Co‐Doped Mn₃O₄ Nanocubes via Galvanic Replacement Reactions for Photocatalytic Reduction of CO₂ with High Turnover Number

Abstract

Dedicated to the 60th Birthday of Professor Licheng SunThe synthesis of Co-doped Mn 3 O 4 nanocubes was achieved via galvanic replacement reactions for photo-reduction of CO 2 . Co@Mn 3 O 4 nanocubes could efficiently photo-reduce CO 2 to CO with a remarkable turnover number of 581.8 using [Ru-(bpy) 3 ]Cl 2 • 6H 2 O as photosensitizer and triethanolamine as sacrificial agent in acetonitrile and water. The galvanic replaced Co species are homogeneously distributed at the outer surface of Mn 3 O 4 , providing catalytic active sites during CO 2 reduction reactions, which facilitate the separation and migration of photogenerated charge carriers, further benefiting the outstanding photocatalytic performance of CO 2 reduction. Density functional theory calculations revealed that the decreasing of conduction band maximum in Co@Mn 3 O 4 was beneficial to the electron attachment from the excited sensitized molecule, which promoted photocatalytic reduction of CO 2 .

Coupling doped halogen sites in copper(i)–organic frameworks with cuprous oxide for high selectivity CO2 photoreduction with H2O

“…3 Nevertheless, numerous vital aspects are challenging to address simultaneously in a majority of composite systems including efficient light absorption, the separation and rapid migration of photo-generated carriers to redox sites and the rapid adsorption and desorption of CO 2 . 4–8 Consequently, the design and fabrication of composite photocatalysts with well-defined structures to achieve highly selective CO 2 photoreduction is of great significance.…”