The influence of well-defined steps on the water formation by reaction
of surface oxygen with postadsorbed hydrogen on Ru(001) has been stud
ied in the temperature range 300-600 K. The reaction rate for the step
ped surface (8% step density) is considerably higher than for the flat
surface, which is partly due to a higher sticking coefficient of hydr
ogen molecules. In agreement with the observations on flat Ru(001), th
e reaction rate vanishes when approaching an oxygen coverage of 0.25 M
L. This is explained by structure sensitivity of the reaction rare: at
0.25 ML an unreactive O(2 x 2) superstructure is formed while at high
er oxygen coverages a transformation into much more reactive O(2 x 1)
domains occurs. At coverages close to 0.5 ML, the reaction slows down
due to the vanishing sticking coefficient of hydrogen molecules on the
O(2 x 1) areas. The reaction of coadsorbed oxygen and hydrogen atoms
therefore occurs primarily at the rim of the reactive O(2 x 1) domains
. At intermediate oxygen coverages a bimodal behavior of the reaction
rate is found which is due to the formation of O(2 x 1) islands of dif
ferent size, depending on the pretreatment of the layer. Under the rea
ction conditions used here the reaction rate is linearly dependent on
the hydrogen background pressure, which indicates that the intermediat
e OH species is only short-lived.