The temperature-programmed desorption of hydrogen from copper surfaces

The desorption kinetics of H₂ from a Cu/ZnO/Al₂O₃ catalyst for methanol synthesis were studied under atmospheric pressure in a microreactor set-up by performing temperature-programmed desorption (TPD) experiments after various pretreatments of the catalyst. Complete saturation with adsorbed atomic hydrogen was obtained by dosing highly purified H₂ for 1 h at 240 K and at a pressure of 15 bar. The TPD spectra showed symmetric H₂ peaks centered at around 300 K caused by associative desorption of H₂ from Cu metal surface sites. H₂ TPD experiments performed with different initial coverages resulted in peak maxima shifting to higher temperatures with lower initial coverages indicating that the desorption of H₂ from Cu is of second order. The microkinetic analysis of the TPD traces obtained with different heating rates yielded an activation energy of desorption of 78 kJ mol^-1 and a corresponding frequency factor of desorption of 3 × 10¹¹ s^-1 in good agreement with the kinetic parameters obtained with Cu(111) under UHV conditions.