Unexpected Promotion Effect of H₂O on the Selective Catalytic Reduction of NO_<i>x</i> with NH₃ over Cu-SSZ-39 Catalysts

Water molecules commonly inhibit the selective catalytic reduction (SCR) of NOx with NH3 on most catalysts, and water resistance is a long-standing challenge for SCR technology. Herein, by combining experimental measurements and density functional theory (DFT) calculations, we found that water molecules do not inhibit and even promote the NOx conversion to some extent over the Cu-SSZ-39 zeolites, a promising SCR catalyst. Water acting as a ligand on active Cu sites and as a reactant in the SCR reaction significantly improves the O2 activation performance and reduces the overall energy barrier of the catalytic cycle. This work unveils the mechanism of the unexpected promotion effect of water on the NH3–SCR reaction over Cu-SSZ-39 and provides fundamental insight into the development of zeolite-based SCR catalysts with excellent activity and water resistance

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NO_<i>x</i> with NH₃

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet–visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu­(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu­(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu­(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NO_<i>x</i> with NH₃

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet–visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu­(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu­(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu­(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NO_<i>x</i> with NH₃

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet–visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu­(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu­(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu­(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites