CN115181281A - Bismuth-based metal organic framework material and preparation method thereof - Google Patents

Bismuth-based metal organic framework material and preparation method thereof Download PDF

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CN115181281A
CN115181281A CN202210709354.8A CN202210709354A CN115181281A CN 115181281 A CN115181281 A CN 115181281A CN 202210709354 A CN202210709354 A CN 202210709354A CN 115181281 A CN115181281 A CN 115181281A
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bismuth
based metal
organic framework
framework material
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应玉龙
杨皓为
王騊
王晟
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Zhejiang Sci Tech University ZSTU
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Abstract

The invention relates to a bismuth-based metal organic framework material and a preparation method thereof. The preparation method of the bismuth-based metal organic framework material comprises the following steps: mixing bismuth salt, a polybasic acid organic ligand and a cationic surfactant to obtain a mixture; and mixing the mixture with water, and carrying out ultrasonic treatment to obtain the bismuth-based metal organic framework material. The preparation method utilizes the cationic surfactant to prepare the bismuth-based metal organic framework material with good crystallinity, smaller size and more uniform mass distribution in a water system, has the advantages of low energy consumption, short period and the like, and is beneficial to large-scale production and application of the bismuth-based metal organic framework material.

Description

铋基金属有机框架材料及其制备方法Bismuth-based metal organic framework material and preparation method thereof

技术领域technical field

本发明涉及有机-无机杂化材料技术领域,特别是涉及一种铋基金属有机框架材料及其制备方法。The invention relates to the technical field of organic-inorganic hybrid materials, in particular to a bismuth-based metal organic framework material and a preparation method thereof.

背景技术Background technique

传统技术中制备铋基金属有机框架材料的主要途径是溶剂热法,且必须使用有机溶剂作为反应体系,溶剂热法虽然操作简便,但在制备过程存在周期长、能耗高等问题。The main way to prepare bismuth-based metal-organic framework materials in the traditional technology is solvothermal method, and organic solvent must be used as the reaction system. Although the solvothermal method is easy to operate, it has the problems of long cycle and high energy consumption in the preparation process.

虽然通过多步反应,能够实现在水体系中制备铋基金属有机框架材料,但是,传统在水体系中制备得到的铋基金属有机框架材料仍然存在空间结构缺陷,降低了铋基金属有机框架材料的产率。Although the preparation of bismuth-based metal-organic frameworks in aqueous systems can be achieved through multi-step reactions, the traditional bismuth-based metal-organic frameworks prepared in aqueous systems still have spatial structural defects, which reduces the reduction of bismuth-based metal-organic frameworks. yield.

发明内容SUMMARY OF THE INVENTION

基于此,有必要针对上述问题,提供一种铋基金属有机框架材料及其制备方法;所述制备方法利用阳离子表面活性剂能够在水体系中制备出结晶性良好、尺寸更小、质量分布更均匀的铋基金属有机框架材料,并且该制备方法具有低能耗、短周期等优势,有利于铋基金属有机框架材料的大规模生产与应用。Based on this, it is necessary to address the above problems to provide a bismuth-based metal organic framework material and a preparation method thereof; the preparation method utilizes a cationic surfactant to prepare a water system with good crystallinity, smaller size, and better mass distribution. The uniform bismuth-based metal organic framework material, and the preparation method has the advantages of low energy consumption, short cycle and the like, which is beneficial to the large-scale production and application of the bismuth-based metal organic framework material.

一种铋基金属有机框架材料的制备方法,包括如下步骤:A preparation method of a bismuth-based metal organic framework material, comprising the following steps:

将铋盐、多元酸有机配体和阳离子表面活性剂混合,得到混合物;以及mixing the bismuth salt, the polyacid organic ligand, and the cationic surfactant to obtain a mixture; and

将所述混合物与水混合,并进行超声处理,得到铋基金属有机框架材料。The mixture is mixed with water and subjected to ultrasonic treatment to obtain a bismuth-based metal organic framework material.

在其中一个实施例中,所述铋盐与所述阳离子表面活性剂的质量比为30:1-2:10。In one embodiment, the mass ratio of the bismuth salt to the cationic surfactant is 30:1-2:10.

在其中一个实施例中,所述阳离子表面活性剂选自卤代烷基季铵盐、高级胺盐中的至少一种。In one embodiment, the cationic surfactant is selected from at least one of haloalkyl quaternary ammonium salts and higher amine salts.

