Spectroscopic IR, EPR, and operandoDRIFT insights into surface reaction pathways of selective reduction of NO by propene over the Co–BEAzeolite

Abstract

Interaction of a Co–BEA catalyst with individual components (NO, C₃H₆, CO, O₂) and mixtures simulating the real feed of the selective catalytic reduction (SCR) of nitric oxide in static and pulse experiments at variable temperatures was investigated by means of IR, EPR, and operando DRIFT spectroscopy coupled with QMS/GC analysis of the products. Speciation of cobalt active sites into Co(II), mono- and polynuclear oxo-cobalt species as well as CoO clusters was quantified by IR using CO and NO as probe molecules. The key intermediates, by-products, and final products of the SCR reaction were identified and their spectroscopic signatures ascertained. Based on the spectroscopic operando results, a concise mechanistic scheme of the selective catalytic reduction of nitric oxide by propene, triggered by a two-electron Co(II)/Co(0) redox couple, was developed. It consists of a complex network of the sequential/parallel selective reduction steps that are interlocked by the rival nonselective oxidation of the intermediates and their thermal decomposition. It has been shown that the SCR process is initiated by the chemoselective capture of NO from the reaction mixture by the cobalt active sites leading to the cobalt(II) dinitrosyls, which in the excess of oxygen are partially oxidized to surface nitrates and nitrites. N₂O is produced by semi-decomposition of the dinitrosyl intermediates on the mononuclear centers, whereas NO₂via NO oxidation on the polynuclear oxo-cobalt sites. Cyanide and isocyanate species, formed together with propene oxygenates in the course of the CC bond scission, are the mechanistically pivotal reaction intermediates of C₃H₆ interaction with the dinitrosyles and NO₃⁻/NO₂⁻ surface species. Dinitrogen is produced by three main reaction routes involving oxidation of cyanides by NO/NO₂, reduction of dinitrosyls, nitrates, and nitrites by propene oxygenates (medium temperature range) or their reduction by carbon monoxide (high temperature range).