Propane dehydrogenation(PDH)on Ga/H-ZSM-5 catalysts is a promising reaction for propylene production,while the detail mechanism remains debatable.Ga_(2)O_(2)^(2+)stabilized by framework Al pairs have been identified a...Propane dehydrogenation(PDH)on Ga/H-ZSM-5 catalysts is a promising reaction for propylene production,while the detail mechanism remains debatable.Ga_(2)O_(2)^(2+)stabilized by framework Al pairs have been identified as the most active species in Ga/H-ZSM-5 for PDH in our recent work.Here we demonstrate a strong correlation between the PDH activity and a fraction of Ga_(2)O_(2)^(2+)species corresponding to the infrared GaH band of higher wavenumber(GaHHW)in reduced Ga/H-ZSM-5,instead of the overall Ga_(2)O_(2)^(2+)species,by employing five H-ZSM-5 supports sourced differently with comparable Si/Al ratio.This disparity in Ga_(2)O_(2)^(2+)species stems from their differing capacity in completing the catalytic cycle.Spectroscopic results suggest that PDH proceeds via a two-step mechanism:(1)C-H bond activation of propane on H-Ga_(2)O_(2)^(2+)species(rate determining step);(2)β-hydride elimination of adsorbed propyl group,which only occurs on active Ga_(2)O_(2)^(2+)species corresponding to GaHHW.展开更多
文摘Propane dehydrogenation(PDH)on Ga/H-ZSM-5 catalysts is a promising reaction for propylene production,while the detail mechanism remains debatable.Ga_(2)O_(2)^(2+)stabilized by framework Al pairs have been identified as the most active species in Ga/H-ZSM-5 for PDH in our recent work.Here we demonstrate a strong correlation between the PDH activity and a fraction of Ga_(2)O_(2)^(2+)species corresponding to the infrared GaH band of higher wavenumber(GaHHW)in reduced Ga/H-ZSM-5,instead of the overall Ga_(2)O_(2)^(2+)species,by employing five H-ZSM-5 supports sourced differently with comparable Si/Al ratio.This disparity in Ga_(2)O_(2)^(2+)species stems from their differing capacity in completing the catalytic cycle.Spectroscopic results suggest that PDH proceeds via a two-step mechanism:(1)C-H bond activation of propane on H-Ga_(2)O_(2)^(2+)species(rate determining step);(2)β-hydride elimination of adsorbed propyl group,which only occurs on active Ga_(2)O_(2)^(2+)species corresponding to GaHHW.
基金supported by the Chinese Academy of Sciences(CAS)the Third World Academy of Sciences(TWAS)+1 种基金Higher Education Commission(HEC) Pakistanthe National Natural Science Foundation of China(21103173)~~