在其中一个实施例中,所述卤代烷基季铵盐选自十六烷基三甲基溴化铵、十二烷基三甲基溴化铵中的至少一种。In one embodiment, the haloalkyl quaternary ammonium salt is selected from at least one of cetyltrimethylammonium bromide and dodecyltrimethylammonium bromide.

在其中一个实施例中,所述高级胺盐选自烷基伯胺盐、烷基仲胺盐、烷基叔胺盐中的至少一种。In one embodiment, the higher amine salt is selected from at least one of primary alkyl amine salts, secondary alkyl amine salts, and tertiary alkyl amine salts.

在其中一个实施例中,所述铋盐与所述多元酸有机配体的质量比为1:1-1:10,所述铋盐与所述水的质量比为10:1-10:3。In one embodiment, the mass ratio of the bismuth salt to the polybasic acid organic ligand is 1:1-1:10, and the mass ratio of the bismuth salt to the water is 10:1-10:3 .

在其中一个实施例中,所述铋盐选自五水硝酸铋、乙酸铋、硝酸氧铋中的至少一种。In one embodiment, the bismuth salt is selected from at least one of bismuth nitrate pentahydrate, bismuth acetate, and bismuth oxynitrate.

在其中一个实施例中,所述多元酸有机配体选自1,3,5-均苯三甲酸、三嗪-2,4,6-三基-三苯甲酸、联苯-3,3′,5,5′-四羧酸中的至少一种。In one embodiment, the polyacid organic ligand is selected from 1,3,5- trimesic acid, triazine-2,4,6-triyl-tribenzoic acid, biphenyl-3,3' , at least one of 5,5'-tetracarboxylic acids.

在其中一个实施例中,所述超声处理的时间为1min-90min,所述超声处理的工作频率为30KHz-90KHz。In one embodiment, the time of the ultrasonic treatment is 1min-90min, and the working frequency of the ultrasonic treatment is 30KHz-90KHz.

一种如上所述的铋基金属有机框架材料制备方法制备得到的铋基金属有机框架材料。A bismuth-based metal-organic framework material prepared by the above-mentioned preparation method of a bismuth-based metal-organic framework material.

本发明所述铋基金属有机框架材料的制备方法中,通过利用阳离子表面活性剂中含有的孤对电子,使阳离子表面活性剂在水体系中能够优先取代多元酸有机配体表面羧基上的氢离子,克服了多元酸有机配体去质子化不完全的问题,从而使多元酸有机配体能够与铋离子有效结合,有利于制备出结晶性良好、尺寸更小、质量分布更均匀的铋基金属有机框架材料。并且,该制备方法具有低能耗、短周期等优势,有利于铋基金属有机框架材料的大规模生产与应用。In the preparation method of the bismuth-based metal organic framework material of the present invention, by utilizing the lone pair electrons contained in the cationic surfactant, the cationic surfactant can preferentially replace the hydrogen on the surface carboxyl group of the organic ligand of the polybasic acid in the aqueous system It overcomes the problem of incomplete deprotonation of polybasic acid organic ligands, so that polybasic acid organic ligands can be effectively combined with bismuth ions, which is conducive to the preparation of bismuth bases with good crystallinity, smaller size and more uniform mass distribution. Metal organic framework material. Moreover, the preparation method has the advantages of low energy consumption, short cycle and the like, which is beneficial to the large-scale production and application of bismuth-based metal organic framework materials.

附图说明Description of drawings

图1为实施例1制备得到的铋基金属有机框架材料的扫描电镜图;Fig. 1 is the scanning electron microscope image of the bismuth-based metal-organic framework material prepared in Example 1;

图2为实施例1制备得到的铋基金属有机框架材料的X-射线衍射图;Fig. 2 is the X-ray diffraction pattern of the bismuth-based metal organic framework material prepared in Example 1;

图3为对比例1、对比例2以及对比例3制备得到的产物的扫描电镜图;Fig. 3 is the scanning electron microscope image of the product prepared by comparative example 1, comparative example 2 and comparative example 3;

图4为对比例1、对比例2以及对比例3制备得到的产物的X-射线衍射图。FIG. 4 is an X-ray diffraction pattern of the products prepared in Comparative Example 1, Comparative Example 2 and Comparative Example 3. FIG.

具体实施方式Detailed ways

为了便于理解本发明,下面将对本发明进行更详细的描述。但是,应当理解,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施方式或实施例。相反地,提供这些实施方式或实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate understanding of the present invention, the present invention will be described in more detail below. It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments or examples described herein. Rather, these embodiments or examples are provided so that a thorough and complete understanding of the present disclosure is provided.

