技术领域technical field
本发明属于金属有机复合材料技术领域，涉及以沸石咪唑酯骨架为模板制备纳米笼复合材料的方法，尤其涉及以ZIF-67为模板制备非球形中空结构纳米笼复合材料的方法。The invention belongs to the technical field of metal-organic composite materials, and relates to a method for preparing a nanocage composite material using a zeolite imidazolate skeleton as a template, in particular to a method for preparing a non-spherical hollow structure nanocage composite material using ZIF-67 as a template.
背景技术Background technique
金属有机骨架(MOFs)作为一种新型有机-无机杂化材料，可以将金属离子与有机配体在合适的溶剂中组装。此外，构成金属有机骨架化合物的金属元素和有机物可以在一定的条件下转化为金属/金属氧化物，由于MOFs 组成的均匀性和纯粹性，得到的金属氧化物具有非常均匀的结构与成分。Metal-organic frameworks (MOFs), as a new type of organic-inorganic hybrid materials, can assemble metal ions and organic ligands in suitable solvents. In addition, the metal elements and organic substances that constitute MOFs can be converted into metal/metal oxides under certain conditions. Due to the uniformity and purity of the composition of MOFs, the obtained metal oxides have a very uniform structure and composition.
金属有机骨架在气体储存、催化、传感和药物输送方面具有很大的潜力。近年来，由于MOF具有较高的表面积，良好的热稳定性和高孔隙率，因此作为模板和前体合成过渡金属的功能纳米材料，引起了广泛的关注。人们已经对MOFs的尺寸和形状控制合成进行了大量的实验，已经可以选择具有各种物种和结构的纳米和微尺度MOF作为模板，这扩大了模板的选择。但是迄今为止，尽管MOF模板策略取得了持续的进步，但由于MOF前体的形态有限，生产具有高度对称几何结构的各向异性空心结构仍然相对较少，并且缺乏形态多样性，阻碍了MOF及其衍生物更广泛地使用。因此，开发一种制造各向异性非球形中空结构的简单可靠的方法是非常必要的，且具有挑战性。Metal-organic frameworks hold great potential for gas storage, catalysis, sensing, and drug delivery. In recent years, due to their high surface area, good thermal stability, and high porosity, MOFs have attracted extensive attention as templates and precursors for the synthesis of functional nanomaterials of transition metals. Extensive experiments have been performed on the size- and shape-controlled synthesis of MOFs, and nano- and micro-scale MOFs with various species and structures can be selected as templates, which expands the choice of templates. But to date, despite continuous progress in MOF template strategies, the production of anisotropic hollow structures with highly symmetric geometries is still relatively rare due to the limited morphology of MOF precursors, and the lack of morphological diversity hinders MOF and Its derivatives are more widely used. Therefore, developing a simple and reliable method to fabricate anisotropic aspheric hollow structures is highly necessary and challenging.
三维(3D)中空结构引起了人们对其有趣结构特征和增强性能的极大兴趣，通常制造的三维(3D)中空纳米结构，可以增加电子的表面积和较短的扩散路径，公开报道的非球形中空结构的高曲率面和各向异性形态对其性质有着很大的影响。然而，关于具有非球形形态的中空结构的合成报道仍然很少。Three-dimensional (3D) hollow structures have aroused great interest in their interesting structural features and enhanced performance, commonly fabricated three-dimensional (3D) hollow nanostructures can increase the surface area and shorter diffusion paths for electrons, and publicly reported non-spherical The high-curvature surfaces and anisotropic morphology of hollow structures have a strong influence on their properties. However, there are still few synthetic reports on hollow structures with non-spherical morphologies.
