Frustrated Lewis Pairs and Metallic Ni Synergistically Enabled Low‐Temperature Hydrogenolysis of Lignin Models

Low‐temperature hydrogenolysis of aromatic ether bonds is a highly promising strategy to convert lignin. However, it remains highly challenging to enable this strategy over non‐noble metal‐based catalysts. Herein, Ni and Al mixed oxide catalysts (denoted as NiAlO x ‐T, where T represented the reduction temperature) were constructed by the reduction of layered Ni‐Al hydroxides. Interestingly, the NiAlO x ‐300 could efficiently promote the hydrogenolysis of various lignin models (i.e., α‐O‐4 referring to benzyl phenyl ether linkage (C α ‐O‐Ar), β‐O‐4 referring to 2‐phenoxy‐1‐phenylethanol linkage (C β ‐O‐Ar), and 4‐O‐5 referring to diphenyl ether linkage (Ar‐O‐Ar)) at a temperature of ≤ 100°C. Notably, benzyl phenyl ether (a typical α‐O‐4 model) could be converted into toluene and phenol at 20°C. Systematic analysis revealed that abundant solid surface frustrated Lewis pairs (ssFLPs) composed by unsaturated Al sites (Al 3+ unsatur. ) proximal to a surface oxygen vacancy and surface Lewis basic OH were generated in NiAlO x ‐300. The excellent performance of the NiAlO x ‐300 catalyst originated from the synergistic effect of ssFLPs sites and metallic Ni 0 sites, which was beneficial to efficient hydrogen activation for hydrogenolysis of lignin models at mild conditions. This work provided a new kind of non‐noble metal‐based catalyst for lignin valorization by creating solid surface frustrated Lewis pairs cooperated with non‐noble metals.