General Synthesis of Mixed Semiconducting Metal Oxide Hollow Spheres with Tunable Compositions for Low-Temperature Chemiresistive Sensing

Metal oxide hollow spheres (MOHSs) with multicomponent metal elements exhibit intriguing properties due to the synergistic effects of different components. However, it remains a great challenge to develop a general method to synthesize multicomponent MOHSs due to the different hydrolysis and condensation rates of precursors for different metal oxides. Herein, we demonstrate a general strategy for the controllable synthesis of MOHSs with up to five metal elements by decomposition of metal-phenolic coordination polymers (MPCPs), which are prepared by chelation of tannic acid with various metal ions. After calcination to burn out the organic component and induce heterogeneous contraction of MPCPs, a series of MOHSs with multishell structure, high specific surface area (55–171 m2/g), and crystalline mesoporous framework are synthesized, including binary (Fe–Co, Ni–Zn, and Ni–Co oxides), ternary (Ni–Co–Mn and Ni–Co–Zn oxides), and quinary (Ni–Co–Fe–Cu–Zn oxides) MOHSs. The gas sensing nanodevices based on quinary MOHSs show much higher response (10.91) than those based on single component toward 50 ppm of ethanol at 80 °C with the response/recovery time of 85/160 s. The quinary oxides sensor also displays high selectivity toward ethanol against other interfering gases (e.g., methanol, formadehyde, toluene, methane, and hydrogen) and long-term stability (∼94.0% after 4 weeks), which are extremely favorable for practical applications.