Ricerc@Sapienza

Co-, Fe- or Ni-exchanged Na-MOR (Si/Al = 9.2) were prepared by ion-exchange method. The catalytic activity for N2O decomposition in the absence or in the presence of NO and for N2O reduction with CH4 in the absence of O2 (CRN2O), or in the presence of O2 (SCRN2O) was investigated. The catalytic measurements were performed in a flow apparatus with GC analysis of reactants and products. On Fe-MOR, in situ FTIR and UV–vis characterization evidenced coordinatively unsaturated sites (c.u.s.) Fe2+ arising from two families of Fe3+ dimers with different reducibility. Characterization and catalytic results combined with operando FTIR experiments gave an insight into the transition metal ion (tmi) species working during N2O abatement and into the reaction pathways. For N2O decomposition the activity order was Co-MOR > Fe-MOR in the absence of NO and Fe-MOR ≥ Co-MOR in the presence of NO, whereas Ni-MOR was always inactive. The decomposition occurred via redox mechanism passing through the formation of activated surface oxygen species, Oads *. The quasi-oxidic character of this activated oxygen in the Fe3+-O(1+δ)−—Fe(2+δ)+ intermediates with respect to the oxyl character of that in Co3+O‒ intermediates accounted for the lower activity and for the activity enhancement by NO addition to the feed of Fe-MOR with respect to Co-MOR. In Ni-MOR, both isolated or dimeric Ni2+ species were unable to be oxidized by N2O yielding Oads *. For N2O reduction, (CRN2O) and (SCRN2O), the activity order was Fe-MOR > Ni-MOR > Co-MOR. On all catalysts operando FTIR experiments revealed CHxOy intermediates (methoxy, formaldehyde and two types of formate species). The investigation of surface species changing the addition order of the reactants evidenced that the formation of CHxOy intermediates was favored on Co-MOR by pre-saturation with N2O, that yielded Co3+O− able to activate CH4, whereas on Ni-MOR by pre-saturation with CH4, that reduced Ni2+ dimers to Ni+ dimers, able to activate N2O. On Fe-MOR, the Fe2+ dimers formed during activation behaved as Co2+, whereas the Fe2+ dimers formed by reduction with CH4 behaved as Ni+ dimers. The formation and the stability of Oads * surface species were key factors for N2O decomposition and reduction pathways. These factors were affected by the mobility of the tmi electrons, that depends on the oxidation state, nuclearity and location in MOR framework of tmi. © 2018 Elsevier B.V.