Reduction Half-cycle Research Articles

Quantitative Kinetic Insights from Operando-UV/Vis Spectroscopy: An Application to NH3-SCR of NOx on Cu-CHA Catalysts.

We employ UV/Vis Diffuse Reflectance spectroscopy directly coupled with a packed bed flow reactor to extract quantitative kinetic information. We use as a show-case the CuII/CuI redox dynamics during the reduction half cycle of the NH3-Selective Catalytic Reduction (SCR) on Cu-CHA catalysts. Our measurements enable quantification of the fraction of oxidized Cu, reconstructed by Multivariate Curve Resolution (MCR) together with monitoring of the gas-phase evolution during the reaction. These data both on the dynamics of the gas-phase and of the active site oxidation state have been used to assess the reduction half cycle rate equation and estimate the rate constant. Our results in terms of reaction orders and kinetic constant are in line with previous findings in the literature. Overall, our results demonstrate that the combined analysis of the UV spectra and of the gas-phase dynamics provides converging and unparalleled kinetic insight: this approach effectively resolves ambiguities concerning RHC kinetics and mechanism. More in general, this work provides evidence that operando spectroscopy can be used to extract quantitative kinetic information on catalytic cycles.

Quantitative Kinetic Insights from Operando‐UV/Vis Spectroscopy: An Application to NH3−SCR of NOx on Cu‐CHA Catalysts

AbstractWe employ UV/Vis Diffuse Reflectance spectroscopy directly coupled with a packed bed flow reactor to extract quantitative kinetic information. We use as a show‐case the CuII/CuI redox dynamics during the reduction half cycle of the NH3‐Selective Catalytic Reduction (SCR) on Cu‐CHA catalysts. Our measurements enable quantification of the fraction of oxidized Cu, reconstructed by Multivariate Curve Resolution (MCR) together with monitoring of the gas‐phase evolution during the reaction. These data both on the dynamics of the gas‐phase and of the active site oxidation state have been used to assess the reduction half cycle rate equation and estimate the rate constant. Our results in terms of reaction orders and kinetic constant are in line with previous findings in the literature. Overall, our results demonstrate that the combined analysis of the UV spectra and of the gas‐phase dynamics provides converging and unparalleled kinetic insight: this approach effectively resolves ambiguities concerning RHC kinetics and mechanism. More in general, this work provides evidence that operando spectroscopy can be used to extract quantitative kinetic information on catalytic cycles.

Transient kinetic analysis of the standard SCR reduction half cycle on Cu-SSZ-13 catalysts: Roles of temperature, hydrothermal aging and H2O feed content

Transient Response Methods (TRM) are applied to investigate the reduction half-cycle (RHC) of the Standard SCR reaction over a state-of-the-art Cu-SSZ-13 catalyst at temperatures ranging from 135 to 350°C. We assess the effects of hydrothermal aging (HTA), water feed content and temperature on the reaction redox chemistry. By testing three samples with different aging levels, we reveal the CuII reduction rate to be unaffected by HTA in the whole T-range under investigation. Kinetic analysis assesses the inhibiting role of water on the RHC, consistent with literature. As long as enough NH3 is stored on the catalyst surface, reduction transients are accurately predicted assuming a second-order dependence of the reduction rate on the copper(II) fraction, also at temperatures exceeding 200°C. Remarkably, under wet conditions the low-T CuII reduction mechanism remains the same at least up to 300°C.

Microstructure and phase evolution of Fe-20Ni-20W foams during high-temperature redox cycling

Freeze-cast Fe-20Ni-20 W (at%) foams suitable for high-temperature redox cycling show excellent microstructural stability and regenerative porosity formation, but they exhibit slower reduction kinetics as compared to previously studied Fe-25 W foams. The Fe-20Ni-20 W lamellar foams, after initial hydrogen reduction, consist of a two-phase mixture of µ-Fe7W6 and γ-Fe(Ni,W), with significant microporosity due to the sintering inhibition of W. During oxidation by steam at 800 °C, these phases are oxidized to a three-phase mixture of (Fe,Ni)WO4, Fe3O4, and γ-Ni(Fe); upon subsequent reduction by H2, the foams return to their initial composition. The chemical vapor transport reduction of FeWO4 results in the formation of submicron pores during each reduction half-cycle which accelerate subsequent reaction and limit sintering in the reduced state. The reduction of mixed oxide is relatively sluggish, which is likely due to the increased stability of the (Fe,Ni)WO4 phase brought on by the substitution of Ni in Fe sites in FeWO4.

Assessing Cu2+ active sites evolution on Cu-SSZ-13 NH3-SCR catalysts during hydrothermal aging: A transient response approach

Hydrothermal aging (HTA) conditions are commonly reached in Diesel engine NH3-SCR architectures based on Cu-CHA catalysts, altering the catalyst performance due to irreversible transformations of the catalytic sites. Relying on transient response methods (TRMs), we study two Cu-SSZ-13 samples with different HTA extents. The following conclusions apply: i) the Cu2+content is invariant with HTA; ii) the ZCu2+(OH)- population decreases concurrent to the increase of the Z2Cu2+ fraction and to iii) the loss of Brønsted acidity. This evidence agrees with the simple stoichiometry proposed for mild HTA processes: ZCu2+(OH)-+ZH+→Z2Cu2++H2O. Furthermore, TRMs permit to observe additional phenomena which comply with a low-T Cu2+-pair mediated reduction pathway recently proposed. The results from a comprehensive set of simple experimental flow reactor methods consolidate the proposed aging mechanism, strengthen the SCR reduction half cycle (RHC) mechanistic understanding and showcase TRMs as a viable alternative to more complex techniques for the characterization of Cu-CHA catalysts.

Transient kinetic analysis of CO oxidation over a Cu-SSZ-13 catalyst proves complete conversion of ZCu2+(OH)- cations to binuclear Cu2+ species

The nuclearity of Cu2+ species active in the low-temperature Reduction Half Cycle (RHC) of NOx Selective Catalytic Reduction with NH3 over Cu-CHA catalysts is controversial. In the past, transient CO to CO2 oxidation protocols have been used to titrate binuclear Cu2+ species, and identified NH3-solvated ZCu2+(OH)- ions as their precursors. However, the prior results relied on asymptotic extrapolation due to the very slow CO oxidation kinetics. We herein present the results from a prolonged (24 h) CO titration experiment under dry conditions over an industrial Cu-SSZ-13 catalyst: the results demonstrate the conversion of all ZCu2+(OH)- ions to binuclear Cu2+ complexes and agree well with the extrapolation of a shorter (90 min) experiment, based on the assumption of the CO oxidation rate being second order in ZCu2+(OH)-. These outcomes confirm the adequacy of short CO oxidation tests to titrate ZCu2+(OH)- ions and support a Cu2+ pair mediated RHC pathway.

Front Cover: First‐principles Assessment of the Role of Water in the Reduction Half Cycle of Low‐Temperature NH3‐SCR over Cu‐CHA (ChemCatChem 20/2023)

Front Cover: First‐principles Assessment of the Role of Water in the Reduction Half Cycle of Low‐Temperature NH₃‐SCR over Cu‐CHA (ChemCatChem 20/2023)

First‐principles Assessment of the Role of Water in the Reduction Half Cycle of Low‐Temperature NH3‐SCR over Cu‐CHA

AbstractDispersion corrected density functional theory calculations show that the presence of H2O in the Reduction Half‐Cycle (RHC) of NH3‐SCR affects the free energy of the kinetically‐relevant transition state (TS) leading to a reduction in the rate and activation energy with respect to dry conditions. In particular, H2O enthalpically stabilizes the kinetically‐relevant TS by 20 kJ mol−1 with respect to the dry counterpart. Such enthalpic stabilization vanishes when van der Waals (vdW) interactions are excluded from the calculations, thus showing the preeminent role of non‐specific dispersion forces in the reduction of the activation enthalpy. At the same time, the enthalpic stabilization is more than compensated by the additional entropy losses of the TS brought forth by the presence of H2O in the CHA cage. Calculated enthalpy and entropy changes with respect to the dry case agree quantitatively with the experimental measurements and reflect the modified reacting environment in the presence of H2O. As a result, this study provides theoretical underpinnings on the mechanistic role of H2O in the RHC and, on a more general basis, highlights the importance of the molecular scale description of the reaction environment in voids of molecular dimensions.

