Cr–Fe–Ni–Cu Quaternary Nanostructure as a Substitute for Precious Metals in Automotive Three-Way Catalysts

Abstract

The replacement of precious metals (Rh, Pd, and Pt) in three-way catalysts with inexpensive and earth-abundant metal alternatives is an ongoing challenge. In this research, we examined various quaternary metal catalysts by selecting from six 3d transition metals, i.e., Cr, Mn, Fe, Co, Ni, and Cu, equimolar amounts (0.1 mol each), which were prepared on the Al 2 O 3 support (1 mol Al) using H 2 reduction treatment at 900 °C. Among 15 combinations, the best catalytic performance was achieved by the CrFeNiCu system. Light-off of NO−CO−C 3 H 6 −O 2 −H 2 O mixtures proceeded at the lowest temperature of ≤200 °C for CO, ≤300 °C for C 3 H 6 , and ≤400 °C for NO when the molar fraction of Cr in Cr x Fe 0.1 Ni 0.1 Cu 0.1 was around x = 0.1. The activity for CO/C 3 H 6 oxidation was superior to that of reference Pt/Al 2 O 3 catalysts but was less active for NO reduction. The structural analysis using scanning transmission electron microscopy and X-ray absorption spectroscopy showed that the as-prepared catalyst consisted of FeNiCu alloy nanoparticles dispersed on the Cr 2 O 3 −Al 2 O 3 support. However, the structural change occurred under a catalytic reaction atmosphere, i.e., producing NiCu alloy nanoparticles dispersed on a NiFe 2 O 4 moiety and Cr 2 O 3 −Al 2 O 3 support. The oxidation of CO/C 3 H 6 can be significantly enhanced in the presence of Cr oxide, resulting in a faster decrease in O 2 concentration and thus regenerating the NiCu metallic surface, which is active for NO reduction to N 2 .

Tandem Base-Metal Oxide Catalyst for Automotive Three-way Reaction: MnFe2O4 for Preferential Oxidation of Hydrocarbon

“…Various types of PGM-free catalysts have been proposed so far [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26], however, the low NO reduction activities are the serious problems in base metal oxide catalysts. For example, although NiFe 2 O 4 showed the highest NO reduction activity among base metal oxide-based TWC catalysts, the rate of NO reduction was only 1/8 of that of Rh/ZrO 2 [27].…”