Chemical and electrochemical processes in low-temperature superionic hydrogen sulfide sensors

Effect the morphology of the surface of the working electrode (PbS) exerts on the sensitivity of a low-temperature potentiometric hydrogen sulfide sensor is studied. The sensor, which is based on electrochemical cell Na _x WO₃/NASICON/PbS, may be used for fast selective detection of hydrogen sulfide in air in natural conditions. It is demonstrated that the sensors with PbS that are deposited out of solution have a faster response than the pressed-to ones. The dependence of EMF on the hydrogen sulfide concentration for the former is linear in semilogarithmic coordinates. Thus difference is explained by the microstructure of the lead sulfide layer. It is shown that the lead sulfide interaction with hydrogen sulfide involves a reversible partial reduction of sulfur and lead at the surface. The species that form in so doing contain sulfur atoms in lower oxidation degrees (poly-and oligo sulfides, sulfite). A mechanism of the sensor operation is proposed on the basis of data yielded by experiment and quantum-chemical simulation. The mechanism includes reversible transport of hydrogen from sulfur atoms to oxygen atoms.