Enhancement of Selective Catalytic Oxidation of Lignin β‐O‐4 Bond via Orbital Modulation and Surface Lattice Reconstruction

Abstract The orbital modulation and surface lattice reconstruction represent an effective strategy to regulate the interaction between catalyst interface sites and intermediates, thereby enhancing catalytic activity and selectivity. In this study, the crystal surface of Au−K/CeO 2 catalyst can undergo reversible transformation by tuning the coordination environment of Ce, which enables the activation of the C β −H bond and the oxidative cleavage of the C β‐O and C α −C β bonds, leading to the cleavage of 2‐phenoxy‐1‐phenylethanol. The t 2g orbitals of Au 5d hybridize with the 2p orbitals of lattice oxygen in CeO 2 via π‐coordination, modulating the coordination environment of Ce 4 f and reconstructing the lattice oxygen in the CeO 2 framework, as well as increasing the oxygen vacancies. The interface sites formed by the synergy between Au clusters in the reconstructed Ce−O L1 −Au structure and doped K play dual roles. On the one hand, it activates the C β −H bond, facilitating the enolization of the pre‐oxidized 2‐phenoxy‐1‐phenylethanone. On the other hand, through single‐electron transfer involving Ce 3+ 4f 1 and the adsorption by oxygen vacancies, it enhances the oxidative cleavage of the C β‐O and C α −C β bonds. This study elucidates the complex mechanistic roles of the structure and properties of Au−K/CeO 2 catalyst in the selective catalytic oxidation of lignin β‐O‐4 bond.