沸石咪唑醋骨架化合物（ZIFs）是一类晶状多孔MOFs，ZIFs材料的结构与传统的沸石分子筛相似，但在构筑模式上又有着区别。ZIFs是由Zn或Co等过渡金属离子取代沸石中的Si和Al，咪唑或咪唑的衍生物取代沸石中的桥氧，通过咪唑环上的Ｎ原子相连接而形成的一种类沸石材料。ZIFs材料具有沸石和金属有机骨架的共同优点，例如高的比表面积、高的结晶度、优越的热稳定性和化学稳定性。Zeolite imidazolate framework compounds (ZIFs) are a kind of crystalline porous MOFs. The structure of ZIFs materials is similar to that of traditional zeolite molecular sieves, but there are differences in the construction mode. ZIFs are a zeolite-like material formed by substituting transition metal ions such as Zn or Co for Si and Al in zeolite, imidazole or imidazole derivatives for bridge oxygen in zeolite, and connecting through N atoms on the imidazole ring. ZIFs materials share the common advantages of zeolites and metal-organic frameworks, such as high specific surface area, high crystallinity, and superior thermal and chemical stability.
使用沸石咪唑ZIF-67纳米晶体作为模板获得具有非球形中空结构的功能性纳米笼复合材料，合成的复合材料具有不同壳组成的纳米笼的特点。特别是与单金属相比，多种过渡金属或各种金属氧化物杂化材料常常提供更好的容量和循环稳定性，这对能量装置是有益的。Using zeolite imidazole ZIF-67 nanocrystals as templates to obtain functional nanocage composites with non-spherical hollow structures, the synthesized composites have the characteristics of nanocages with different shell compositions. Especially compared with single metals, hybrid materials of multiple transition metals or various metal oxides often provide better capacity and cycle stability, which is beneficial for energy devices.
发明内容Contents of the invention
本发明的目的是以ZIF-67为模板制备非球形中空结构纳米笼复合材料。The purpose of the invention is to prepare non-spherical hollow structure nano cage composite material by using ZIF-67 as template.
模板法制备非球形中空结构纳米笼复合材料的方法，先合成ZIF-67纳米晶体，再以ZIF-67为模板，将其分散于硝酸盐的乙醇溶液中，搅拌、离心、干燥后，在300～350℃的空气中以2℃min-1的速率退火2～3ｈ制备而成。The method for preparing the non-spherical hollow structure nanocage composite material by the template method first synthesizes ZIF-67 nanocrystals, then uses ZIF-67 as a template, disperses it in the ethanol solution of nitrate, stirs, centrifuges, and dries it at 300 Prepared by annealing at a rate of 2°C min-1 in air at ~350°C for 2~3h.
其中，所述ZIF-67纳米晶体的合成，包括：称取硝酸钴和2-甲基咪唑分别溶解在甲醇中搅匀成溶液，其中硝酸钴和2-甲基咪唑的摩尔比为1：4.0～16，优选1:4，甲醇体积为25～45mL ，溶质单位为毫摩尔，优选25mL甲醇；然后将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，充分搅拌后室温老化12～36h，优选24h，经离心收集得到紫色沉淀物并在60℃下干燥12h得到ZIF-67纳米晶体。Wherein, the synthesis of the ZIF-67 nanocrystals includes: taking cobalt nitrate and 2-methylimidazole, respectively dissolving them in methanol and stirring to form a solution, wherein the molar ratio of cobalt nitrate and 2-methylimidazole is 1:4.0 ～16, preferably 1:4, the volume of methanol is 25～45mL, the unit of solute is millimole, preferably 25mL methanol; then quickly pour the 2-methylimidazole solution into the cobalt nitrate solution under stirring, and aging at room temperature for 12 ~36h, preferably 24h, the purple precipitate was collected by centrifugation and dried at 60°C for 12h to obtain ZIF-67 nanocrystals.
本发明的较优公开例中，所述硝酸盐为硝酸锌，硝酸铜或硝酸锌和硝酸铜二者混合物。In a preferred disclosed example of the present invention, the nitrate is zinc nitrate, copper nitrate or a mixture of zinc nitrate and copper nitrate.
本发明的较优公开例中，所述硝酸盐为六水合硝酸盐。In a preferred disclosed example of the present invention, the nitrate is nitrate hexahydrate.