除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式或实施例的目的,不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments or examples only, and are not intended to limit the present invention.

申请人经过长期而深入的研究发现,在金属有机框架材料(MOFs)的合成过程中,有机配体溶于溶剂体系时需要去质子化使其更易与金属离子发生键合,从而构成完整的金属有机骨架。然而,在水体系中,多元酸有机配体去质子化不完全,导致铋离子仅与部分去质子化的羧基进行反应,从而产生了中间体。在水体系中,这些中间体难以生长完全构成完整的金属有机骨架。After long-term and in-depth research, the applicant found that during the synthesis of metal-organic frameworks (MOFs), the organic ligands need to be deprotonated when dissolved in a solvent system to make it easier to bond with metal ions, thereby forming a complete metal. organic skeleton. However, in aqueous systems, the deprotonation of polyacid organic ligands is incomplete, resulting in the reaction of bismuth ions with only partially deprotonated carboxyl groups, resulting in intermediates. In aqueous systems, it is difficult for these intermediates to grow to form complete metal-organic frameworks.

基于此,本发明提供一种铋基金属有机框架材料的制备方法,包括如下步骤:Based on this, the present invention provides a preparation method of a bismuth-based metal organic framework material, comprising the following steps:

S1,将铋盐、多元酸有机配体和阳离子表面活性剂混合,得到混合物;以及S1, mixing bismuth salt, polyacid organic ligand and cationic surfactant to obtain a mixture; and

S2,将所述混合物与水混合,并进行超声处理,得到铋基金属有机框架材料。S2, mixing the mixture with water and performing ultrasonic treatment to obtain a bismuth-based metal organic framework material.

步骤S1中,由于阳离子表面活性剂能够有效地与多元酸有机配体结合,从而有利于提高多元酸有机配体的完全去质子化。In step S1, since the cationic surfactant can effectively combine with the organic ligand of the polybasic acid, it is beneficial to improve the complete deprotonation of the organic ligand of the polybasic acid.

为了使多元酸有机配体去质子化完全,所述铋盐与所述阳离子表面活性剂的质量比为30:1-2:10,优选为20:1-2:10,其中,所述阳离子表面活性剂选自卤代烷基季铵盐、高级胺盐中的至少一种。In order to completely deprotonate the organic ligand of the polybasic acid, the mass ratio of the bismuth salt to the cationic surfactant is 30:1-2:10, preferably 20:1-2:10, wherein the cationic surfactant is The surfactant is selected from at least one of haloalkyl quaternary ammonium salts and higher amine salts.

具体地,所述卤代烷基季铵盐选自十六烷基三甲基溴化铵、十二烷基三甲基溴化铵中至少一种;所述高级胺盐选自烷基伯胺盐、烷基仲胺盐、烷基叔胺盐中的至少一种,其中,所述烷基伯胺盐选自十二烷基胺盐酸盐,所述烷基仲胺盐选自双十八烷基胺盐酸盐,所述烷基叔胺盐选自N,N-二甲基十八胺盐酸盐。Specifically, the haloalkyl quaternary ammonium salt is selected from at least one of cetyltrimethylammonium bromide and dodecyltrimethylammonium bromide; the higher amine salt is selected from alkyl primary amine salts , at least one of secondary alkyl amine salts and tertiary alkyl amine salts, wherein the primary alkyl amine salt is selected from dodecylamine hydrochloride, and the secondary alkyl amine salt is selected from dioctadecylamine Alkylamine hydrochloride, the alkyl tertiary amine salt is selected from N,N-dimethyloctadecylamine hydrochloride.

由于阳离子表面活性剂能够在溶液中形成胶束,实现富集铋离子和多元酸有机配体的效果,从而促进铋基金属有机框架材料的合成,所述阳离子表面活性剂优选为卤代烷基季铵盐,进一步优选为十六烷基三甲基溴化铵。Since cationic surfactants can form micelles in solution to achieve the effect of enriching bismuth ions and organic ligands of polybasic acids, thereby promoting the synthesis of bismuth-based metal-organic framework materials, the cationic surfactants are preferably haloalkyl quaternary ammonium The salt is more preferably cetyltrimethylammonium bromide.

为保证铋基金属有机框架材料的生成,调控所述铋盐与所述多元酸有机配体的质量比为1:1-1:10,进一步地,为了提高产物转化率,所述铋盐与所述多元酸有机配体的质量比优选为1:1-1:5。In order to ensure the generation of bismuth-based metal organic framework materials, the mass ratio of the bismuth salt to the polybasic acid organic ligand is regulated to be 1:1-1:10. Further, in order to improve the product conversion rate, the bismuth salt and The mass ratio of the polybasic acid organic ligands is preferably 1:1-1:5.

