Precious Metal-Free LaMnO3 Perovskite Catalyst with an Optimized Nanostructure for Aerobic C–H Bond Activation Reactions: Alkylarene Oxidation and Naphthol Dimerization

• Published in: ACS applied materials & interfaces Vol. 13; no. 4; pp. 5099 - 5110
• Main Authors: Sahin, Yesim, Sika-Nartey, Abel T, Ercan, Kerem E, Kocak, Yusuf, Senol, Sinem, Ozensoy, Emrah, Türkmen, Yunus E
• Format: Journal Article
• Language: English
• Published: American Chemical Society 03.02.2021
• Subjects: Energy, Environmental, and Catalysis Applications; perovskites; alkylarenes; C−H oxidation; surface chemistry; heterogeneous catalysis
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.0c20490

In this article, we describe the development of a new aerobic C–H oxidation methodology catalyzed by a precious metal-free LaMnO3 perovskite catalyst. Molecular oxygen is used as the sole oxidant in this approach, obviating the need for other expensive and/or environmentally hazardous stoichiometric oxidants. The electronic and structural properties of the LaMnO3 catalysts were systematically optimized, and a reductive pretreatment protocol was proved to be essential for acquiring the observed high catalytic activities. It is demonstrated that this newly developed method was extremely effective for the oxidation of alkylarenes to ketones as well as for the oxidative dimerization of 2-naphthol to 1,1-binaphthyl-2,2-diol (BINOL), a particularly important scaffold for asymmetric catalysis. Detailed spectroscopic and mechanistic studies provided valuable insights into the structural aspects of the active catalyst and the reaction mechanism.