本发明的一个较优公开例，所述硝酸盐为硝酸锌时制得ZnCo2O4@Co3O4非球形中空结构纳米笼，包括：将ZIF-67分散在硝酸锌的乙醇溶液中，所述ZIF-67：硝酸锌：乙醇的质量体积比为40mg ：20～80mg ：15～35mL，优选40mg ：80mg： 25mL，持续搅拌1h后，形成ZIF-67/ Zn-Co氢氧化物纳米笼颗粒通过离心并收集，60℃下干燥12h，然后在300～350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2～3ｈ，优选350℃，2h，得到ZnCo2O4@Co3O4非球形中空结构纳米笼。In a preferred disclosure example of the present invention, when the nitrate is zinc nitrate, ZnCo2 O4 @Co3 O4 non-spherical hollow structure nanocages are prepared, comprising: dispersing ZIF-67 in an ethanol solution of zinc nitrate, The mass volume ratio of ZIF-67: zinc nitrate: ethanol is 40mg: 20-80mg: 15-35mL, preferably 40mg: 80mg: 25mL, after continuous stirring for 1h, ZIF-67/ Zn-Co hydroxide nanocages are formed The particles were collected by centrifugation, dried at 60°C for 12h, and then annealed ZIF-67/Zn-Co hydroxide nanocage particles at a rate of 2°C min-1 in air at 300°C to 350°C for 2 to 3h, preferably at 350°C ℃, 2h, ZnCo2 O4 @Co3 O4 non-spherical hollow nanocages were obtained.
本发明的一个较优公开例，所述硝酸盐为硝酸铜时制得CuO@Co3O4非球形中空结构纳米笼，包括：将ZIF-67分散在硝酸铜的乙醇溶液中，所述ZIF-67：硝酸铜：乙醇的质量体积比为40mg ：20～80mg ：15～35mL，优选40mg ：80mg： 25mL，持续搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒通过离心并收集，在60℃下干燥12h，然后在300～350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2～3h，优选350℃，2h，得到CuO@Co3O4非球形中空结构纳米笼。In a preferred disclosure example of the present invention, when the nitrate is copper nitrate, CuO@Co3 O4 non-spherical hollow structure nanocages are prepared, comprising: dispersing ZIF-67 in an ethanol solution of copper nitrate, the ZIF -67: The mass volume ratio of copper nitrate: ethanol is 40mg: 20~80mg: 15~35mL, preferably 40mg: 80mg: 25mL. After continuous stirring for 1h, ZIF-67/Cu-Co hydroxide nanocage particles are formed by centrifugation and collected, dried at 60°C for 12h, and then annealed the ZIF-67/Cu-Co hydroxide nanocage particles at a rate of 2°C min-1 in the air at 300°C to 350°C for 2 to 3h, preferably at 350°C, 2h, CuO@Co3 O4 nanocages with non-spherical hollow structure were obtained.
本发明的一个较优公开例，所述硝酸盐为硝酸锌和硝酸铜等比例混合时制得CuO@ZnCo2O4@Co3O4非球形中空结构纳米笼：将ZIF-67分散在硝酸锌和硝酸铜的乙醇溶液中，所述ZIF-67：硝酸锌：硝酸铜：乙醇的质量体积比为40mg ：10～70mg：10～70mg ：15～35mL，优选40mg ：40mg：40mg：25mL，搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒通过离心并收集，在60℃下干燥12h，然后在300～350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2～3h，优选350℃，2h，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。In a preferred disclosure example of the present invention, the nitrate is CuO@ZnCo2 O4 @Co3 O4 non-spherical hollow structure nanocages obtained when zinc nitrate and copper nitrate are mixed in equal proportions: ZIF-67 is dispersed in nitric acid In the ethanol solution of zinc and copper nitrate, the mass volume ratio of ZIF-67: zinc nitrate: copper nitrate: ethanol is 40mg: 10～70mg: 10～70mg: 15～35mL, preferably 40mg: 40mg: 40mg: 25mL, After stirring for 1 h, the formed ZIF-67/Cu-Zn-Co hydroxide nanocage particles were collected by centrifugation, dried at 60 °C for 12 h, and then heated at a rate of 2 °C min in300–350 °C air The ZIF-67/Cu-Zn-Co hydroxide nanocage particles are annealed for 2-3 hours, preferably at 350° C. for 2 hours, to obtain CuO@ZnCo2 O4 @Co3 O4 nanocages with non-spherical hollow structure.
