Efficacy analysis of compartmentalization for ambient CH4 activation mediated by a RhII metalloradical in a nanowire array electrode

Abstract

Compartmentalization is a viable approach for ensuring the turnover of a solution cascade reaction with ephemeral intermediates, which may otherwise deactivate in the bulk solution. In biochemistry or enzyme-relevant cascade reactions, extensive models have been constructed to quantitatively analyze the efficacy of compartmentalization. Nonetheless, the application of compartmentalization and its quantitative analysis in non-biochemical reactions is seldom performed, leaving much uncertainty about whether compartmentalization remains effective for non-biochemical reactions, such as organometallic, cascade reactions. Here, we report our exemplary efficacy analysis of compartmentalization in our previously reported cascade reaction for ambient CH₄-to-CH₃OH conversion, mediated by an O₂-deactivated Rh^II metalloradical with O₂ as the terminal oxidant in a Si nanowire array electrode. We experimentally identified and quantified the key reaction intermediates, including the Rh^II metalloradical and reactive oxygen species (ROS) from O₂. Based on such findings, we experimentally determined that the nanowire array enables about 81% of the generated ephemeral intermediate Rh^II metalloradical in air, to be utilized towards CH₃OH formation, which is 0% in a homogeneous solution. Such an experimentally determined value was satisfactorily consistent with the results from our semi-quantitative kinetic model. The consistency suggests that the reported CH₄-to-CH₃OH conversion surprisingly possesses minimal unforeseen side reactions, and is favorably efficient as a compartmentalized cascade reaction. Our quantitative evaluation of the reaction efficacy offers design insights and caveats into application of nanomaterials to achieve spatially controlled organometallic cascade reactions.