Regulation of the copper-oxide cluster structure and DeNOx activity of Cu-ZSM-5 catalysts by variation of OH/Cu2+
The present work studies RedOx properties and reactivity in N2O decomposition and selective catalytic reduction of NO (NO-SCR) by propane of Cu-modified ZSM-5 catalysts prepared by hydrolytic polycondensation (HPC). Their characteristics are compared with properties of Cu-ZSM-5 samples having the same copper content (1 wt.%) and produced by ion exchange (IEX) with water–ammonia solutions of copper chloride at NH4OH/Cu2+ equal to 6–30.The HPC method consists in the treatment of the copper-impregnated zeolite by water–ammonia solution for polycondensation of hydrolyzed copper ions in the zeolite pores. It is shown that varying the NH4OH/Cu2+ ratio allows a regulation of the size and structure of copper active complexes. The copper-impregnated zeolite contains copper as CuO-like particles after calcination. At NH4OH/Cu2+ equal to 1–3, active sites in dried samples are disordered polynuclear copper-hydroxo complexes, which are characterized by symmetric ESR signal with g0 = 2.18. Increase of NH4OH/Cu2+ to 6–30 lead to the orbital ordering of Cu2+ ions in the copper–ammoniate complexes, observed as the rhombic ESR signals (gzex,1 = 2.18, gyex,1 = 2.08, gxex,1 = 2.03 and g∥ex,2 = 2.24, g⊥ex,2 = 2.03), and to dispersion of CuO-like particles during following thermal treatment at 500 °C. The dried 1%Cu(30)ZSM-5-HPC sample prepared at NH4OH/Cu2+ = 30 has a higher amount of isolated tetraammine–copper complex and a lower number of weak associates of Cu2+ ions among samples.The addition of ammonia solution to the copper-impregnated zeolite for hydrolytic polycondensation has a favorable impact on the Cu-ZSM-5 activity in DeNOx processes. In N2O decomposition, the ion-exchanged CuZSM-5 catalysts were more reactive in the low-temperature region, while the ex-polycondensation catalysts provided a high N2O conversion at high temperatures. In NO-SCR by propane, the more reactive were the ion-exchanged catalysts, and NO reduction rate increased with NH4OH/Cu2+ grew for 10. It is suggested that the ordered associated Cu2+ ions of ex-polycondensation and ion-exchanged catalysts have higher reactivity and selectivity in both DeNOx processes as compared to the isolated copper ions.
Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (179 K)Download as PowerPoint slideHighlights► The structure of copper-oxide cluster in 1 wt.%Cu-ZSM-5 prepared by polycondensation at different NH4OH/Cu2+ is studied. ► At NH4OH/Cu2+ equal to 1–3, the disordered polynuclear copper-hydroxo complexes are formed in dried samples. ► Increase in NH4OH/Cu2+ to 6–30 leads to formation of Cu2+ ammoniate ions and their orbital ordering in weak associates. ► The addition of ammonia promoted dispersion of CuO-like particles during following thermal treatment at 500 °C. ► Variation of the NH4OH/Cu2+ has a favorable impact on the 1 wt.%Cu-ZSM-5 activity in N2O decomposition and NO-SCR by propane.
Journal: Catalysis Today - Volume 197, Issue 1, 15 December 2012, Pages 214–227