本发明所用的试剂皆为市售，分析纯。The reagents used in the present invention are all commercially available and analytically pure.
有益效果Beneficial effect
本发明以溶剂热法合成沸石咪唑ZIF-67纳米晶体，并以其作为模板，通过调节硝酸锌和硝酸铜的质量比合成中空结构的纳米笼复合材料。其操作条件易于控制，设备简单，制备成本低，所制产物颗粒分布均匀，粒径分散性良好，分体团聚程度较小，形貌较好，本发明工艺简单，原料易于得到，成本低廉，污染较少，适于工业化生产。The invention synthesizes zeolite imidazole ZIF-67 nano crystals by a solvothermal method, and uses the nano crystals as a template to synthesize a nano cage composite material with a hollow structure by adjusting the mass ratio of zinc nitrate and copper nitrate. The operating conditions are easy to control, the equipment is simple, the preparation cost is low, the particle distribution of the produced product is uniform, the particle size dispersion is good, the degree of separation and agglomeration is small, and the appearance is good. The process of the invention is simple, the raw materials are easy to obtain, and the cost is low. Less pollution, suitable for industrial production.
附图说明Description of drawings
图1为实施例1制得的非球形中空结构的CuO@ ZnCo2O4@Co3O4纳米笼复合材料的电子显微扫描电镜图（SEM）Figure 1 is the scanning electron micrograph (SEM) of the CuO@ZnCo2 O4 @Co3 O4 nanocage composite material with non-spherical hollow structure prepared in Example 1
图2为制得的非球形中空结构的纳米笼复合材料的X射线衍射图谱（XRD），其中a为实施例1制得的CuO@Co3O4非球形中空结构纳米笼，b为实施例1制得的ZnCo2O4@Co3O4非球形中空结构纳米笼,c为实施例1制得的CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。Figure 2 is the X-ray diffraction pattern (XRD) of the aspherical hollow nanocage composite material, where a is the CuO@Co3 O4 nonspherical hollow nanocage prepared in Example 1, and b is the example 1 is the ZnCo2 O4 @Co3 O4 non-spherical hollow nanocage prepared in Example 1, and c is the CuO@ZnCo2 O4 @Co3 O4 non-spherical hollow nanocage prepared in Example 1.
具体实施方式detailed description
下面结合具体实施实例对本发明做进一步说明，以使本领域技术人员更好地理解本发明，但本发明并不局限于以下实施例。The present invention will be further described below in conjunction with specific implementation examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
实施例1Example 1
称取1.0mmol硝酸钴和4.0mmol 2-甲基咪唑分别溶解在25mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化24小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 4.0 mmol of 2-methylimidazole and dissolve them in 25 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 24 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在25mL含有80mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Zn-Co hydroxide nanocage particles were annealed at 2°C min in air at 350°C for 2 hours to obtainZnCo2 O4 @Co3 O4 nanocages with non-spherical hollow structure .
将40mg ZIF-67分散在25mL含有80mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain CuO@Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在25mL含有40mg硝酸铜和40mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 40 mg of copper nitrate and 40 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn- Co hydroxide nanocage particles were annealed at a rate of 2 °C min in air at 350 °C for2 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
从图1可以看出合成的复合金属氧化物仍然保持着ZIF-67的空心多面体结构，表面变得粗糙，使得其有较多的活性位点，可以更好地与电解液接触，从多面体外壳的破碎处能够观察到纳米笼内壳的中空结构。而且纳米笼晶体尺寸差别不大，有利于电化学性能的发挥。从图2 XRD与标准卡片对比，没有检测到其它杂质的信号，表明产品的纯度高。It can be seen from Figure 1 that the synthesized composite metal oxide still maintains the hollow polyhedral structure of ZIF-67, and the surface becomes rough, so that it has more active sites and can better contact with the electrolyte, from the polyhedral shell The hollow structure of the inner shell of the nanocage can be observed at the broken place. Moreover, there is little difference in the size of the nanocage crystals, which is conducive to the exertion of electrochemical performance. From the comparison of XRD in Figure 2 with the standard card, no signals of other impurities are detected, indicating that the product is of high purity.