A redox model for NO oxidation, NH3 oxidation and high temperature standard SCR over Cu-SSZ-13

A kinetic model is developed to predict the influence of temperature and hydrothermal aging on the redox of active Cu sites under standard SCR, NO oxidation and NH3 oxidation conditions over a practically relevant fully-formulated Cu-SSZ-13 catalyst. NO2/N2 production during NO/NH3 titration of CuII sites is utilized to identify rate parameters associated with NO-only RHC (reduction half cycle) and NH3-only RHC respectively. Integral N2 formation during subsequent NO + NH3 titration is consistent with the production of one NO2 per two CuII sites reduced during NO-only RHC and one N2 per six CuII sites reduced during NH3-only RHC. Decreased reduction of CuII sites by NO/NH3 upon hydrothermal aging, along with the production of one NO2 per two CuII sites during NO-only RHC, is accordant with the involvement of proximal ZCuOH and oxygen-bridged dimeric CuII sites. Oxidation of partially solvated and framework coordinated ZCu (CuI) sites occurs in presence of O2, does not produce N2 and can lead to the consumption of Brønsted acid sites. A global OHC kinetic model is developed to predict transient and integral N2 formation during exposure of CuI sites to a mixture of NO and O2. The resulting redox kinetic model quantitatively predicts NO and NH3 consumption during isothermal transient response Cu redox (TRCR) protocols, along with temperature and age dependent steady-state standard SCR and oxidation conditions. The redox model presented in this work synthesizes recent kinetic, spectroscopic and computational findings to provide a foundational description of active site redox during standard SCR, NO oxidation and NH3 oxidation over Cu-SSZ-13.

In Situ/Operando Spectroscopic Studies on the NH3–SCR Mechanism over Fe–Zeolites

Reduction/oxidation half-cycles of the selective catalytic reduction of NO with NH3 (NH3–SCR) over Fe-exchanged mordenite (MOR) zeolites at 300 °C were investigated by in situ/operando spectroscopy (infrared, UV–vis, and Fe K-edge X-ray absorption near edge structure) and density functional theory (DFT) calculation. The reduction of Fe3+ into Fe2+ and the simultaneous formation of N2 and H2O in the reduction half-cycle (under NO + NH3) were demonstrated by different spectroscopic results. In the subsequent oxidation half-cycle (under O2 or NO + O2), Fe2+ was reoxidized into Fe3+. The reduction half-cycle comprises several elementary steps. Reduction of Fe3+–OH by NO producing Fe2+ and NO+ species was observed at low temperatures (<100 °C), while N2 formation due to the reduction of NO+ was observed under subsequent NH3 exposure at 100 °C. Under transient conditions, NH3 on Brønsted acid sites (B–NH3) reacted with NO to generate N2 when the coverage of B–NH3 was low, indicating that B–NH3 is not a spectator but a reservoir of NH3. Transition state calculation theoretically suggested that the formation of nitrous acid (HONO) intermediates from [Fe3+(OH–)2]+ at a Al site and gaseous NO was a facile process (Ea = 29.2 kJ/mol). Combining the experimental observation and DFT calculation, the mechanism of the reduction half-cycle over Fe–zeolites was proposed; [Fe3+(OH–)2]+ is reduced by NO to produce a HONO intermediate, which then reacts with NH3 on Brønsted acid sites to yield H2O and N2 via NO+ species. Based on the mechanistic insights above, Fe–zeolites (MOR and β) with different Fe loadings and Si/Al ratios were tested for NH3–SCR reaction. Consequently, 2.7 wt % Fe-loaded zeolites with a relatively large number of Brønsted acid sites (Al-rich β with a Si/Al ratio of 5) showed the highest NOx conversion in a low-temperature region.

On the various Cu-redox pathways and O2-mediated Bronsted-to-Lewis adsorbed-NH3 redistribution under SCR half-cycle conditions

The Standard SCR reaction on Cu-SSZ-13 is a complex redox process facilitated by a reduction half cycle (RHC) and an oxidation half cycle (OHC). It is generally accepted that RHC requires the simultaneous presence of NO and NH3, while OHC requires both NO and O2; however understanding of how these individual reactants impact the Cu redox cycle is limited. In this study, we provide experimental investigation of NO-only, NH3-only and NO+NH3 RHC, and their relative rates. Simple kinetic models were developed to understand the dependance of NO-only and NH3-only RHC on Cu speciation. Various OHC routes including NO+O2 and O2-only OHC, and a previously unreported H2O-mediated OHC pathway were also investigated. Detailed NH3 temperature-programmed desorption studies showed that RHC selectively consumes NH3 adsorbed on Lewis-acid sites, and that part of the remaining Bronsted-bound NH3 moves to the Lewis-acid sites during subsequent OHC, thereby resulting in a repartitioning of adsorbed NH3.