具体地,所述铋盐选自五水硝酸铋、乙酸铋、硝酸氧铋中的至少一种,优选为五水硝酸铋;所述多元酸有机配体选自1,3,5-均苯三甲酸、三嗪-2,4,6-三基-三苯甲酸、联苯-3,3′,5,5′-四羧酸中的至少一种,优选为1,3,5-均苯三甲酸。Specifically, the bismuth salt is selected from at least one of bismuth nitrate pentahydrate, bismuth acetate, and bismuth oxynitrate, preferably bismuth nitrate pentahydrate; the polybasic acid organic ligand is selected from 1,3,5-isophenylene At least one of tricarboxylic acid, triazine-2,4,6-triyl-tribenzoic acid, and biphenyl-3,3',5,5'-tetracarboxylic acid, preferably 1,3,5-homogenous Benzene tricarboxylic acid.

进一步地,所述1,3,5-均苯三甲酸与所述铋盐能够反应构成CAU-7、CAU-17,所述三嗪-2,4,6-三基-三苯甲酸与所述铋盐能够反应构成CAU-35,所述联苯-3,3′,5,5′-四羧酸与所述铋盐能够反应构成NOTT-220,CAU-7、CAU-17、CAU-35以及NOTT-220为具有不同拓扑结构的铋基金属有机框架材料。Further, the 1,3,5- trimesic acid and the bismuth salt can react to form CAU-7 and CAU-17, and the triazine-2,4,6-triyl-tribenzoic acid and the The bismuth salt can react to form CAU-35, and the biphenyl-3,3',5,5'-tetracarboxylic acid and the bismuth salt can react to form NOTT-220, CAU-7, CAU-17, CAU- 35 and NOTT-220 are bismuth-based metal-organic framework materials with different topological structures.

步骤S2中,在常温常压的水溶液中,利用阳离子表面活性剂中含有的孤对电子,使阳离子表面活性剂在水体系中能够优先取代多元酸有机配体表面羧基上的氢离子,克服了多元酸有机配体去质子化不完全的问题,有利于促进去质子化多元酸有机配体与铋离子高效键合。In step S2, in an aqueous solution at room temperature and pressure, the lone pair electrons contained in the cationic surfactant are used to enable the cationic surfactant to preferentially replace the hydrogen ions on the surface carboxyl groups of the organic ligands of the polybasic acid in the aqueous system, which overcomes the problem of The problem of incomplete deprotonation of polyacid organic ligands is beneficial to promote efficient bonding between deprotonated polyacid organic ligands and bismuth ions.

为了提高产物转化率,所述铋盐与所述水的质量比为10:1-10:3,优选为20:3-5:1。In order to improve the product conversion rate, the mass ratio of the bismuth salt to the water is 10:1-10:3, preferably 20:3-5:1.

为了进一步降低水中微离子对反应过程的影响,所述水优选为去离子水。In order to further reduce the influence of micro ions in the water on the reaction process, the water is preferably deionized water.

由于水体系中混合了一定比例的铋盐、多元酸有机配体和阳离子表面活性剂,在一定的超声频率条件下进行超声处理时,阳离子表面活性剂优先取代多元酸有机配体表面羧基上的氢离子,使多元酸有机配体去质子化完全,有利于铋离子与去质子化的多元酸有机配体进行键合。Since a certain proportion of bismuth salt, polybasic acid organic ligands and cationic surfactants are mixed in the water system, the cationic surfactants preferentially replace the carboxyl groups on the surface of polybasic acid organic ligands during ultrasonic treatment under certain ultrasonic frequency conditions. The hydrogen ion can completely deprotonate the organic ligand of the polybasic acid, which is beneficial to the bonding between the bismuth ion and the deprotonated organic ligand of the polybasic acid.

同时,由于超声处理的作用,铋离子与去质子化的多元酸有机配体发生剧烈的的分子间振动,促使分子内部产生微小的空隙,该微小空隙伴随超声频率迅速胀大和闭合,使分子之间发生剧烈的碰撞作用,进一步提高了铋离子与去质子化的多元酸有机配体的键合,高效促进了铋基有机金属框架的晶体生长,从而使铋基金属有机框架材料的结晶性良好、尺寸更小、质量分布更均匀。At the same time, due to the effect of ultrasonic treatment, the bismuth ions and the deprotonated organic ligands of polyacids undergo violent intermolecular vibrations, which promotes the formation of tiny voids inside the molecules. The tiny voids rapidly expand and close with the ultrasonic frequency, making the molecules Violent collision occurs between bismuth ions and deprotonated organic ligands of polyacids, which further improves the bonding of bismuth ions and deprotonated polyacid organic ligands, and efficiently promotes the crystal growth of bismuth-based metal organic frameworks. , smaller size and more uniform mass distribution.

