Rational Design of Mn-Doped ZIF-67-Derived Mn _<i>x</i> CoO _<i>y</i> Catalysts with Tailored Oxygen Vacancies for Sustainable Synthesis of Carbonyl Compounds

Catalytic oxidation plays a pivotal role in the chemical industry. Among various approaches, the strategy involving O2 as a green oxidant and H2O as a solvent for the efficient oxidation of organic compounds has garnered significant interest because it aligns with the principles of sustainable development. However, the inherent inertness of ground-state oxygen molecules poses a significant challenge in the development of non-noble-metal catalysts that can activate O2 to reactive oxygen species. Inspired by the regulatory effects of metal doping on the oxygen vacancy content and electronic properties of materials, we developed a bimetallic oxide catalyst MnxCoOy, derived from Mn-doped ZIF-67, for catalytic oxidation with oxygen. Comprehensive characterization (XRD, XPS, N2 adsorption–desorption, Raman, and FTIR) reveals that Mn species doping substitutes Co2+ at tetrahedral CoO4 sites, modulating the catalyst’s oxygen vacancy concentration and electronic distribution. The optimized MnxCoOy with suitable oxygen vacancy concentration exhibits superior performance in the selective oxidation of organic molecules containing benzyl sp3 C–H bonds. The cyclic and amplification experiments indicate the potential application value of the catalyst. This work provides fundamental insights into the design of multipurpose catalysts for catalytic oxidation through the metal doping strategy, which also offers a sustainable approach for obtaining carbonyl compounds.