技术领域technical field
本发明属于纳米材料及其制备方法，具体地说是一种核壳型金属氧化物材料及其制备方法。The invention belongs to nanometer materials and preparation methods thereof, in particular to a core-shell type metal oxide material and preparation methods thereof.
背景技术Background technique
内核@空隙@外壳构型的核壳型纳米材料，也叫做yolk shell材料。核壳材料因其组成、大小和结构排列的不同而具有特殊的光、电和化学等特性，近年来备受科学家的关注。核壳材料一般由中心的核以及包覆在外部的壳组成。核壳部分可由多种材料组成,包括高分子、无机物和金属等。外壳材料可以改变并赋予颗粒光、电、磁、催化和生物活性等性质。如今核壳材料已经拓展为化学、物理、生物、材料等诸多科学的交叉领域,并在医药、非线性光学器件、电发光器件以及催化等方面显示出诱人的应用前景。Core-shell nanomaterials in core@void@shell configuration are also called yolk shell materials. Due to their different composition, size and structural arrangement, core-shell materials have special optical, electrical and chemical properties, and have attracted the attention of scientists in recent years. Core-shell materials generally consist of a central core and an outer shell. The core-shell part can be composed of a variety of materials, including polymers, inorganic substances and metals. Shell materials can alter and impart properties such as optical, electrical, magnetic, catalytic, and biological activity to particles. Nowadays, core-shell materials have expanded into many interdisciplinary fields such as chemistry, physics, biology, and materials, and have shown attractive application prospects in medicine, nonlinear optical devices, electroluminescent devices, and catalysis.
近年来，核壳材料得到了广泛的研究。主要有以下方法：一种是硬模板法，首先核A先被B包裹形成A@B核壳。A@B再被C包裹，形成A@B@C核壳材料；最后将B通过溶解和煅烧等方法去掉。形成A@空隙@C yolk shell结构；另一种方法是软模版法，核A在一些表面活性剂等分子的导向下，直接形成A@空隙@C核壳材料；此外，还有同galvanic replacement，Kirkendall diffusion和瓶中造船等方法制备yolk shell结构（Chem.Commun.,2011,47,12578-12591）。In recent years, core-shell materials have been extensively studied. There are mainly the following methods: one is the hard template method, first core A is wrapped by B to form A@B core-shell. A@B is then wrapped by C to form A@B@C core-shell material; finally, B is removed by dissolution and calcination. Form A@gap@C yolk shell structure; Another method is the soft template method, the core A is directly formed A@gap@C core-shell material under the guidance of molecules such as surfactants; in addition, there is the same galvanic replacement , Kirkendall diffusion and shipbuilding in a bottle to prepare yolk shell structures (Chem. Commun., 2011, 47, 12578-12591).
虽然已经发展了很多种方法来制备核壳材料。金属氧化物@空隙@金属氧化物材料的制备方法仍然是一个挑战。本发明发展了一种新的合成方法，能够合成金属氧化物@空隙@金属氧化物材料纳米材料。并且能实现尺寸和组成的可控调节。这种材料在催化、生物、医药、荧光等领域有着广泛的应用前景。Although many methods have been developed to prepare core-shell materials. The fabrication methods of metal oxide@void@metal oxide materials are still a challenge. The present invention develops a new synthesis method capable of synthesizing metal oxide@void@metal oxide material nanomaterials. Moreover, the controllable adjustment of size and composition can be realized. This material has broad application prospects in catalysis, biology, medicine, fluorescence and other fields.
发明内容Contents of the invention
本发明的目的提供一种核壳型金属氧化物材料及其制备方法，具体来说是金属氧化物@空隙@金属氧化物材料，也叫做yolk shell材料。核壳均为同一金属氧化物。所述金属氧化物为Mg、Ni、Zn、In、Y、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu金属氧化物中的一种或者多种。粒径为50-1000nm。The purpose of the present invention is to provide a core-shell metal oxide material and a preparation method thereof, specifically a metal oxide@void@metal oxide material, also called a yolk shell material. The core and shell are both the same metal oxide. The metal oxide is one or more of Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu metal oxides. The particle size is 50-1000nm.
