Correlating the Integral Sensing Properties of Zeolites with Molecular Processes by Combining Broadband Impedance and DRIFT Spectroscopy--A New Approach for Bridging the Scales.

Zeolites have been found to be promising sensor materials for a variety of gas molecules such as NH3, NOx, hydrocarbons, etc. The sensing effect results from the interaction of the adsorbed gas molecules with mobile cations, which are non-covalently bound to the zeolite lattice. The mobility of the cations can be accessed by electrical low-frequency (LF; mHz to MHz) and high-frequency (HF; GHz) impedance measurements. Recent developments allow in situ monitoring of catalytic reactions on proton-conducting zeolites used as catalysts. The combination of such in situ impedance measurements with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), which was applied to monitor the selective catalytic reduction of nitrogen oxides (DeNOx-SCR), not only improves our understanding of the sensing properties of zeolite catalysts from integral electric signal to molecular processes, but also bridges the length scales being studied, from centimeters to nanometers. In this work, recent developments of zeolite-based, impedimetric sensors for automotive exhaust gases, in particular NH3, are summarized. The electrical response to NH3 obtained from LF impedance measurements will be compared with that from HF impedance measurements, and correlated with the infrared spectroscopic characteristics obtained from the DRIFTS studies of molecules involved in the catalytic conversion. The future perspectives, which arise from the combination of these methods, will be discussed.

Electronic parameters in cobalt-based perovskite-type oxides as descriptors for chemocatalytic reactions.

Perovskite-type transition metal (TM) oxides are effective catalysts in oxidation and decomposition reactions. Yet, the effect of compositional variation on catalytic efficacy is not well understood. The present analysis of electronic characteristics of B-site substituted LaCoO3 derivatives via in situ X-ray absorption spectroscopy (XAS) establishes correlations of electronic parameters with reaction rates: TM t2g and eg orbital occupancy yield volcano-type or non-linear correlations with NO oxidation, CO oxidation and N2O decomposition rates. Covalent O 2p-TM 3d interaction, in ultra-high vacuum, is a linear descriptor for reaction rates in NO oxidation and CO oxidation, and for N2O decomposition rates in O2 presence. Covalency crucially determines the ability of the catalytically active sites to interact with surface species during the kinetically relevant step of the reaction. The nature of the kinetically relevant step and of surface species involved lead to the vast effect of XAS measurement conditions on the validity of correlations.