Microenvironment Engineering of Ru Single‐Atom Catalysts by Regulating the Cation Vacancies in NiFe‐Layered Double Hydroxides

Abstract Single‐atom catalysts (SACs) with rationally designed microenvironments (defined as coordination environments and electronic configurations) show superior catalytic activity, selectivity, and stability in a majority of reactions. However, the construction of isolated SACs with definite microenvironments to understand the microenvironment–activity relationship is still challenging. Herein, a facile strategy is developed to construct a series of Ru SACs with tunable geometric and electronic structures by employing NiFe‐layered double hydroxides (LDH) with different cation vacancies (M II or M III ) as supports. Detailed spectroscopic characterizations and theoretical calculations reveal that the Ru‐O coordination environments and electronic configurations of single‐atomic Ru can be easily tailored by the vacancy regulation. As a result, isolated Ru atoms anchored by M III vacancies (denoted as Ru 1 /LDH‐V III ) with Ru‐O‐Ni coordination environments facilitate the desorption of benzaldehyde, thus leading to higher efficiency of benzyl alcohol oxidation with a superior turnover frequency of 1331 h −1 .