在一些实施方式中,所述超声处理的时间为1min-90min,所述超声处理的工作频率为30KHz-90KHz;进一步地,为了降低能量损耗、提升制备效率、缩短制备周期,所述超声处理的时间优选为30min-60min;所述超声处理的工作频率优选为35KHz-50KHz。In some embodiments, the time of the ultrasonic treatment is 1min-90min, and the working frequency of the ultrasonic treatment is 30KHz-90KHz; further, in order to reduce energy loss, improve production efficiency, and shorten the production cycle, the ultrasonic treatment The time is preferably 30min-60min; the operating frequency of the ultrasonic treatment is preferably 35KHz-50KHz.

因此,本发明利用阳离子表面活性剂在水体系中制备出结晶性良好、尺寸更小、质量分布更均匀的铋基金属有机框架材料,并且该制备方法具有低能耗、短周期、制备过程温和安全、无污染等优势,有利于铋基金属有机框架材料的大规模生产与应用。Therefore, the present invention utilizes a cationic surfactant to prepare a bismuth-based metal-organic framework material with good crystallinity, smaller size and more uniform mass distribution in an aqueous system, and the preparation method has the advantages of low energy consumption, short cycle, mild and safe preparation process , pollution-free and other advantages, is conducive to the large-scale production and application of bismuth-based metal organic framework materials.

另外,本发明制备得到的铋基金属有机框架材料具有独特的三维多孔结构单元、高比表面积和高结构稳定性等特点,且孔径尺寸可调控,能够广泛用于二氧化碳吸附还原、水体中污染物的吸附以及作为前驱体制备具有光催化活性的BiVO4材料等领域。In addition, the bismuth-based metal-organic framework material prepared by the invention has the characteristics of unique three-dimensional porous structural unit, high specific surface area, high structural stability, etc., and the pore size can be adjusted, and can be widely used in carbon dioxide adsorption and reduction, pollutants in water. adsorption and preparation of photocatalytically active BiVO 4 materials as precursors.

本发明还提供一种采用上述制备方法得到的铋基金属有机框架材料。The present invention also provides a bismuth-based metal organic framework material obtained by the above preparation method.

与传统水热法以及水体系中的多步法制备得到的铋基金属有机框架材料相比,通过本发明提供的制备方法制备得到的铋基金属有机框架材料尺寸更小、更均匀。Compared with the bismuth-based metal organic framework materials prepared by the traditional hydrothermal method and the multi-step method in the water system, the bismuth-based metal organic framework materials prepared by the preparation method provided by the present invention are smaller in size and more uniform.

具体的,所述铋基金属有机框架材料呈短棒状,所述铋基金属有机框架材料的长度为200nm-2μm,优选为800nm-1.5μm。Specifically, the bismuth-based metal organic framework material is in the shape of a short rod, and the length of the bismuth-based metal organic framework material is 200 nm-2 μm, preferably 800 nm-1.5 μm.

以下,将通过以下具体实施例对所述铋基金属有机框架材料的制备方法做进一步的说明。Hereinafter, the preparation method of the bismuth-based metal organic framework material will be further described by the following specific examples.

实施例中,扫描电子显微镜(Zeiss vltra55)测试时加速电压为0.5kV-30kV,放大倍数为10万倍-50万倍。In the embodiment, the acceleration voltage is 0.5kV-30kV and the magnification is 100,000 times-500,000 times during the scanning electron microscope (Zeiss vltra55) test.

实施例中,X-射线粉末衍射仪(Bruker D8)在40mA扫描电流和40kV扫描电压条件下进行测试,X-射线粉末衍射仪的光源为Cu-Kal,测试角度为5°-50°。In the embodiment, the X-ray powder diffractometer (Bruker D8) is tested under the conditions of 40mA scanning current and 40kV scanning voltage, the light source of the X-ray powder diffractometer is Cu-Kal, and the test angle is 5°-50°.

