The effects of amino substituents on the enhanced ammonia sensing performance of PcCo/rGO hybrids

Three reversible ammonia (NH3) gas sensors were fabricated using tetra-α-(p-aminobenzyloxy)phthalocyanine cobalt (ABOPcCo), tetra-α-aminophthalocyanine cobalt (APcCo) and substituent-free phthalocyanine cobalt (FPcCo) functionalized reduced graphene oxide (rGO), with cost-efficient, highly sensitive and stable sensing performance. These hybrid materials were prepared via a facile physical solution mixing self-assembly reaction with rGO and PcCo solutions. The obtained PcCo/rGO hybrid sensors exhibit excellent sensing performance; especially the ABOPcCo/rGO sensor, whose response is about 23.3% (50 ppm), with a limit of detection as low as 78 ppb, and response and recovery times about as fast as 225 s and 250 s. The performance of the PcCo/rGO hybrid sensors can be optimized by adjusting the concentrations of the PcCo/rGO aqueous dispersions. More importantly, the NH3-sensing performance of the PcCo/rGO sensors was tuned by adjusting the substituent structure of PcCo. The enhanced NH3-sensing performance may be attributed to synergistic effects between PcCo and rGO, e.g., stronger adsorption interactions between PcCo with an aminophenoxy substituent and NH3, the high electrical conductivity of rGO, and fast charge transfer between PcCo and rGO. These are further confirmed via first-principle density functional theory (DFT) calculations and electrochemical impedance spectra (EIS) measurements.