Assessing impact of real-world aging on Cu-redox half cycles of a Cu-SSZ-13 SCR catalyst via transient response measurements and kinetic modeling

The SCR reaction on Cu-SSZ-13 is a redox process consisting of a reduction half-cycle (RHC) and an oxidation half-cycle (OHC). Despite extensive efforts to understand hydrothermal aging and sulfur poisoning, the impact of real-world aging on the SCR activity of Cu-SSZ-13 has not been reported. This work employs a transient response methodology consisting of experiments and kinetic models to investigate the SCR redox cycles at intra-catalyst locations of commercial Cu-SSZ-13 monolith catalysts in their degreened and real-world aged states, in the temperature range of 200–450 °C. Moreover, H2-TPR, NH3-TPD, SO2-TPD, ICP-OES and solid-state NMR were performed to investigate the catalyst properties. Sulfur aging and dealumination caused by real-world exposure decreased the reducible Cu density and SCR performance. Real-world aging was found to selectively slow OHC more than RHC, mainly due to lower mobility of the Cu ions coordinated to sulfur-related species leading to decreased formation of Cu-dimers necessary for OHC.

A Transient-Response methodology based on experiments and modeling for Cu-Redox Half-Cycle kinetic analysis on a Cu-SSZ-13 SCR catalyst

The Standard SCR reaction catalyzed by Cu-SSZ-13 is a redox process consisting of a reduction half cycle (RHC) and an oxidation half cycle (OHC) that cycle the active Cu sites between the Cu(II) and Cu(I) states. In the current work, a transient-response methodology consisting of experimental transient response Cu-redox (TRCR) measurements and kinetic modeling was developed for detailed study of individual SCR Cu-redox half cycles. The TRCR protocol allows quantification of the reducible Cu density, Cu(II)-Cu(I) partitioning, relative native RHC and OHC rates, and limiting half cycle during SCR. The half-cycle kinetics are studied over a wide (170–450 °C) temperature, and in differential segments along the catalyst length using spatially resolved capillary inlet mass-spectrometry (SpaciMS). The protocol alone provides two independent measures indicating that OHC increases faster than RHC with temperature, and that at all but the lowest temperature SCR is RHC limited. Introducing the transient kinetic models allows half-cycle reaction pathways, orders and activation energies to be studied and determined; e.g., RHC involves surface and gas-phase NH3 routes, and OHC with O2 involves dimer formation. Application of the full methodology provides further confirmation and quantification of the protocol conclusions, and specifically the first measurements of RHC and OHC activation energies; specifically for parallel RHC surface and gas-phase routes, and experimentally obtained OHC activation energy vs. first-principle calculations in the literature. Beyond insights related to the degreened catalyst studied here, the methodology provides a broadly available approach for quantifying how aging processes selectively impact RHC and OHC.

Transient Kinetic Analysis of Low-Temperature NH3-SCR over Cu-CHA Catalysts Reveals a Quadratic Dependence of Cu Reduction Rates on CuII

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)...

On the Redox Mechanism of Low‐Temperature NH3‐SCR over Cu‐CHA: A Combined Experimental and Theoretical Study of the Reduction Half Cycle

AbstractCu‐CHA is the state‐of‐the‐art catalyst for the Selective Catalytic Reduction (SCR) of NOx in vehicle applications. Although extensively studied, diverse mechanistic proposals still stand in terms of the nature of active Cu‐ions and reaction pathways in SCR working conditions. Herein we address the redox mechanism underlying Low‐Temperature (LT) SCR on Cu‐CHA by an integration of chemical‐trapping techniques, transient‐response methods, operando UV/Vis‐NIR spectroscopy with modelling tools based on transient kinetic analysis and density functional theory calculations. We show that the rates of the Reduction Half‐Cycle (RHC) of LT‐SCR display a quadratic dependence on CuII, thus questioning mechanisms based on isolated CuII‐ions. We propose, instead, a CuII‐pair mediated LT‐RHC pathway, in which NO oxidative activation to mobile nitrite‐precursor intermediates accounts for CuII reduction. These results highlight the role of dinuclear Cu complexes not only in the oxidation part of LT‐SCR, but also in the RHC reaction cascade.

On the Redox Mechanism of Low-Temperature NH3 -SCR over Cu-CHA: A Combined Experimental and Theoretical Study of the Reduction Half Cycle.