实施例1Example 1

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the oscillator, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

图1包含制得的铋基金属有机框架材料的扫描电镜图,从图1可知,所述铋基金属有机框架材料呈短棒状,长度为800nm-1.5μm,且尺寸大小分布均匀。FIG. 1 includes a scanning electron microscope image of the prepared bismuth-based metal-organic framework material. It can be seen from FIG. 1 that the bismuth-based metal-organic framework material is in the shape of a short rod, with a length of 800 nm-1.5 μm, and a uniform size distribution.

图2包含制得的铋基金属有机框架材料的X射线衍射图,从图2可知,所述铋基金属有机框架材料结晶性能良好,在5°-50°的衍射角中显示出铋基金属有机框架材料特有的层状衍射峰,并且铋基金属有机框架材料的所有衍射峰的位置都与已知CAU-17晶体结构的衍射峰的位置一一对应,说明所述铋基金属有机框架材料与CAU-17具有相同的晶体结构,即所述铋基金属有机框架材料为CAU-17。FIG. 2 includes the X-ray diffraction pattern of the prepared bismuth-based metal-organic framework material. It can be seen from FIG. 2 that the bismuth-based metal-organic framework material has good crystalline properties, and shows bismuth-based metal organic framework materials at diffraction angles of 5°-50°. The unique layered diffraction peaks of organic framework materials, and the positions of all diffraction peaks of bismuth-based metal organic framework materials correspond one-to-one with the positions of diffraction peaks of known CAU-17 crystal structure, indicating that the bismuth-based metal organic framework materials It has the same crystal structure as CAU-17, that is, the bismuth-based metal organic framework material is CAU-17.

实施例2Example 2

将100mg的五水硝酸铋、100mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 100 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the oscillator, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例3Example 3

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和50mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 50 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the oscillator, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例4Example 4

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和100mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 100 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the oscillator, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例5Example 5

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在50KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the shaker, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 50KHz. Transfer the final product to a large beaker, add deionized water, and centrifuge and wash three times to obtain the bismuth base. Metal organic framework material.

实施例6Example 6

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在90KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the shaker, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 90KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例7Example 7

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理20min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the oscillator, perform ultrasonic vibration treatment for 20 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例8Example 8

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理90min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the oscillator, and perform ultrasonic vibration treatment for 90 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例9Example 9

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入30mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 30 mL of deionized water to the oscillator, perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例10Example 10

将100mg的乙酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth acetate, 500 mg of 1,3,5- trimesic acid and 5 mg of cetyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample on an ultrasonic oscillator Then add 15mL of deionized water, under the condition of ultrasonic working frequency of 37KHz, carry out ultrasonic vibration treatment for 40min, transfer the final product to a large beaker, add deionized water, centrifuge and wash three times to obtain bismuth-based metal organic frame material.

实施例11Example 11

将100mg的五水硝酸铋、500mg的三嗪-2,4,6-三基-三苯甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of triazine-2,4,6-triyl-tribenzoic acid and 5 mg of hexadecyltrimethylammonium bromide to obtain a mixture; The container was placed in an ultrasonic oscillator, and then 15 mL of deionized water was added. Under the ultrasonic working frequency of 37KHz, ultrasonic vibration was performed for 40 min. The final product was transferred to a large beaker, and deionized water was added. After washing three times, , that is, the bismuth-based metal organic framework material is obtained.

实施例12Example 12

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十二烷基三甲基溴化铵混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of dodecyltrimethylammonium bromide to obtain a mixture; place the container containing the mixture sample in an ultrasonic Then add 15 mL of deionized water to the oscillator, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 37KHz, transfer the final product to a large beaker, add deionized water, and centrifuge for three times. Metal organic framework material.

实施例13Example 13

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的双十八烷基胺盐酸盐混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入15mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min,将最终产物转移到大烧杯中,加入去离子水,离心洗涤三次后,即得到铋基金属有机框架材料。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of dioctadecylamine hydrochloride to obtain a mixture; place the container containing the mixture sample in ultrasonic vibration Then, add 15 mL of deionized water, and perform ultrasonic vibration treatment for 40 min under the ultrasonic working frequency of 37KHz. Transfer the final product to a large beaker, add deionized water, and centrifuge for three times. After washing, the bismuth-based metal is obtained. Organic frame material.

对比例1Comparative Example 1

将100mg的五水硝酸铋和500mg的1,3,5-均苯三甲酸混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入20mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min。超声震荡后,混合溶液中生成产物,将产物用去离子水离心洗涤三次。Mix and stir 100 mg of bismuth nitrate pentahydrate and 500 mg of 1,3,5- trimesic acid to obtain a mixture; place the container containing the mixture sample in an ultrasonic shaker, then add 20 mL of deionized water, and put it in the Under the condition of ultrasonic working frequency of 37KHz, ultrasonic vibration treatment was carried out for 40min. After sonication, a product was formed in the mixed solution, and the product was centrifuged and washed three times with deionized water.

