Field emission techniques for studying surface reactions: Applying them to NO–H2 interaction with Pd tips

Abstract

The adsorption of NO and its reaction with H(2) over Pd tips were investigated by means of field ion microscopy (FIM) and pulsed field desorption mass spectrometry (PFDMS) in the 10(-3)Pa pressure range and at sample temperatures between 400 and 600K. By varying the H(2) partial pressure while keeping the other control parameters constant, the NO+H(2) reaction over Pd crystallites is shown to exhibit a strong hysteresis effect. The hysteresis region narrows with increase in temperature and the H(2) pressures delimiting this hysteresis decrease as well. Abrupt transformations of the micrographs are observed by FIM from bright to dark patterns and vice versa. These transformations define the hysteresis region. The collected data allow establishing a novel kinetic phase diagram of the NO+H(2)/Pd system within the range of temperatures and pressures indicated. The observed features are correlated with a local chemical analysis by means of field pulses. NO(+) seems to be the dominating imaging species under all conditions. At high relative H(2) pressures (the "hydrogen-side"), H atoms seem to diffuse subsurface. This process is blocked at lower H(2) pressure (the "NO-side") due to NO(ad) and O(ad) accumulation on the surface. Probe-hole measurements with field pulses indicate that the Pd surface undergoes oxidation as revealed by the occurrence of PdO(2)(+) species in the mass spectra.