Cu-CHA is the state-of-the-art catalyst for the Selective Catalytic Reduction (SCR) of NOx in vehicle applications. Although extensively studied, diverse mechanistic proposals still stand in terms of the nature of active Cu-ions and reaction pathways in SCR working conditions. Herein we address the redox mechanism underlying Low-Temperature (LT) SCR on Cu-CHA by an integration of chemical-trapping techniques, transient-response methods, operando UV/Vis-NIR spectroscopy with modelling tools based on transient kinetic analysis and density functional theory calculations. We show that the rates of the Reduction Half-Cycle (RHC) of LT-SCR display a quadratic dependence on CuII , thus questioning mechanisms based on isolated CuII -ions. We propose, instead, a CuII -pair mediated LT-RHC pathway, in which NO oxidative activation to mobile nitrite-precursor intermediates accounts for CuII reduction. These results highlight the role of dinuclear Cu complexes not only in the oxidation part of LT-SCR, but also in the RHC reaction cascade.

Selective catalytic reduction of NO over Cu-AFX zeolites: mechanistic insights from in situ/operando spectroscopic and DFT studies

In situ/operando spectroscopic experiments and DFT calculations unravel the redox mechanism of NH3-SCR over Cu-AFX zeolites.

Spectral and structural insights of copper reduction pathways in the system of CuX2-R2S (X=Cl, Br; R=allyl, n-propyl)

We have explored the behaviour of Cu(II)/Cu(I) redox couple in the system CuX2-R2S, X = Cl, Br; R = allyl, n-propyl, under anhydrous and anaerobic conditions, thus simulating the reduction half cycle in the copper catalyzed oxidation of thioethers. In doing so, the Cl−Br substitution was critical for tuning the reduction potentials, while the replacement of propyl group by allyl group supported the trapping of oxidation by-product, halogen molecules. It was therefore possible to use the spectrophotometric titration, thereby providing information on the distribution of complex species in acetonitrile solution. The study showed that the trinuclear mixed−valence copper (I-II-II) aggregates play a crucial role in the evolution of the redox process. The crystal structures of mixed-valence phase, [CuICuII2Cl5(dipropylsulfide)2], as well as full-reduced Cu(I) species, [Cu5Br5(dipropylsulfide)3], have been also determined by single crystal X-ray diffraction. The first one is considered as one of crystallographic “snapshots” of an intermediate involved in sulfoxide formation, while the latter represents the end product built from porous chiral networks.

An experimental and modelling study of the reactivity of adsorbed NH3 in the low temperature NH3-SCR reduction half-cycle over a Cu-CHA catalyst

The reactivity of Lewis and Brønsted ammonia in the reduction half-cycle (RHC) of the NH3-SCR low temperature redox mechanism was studied over a model Cu−CHA catalyst by transient kinetic tests involving reductive NO pulses. The CuII sites were reduced according to a 1:1:1:1 molar ratio with NO and NH3 conversion and N2 formation. The ammonia coordinated to Cu sites (Lewis ammonia) was preferentially consumed prior to that stored on the Brønsted acid sites. The catalyst was effectively re-oxidized by O2 in He at 150 °C even when the Cu-coordinated ammonia was depleted. A redox kinetic model assuming NO activation by CuII to a gaseous mobile intermediate (HONO) which reacts first with Lewis-NH3 and then with Brønsted-NH3 was successfully fitted to our transient data assuming the CuII reduction rate to be second order in the CuII sites. This suggests a possible role of CuII dimeric complexes in the RHC of Standard SCR.

Low‐T CO Oxidation over Cu−CHA Catalysts in Presence of NH3: Probing the Mobility of CuII Ions and the Role of Multinuclear CuII Species

The Cover Feature portrays two CuII ions as trapeze artists swinging inside a CHA zeolite cage until they join hands to form a single complex. In their Communication, reporting CO titration experiments over preoxidized Cu-CHA catalysts, R. Villamaina et al. provide evidence that NH3 ligands, like trapezes, mobilize initially isolated CuII ions to form the dimeric complexes with removable oxygen needed for CO oxidation. This is confirmed by transient kinetic analysis, which shows that the rate of CuII reduction is 2nd order in the ZCuIIOH species. These findings may be relevant for elucidation of the reduction half cycle in the redox mechanism of the Standard NH3-SCR reaction over Cu-CHA systems. More information can be found in the Communication by R. Villamaina et al.