Catalytically activated palladium@platinum nanowires for accelerated hydrogen gas detection.

Abstract

Platinum (Pt)-modified palladium (Pd) nanowires (or Pd@Pt nanowires) are prepared with controlled Pt coverage. These Pd@Pt nanowires are used as resistive gas sensors for the detection of hydrogen gas in air, and the influence of the Pt surface layer is assessed. Pd nanowires with dimensions of 40 nm (h) × 100 nm (w) × 50 μm (l) are first prepared using lithographically patterned nanowire electrodeposition. A thin Pt surface layer is electrodeposited conformally onto a Pd nanowire at coverages, θPt, of 0.10 monolayer (ML), 1.0 ML, and 10 ML. X-ray photoelectron spectroscopy coupled with scanning electron microscopy and electrochemical measurements is consistent with a layer-by-layer deposition mode for Pt on the Pd nanowire surface. The resistance of a single Pd@Pt nanowire is measured during the exposure of these nanowires to pulses of hydrogen gas in air at concentrations ranging from 0.05 to 5.0 vol %. Both Pd nanowires and Pd@Pt nanowires show a prompt and reversible increase in resistance upon exposure to H2 in air, caused by the conversion of Pd to more resistive PdHx. Relative to a pure Pd nanowire, the addition of 1.0 ML of Pt to the Pd surface alters the H2 detection properties of Pd@Pt nanowires in two ways. First, the amplitude of the relative resistance change, ΔR/R0, measured at each H2 concentration is reduced at low temperatures (T = 294 and 303 K) and is unaffected at higher temperatures (T = 316, 344, and 376 K). Second, response and recovery rates are both faster at all temperatures in this range and for all H2 concentrations. For higher θPt = 10 ML, sensitivity to H2 is dramatically reduced. For lower θPt = 0.1 ML, no significant influence on sensitivity or the speed of response/recovery is observed.