图3包含制得的产物的扫描电镜图,从图3(a)可知,所述产物呈微米级的片状,且尺寸大小分布不均匀。FIG. 3 includes a scanning electron microscope image of the prepared product, and it can be seen from FIG. 3( a ) that the product is in the form of micron-scale flakes, and the size distribution is not uniform.

图4包含制得的产物的X-射线衍射图,从图4(a)可知,所述产物衍射峰的位置与已知CAU-17晶体结构的衍射峰的位置不同,说明所述产物不是CAU-17。Fig. 4 contains the X-ray diffraction pattern of the prepared product. From Fig. 4(a), it can be seen that the position of the diffraction peak of the product is different from the position of the diffraction peak of the known CAU-17 crystal structure, indicating that the product is not CAU -17.

对比例2Comparative Example 2

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;然后加入20mL的去离子水后将容器静置于在室温下40min,混合溶液中生成产物,将产物用去离子水离心洗涤三次。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of hexadecyltrimethylammonium bromide to obtain a mixture; then add 20 mL of deionized water and put the container After standing at room temperature for 40 min, a product was generated in the mixed solution, and the product was centrifuged and washed three times with deionized water.

图3包含制得的产物的扫描电镜图,从图3(b)可知,所述产物呈团聚的碎块状,其中掺杂有部分碎片。Fig. 3 contains a scanning electron microscope image of the prepared product, and it can be seen from Fig. 3(b) that the product is in the form of agglomerated fragments, which are doped with some fragments.

图4包含制得的产物的X-射线衍射图,从图4(b)可知,所述产物衍射峰的位置与已知CAU-17晶体结构的衍射峰的位置不同,说明所述产物不是CAU-17。Figure 4 contains the X-ray diffraction pattern of the prepared product, and it can be seen from Figure 4(b) that the position of the diffraction peak of the product is different from the position of the diffraction peak of the known CAU-17 crystal structure, indicating that the product is not CAU -17.

对比例3Comparative Example 3

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十六烷基三甲基溴化铵混合搅拌均匀,得到混合物;然后加入20mL的去离子水后将容器置于搅拌台于在室温下搅拌40min,混合溶液中生成产物,将产物用去离子水离心洗涤三次。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of hexadecyltrimethylammonium bromide to obtain a mixture; then add 20 mL of deionized water and put the container The mixture was placed on a stirring table and stirred at room temperature for 40 min to generate a product in the mixed solution, and the product was centrifuged and washed three times with deionized water.

图3包含制得的产物的扫描电镜图,从图3(c)可知,所述产物呈微米级的大块状,其表面分布有碎片。FIG. 3 includes a scanning electron microscope image of the prepared product, and it can be seen from FIG. 3( c ) that the product is in the form of a micron-sized block with fragments distributed on its surface.

图4包含制得的产物的X-射线衍射图,从图4(c)可知,所述产物衍射峰的位置与已知CAU-17晶体结构的衍射峰的位置不同,说明所述产物不是CAU-17。Fig. 4 contains the X-ray diffraction pattern of the prepared product, and it can be seen from Fig. 4(c) that the position of the diffraction peak of the product is different from the position of the diffraction peak of the known CAU-17 crystal structure, indicating that the product is not CAU -17.

对比例4Comparative Example 4

将100mg的五水硝酸铋、500mg的1,3,5-均苯三甲酸和5mg的十二烷基硫酸钠混合搅拌均匀,得到混合物;将盛有混合物样品的容器置于超声振荡器中,然后加入20mL的去离子水,在37KHz的超声工作频率条件下,进行超声震荡处理40min。超声震荡后,混合溶液中无产物生成。Mix and stir 100 mg of bismuth nitrate pentahydrate, 500 mg of 1,3,5- trimesic acid and 5 mg of sodium dodecyl sulfate to obtain a mixture; place the container containing the mixture sample in an ultrasonic oscillator, Then, 20 mL of deionized water was added, and under the condition of ultrasonic working frequency of 37 KHz, ultrasonic vibration treatment was carried out for 40 min. After sonication, no product was formed in the mixed solution.

