Interaction of a Co–BEA catalyst with individual components (NO, C 3 H 6,CO,O 2) 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 spectroscopicoperando
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. N 2 Oisproduced
by semi-decomposition of the dinitrosyl intermediates on the mononuclear centers, whereas NO 2 via NO oxidation on the polynuclear oxo-cobalt sites. Cyanide and isocyanate species, formed together with propene oxygenates in the course of the CQC bond scission, are the mechanistically pivotal reaction intermediates of C 3 H 6 interaction with the dinitrosyles and NO 3 /NO 2 surface species.
Dinitrogen is produced by three main reaction routes involving oxidation of cyanides by NO/NO 2, reduction of dinitrosyls, nitrates, and nitrites by propene oxygenates (medium temperature range)
or their reduction by carbon monoxide (high temperature range)