MOF/MWCNT-Nanocomposite Manipulates High Selectivity to Gas via Different Adsorption Sites with Varying Electron Affinity: A Study in Methane Detection in Parts-per-Billion.

Abstract

Metal-organic frameworks (MOFs) present specific adsorption sites with varying electron affinity which are uniquely conducive to selective gas sensing but are typically large-band-gap insulators. On the contrary, multiwall carbon nanotubes (MWCNTs) exhibit superior mesoscopic transport exploiting strong electron correlations among sub-bands below and above the Fermi level at room temperature. We synergize them in a new class of nanocomposites based on zeolitic imidazolate framework-8 (ZIF-8) and report selective sensing of CH4 in ∼10 parts-per-billion (ppb) with a determined limit of detection of ∼0.22 ppb, hitherto unprecedented. The observed selectivity to CH4 over non-polar CO2, polar volatile organic compounds, and moisture has roots in competing electron-sharing mechanisms at its different adsorption sites. This important result provides a significant reference to guide future MOF-related composite research to achieve the best sensing performance. On molecular adsorption, MWCNTs facilitate electrical transport via manipulating the ZIF-8 band gap to show a p-type semiconductor behavior with lower activation energy to induce a measurable resistance change. Excellent repeatability and reversibility are shown. A carbon-engineered MOF composite has the potential to actuate similar selective response to low reactive gases via carrier manipulation in the energy band gap.