Activation and catalytic transformation of methane under mild conditions

In the last few decades, worldwide scientists have been motivated by the promising production of chemicals from the widely existing methane (CH4) under mild conditions for both chemical synthesis with low energy consumption and climate remediation. To achieve this goal, a whole library of catalytic chemistries of transforming CH4 to various products under mild conditions is required to be developed. Worldwide scientists have made significant efforts to reach this goal. These significant efforts have demonstrated the feasibility of oxidation of CH4 to value-added intermediate compounds including but not limited to CH3OH, HCHO, HCOOH, and CH3COOH under mild conditions. The fundamental understanding of these chemical and catalytic transformations of CH4 under mild conditions have been achieved to some extent, although currently neither a catalyst nor a catalytic process can be used for chemical production under mild conditions at a large scale. In the academic community, over ten different reactions have been developed for converting CH4 to different types of oxygenates under mild conditions in terms of a relatively low activation or catalysis temperature. However, there is still a lack of a molecular-level understanding of the activation and catalysis processes performed in extremely complex reaction environments under mild conditions. This article reviewed the fundamental understanding of these activation and catalysis achieved so far. Different oxidative activations of CH4 or catalytic transformations toward chemical production under mild conditions were reviewed in parallel, by which the trend of developing catalysts for a specific reaction was identified and insights into the design of these catalysts were gained. As a whole, this review focused on discussing profound insights gained through endeavors of scientists in this field. It aimed to present a relatively complete picture for the activation and catalytic transformations of CH4 to chemicals under mild conditions. Finally, suggestions of potential explorations for the production of chemicals from CH4 under mild conditions were made. The facing challenges to achieve high yield of ideal products were highlighted and possible solutions to tackle them were briefly proposed.