Multiwalled Carbon Nanotube-Templated Nickel Porphyrin Covalent Organic Framework for Pencil-Drawn Noninvasive Respiration Sensors

Paper-integrated configuration with miniaturized functionality represents one of the future main green electronics. In this study, a paper-based respiration sensor was prepared using a multiwalled carbon nanotube-templated nickel porphyrin covalent organic framework (MWCNTs@COF_NiP-Ph) as an electrical identification component and pencil-drawn graphite electric circuits as interdigitated electrodes (IDEs). The MWCNTs@COF_NiP-Ph not only inherited the high gas sensing performance of porphyrin and the aperture induction effect of COFs but also overcame the shielding effect between phases through the MWCNT template. Furthermore, it possessed highly exposed M-N₄ metallic active sites and unique periodic porosity, thereby effectively addressing the key technical issue of room-temperature sensing for the respiration sensor. Meanwhile, the introduction of a pencil-drawing approach on common printing papers facilitates the inexpensive and simple manufacturing of the as-fabricated graphite IDE. Based on the above advantages, the MWCNTs@COF_NiP-Ph respiration sensor had the characteristics of wide detection range (1-500 ppm), low detection limit (30 ppb), acceptable flexibility for toluene, and rapid response/recovery time (32 s/116 s). These advancements facilitated the integration of the respiration sensor into surgical masks and clothes with maximum functionality at a minimized size and weight. Moreover, the primary internal mechanism of COF_NiP-Ph for this efficient toluene detection was investigated through in situ FTIR spectra, thereby directly elucidating that the chemisorption interaction of oxygen modulated the depletion layers, resulting in alterations in sensor resistance upon exposure to the target gas. The encouraging results revealed the feasibility of employing a paper-sensing system as a wearable platform in green electronics.