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Among oxide semiconductors, p -type Mn 3 O 4 systems have been exploited in chemo-resistive sensors for various analytes, but their use in the detection of H 2 , an important, though flammable, energy vector, has been scarcely investigated. Herein, we report for the first time on the plasma assisted-chemical vapor deposition (PA-CVD) of Mn 3 O 4 nanomaterials, and on their on-top functionalization with Ag and SnO 2 by radio frequency (RF)-sputtering, followed by air annealing. The obtained Mn 3 O 4 -Ag and Mn 3 O 4 -SnO 2 nanocomposites were characterized by the occurrence of phase-pure tetragonal α-Mn 3 O 4 (hausmannite) and a controlled Ag and SnO 2 dispersion. The system functional properties were tested towards H 2 sensing, yielding detection limits of 18 and 11 ppm for Mn 3 O 4 -Ag and Mn 3 O 4 -SnO 2 specimens, three orders of magnitude lower than the H 2 explosion threshold. These performances were accompanied by responses up to 25% to 500 ppm H 2 at 200 °C, superior to bare Mn 3 O 4 , and good selectivity against CH 4 and CO 2 as potential interferents. A rationale for the observed behavior, based upon the concurrence of built-in Schottky (Mn 3 O 4 /Ag) and p - n junctions (Mn 3 O 4 /SnO 2 ), and of a direct chemical interplay between the system components, is proposed to discuss the observed activity enhancement, which paves the way to the development of gas monitoring equipments for safety end-uses.

Hydrogen Gas Sensing Performances of p-Type Mn3O4 Nanosystems: The Role of Built-in Mn3O4/Ag and Mn3O4/SnO2 Junctions