Highly selective methane sensing based on enhanced dual sieving effects by ZnO/Pd@Co node-replaced ZIF-8 nanorods

Abstract

Highly selective methane sensing remains a formidable challenge in the field of metal oxide semiconductor (MOS)-based gas sensors. To address this issue, zeolitic imidazolate framework (ZIF) modulation is considered as an effective approach because of its pore size sieving and polarity sieving effects. In this work, core-shell ZnO/Pd@Co node-replaced ZIF-8 (ZIF-8/67) nanorods were synthesized by self-sacrificial template method, followed by post-synthetic modification of ZIF-8. When the replacement ratio of Co nodes reached 12.4%, ZnO/Pd@ZIF-8/67 exhibited a response of 12.2% to 500 ppm CH4 at 210°C but no response to 50 ppm CO, 50 ppm NH3 and 5 ppm NO2, showing excellent selectivity. By limiting rotational freedom of 2-methylimidazole, Co node replacement decreased the effective pore size from 4.0 to 4.2 Å to 3.8–4.0 Å and hindered the diffusion of NO2 with the dynamic diameter of 4.5 Å, thus enhancing the pore size sieving effect. Moreover, polarity sieving effect is also enhanced due to the favourable adsorption of polar CO (3.76 Å) and NH3 (2.6 Å) by ZIF. Therefore, the selectivity of nonpolar CH4 (3.8 Å) was improved. This work provides a new strategy for reasonably controlling and modulating the ZIF structure to achieve high selectivity in MOS-based sensors.