How does the defect ZnO@Au surface activate the methane via the precursor-mediated mechanism?

Abstract It is imperative to explore advanced catalysts that could activate methane in a mild manner. Herein, using density function theory (DFT), we have investigated the activation mechanism for the dissociation of methane, which is adsorbed on the triangle defect surface of ZnO@Au, where the defect ZnO(0 0 1) nanosheet is supported by Au(1 1 1). We found that the triangle defects induced coordination unsaturated O and Zn on the ZnO@Au are of great importance for this dissociation process, as the coordination unsaturated O and Zn not only can stabilize the methane, but also can polarize the C H bond through the dynamic frustrated Lewis pairs. Compared with perfect ZnO@Au heterojunction, the defect ZnO@Au can activate methane via precursor-mediated mechanism where the activation energy (0.21 eV) is lower than the absolute value of adsorption energy (0.48 eV). Such outstanding activation mainly originates from the electronic interaction between the methane and the coordination unsaturated O as well as Zn. Overall, the result not only provide a vital insight into the catalytic mechanism of the methane activation on ZnO@Au, but also give a new thought to develop catalysts for the facile methane activation.