N2 emission-channel change in NO reduction over stepped Pd(211) by angle-resolved desorption

A sharp change in the N2 emission channel from N2O(a) → N2(g) + O(a) to N(a) + N(a) → N2(g) has been found at around 500 K in a steady-state NO + D2 reaction over stepped Pd(211) = [(S)3(111) × (100)] by means of angle-resolved desorption. The desorbing N2 is highly collimated at around 30° off normal toward the step-down direction below about 500 K due to the intermediate N2O decomposition, whereas, above 500 K, the near normally directed desorption due to the recombination of N(a) is relatively enhanced. The N2O decomposition channel is promoted when the reaction is carried out with hydrogen (deuterium) and the channel change is accelerated by quick changes of the amounts of surface hydrogen and oxygen (or NO(a)) into the opposite directions, and enhanced nitrogen removal as ammonia on the resultant hydrogen-rich surface. In the steady-state NO + CO reaction, the N2 emission channel gradually changes above 500 K toward recombination. A model for the off-normal N2 emission is briefly described.