该材料是以具有球形形貌的金属有机配位聚合物材料为前体，在一定的温度下煅烧，有机组分被烧掉，材料骨架收缩，材料内部和外部收缩不一致，导致形成金属氧化物核@空隙@金属氧化物壳的纳米材料。The material is based on a metal-organic coordination polymer material with a spherical shape as a precursor. When calcined at a certain temperature, the organic components are burned off, the material skeleton shrinks, and the internal and external shrinkage of the material is inconsistent, resulting in the formation of metal oxides. Core@void@metal oxide shell nanomaterials.
制备核壳材料的一个关键是以具有球形形貌的金属有机配位聚合物为前体。金属有机配位聚合物的是由金属离子与含有羧基基团的有机分子，在一定的溶剂和温度下配位聚合而成。A key to the preparation of core-shell materials is metal-organic coordination polymers with spherical morphology as precursors. Metal-organic coordination polymers are formed by coordination polymerization of metal ions and organic molecules containing carboxyl groups in a certain solvent and temperature.
所述具有球形形貌的金属有机配位聚合物材料的制备，其特征在于：所述金属盐指的是Mg、Ni、Zn、In、Y、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu的硝酸盐、硫酸盐、氯化盐、醋酸盐中的一种或者多种。有机配体为含有两个羧基基团的刚性有机分子，指的是间苯二甲酸及其芳环取代的衍生物,3,5-二羧酸吡啶及其芳环取代的衍生物，和1,5-萘二酸及其芳环取代的衍生物中的一种或者多种（图1）。取代基（R1-R6）为F、Cl、Br、I、NO2、CH3、OH、OCH3、NH2中的一种或者多种。The preparation of the metal-organic coordination polymer material with spherical morphology is characterized in that: the metal salt refers to Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, One or more of nitrates, sulfates, chlorides, and acetates of Ho, Er, Tm, Yb, and Lu. Organic ligands are rigid organic molecules containing two carboxyl groups, referring to isophthalic acid and its aromatic ring-substituted derivatives, 3,5-dicarboxylic acid pyridine and its aromatic ring-substituted derivatives, and 1 , one or more of 5-naphthalenedioic acid and its aromatic ring substituted derivatives (Figure 1). The substituent (R1 -R6 ) is one or more of F, Cl, Br, I, NO2 , CH3 , OH, OCH3 , NH2 .
为了使有机分子和金属盐单体充分均匀混合反应，需要使用合适的溶剂溶解有机分子单体，均匀反应。所述有机溶剂为乙腈、二甲基亚砜、二氧六环、甲苯、四氢呋喃和二甲酰胺中的一种或几种。In order to fully and uniformly mix and react organic molecules and metal salt monomers, it is necessary to use a suitable solvent to dissolve the organic molecule monomers and react uniformly. The organic solvent is one or more of acetonitrile, dimethyl sulfoxide, dioxane, toluene, tetrahydrofuran and dimethylamide.
反应温度和时间直接影响配位聚合和生长的速度，从而影响材料的尺寸。为了控制材料的尺寸在纳米级至微米级，优化条件为：反应温度为30-200℃,反应时间为10min-72h；Reaction temperature and time directly affect the speed of coordination polymerization and growth, thereby affecting the size of the material. In order to control the size of the material from nanometer to micrometer, the optimal conditions are: the reaction temperature is 30-200°C, and the reaction time is 10min-72h;
金属盐和有机分子单体的浓度影响着反应速率，反应速率快慢也直接影响材料的尺寸，同时金属盐和有机分子单体摩尔比例会直接关系材料的最终形貌。聚合反应中，所加原料中优化条件为：金属与有机分子的摩尔浓度为0.1-100mM；金属与含有羧酸基团的有机分子摩尔比为0.5-2。The concentration of metal salt and organic molecular monomer affects the reaction rate, and the speed of reaction also directly affects the size of the material. At the same time, the molar ratio of metal salt and organic molecular monomer will directly affect the final shape of the material. In the polymerization reaction, the optimized conditions in the added raw materials are: the molar concentration of the metal and the organic molecule is 0.1-100 mM; the molar ratio of the metal to the organic molecule containing the carboxylic acid group is 0.5-2.
