Selective CH₄ Partial Photooxidation by Positively Charged Metal Clusters Anchored on Carbon Aerogel under Mild Conditions

Abstract

Selective partial photooxidation of CH₄ into value-added chemicals under mild conditions still remains a huge bottleneck. Herein, we design positively charged metal clusters anchored on a three-dimensional porous carbon aerogel. With 0.75FeCA800-4 as an example, X-ray photoelectron spectra and Raman spectra disclose that the iron sites are positively charged. <i>In situ</i> electron paramagnetic resonance spectra show that the Fe^δ+ sites could donate electrons to activate CH₄ into CH₄^- by virtue of the excited-state carbon atoms; meanwhile, they could convert H₂O₂ into ^•OH radicals under irradiation. In addition, <i>in situ</i> diffuse Fourier-transform infrared spectra suggest the CH₃OOH obtained is derived from CH₄ oxidation by the hydroxylation of *CH₃ and *CH₃O intermediates. Consequently, 0.75FeCA800-4 displays a CH₃OOH selectivity of near 100% and a CH₃OOH evolution rate of 13.2 mmol g_Fe^-1 h^-1, higher than those of most previously reported supported catalysts under similar conditions.