Departamento de Química, Facultad de Ciencias, Universidad de Chile, Las Palmeras 3425, Ñuñoa, Casilla 653, Santiago 7800003, Chile.
Instituto de Ciencias Químicas Aplicadas, Grupo de Investigación en Energía y Procesos Sustentables, Facultad de Ingeniería, Universidad Autónoma de Chile, Av. El Llano Subercaseaux 2801, Santiago 8900000, Chile.
Int J Mol Sci. 2022 Jan 20;23(3):1093. doi: 10.3390/ijms23031093.
Nanomaterials have attracted much attention over the last decades due to their very different properties compared to those of bulk equivalents, such as a large surface-to-volume ratio, the size-dependent optical, physical, and magnetic properties. A number of solution fabrication methods have been developed for the synthesis of metal and metal oxides nanoparticles, but few solid-state methods have been reported. The application of nanostructured materials to electronic solid-state devices or to high-temperature technology requires, however, adequate solid-state methods for obtaining nanostructured materials. In this review, we discuss some of the main current methods of obtaining nanomaterials in solid state, and also we summarize the obtaining of nanomaterials using a new general method in solid state. This new solid-state method to prepare metals and metallic oxides nanostructures start with the preparation of the macromolecular complexes chitosan·Xn and PS-co-4-PVP·MXn as precursors (X = anion accompanying the cationic metal, n = is the subscript, which indicates the number of anions in the formula of the metal salt and PS-co-4-PVP = poly(styrene-co-4-vinylpyridine)). Then, the solid-state pyrolysis under air and at 800 °C affords nanoparticles of M°, MO depending on the nature of the metal. Metallic nanoparticles are obtained for noble metals such as Au, while the respective metal oxide is obtained for transition, representative, and lanthanide metals. Size and morphology depend on the nature of the polymer as well as on the spacing of the metals within the polymeric chain. Noticeably in the case of TiO, anatase or rutile phases can be tuned by the nature of the Ti salts coordinated in the macromolecular polymer. A mechanism for the formation of nanoparticles is outlined on the basis of TG/DSC data. Some applications such as photocatalytic degradation of methylene by different metal oxides obtained by the presented solid-state method are also described. A brief review of the main solid-state methods to prepare nanoparticles is also outlined in the introduction. Some challenges to further development of these materials and methods are finally discussed.
在过去的几十年中，由于纳米材料具有与块状材料非常不同的性质，例如大的表面积与体积比、尺寸相关的光学、物理和磁性质，因此引起了人们的极大关注。已经开发了许多用于合成金属和金属氧化物纳米粒子的溶液制备方法，但很少有报道固相方法。然而，将纳米结构材料应用于电子固态器件或高温技术需要获得纳米结构材料的适当的固态方法。在这篇综述中，我们讨论了一些获得固态纳米材料的主要当前方法，并且还总结了使用新的固态通用方法获得纳米材料的情况。这种用于制备金属和金属氧化物纳米结构的新型固态方法从制备高分子复合物壳聚糖·Xn 和 PS-co-4-PVP·MXn 作为前体开始（X 是伴随阳离子的阴离子，n 是下标，这表明金属盐的化学式中阴离子的数量和 PS-co-4-PVP = 聚（苯乙烯-co-4-乙烯基吡啶））。然后，在空气中并在 800°C 下进行固态热解，根据金属的性质得到 M°、MO 的纳米粒子。对于贵金属，如 Au，获得金属纳米粒子，而对于过渡金属、代表性金属和镧系金属，则获得相应的金属氧化物。纳米粒子的尺寸和形态取决于聚合物的性质以及聚合物链内金属的间隔。值得注意的是，在 TiO2 的情况下，可以通过配位在高分子聚合物中的钛盐的性质来调节锐钛矿或金红石相。基于 TG/DSC 数据概述了纳米粒子形成的机理。还描述了通过所提出的固态方法获得的不同金属氧化物的光催化降解亚甲基等一些应用。在引言中还概述了制备纳米粒子的主要固态方法的简要综述。最后讨论了这些材料和方法进一步发展的一些挑战。
