Microplasma Band Structure Engineering in Graphene Quantum Dots for Sensitive and Wide-Range pH Sensing

pH sensing using active nanomaterials is promising in many fields ranging from chemical reactions to biochemistry, biomedicine, and environmental safety especially in the nanoscale. However, it is still challenging to achieve nanotechnology-enhanced rapid, sensitive, and quantitative pH detection with stable, biocompatible, and cost-effective materials. Here, we report a rational design of nitrogen-doped graphene quantum dot (NGQD)-based pH sensors by boosting the NGQD pH sensing properties via microplasma-enabled band-structure engineering. Effectively and economically, the emission-tunable NGQDs can be synthesized from earth-abundant chitosan biomass precursor by controlling the microplasma chemistry under ambient conditions. Advanced spectroscopy measurements and density functional theory (DFT) calculations reveal that functionality-tuned NGQDs with enriched -OH functional groups and stable and large Stokes shift along the variations of pH value can achieve rapid, label-free, and ionic-stable pH sensing with a wide sensing range from pH 1.8 to 13.6. The underlying mechanism of pH sensing is related to the protonation/deprotonation of -OH group of NGQDs, leading to the maximum pH-dependent luminescence peak shift along with the bandgap broadening or narrowing. In just 1 h, a single microplasma jet can produce a stable colloidal NGQD dispersion with 10 mg/mL concentration lasting for at least 100 pH detections, and the process is scalable. This approach is generic and opens new avenues for nanographene-based materials synthesis for applications in sensing, nanocatalysis, energy generation and conversion, quantum optoelectronics, bioimaging, and drug delivery.