We combine gas phase Transient Response Methods with Transient Kinetic Analysis to investigate the reduction half-cycle (RHC: CuII → CuI) of the Standard SCR redox mechanism over Cu-CHA (chabazite) catalysts. The results confirm that NO + NH3 can readily reduce CuII at low temperatures (150–220 °C) according to a Cu:NO:NH3:N2 = 1:1:1:1 stoichiometry. The observed CuII reduction dynamics are invariant with the CuII speciation. Unexpectedly, the CuII reduction rates show a quadratic dependence on CuII, which is hardly compatible with the so far proposed single-site RHC mechanisms. The second order kinetics are found to apply under both dry and wet conditions (0% and 2% H2O v/v in the feed gas, respectively) across different temperatures, space velocities, and NO feed concentrations over two powdered Cu-CHA catalysts with different Cu loadings as well as over a commercial Cu-CHA washcoated honeycomb monolith catalyst. Another unprecedented finding is that H2O significantly inhibits the CuII reduction rate and lowers the RHC apparent activation energy. These findings provide for the first time a complete kinetic description of the low-temperature RHC reaction cascade and, from a mechanistic perspective, strongly suggest a dinuclear-CuII mediated RHC pathway, which may renew interrogations on the current mechanistic understanding of the CuII reduction pathway in the low-temperature NH3-SCR redox chemistry over Cu-CHA.

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As the state-of-the-art catalyst for the selective catalytic reduction (SCR) of NOx from lean-burn engines, Cu-exchanged chabazite zeolite (Cu-CHA) has been a spotlight in environmental catalysis because of its preeminence in DeNOx performance and hydrothermal stability. The microscopic cycling of active Cu cations between CuII and CuI in response to dynamic, macroscopic reaction conditions dominates SCR catalysis over Cu-CHA zeolites. In such cycling, Cu cations are solvated by gas-phase reactants, e.g., NH3, under low-temperature (LT) conditions, conferring peculiar mobility to Cu-NH3 complexes and making them act as mobilized entities during LT-SCR turnovers. Such motions provide LT-SCRa typical heterogeneous catalytic processwith homogeneous features over Cu-CHA, but, differently from conventional homogeneous catalysis, the motions are tethered by electrostatic interactions between Cu cations and conjugate Al centers. These features affect distinctly the LT-SCR redox chemistry on Cu-CHA, resulting in, for example, the involvement of two CuI-diamines in activating O2 and reoxidizing CuI to CuII (oxidation half-cycle, OHC). The kinetically relevant reduction half-cycle (RHC) that reduces CuII to CuI is far less understood particularly within the context of such linked homo- and heterogeneous catalysis. Here, we focus on the LT-RHC chemistry over Cu-CHA and summarize observations from a series of recent, dedicated works from our group, benchmarking these findings against those closely relevant in the literature. We thus attempt to reconcile and rationalize results informed from independent, multitechnique evidence and to further progress mechanistic insights into LT-SCR catalysis, especially in the context of dynamic interconversion between mono- and binuclear Cu sites.

The reduction (RHC: Cu II → Cu I ) and oxidation (OHC: Cu I → Cu II ) half-cycles of low-temperature (150−200 °C) NH 3 -selective catalytic reduction (SCR) were investigated by transient response methods over a model Cu-CHA catalyst (Cu loading = 1.8% w/w; silica to alumina ratio = 25). In line with previous findings: i) RHC proceeded via second-order kinetics in Cu II and with an equimolar stoichiometry between Cu II reduced and NO consumed; ii) complete reoxidation of reduced NH 3solvated Cu sites was achieved by exposing the catalyst to O 2 + H 2 O only, no other species (e.g., NO) were found to be relevant to the OHC pathway. Dedicated kinetic tests highlighted a secondorder dependence of the OHC rate on Cu I and a first-order dependence on O 2 . Coupling the RHC and OHC kinetic models, independently developed from transient tests, resulted in an accurate description of Standard SCR turnovers, predicting steady-state NO conversion, N 2 formation, and bed-average Cu-oxidation states, as well as light-off and extinction transients closely consistent with experimental measurements. These results demonstrate the rational dissection of the complex steady-state SCR reaction network into two redox half-cycles and provide a stoichiometrically and kinetically consistent closure of the Standard SCR redox cycle over Cu-CHA catalysts.

Low-temperature operation of NH3-SCR (selective catalytic reduction) systems for NOx abatement in lean streams raises major challenges caused by the need to fix different problems related to poor catalyst activity and to urea injection handling. In this respect, an important issue is related to the presence of unburned hydrocarbons (HCs) in the exhausts that may damage irreversibly the activity of the DeNOx catalysts. The purpose of the present perspective is to summarize the most important effects of HCs on NH3-SCR performances of commercial SCR catalysts, as well as to present a comprehensive inventory of available kinetic models. In particular, the following main aspects will be discussed, according to recent literature indications: (i) competitive adsorption between HC and NH3; (ii) effect of the zeolite structure on HC deactivation; (iii) potential formation of surface intermediates and active site blocking; (iv) pore physical blocking due to large HC molecules or coke formation; (v) possible parasitic reactions between HCs and SCR reagents; vi) description of the available kinetic models able to account for these effects; and vii) design of improved catalysts with enhanced hydrocarbon poisoning resistance.