The segregation of boron and its reactivity toward nitric oxide have been investigated by means of high-resolution Auger spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and thermal desorption spectroscopy (TDS). The segregation of boron from a Rh foil started from 700 K. Its presence altered the surface behaviors of Rh; the uptake of NO increased by about 30-37%. Whereas the dissociation of NO was about 3-10% on a clean, boron-free surface, the extent of dissociation (at saturation) at highest boron level was almost 98%. This feature strongly suggest a direct interaction between NO and boron on the surface. The presence of boron greatly stabilized the adsorbed nitrogen and oxygen formed in NO dissociation. Boron oxide (BO, B2O2) sublimated from the surface below 1000 K. Clean, single BN layer formed on the surface close to a monolayer regime, presumable in nanomash structure. (C) 2012 Elsevier B. V. All rights reserved.