Room-Temperature Photooxidation of CH₄ to CH₃OH with Nearly 100% Selectivity over Hetero-ZnO/Fe₂O₃ Porous Nanosheets

The huge challenge for CH₄ photooxidation into CH₃OH lies in the activation of the inert C-H bond and the inhibition of CH₃OH overoxidation. Herein, we design two-dimensional in-plane Z-scheme heterostructures composed of two different metal oxides, with efforts to polarize the symmetrical CH₄ molecules and strengthen the O-H bond in CH₃OH. As a prototype, we first fabricate ZnO/Fe₂O₃ porous nanosheets, where high-resolution transmission electron microscopy and in situ X-ray photoelectron spectroscopy affirm their in-plane Z-scheme heterostructure. In situ Fourier transform infrared spectra and in situ electron paramagnetic resonance spectra demonstrate their higher amount of ·CH₃ radicals relative to the pristine ZnO porous nanosheets, in which density functional theory calculations validate that the high local charge accumulation on Fe sites lowers the CH₄ adsorption energy from 0.14 to 0.06 eV. Moreover, the charge-accumulated Fe sites strengthen the polarity of the O-H bond in CH₃OH through transferring electrons to the O atoms, confirmed by the increased barrier from 0.30 to 2.63 eV for *CH₃O formation, which inhibits the homolytic O-H bond cleavage and thus suppresses CH₃OH overoxidation. Accordingly, the CH₃OH selectivity over ZnO/Fe₂O₃ porous nanosheets reaches up to nearly 100% with an activity of 178.3 μmol⁻¹ gcat⁻¹, outperforming previously reported photocatalysts without adding any oxidants under room temperature and ambient pressure.