An ultra-sensitive NH3 gas sensor enabled by an ion-in-conjugated polycroconaine/Ti3C2Tx core–shell composite†

Abstract

MXenes are emerging sensing materials due to their metallic conductivity and rich surface chemistry for analytes; they, however, suffer from poor stability. Incorporation with functional polymers can largely prevent the performance decay and enhance the sensing performance. Herein, we demonstrate a core–shell composite, Ti₃C₂T_x@croconaine (poly(1,5-diaminonaphthalene-croconaine), PDAC) prepared by a facile in situ polymerization reaction, suitable for NH₃ detection. Compared to pristine Ti₃C₂T_x, the sensor made of a Ti₃C₂T_x–polycroconaine composite exhibits a significantly enhanced sensitivity of 2.8% ppm^?1 and an estimated achievable limit of detection of 50 ppb. The improved sensing performance could be attributed to the presence of PDAC facilitating the adsorption of NH₃ and changing the tunneling conductivity between Ti₃C₂T_x domains. Density functional theory (DFT) calculations reveal that the adsorption energy of NH₃ on PDAC is the highest among the tested gases, which supports the selectivity of the sensor to this analyte. Benefiting from the protection conferred by the PDAC shell, the composite has a reliable operation period of at least 40 days. In addition, we demonstrated a flexible paper-based sensor of the Ti₃C₂T_x@PDAC composite, without attenuated performance upon mechanical deformation. This work proposed a novel mechanism and a feasible methodology to synthesize MXene–polymer composites with improved sensitivity and stability for chemical sensing.