General Synthesis and Gas‐Sensing Properties of Multiple‐Shell Metal Oxide Hollow Microspheres

Abstract

Hollow spheres with nanometer-to-micrometer dimensions, controlled internal structure, and shell composition have attracted tremendous attention because of their potential application in catalysis, drug delivery, nanoreactors, energy conversion and storage systems, photonic devices, chemical sensors, and biotechnology. Single-shell and double-shell hollow spheres of various compositions have been synthesized by a number of methods, such as vesicles, emulsions, micelles, gas-bubble, and hard-templating methods. More recently, efforts have focused on the fabrication of hollow spheres with multiple shells, as these materials are expected to have better properties for applications such as drug release with prolonged release time, heterogeneous catalysis, lithiumion batteries, and photocatalysis. For example, multipleshell hollow microspheres of Cu2O have been prepared by vesicle templating and an intermediate-templating phasetransformation process. Multiple-shell azithromycin hollow microspheres were fabricated by hierarchical assembly. Cao and co-workers reported the synthesis of tripleshelled SnO2 hollow microspheres by chemically induced selfassembly in the hydrothermal environment which exhibited enhanced electrochemical performance. Yao and co-workers reported excellent cycle performance and enhanced lithium storage capacity of multiple-shell Co3O4 hollow microspheres synthesized by oriented self-assembly. These preparative methods, however, are suited for each specific material and cannot be applied generally to a wide range of materials. Currently, there is no general synthetic approach for fabricating multiple-shell hollow nanostructures of any desired material. Herein, we present a straightforward and general strategy to prepare metal oxide hollow microspheres with a controlled number of shells. Carbonaceous microspheres were used as sacrificial templates. The microspheres were saturated with a desired metal salt solution and then heated in air; the carbonaceous template evaporates and templates the formation of metal oxide shells. The number of shells is controlled by the metal ion loading and the process is general for a wide range of metal oxide materials. Scheme 1 illustrates the general process of fabricating multiple-shell hollow metal oxide microspheres. The key to this process is the use of carbonaceous particles rich with surface functional groups available for metal ion adsorption.