一种核壳型金属氧化物及其制备方法，煅烧温度和时间影响了有机组分的去掉和材料的骨架收缩，直接影响到材料的结构。优化后煅烧温度为300-1000℃煅烧时间为0.5-24h。A core-shell metal oxide and a preparation method thereof, the calcination temperature and time affect the removal of organic components and the shrinkage of the material skeleton, directly affecting the structure of the material. After optimization, the calcining temperature is 300-1000°C and the calcining time is 0.5-24h.
本发明制备的金属氧化物核壳材料，具有颗粒大小可以调控，粒径均匀，分散性好等特点。The metal oxide core-shell material prepared by the invention has the characteristics of adjustable particle size, uniform particle size, good dispersibility and the like.
附图说明Description of drawings
图1羧酸有机配体结构示意图。Figure 1 Schematic diagram of the structure of carboxylic acid organic ligands.
图2材料A扫描电镜照片。Fig. 2 Scanning electron micrograph of material A.
图3材料AA透射电镜照片。Figure 3 Transmission electron micrograph of material AA.
具体实施方式detailed description
将一定浓度，和一定金属盐和有机羧酸小分子比例的有机分子溶解在溶剂之中，一定温度和时间下，反应聚合而成。金属盐为Mg、Ni、Zn、In、Y、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu中的硝酸盐、硫酸盐、氯化盐、醋酸盐中的一种或者多种。有机羧酸分子为间苯二甲酸及其芳环取代的衍生物，3,5-二羧酸吡啶及其取代的衍生物，和1,5-萘二酸及其芳环取代的衍生物中的一种或者多种。所述有机溶剂为乙腈、二甲基亚砜、二氧六环、甲苯、四氢呋喃和二甲酰胺中的一种或多种。将所得到的金属有机配位聚合物在一定温度下煅烧一定时间，得到金属氧化物核壳材料。反应优化条件为：金属盐与有机分子的摩尔浓度为0.1-100mM；金属与含有羧酸基团的有机分子摩尔比为0.5-2。反应温度为30-200℃，反应时间为10min-72h。煅烧温度为300-1000℃，煅烧时间为0.5-24h。Dissolve organic molecules with a certain concentration and a certain ratio of metal salts and organic carboxylic acid small molecules in a solvent, and react and polymerize at a certain temperature and time. Metal salts are Mg, Ni, Zn, In, Y, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu in nitrate, sulfate, chloride, acetate one or more of. Organic carboxylic acid molecules are isophthalic acid and its aromatic ring substituted derivatives, 3,5-dicarboxylic acid pyridine and its substituted derivatives, and 1,5-naphthalene dicarboxylic acid and its aromatic ring substituted derivatives one or more of. The organic solvent is one or more of acetonitrile, dimethyl sulfoxide, dioxane, toluene, tetrahydrofuran and dimethylformamide. Calcining the obtained metal-organic coordination polymer at a certain temperature for a certain period of time to obtain a metal oxide core-shell material. The optimized reaction conditions are as follows: the molar concentration of the metal salt and the organic molecule is 0.1-100 mM; the molar ratio of the metal to the organic molecule containing a carboxylic acid group is 0.5-2. The reaction temperature is 30-200°C, and the reaction time is 10min-72h. The calcination temperature is 300-1000°C, and the calcination time is 0.5-24h.
下面通过实施例对本发明提供的方法进行详述，但不以任何形式限制本发明。The method provided by the present invention is described in detail below through examples, but the present invention is not limited in any form.
实施例1材料A的制备The preparation of embodiment 1 material A
取0.3mmol间苯二甲酸和0.3mmol硝酸铕溶解在20mL二甲基亚砜中。100℃反应48h。冷却至室温后，离心，所得固体用50mL乙腈清洗，100℃下干燥24h。如图2所示，从扫描电镜可以看出所制的材料粒径均匀，具有规则的球形形貌，粒径约400nm。Take 0.3 mmol of isophthalic acid and 0.3 mmol of europium nitrate and dissolve in 20 mL of dimethyl sulfoxide. Reaction at 100°C for 48h. After cooling to room temperature, it was centrifuged, and the obtained solid was washed with 50 mL of acetonitrile, and dried at 100° C. for 24 h. As shown in Figure 2, it can be seen from the scanning electron microscope that the prepared material has a uniform particle size, a regular spherical shape, and a particle size of about 400nm.
实施例2材料B－O的制备The preparation of embodiment 2 material B-O
材料B－O的制备方法同材料A，不同之处在于金属源和有机配体及其浓度和摩尔比，反应温度、反应时间和反应溶剂。有机配体为间苯二甲酸、3，5-二羧酸吡啶、1,5-萘二酸及其它们芳环上取代的衍生物，制备条件和所得到的材料列于表1。The preparation method of material B-O is the same as that of material A, the difference lies in the metal source and organic ligand and its concentration and molar ratio, reaction temperature, reaction time and reaction solvent. The organic ligands are isophthalic acid, 3,5-pyridine dicarboxylate, 1,5-naphthalene dicarboxylic acid and their derivatives substituted on the aromatic ring. The preparation conditions and obtained materials are listed in Table 1.
表1材料B－O材料及其制备条件Table 1 Materials B-O materials and their preparation conditions
实施例3材料AA的制备The preparation of embodiment 3 material AA
将材料A放入管式炉中，空气气氛下，从室温下10℃min加热到600℃，保持3h。得到核壳材料AA。从图3电镜图片可以看到，所制备的材料为球形颗粒，具有明显的核壳结构，在外壳包裹的空腔中有明显的一个核，整个颗粒粒径约为350nm。Put material A into a tube furnace, heat it from room temperature at 10°C min to 600°C under air atmosphere, and keep it for 3h. The core-shell material AA is obtained. It can be seen from the electron microscope picture in Figure 3 that the prepared material is a spherical particle with an obvious core-shell structure, and there is an obvious core in the cavity wrapped by the shell, and the particle size of the whole particle is about 350nm.
实施例4材料BB-OO的制备The preparation of embodiment 4 material BB-OO
材料BB－OO的制备方法同材料AA，不同之处在于采用不同的金属有机配位聚合物，煅烧温度和时间。制备条件和所得到的材料列于表2。The preparation method of material BB-OO is the same as that of material AA, the difference lies in the use of different metal organic coordination polymers, calcination temperature and time. The preparation conditions and the obtained materials are listed in Table 2.
表2材料BB－OO材料及其制备条件Table 2 Material BB-OO material and its preparation conditions
具体应用用途：Specific application use:
本材料可以作为酸催化反应的催化剂。以苯甲醛与甲醇的缩合反应为例子：This material can be used as a catalyst for acid-catalyzed reactions. Take the condensation reaction of benzaldehyde and methanol as an example:
0.5mmol苯甲醛，0.05g催化剂和5mL甲醇加入到反应器中，室温下搅拌反应4h。产物用气相色谱分析。反应结果见表1。从表4可以看出，本发明合成的核壳型金属氧化物材料是一种非常好的酸催化剂，在苯甲醛与甲醇的缩合反应中表现出很好的催化效果。0.5mmol benzaldehyde, 0.05g catalyst and 5mL methanol were added to the reactor, and the reaction was stirred at room temperature for 4h. The product was analyzed by gas chromatography. The reaction results are shown in Table 1. It can be seen from Table 4 that the core-shell metal oxide material synthesized by the present invention is a very good acid catalyst, and shows a good catalytic effect in the condensation reaction of benzaldehyde and methanol.
表3苯甲醛与甲醇的缩合反应反应结果The condensation reaction reaction result of table 3 benzaldehyde and methanol
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