TY - JOUR
T1 - Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios
AU - Giordanino, Filippo
AU - Vennestrøm, Peter N. R.
AU - Lundegaard, Lars Fahl
AU - Stappen, Frederick N.
AU - Mossin, Susanne
AU - Beato, Pablo
AU - Bordiga, Silvia
AU - Lamberti, Carlo
PY - 2013
Y1 - 2013
N2 - Cu-SSZ-13 has been characterized by different spectroscopic techniques and compared with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios and prepared by the same ion exchange procedure. On vacuum activated samples, low temperature FTIR spectroscopy allowed us to appreciate a high concentration of reduced copper centres, i.e. isolated Cu+ ions located in different environments, able to form Cu+(N2), Cu+(CO)n (n = 1, 2, 3), and Cu+(NO)n (n = 1, 2) upon interaction with N2, CO and NO probe molecules, respectively. Low temperature FTIR, DRUV-Vis and EPR analysis on O2 activated samples revealed the presence of different Cu2+ species. New data and discussion are devoted to (i) [Cu–OH]+ species likely balanced by one framework Al atom; (ii) mono(μ-oxo)dicopper [Cu2(μ-O)]2+ dimers observed in Cu-ZSM-5 and Cu-β, but not in Cu-SSZ-13. UV-Vis-NIR spectra of O2 activated samples reveal an intense and finely structured d–d quadruplet, unique to Cu-SSZ-13, which is persistent under SCR conditions. This differs from the 22 700 cm−1 band of the mono(μ-oxo)dicopper species of the O2 activated Cu-ZSM-5, which disappears under SCR conditions. The EPR signal intensity sets Cu-β apart from the others.
AB - Cu-SSZ-13 has been characterized by different spectroscopic techniques and compared with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios and prepared by the same ion exchange procedure. On vacuum activated samples, low temperature FTIR spectroscopy allowed us to appreciate a high concentration of reduced copper centres, i.e. isolated Cu+ ions located in different environments, able to form Cu+(N2), Cu+(CO)n (n = 1, 2, 3), and Cu+(NO)n (n = 1, 2) upon interaction with N2, CO and NO probe molecules, respectively. Low temperature FTIR, DRUV-Vis and EPR analysis on O2 activated samples revealed the presence of different Cu2+ species. New data and discussion are devoted to (i) [Cu–OH]+ species likely balanced by one framework Al atom; (ii) mono(μ-oxo)dicopper [Cu2(μ-O)]2+ dimers observed in Cu-ZSM-5 and Cu-β, but not in Cu-SSZ-13. UV-Vis-NIR spectra of O2 activated samples reveal an intense and finely structured d–d quadruplet, unique to Cu-SSZ-13, which is persistent under SCR conditions. This differs from the 22 700 cm−1 band of the mono(μ-oxo)dicopper species of the O2 activated Cu-ZSM-5, which disappears under SCR conditions. The EPR signal intensity sets Cu-β apart from the others.
U2 - 10.1039/c3dt50732g
DO - 10.1039/c3dt50732g
M3 - Journal article
C2 - 23842567
SN - 1477-9226
VL - 42
SP - 12741
EP - 12761
JO - Dalton Transactions
JF - Dalton Transactions
IS - 35
ER -