Enhanced Replenishment of Active Lattice Oxygen Using Chiral Copper Oxide

Abstract

Effective catalytic performance of the transition metal oxide is attributed to high specific surface areas, abundant surface oxygen atoms, and balanced valence ratios. Although the chirality of the transition metal has attracted attention, most studies have focused on optical application. A few chiral transition metal oxides were used as electrocatalysts and photocatalysts. The influence of the chiral catalysts on the thermal catalysis process has been less explored. In this study, Mn-loaded chiral (M/l-CuO and M/d-CuO) and achiral CuO (M/a-CuO) were synthesized and compared in the catalytic oxidization of toluene. Spectrally analyzed Mn was well-dispersed on both chiral and achiral CuO. l-CuO and d-CuO showed nanoflower-like chirality. The angles between each (001) plane of CuO were the source of chirality. The toluene turnover frequency (TOF) of the samples was in the order of Mn/d-CuO (5.6 × 10–5 s–1) > Mn/l-CuO (4.4 × 10–5 s–1) > Mn/a-CuO (3.2 × 10–5 s–1) at 240 °C, consistent with the order of the oxygen replenishment rate. The as-prepared catalysts had similar ratios of lattice oxygen/surface adsorbed oxygen, Mn3+/Mn4+, and Cu+/Cu2+. A higher TOF was attributed to chirality, which increased the lattice oxygen replenishment speed from the gaseous phase to the solid surface. Our study indicates gas–solid catalysis from a structure–activity viewpoint.