Insights into effects of grain boundary engineering in composite metal oxide catalysts for improving catalytic...

Volatile Organic Compounds (VOCs) have long been a threat to human health. However, designing economical and efficient transition metal composite oxide catalysts for VOCs purification remains a challenge. Herein, this study demonstrates the enormous potential of grain boundary engineering in facilitating VOCs decomposition over ordered mesoporous composite oxide denoted as 3D-Mn_xCo_y (x, y = 1, 3, 5, 7, 9). Specifically, the three-dimensional (3D) Mn7Co1 catalyst shows 100% ethyl acetate removal efficiency for a continuous airflow containing 1000 ppm ethyl acetate over 60000 h^-1 space velocity at 160 °C. Mechanism study suggests that the high catalytic performance originates from the lattice distortion caused by the introduction of heteroatoms, along with the size effect of nanopore walls, which leads to the formation of various grain boundaries on the catalyst surface. The presence of grain boundaries facilitates the generation of oxygen vacancies, thus promoting the migration and activation of oxygen species. Furthermore, the near-atmospheric pressure X-ray photoelectron spectroscopy (NAP- XPS) monitoring results reveal that the bimetallic synergy enhanced by grain boundary accelerates the catalytic reaction rate of VOCs through Mn³⁺+Co³⁺↔Mn⁴⁺+Co²⁺ redox cycle. This study may shed light on the great potential of ordered mesoporous bimetallic oxide catalysts in VOCs pollution control.