Nanoarchitectured porous carbons derived from ZIFs toward highly sensitive and selective QCM sensor for hazardous aromatic vapors

Abstract

Metal-organic frameworks (MOFs) are a versatile source of carbon nanoarchitectures in gas sensing applications (Torad et al., 2019). Herein, several types of nanoporous carbons (NPCs) have been prepared by in-situ carbothermal treatment of zeolitic imidazolate frameworks (ZIFs) under different inert atmospheres to achieve a highly sensitive discrimination of vaporized aromatic compounds. In this study, we demonstrate how different carbonization conditions under the flow of N2 or H2 gases affect the surface area and the degree of graphitization of the resulting NPCs polyhedrons, and their consequent effect on the sensing performance in terms of sensitivity and selectivity toward toxic volatile hydrocarbons. A growth of carbon nanotubes (CNTs) is observed on the surface of polyhedral NPCs after careful carbonization of ZIF crystals under H2 atmosphere. The fabricated quartz crystal microbalance (QCM) sensor with CNT-containing NPCs demonstrates increased sensitivity and selectivity towards toxic volatile aromatic hydrocarbons over the aliphatic analogues, suggesting the rich growth of hairy graphitic-like CNTs on the surface of carbon framework act as highly selective sensing antennae for vapor molecular discrimination of toxic aromatic hydrocarbons. Despite of increased selectivity towards volatile aromatic compounds, however, the surface area of CNT-rich NPCs derived from hybrid ZIFs and ZIF-67 is greatly sacrificed as compared to CNT-free NPCs from ZIF-8 polyhedron. In the case of Co-containing ZIF-67, the rich growth of hair-like CNTs, which is induced by the presence of Co, is observed during carbothermal reduction under a flow of H2 gas, thus allowing ultra-selective detection of aromatic hydrocarbons in the vapor phase, such as benzene (C6H6) and toluene (C6H5CH3) over their aliphatic analogue, c-hexane (c-C6H12) of same molecular mass, size and vapor pressure.