Optimizing the sulfur-resistance and activity of perovskite oxygen carrier for chemical looping dry reforming of methane

Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modulate both the activity and resistance to sulfur poisoning by dual substitution of Mo and Ni ions with the Fe-sites of LaFeO_(3)perovskite.It is found that partial substitution of Ni for Fe substantially improves the activity of LaFeO_(3)perovskite,while Ni particles prefer to grow and react with H_(2)S during the long-term successive redox process,resulting in the deactivation of oxygen carriers.With the presence of Mo in LaNi_(0.05)Fe_(0.95)O_(3−σ)perovskite,H_(2)S preferentially reacts with Mo to generate MoS_(2),and then the CO_(2)oxidation can regenerate Mo via removing sulfur.In addition,Mo can inhibit the accumulation and growth of Ni,which helps to improve the redox stability of oxygen carriers.The LaNi_(0.05)Mo_(0.07)Fe_(0.88)O_(3−σ)oxygen carrier exhibits stable and excellent performance,with the CH_(4)conversion higher than 90%during the 50 redox cycles in the presence of 50 ppm H_(2)S at 800℃.This work highlights a synergistic effect in the perovskite oxides induced by dual substitution of different cations for the development of high-performance oxygen carriers with excellent sulfur tolerance.

Suppressing byproduct formation for high selective CO_(2) reduction over optimized Ni/TiO_(2) based catalysts

One of the challenges for catalytic CO_(2)reduction is to control product selectivity,and new findings that can modify selectivity would be transformative.Herein,two kinds of TiO_(2)(homemade and commercial)with the same crystal phase but different surface properties are chosen as supports to prepare Ni-based catalysts for CO_(2)reduction,which show distinctly different product selectivity for CO_(2)reduction to CH_(4) or CO,as well as the CO_(2)conversion.The catalysts based on the homemade TiO_(2)support are highly selective for CH_(4) formation,while the latter ones are about 100%selective for CO formation under the same reaction conditions.In addition,the former ones are much active(more than 3 times)than the latter ones.We found that the collaborative contribution of Ti^(3+)and Ni^(2+)species and the electronic metal-support interactions effect maybe the main driving force behind for determining the product selectivity.Methane is almost exclusively produced over the catalysts with abundant Ti^(3+)and Ni^(2+)species and greater electronic metal-support interaction,otherwise,it will give priority to CO generation.The addition of CeO_(2)can reduce the Ni particle size and improve the dispersion of Ni nanoparticles,as well as create more Ti^(3+)species,contributing to the enhancement of CO_(2)conversion,but shows a negligible effect on product selectivity.Furthermore,the in situ DRIFT experiments and kinetic experiments indicate that the CO route is probably involved in the CO_(2)reduction process over the homemade Ni-CeO_(2)/TiO_(2)-CO catalyst with abundant Ti^(3+)and Ni^(2+)species and a strong electronic transform effect.