根据实施例1-13和对比例1可知,将铋盐和多元酸有机配体放入去水反应体系中而不加入阳离子表面活性剂只进行超声震荡反应,无法制备出铋基金属有机框架材料。According to Examples 1-13 and Comparative Example 1, it is known that the bismuth salt and the organic ligand of polybasic acid are put into the dewatering reaction system without adding cationic surfactant and only ultrasonic vibration reaction is carried out, and the bismuth-based metal organic framework material cannot be prepared. .

根据实施例1-13和对比例2、对比例3可知,将铋盐、多元酸有机配体和阳离子表面活性剂放入水反应体系中不进行超声震荡反应也无法制备出铋基金属有机框架材料。According to Examples 1-13 and Comparative Example 2 and Comparative Example 3, it can be known that the bismuth-based metal organic framework cannot be prepared by putting bismuth salt, polybasic acid organic ligand and cationic surfactant into the water reaction system without performing ultrasonic vibration reaction. Material.

根据实施例1-13和对比例4可知,采用十二烷基硫酸钠与铋盐、多元酸有机配体在水反应体系中进行超声震荡反应无产物生成。According to Examples 1-13 and Comparative Example 4, it can be known that no product is produced by using sodium dodecyl sulfate, bismuth salt, and polybasic acid organic ligand to carry out ultrasonic vibration reaction in a water reaction system.

综上所述,本发明提出的铋基金属有机框架材料的制备方法中,阳离子表面活性剂与超声处理是制备铋基金属有机框架材料的必要技术条件,只有在阳离子表面活性剂的作用下同时通过超声作用才能制备出结晶性良好、尺寸更小、质量分布更均匀的铋基金属有机框架材料。To sum up, in the preparation method of the bismuth-based metal organic framework material proposed by the present invention, the cationic surfactant and ultrasonic treatment are necessary technical conditions for the preparation of the bismuth-based metal organic framework material, and only under the action of the cationic surfactant simultaneously The bismuth-based metal-organic framework material with good crystallinity, smaller size and more uniform mass distribution can be prepared by ultrasonic action.

以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those skilled in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the appended claims.

Claims (10)

1. The preparation method of the bismuth-based metal organic framework material is characterized by comprising the following steps of:
mixing bismuth salt, a polybasic acid organic ligand and a cationic surfactant to obtain a mixture; and
and mixing the mixture with water, and carrying out ultrasonic treatment to obtain the bismuth-based metal organic framework material.
2. The method for producing a bismuth-based metal-organic framework material according to claim 1, wherein the mass ratio of the bismuth salt to the cationic surfactant is 30.
3. The method for preparing a bismuth-based metal organic framework material according to claim 1, wherein the cationic surfactant is at least one selected from the group consisting of halogenated alkyl quaternary ammonium salts and higher amine salts.
4. The method of claim 3, wherein the quaternary ammonium haloalkyl salt is at least one selected from the group consisting of cetyltrimethylammonium bromide and dodecyltrimethylammonium bromide.
5. The method for producing a bismuth-based metal organic framework material according to claim 3, wherein the higher amine salt is at least one selected from the group consisting of primary alkyl amine salts, secondary alkyl amine salts, and tertiary alkyl amine salts.
6. The method for producing a bismuth-based metal-organic framework material according to any one of claims 1 to 5, wherein the mass ratio of the bismuth salt to the polybasic acid organic ligand is 1 to 1.
7. A method for preparing a bismuth-based metal organic framework material as claimed in any one of claims 1 to 5, wherein the bismuth salt is selected from at least one of bismuth nitrate pentahydrate, bismuth acetate, and bismuth subnitrate.
8. The method for preparing a bismuth-based metal-organic framework material according to any one of claims 1 to 5, wherein the polyacid organic ligand is selected from at least one of 1,3, 5-trimesic acid, triazine-2, 4, 6-triyl-tribenzoic acid, biphenyl-3, 3', 5' -tetracarboxylic acid.
9. The method for preparing a bismuth-based metal organic framework material according to any one of claims 1 to 5, wherein the time of the ultrasonic treatment is 1min to 90min, and the working frequency of the ultrasonic treatment is 30KHz to 90KHz.
10. A bismuth-based metal organic framework material prepared by the method for preparing the bismuth-based metal organic framework material as claimed in any one of claims 1 to 9.
CN202210709354.8A 2022-06-22 2022-06-22 Bismuth-based metal organic framework material and preparation method thereof Pending CN115181281A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116333333A (en) * 2023-04-07 2023-06-27 华南理工大学 Bismuth-based metal organic framework material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116333333A (en) * 2023-04-07 2023-06-27 华南理工大学 Bismuth-based metal organic framework material and preparation method and application thereof

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