Surface Facet of CuFeO₂ Nanocatalyst: A Key Parameter for H₂O₂ Activation in Fenton-Like Reaction and Organic Pollutant Degradation

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Abstract

The development of efficient heterogeneous Fenton catalysts is mainly by "trial-and-error" concept and the factor determining H₂O₂ activation remains elusive. In this work, we demonstrate that suitable facet exposure to elongate O-O bond in H₂O₂ is the key parameter determining the Fenton catalyst's activity. CuFeO₂ nanocubes and nanoplates with different surface facets of {110} and {012} are used to compare the effect of exposed facets on Fenton activity. The results indicate that ofloxacin (OFX) degradation rate by CuFeO₂ {012} is four times faster than that of CuFeO₂ {110} (0.0408 vs 0.0101 min-1). In CuFeO₂ {012}-H₂O₂ system, OFX is completely removed at a pH range 3.2-10.1. The experimental results and theoretical simulations show that •OH is preferentially formed from the reduction of absorbed H₂O₂ by electron from CuFeO₂ {012} due to suitable elongation of O-O (1.472 Å) bond length in H₂O₂. By contrast, the O-O bond length is elongated from 1.468 to 3.290 Å by CuFeO₂ {110} facet, H₂O₂ tends to be dissociated into -OH group and passivates {110} facet. Besides, the new formed ≡Fe2+* on CuFeO₂ {012} facet can accelerate the redox cycle of Cu and Fe species, leading to excellent long-term stability of CuFeO₂ nanoplates.

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