The effect of the temperature on the reduction kinetics of oxidized Ni(111) surfaces by hydrogen

The reduction kinetics of oxidized Ni(111) surfaces are measured in situ with ellipsometry in a temperature range between 450 and 675 K. The reaction rate is proportional to the square root of the hydrogen pressure below reduction temperatures of 525 K. The rate limiting step is the reaction between chemisorbed oxygen and dissociated hydrogen and has an experimental activation energy of 57 ± 7 kJ/mol. This reaction takes only place on the oxide free part of the Ni surface. Above 600 K, the reaction rate is proportional to the hydrogen pressure. The rate limiting step is the formation of water and has no experimental activation energy. At temperatures above 600 K the distribution of oxygen throughout the Ni crystal has a large effect on the reduction curves. A new reduction model is proposed that describes all the observed curves satisfactorily.