The topography of nickel crystals during the reaction towards Ni(CO) 4; A field ion microscope study

Abstract

The structural aspect of the formation of Ni(CO) 4 by the reaction of CO with solid nickel has been studied. The nickel initial state was a nearly hemispherical single crystal as prepared by field evaporation of a nickel field emitter tip. Field-free reaction of CO with the clean nickel surface took place at pressures up to 2 mbar, reaction times up to 45 h, and at a temperature of 373 K, which as a result from work by others was found optimum for highest rates of Ni(CO) 4 formation. Neon field ion imaging at 80 K after reaction with CO showed the crystal always in an intermediate state, which had the features: (1) Areas of {;111} were increased; (2) at half angles between a central (111) and peripherical {111} planes there were {110} planes flanked by {210}, and {100} flanked by {511}, respectively; (3) with the exception of the planes mentioned in feature (2), the remaining surface area was more than mono-atomically stepped. From these results and in accordance with the theory of crystal growth (Kossel, Stranski) and the theory of crystal dissolution (Lacmann, Franke, Heimann) a pure octahedron is expected to be the final state of the crystal. This implies that nickel atoms removed by the reaction are most frequently taken from 〈110〉 atom chains of the {111} planes.