Heterogeneously Catalyzed Aerobic Oxidation of Methane to a Methyl Derivative.

A promising strategy to break through the selectivity-conversion limit of direct methane conversion to achieve high yields is the protection of methanol via esterification to a more stable methyl ester. We present an aerobic methane-to-methyl-ester approach that utilizes a highly dispersed, cobalt-containing solid catalyst, along with significantly more favorable reaction conditions compared to existing homogeneously-catalyzed approaches (e.g. diluted acid, O2 oxidant, moderate temperature and pressure). The trifluoroacetic acid medium is diluted (<25 wt %) with an inert fluorous co-solvent that can be recovered after the separation of the methyl trifluoroacetate via liquid-liquid extraction at ambient conditions. Silica-supported cobalt catalysts are highly active in this system, with competitive yields and turnovers in comparison to known aerobic transition metal-based catalytic systems.

Esterification Product Protection Strategies for Direct and Selective Methane Conversion.

A scale-flexible process for the direct and selective oxidation of methane to primary oxygenates is of great interest, however, a commercially feasible approach has yet to be realized due to a number of challenges. Low product yields imposed by a well-established selectivity-conversion limit are particularly burdensome for direct methane-to-methanol chemistry. One strategy that has emerged to break out of this limit is the in situ esterification of produced methanol to the more oxidation-resistant methyl ester. However, these methaneto-methyl-ester approaches still elude commercialization despite their unprecedented high yields. Herein, we outline some of the key barriers that hinder the commercial prospects of this otherwise promising route for highyield direct catalytic methane conversion, including extremely corrosive reagents, homogeneous catalysts, and inviable oxidants. We then highlight directions to address these challenges while maintaining the characteristic high performance of these systems. These discussions support the efficacy of product protection strategies for the direct, selective oxidation of methane and encourage future work in developing creative solutions to merge this promising chemistry with more practical industrial requirements.