MOF-Derived Co₃O₄ Dodecahedrons with Abundant Active Co³⁺ for CH₄ Gas Sensing at Room Temperature

Gas sensors based on metal oxide semiconductors (MOS) have attracted significant attention in monitoring of methane emission and leakage monitoring due to their high sensitivity, fast response time, simple structure and low cost. However, the high power consumption caused by long-term high-temperature operation of MOS sensors restricts their application in mobile and portable devices. In this study, MOF-derived Co₃O₄ dodecahedrons for low-concentration methane detection at room temperature was prepared using Zeolitic Imidazolate Framework-67 (ZIF-67) as a template and with various calcination temperatures. Among them, the Co₃O₄-350 calcined at 350 °C exhibited the optimal CH₄ sensing performance at room temperature, with a response of R_g/R_a = 1.53 to 2000 ppm CH₄. This enhanced gas sensing performance is attributed to the highest Co³⁺ proportions and the largest specific surface area in Co₃O₄-350 nanomaterials, which provided more active sites for gas adsorption and reaction. To address the challenge of slow response speed and irrecoverability during CH₄ detection at room temperature, the Co₃O₄ nanomaterials were printed onto a micro-heater plate (MHP) to form a MEMS gas sensor. By introducing a pulse heating mode to the MEMS sensor, the response and recovery time were significantly reduced to 26 s and 21 s, respectively. This enhancement improves both the efficiency and reliability of the MEMS gas sensor for early-stage detection of CH₄ leaks in various industrial applications.