La_1–<i>x</i>Sr_<i>x</i>FeO_3−δ Perovskite Oxide Nanoparticles for Low-Temperature Aerobic Oxidation of Isobutane to <i>tert</i>-Butyl Alcohol

Abstract

High Resolution Image Download MS PowerPoint Slide The development of reusable solid catalysts based on naturally abundant metal elements for the liquid-phase selective oxidation of light alkanes under mild conditions to obtain desired oxygenated products, such as alcohols and carbonyl compounds, remains a challenge. In this study, various perovskite oxide nanoparticles were synthesized by a sol–gel method using aspartic acid, and the effects of A- and B-site metal cations on the liquid-phase oxidation of isobutane to tert -butyl alcohol with molecular oxygen as the sole oxidant were investigated. Iron-based perovskite oxides containing Fe 4+ such as BaFeO 3−δ, SrFeO 3−δ, and La 1– x Sr x FeO 3−δ exhibited catalytic performance superior to those of other Fe 3+ - and Fe 2+ -based iron oxides and Mn-, Ni-, and Co-based perovskite oxides. The partial substitution of Sr for La in LaFeO 3 significantly enhanced the catalytic performance and durability. In particular, the La 0.8 Sr 0.2 FeO 3−δ catalyst could be recovered by simple filtration and reused several times without an obvious loss of its high catalytic performance, whereas the recovered BaFeO 3−δ and SrFeO 3−δ catalysts were almost inactive. La 0.8 Sr 0.2 FeO 3−δ promoted the selective oxidation of isobutane even under mild conditions (60 °C), and the catalytic activity was comparable to that of homogeneous systems, including halogenated metalloporphyrin complexes. On the basis of mechanistic studies, including the effect of Sr substitution in La 1– x Sr x FeO 3−δ on surface redox reactions, the present oxidation proceeds via a radical-mediated oxidation mechanism, and the surface-mixed Fe 3+ /Fe 4+ valence states of La 1– x Sr x FeO 3−δ nanoparticles likely play an important role in promoting C–H activation of isobutane as well as decomposition of tert -butyl hydroperoxide.

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