Heterogeneous catalysis is one of the most important chemical processes of various industries performed on catalyst nanoparticles with different sizes or/and shapes.

Catalytic transformation of CH₄ under a mild condition is significant for efficient utilization of shale gas under the circumstance of switching raw materials of chemical industries to shale gas. Here, we report the transformation of CH₄ to acetic acid and methanol through coupling of CH₄, CO and O₂ on single-site Rh₁O₅ anchored in microporous aluminosilicates in solution at ≤150 °C. The activity of these singly dispersed precious metal sites for production of organic oxygenates can reach about 0.10 acetic acid molecules on a Rh₁O₅ site per second at 150 °C with a selectivity of ~70% for production of acetic acid. It is higher than the activity of free Rh cations by >1000 times. Computational studies suggest that the first C–H bond of CH₄ is activated by Rh₁O₅ anchored on the wall of micropores of ZSM-5; the formed CH₃ then couples with CO and OH, to produce acetic acid over a low activation barrier.

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.