水乙醇洗涤3次，最终所得固体产物在60℃烘箱内干燥。
产物的晶体结构由单晶X-射线衍射仪确定，如图1所示，每个Eu原子连接7个Cl原子和1个H 2O，每个Cl原子连接2个Eu原子，每个H 2O连接2个Eu原子，构成三维有序的结构，解析后的最简化学结构式为Eu(H 2O)Cl 2。
产物的纯度由多晶粉末衍射仪确定，如图2所示，实验测得的粉末衍射图与理论模拟的粉末衍射图一致，表明所制备的产物纯度高。
通过固态光谱仪研究产物的紫外-可见光吸收性能和荧光发射性能，如图3所示，产物在300-400nm处存在一个紫外-可见光吸收峰，最大吸收波长为368nm；如图4所示，产物在处存在410-460nm一个荧光发射峰，最大发射波长为427nm。
实施例2
电子束辐射制备二价铕化合物(Eu(H 2O)Cl 2)，具体步骤如下：
(1)EuCl 3乙醇溶液的配制：称取1.0g的EuCl 3·6H 2O到18cm×24cm的塑料袋中，再加入25mL无水乙醇。将上述混合物超声3min左右，得到无色 澄清的EuCl 3乙醇溶液。
(2)鼓入氮气：将所配制EuCl 3乙醇溶液鼓入氮气，鼓入氮气15min后密封，保证EuCl 3乙醇溶液处在氮气氛围下。
(3)电子束照射：将上述密封好的EuCl 3乙醇溶液置于电子加速器下照射，吸收剂量为1000kGy，照射时间为27min。照射后产生的结晶化合物用无水乙醇洗涤3次，最终所得固体产物在60℃烘箱内干燥。
实施例3
X射线辐射制备二价铕化合物(Eu(H 2O)Cl 2)，具体步骤如下：
(1)EuCl 3乙醇溶液的配制：称取1.0g的EuCl 3·6H 2O到18cm×24cm的塑料袋中，再加入25mL无水乙醇。将上述混合物超声3min左右，得到无色澄清的EuCl 3乙醇溶液。
(2)鼓入氮气：将所配制EuCl 3乙醇溶液鼓入氮气，鼓入氮气15min后密封，保证EuCl 3乙醇溶液处在氮气氛围下。
(3)X射线照射：将上述密封好的EuCl 3乙醇溶液置于电子加速器下照射，吸收剂量为10kGy，照射时间为500min。照射后产生的结晶化合物用无水乙醇洗涤3次，最终所得固体产物在60℃烘箱内干燥。
实施例4
伽玛射线辐射制备二价铕化合物(Eu(H 2O)Cl 2)，具体步骤如下：
(1)EuCl 3乙醇溶液的配制：称取0.2g的EuCl 3到20mL的玻璃瓶中，再加入5mL无水乙醇。将上述混合物超声3min左右，得到无色澄清的EuCl 3乙醇溶液。
(2)鼓入氮气：将所配制EuCl 3乙醇溶液鼓入氮气，鼓入氮气3min后密封，保证EuCl 3乙醇溶液处在氮气氛围下。
(3)伽玛射线照射：将上述密封好的EuCl 3乙醇溶液置于伽玛源下照射，吸收剂量为200kGy，照射时间为17h。照射后产生的结晶化合物用无水乙醇洗涤3次，最终所得固体产物在60℃烘箱内干燥。
实施例5
伽玛射线辐射制备二价铕化合物(Eu(H 2O)Cl 2)，具体步骤如下：
(1)EuCl 3乙醇溶液的配制：称取1.0g的EuCl 3·6H 2O到20mL的玻璃瓶中，再加入5mL无水乙醇。将上述混合物超声3min左右，得到无色澄清的EuCl 3乙醇溶液。
(2)鼓入氮气：将所配制EuCl 3乙醇溶液鼓入氮气，鼓入氮气3min后密封，保证EuCl 3乙醇溶液处在氮气氛围下。
(3)伽玛射线照射：将上述密封好的EuCl 3乙醇溶液置于伽玛源下照射，吸收剂量为200kGy，照射时间为17h。照射后产生的结晶化合物用无水乙醇洗涤3次，最终所得固体产物在60℃烘箱内干燥。
实施例6
伽玛射线辐射制备二价铕化合物(Eu(H 2O)Cl 2)，具体步骤如下：
(1)EuCl 3乙醇溶液的配制：称取0.2g的EuCl 3·6H 2O到20mL的玻璃瓶中，再加入5mL无水乙醇。将上述混合物超声3min左右，得到无色澄清的EuCl 3乙醇溶液。
(2)鼓入氮气：将所配制EuCl 3乙醇溶液鼓入氮气，鼓入氮气3min后密封，保证EuCl 3乙醇溶液处在氮气氛围下。
(3)伽玛射线照射：将上述密封好的EuCl 3乙醇溶液置于伽玛源下照射，吸收剂量为100kGy，照射时间为17h。照射后产生的结晶化合物用无水乙醇洗涤3次，最终所得固体产物在60℃烘箱内干燥。
图5为本发明实施例的化合物的示意图。EuCl 3·6H 2O中在高能射线照射下，得到Eu(H 2O)Cl 2。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

  1. 一种二价铕化合物的制备方法，其特征在于，包括如下步骤：保护气氛下，对三价铕化合物的有机溶液进行电离辐射，得到所述二价铕化合物。
  2. 根据权利要求1所述的二价铕化合物的制备方法，其特征在于，所述三价铕化合物的有机溶液中的有机溶剂为乙醇。
  3. 根据权利要求1所述的二价铕化合物的制备方法，其特征在于，所述三价铕化合物为三氯化铕、硝酸铕和醋酸铕中的一种或多种。
  4. 根据权利要求1所述的二价铕化合物的制备方法，其特征在于，所述电离辐射的辐射源为电子束、伽玛射线和X-射线中的一种或多种。
  5. 根据权利要求1所述的二价铕化合物的制备方法，其特征在于，所述电离辐射的照射剂量为10-1000kGy；电离辐射的照射时间为27min-17h。
  6. 根据权利要求1所述的二价铕化合物的制备方法，其特征在于，所述保护气氛中的气体为氮气和/或氩气。
  7. 根据权利要求1所述的二价铕化合物的制备方法，其特征在于，还包括对照射后产生的结晶化合物进行洗涤、干燥，得到所述的二价铕化合物。
  8. 根据权利要求7所述的二价铕化合物的制备方法，其特征在于，所述洗涤为用乙醇洗涤2-3次。
  9. 根据权利要求7所述的二价铕化合物的制备方法，其特征在于，所述干燥的温度为50-70℃。
  10. 根据权利要求7所述的二价铕化合物的制备方法，其特征在于，所述干燥的时间为30-60min。
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