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水热法制备的锰掺杂二氧化铈纳米颗粒的相组成、形态、性质及催化活性的提高

Phase composition, morphology, properties and improved catalytic activity of hydrothermally-derived manganese-doped ceria nanoparticles.

作者信息

Kurajica S, Ivković I K, Dražić G, Shvalya V, Duplančić M, Matijašić G, Cvelbar U, Mužina K

机构信息

University of Zagreb, Faculty of Chemical Engineering and Technology, Marulićev trg 19, HR-10 000 Zagreb, Croatia.

National Institute of Chemistry, Hajdrihova 19, SI-1001, Ljubljana, Slovenia.

出版信息

Nanotechnology. 2022 Jan 7;33(13). doi: 10.1088/1361-6528/ac44ed.

Abstract

Manganese-doped ceria nanoparticles were prepared by hydrothermal synthesis and the prepared samples were thermally treated at 500 °C for 2 h. The samples were investigated using x-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), energy-dispersive x-ray spectroscopy (EDS), Nadsorption and x-ray photoelectron spectroscopy (XPS). XRD revealed that nanocrystalline ceria is the main phase in all samples, while a romanechite-like phase (NaMnO) appears in the sample doped with 30% of Mn. TEM coupled with EDS exposed the presence of the same phase in the sample doped with 20% Mn. While ceria particles have spherical morphology and particle size ranging from 4.3 to 9.2 nm, the rare crystals of the romanechite-like phase adopt a tubular morphology with a length of at least 1m. However, the decrease in the ceria lattice constant and the EDS spectra of the ceria nanoparticles clearly indicate that a substantial amount of manganese entered the ceria crystal lattice. Manganese doping has a beneficial impact on the specific surface area of ceria. XPS measurements reveal a decrease in the Ce/Ce + Cecontent in the doped samples which is replaced by Mn. Moreover, a drastic increase in adsorbed oxygen is observed in the doped samples which is the consequence of the increase in Mnspecies that promotes oxygen migrations to the surface of the sample. Compared to the pure sample, the doped samples showed significantly higher catalytic activity for the process of toluene oxidation.

摘要

通过水热合成法制备了锰掺杂二氧化铈纳米颗粒,并将制备的样品在500℃下热处理2小时。使用X射线衍射(XRD)、高分辨率透射电子显微镜(HR-TEM)、能量色散X射线光谱(EDS)、N吸附和X射线光电子能谱(XPS)对样品进行了研究。XRD表明,纳米晶二氧化铈是所有样品中的主要相,而在掺杂30% Mn的样品中出现了一种类似锰钠矿的相(NaMnO)。TEM与EDS联用表明,在掺杂20% Mn的样品中也存在相同的相。虽然二氧化铈颗粒具有球形形态,粒径范围为4.3至9.2 nm,但类似锰钠矿相的稀有晶体采用管状形态,长度至少为1μm。然而,二氧化铈晶格常数的降低和二氧化铈纳米颗粒的EDS光谱清楚地表明,大量的锰进入了二氧化铈晶格。锰掺杂对二氧化铈的比表面积有有益影响。XPS测量表明,掺杂样品中Ce/Ce + Ce含量降低,被Mn取代。此外,在掺杂样品中观察到吸附氧的急剧增加,这是促进氧向样品表面迁移的Mn物种增加的结果。与纯样品相比,掺杂样品对甲苯氧化过程表现出显著更高的催化活性。

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