Catalytic reduction of NO on copper/MCM-41 studied by in situ EXAFS and XANES

Speciation of copper in the channels of MCM-41 during reduction of NO with CO at 473–773 K was studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The component fitted (in situ) XANES spectra of the catalyst showed that about 72% of metallic copper (Cu(0)) in MCM-41 was oxidized to higher oxidation state coppers (Cu(II) (46%) and Cu(I) (26%)) during the NO reduction process (at 473 K). By EXAFS, we also found that in the NO reduction process, oxygen was inserted into the metallic copper matrix and led to a formation of the copper oxide species with a Cu–O bond distance of 1.93 Å which was greater than that of the model compound Cu2O (typically 1.86 Å). At 573–673 K, mainly Cu(II) was found in the channels of MCM-41. Nevertheless, at a higher temperature (e.g., 773 K), about 61% Cu(I), 31% Cu(II), and 8% Cu(O) with averaged Cu–Cu and Cu–O bond distances of 3.04 and 1.88 Å, respectively were observed, that might account for the high selectivity-to-decomposition (S/D) ratios for yields of N2 and CO2 in the catalytic reduction of NO with CO.