On the role of redox properties of CuO/CeO2 catalysts in the preferential oxidation of CO in H2-rich gases

Abstract

Abstract CuO/CeO 2 catalysts with CuO content ranging from 0.5 wt.% to 8 wt.%, prepared by wet impregnation of commercial ceria, have been tested for the preferential oxidation of CO (CO-PROX) under H 2 -rich conditions at 70–210 °C. Catalytic activity increases up to 4 wt.% CuO content, with less concentrated catalysts showing higher intrinsic activity. Catalysts have been characterized by means of XRD, BET analysis and UV spectroscopy. Formation of segregated CuO clusters has been detected for Cu richest CuO/CeO 2 sample. Redox properties have been deeply investigated using TP analysis (H 2 TPR, CO TPR, TPO) of fresh or pre-treated samples. Participation of surface ceria, induced by the strong interaction with copper, to reduction/oxidation reactions in the temperature range explored (up to 430 °C) has been demonstrated. Different copper species and their reactivity towards H 2 and CO have been individuated by comparing TPR of fully oxidized catalysts with those of partially oxidized catalysts. Active species have been identified as copper-ceria sites able to oxidize CO even at room temperature and to be re-oxidized by O 2 at the same temperature. Transient experiments have been carried out at different temperature using a diluted mixture starting from oxidized or reduced catalysts and followed by a H 2 TPR of the used samples. The results of these tests have showed that active centres for CO oxidation contain copper in the +2 oxidation state. At T > 100 °C some reduced copper sites are stabilized which promote H 2 oxidation thus lowering the selectivity of the CO-PROX process.