实施例2Example 2
称取1.0mmol硝酸钴和4.0mmol 2-甲基咪唑分别溶解在25mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化24小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 4.0 mmol of 2-methylimidazole and dissolve them in 25 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 24 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在25mL含有80mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在300℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Zn- Co hydroxide nanocage particles were annealed at a rate of 2°C min in air at 300°C for 2 hours to obtain ZnCo2 O4 @Co3 O4 nanocages with non-spherical hollow structure .
将40mg ZIF-67分散在25mL含有80mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在300℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 300°C for 2 hours to obtain CuO@Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在25mL含有40mg 硝酸铜和40mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在300℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 40 mg copper nitrate and 40 mg zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn- Co hydroxide nanocage particles were annealed at a rate of 2 °C min in air at 300 °C for2 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
实施例3Example 3
称取1.0mmol硝酸钴和16.0mmol 2-甲基咪唑分别溶解在45mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化36小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 16.0 mmol of 2-methylimidazole and dissolve them in 45 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 36 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在25mL含有80mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Zn-Co hydroxide nanocage particles were annealed at 2°C min in air at 350°C for 2 hours to obtainZnCo2 O4 @Co3 O4 nanocages with non-spherical hollow structure .
将40mg ZIF-67分散在25mL含有80mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain CuO@Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在25mL含有40mg硝酸铜和40mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 40 mg of copper nitrate and 40 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn- Co hydroxide nanocage particles were annealed at a rate of 2 °C min in air at 350 °C for2 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
实施例4Example 4
称取1.0mmol硝酸钴和4.0mmol 2-甲基咪唑分别溶解在25mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化12小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 4.0 mmol of 2-methylimidazole and dissolve them in 25 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 12 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在25mL含有80mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Zn-Co hydroxide nanocage particles were annealed at 2°C min in air at 350°C for 2 hours to obtainZnCo2 O4 @Co3 O4 nanocages with non-spherical hollow structure .
将40mg ZIF-67分散在25mL含有80mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain CuO@Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在25mL含有40mg硝酸铜和40mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 40 mg of copper nitrate and 40 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn- Co hydroxide nanocage particles were annealed at a rate of 2 °C min in air at 350 °C for2 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
实施例5Example 5
称取1.0mmol硝酸钴和4.0mmol 2-甲基咪唑分别溶解在25mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化24小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 4.0 mmol of 2-methylimidazole and dissolve them in 25 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 24 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在15mL含有20mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后在350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 15 mL of ethanol containing 20 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then the ZIF-67/Zn-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain ZnCo2 O4 @Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在15mL含有20mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 15 mL of ethanol containing 20 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain CuO@Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在15mL含有10mg硝酸铜和10mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 15 mL of ethanol containing 10 mg copper nitrate and 10 mg zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn- Co hydroxide nanocage particles were annealed at a rate of 2 °C min in air at 350 °C for2 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
实施例6Example 6
称取1.0mmol硝酸钴和4.0mmol 2-甲基咪唑分别溶解在25mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化24小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 4.0 mmol of 2-methylimidazole and dissolve them in 25 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 24 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在35mL含有80mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后在350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 35 mL of ethanol containing 80 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then the ZIF-67/Zn-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain ZnCo2 O4 @Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在35mL含有80mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 35 mL of ethanol containing 80 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain CuO@Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在35mL含有10mg硝酸铜和70mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 35 mL of ethanol containing 10 mg of copper nitrate and 70 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn- Co hydroxide nanocage particles were annealed at a rate of 2 °C min in air at 350 °C for2 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
实施例7Example 7
称取1.0mmol硝酸钴和4.0mmol 2-甲基咪唑分别溶解在25mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化24小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 4.0 mmol of 2-methylimidazole and dissolve them in 25 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 24 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在35mL含有80mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火2小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 35 mL of ethanol containing 80 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Zn-Co hydroxide nanocage particles were annealed at 2°C min in air at 350°C for 2 hours to obtainZnCo2 O4 @Co3 O4 nanocages with non-spherical hollow structure .
将40mg ZIF-67分散在35mL含有80mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火2小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 35 mL of ethanol containing 80 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed at 2°C min-1 in air at 350°C for 2 hours to obtain CuO@Co3 O4 non-spherical hollow nanocages.
将40mg ZIF-67分散在35mL含有70mg硝酸铜和10mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火2小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 35 mL of ethanol containing 70 mg of copper nitrate and 10 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn- Co hydroxide nanocage particles were annealed at a rate of 2 °C min in air at 350 °C for2 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
实施例8Example 8
称取1.0mmol硝酸钴和4.0mmol 2-甲基咪唑分别溶解在25mL甲醇中形成两种溶液。然后，将2-甲基咪唑溶液在搅拌下迅速倒入硝酸钴溶液中，搅拌5分钟后，所得混合溶液在室温下老化24小时。离心收集紫色沉淀物并在60℃下干燥12小时得到产物ZIF-67纳米晶体。Weigh 1.0 mmol of cobalt nitrate and 4.0 mmol of 2-methylimidazole and dissolve them in 25 mL of methanol to form two solutions. Then, the 2-methylimidazole solution was quickly poured into the cobalt nitrate solution under stirring, and after stirring for 5 minutes, the resulting mixed solution was aged at room temperature for 24 hours. The purple precipitate was collected by centrifugation and dried at 60°C for 12 hours to obtain the product ZIF-67 nanocrystals.
将40mg ZIF-67分散在25mL含有80mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 /Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Zn-Co氢氧化物纳米笼粒子退火3小时，得ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Zn- Co hydroxide nanocage particles were annealed at a rate of 2°C min in air at 350°C for 3 hours to obtain ZnCo2 O4 @Co3 O4 nanocages with non-spherical hollow structure .
将40mg ZIF-67分散在25mL含有80mg硝酸铜的乙醇中。搅拌1h后，形成ZIF-67 /Cu-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/Cu-Co氢氧化物纳米笼粒子退火3小时，得CuO@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 80 mg of copper nitrate. After stirring for 1 h, ZIF-67/Cu-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Co hydroxide nanocage particles were annealed in air at 350°C at a rate of 2°C min-1 for 3 hours to obtain CuO@Co3 O4 nanocages with non-spherical hollow structure.
将40mg ZIF-67分散在25mL含有40mg硝酸铜和40mg硝酸锌的乙醇中。搅拌1h后，形成ZIF-67 / Cu-Zn-Co氢氧化物纳米笼颗粒，离心并收集，最后在60℃下干燥12小时。然后，在350℃的空气中以2℃min-1的速率将ZIF-67/ Cu-Zn-Co氢氧化物纳米笼粒子退火3小时，得到CuO@ ZnCo2O4@Co3O4非球形中空结构纳米笼。40 mg of ZIF-67 was dispersed in 25 mL of ethanol containing 40 mg of copper nitrate and 40 mg of zinc nitrate. After stirring for 1 h, ZIF-67/Cu-Zn-Co hydroxide nanocage particles were formed, centrifuged and collected, and finally dried at 60 °C for 12 h. Then, the ZIF-67/Cu-Zn-Co hydroxide nanocage particles were annealed in air at 350 °C at a rate of2 °C min for3 h to obtainCuO @ZnCo2O4 @Co3O4 non- spherical Hollow structured nanocages.
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above is only an embodiment of the present invention, and does not limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made by the description of the present invention, or directly or indirectly used in other related technical fields, shall be the same as The theory is included in the patent protection scope of the present invention.
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| CN201710504837.3ACN107381659A (en) | 2017-06-28 | 2017-06-28 | The method that template prepares aspherical hollow structure nanocages composite |
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