Direct Electrochemical Sensing of Hydrogen Sulfide without Sulfur Poisoning

An electrochemical method capable of direct, real-time detection of hydrogen sulfide was developed using triple pulse amperometry (TPA) to mitigate sulfur poisoning and its related passivation of the working electrode surface. Through repeated cycles of discrete potential pulses, the electrooxidation of surface-adsorbed elemental sulfur to water-soluble sulfate ions was exploited to regenerate the glassy carbon electrode surface and maintain consistent sensor performance. Amperometric measurements and X-ray photoelectron spectroscopy surface analysis demonstrated that the TPA sensors provided enhanced analytical performance via decreased sulfur accumulation relative to low-potential (<=+0.7 V) constant potential amperometry. Sensors operated under optimized TPA parameters retained high sensitivity (57.4 +/- 13.0 nA/mu M), a wide linear dynamic range (150 nM-15 mu M), fast response times (<10 s), and a submicromolar detection limit (<100 nM) upon consecutive calibration cycles. The sensitivity and response time achieved were comparable to or better than current electrochemical sensors. Moreover, the simplicity of the method eliminates the need for external redox mediators or semipermeable membranes.