A Dual-Coordination Strategy for Constructing Highly Active Pd Clusters to Enhance Methane Catalytic Combustion.

The rational construction of highly efficient and stable subnanometer Pd clusters for methane catalytic combustion still faces severe challenges. We developed a dual-coordination strategy to construct high-activity Pd clusters through synergistically modulating the electronic structure of both active component Pd and the CeO2 support. g-C3N4 as the Pd2+ anchoring agent and H3BTC as the support defect-regulating ligand were utilized, achieving confined growth of low-coordination PdOx clusters on defect-rich ceria. Advanced structural and electronic characterization verified the formation of electron-deficient Pdn clusters with optimized metal-support interactions. The Pdn/CeO2 catalyst exhibited superior methane combustion activity (T90 = 367 °C) and high stability, demonstrating a remarkable turnover frequency of 0.064 s-1 at 350 °C, significantly exceeding that of the Pd1/CeO2 single-atom catalyst. This superior performance was attributed to enhanced oxygen mobility and efficient methane C-H bond activation. This research establishes a promising method for engineering cluster-based catalysts with a dual-coordination-mediated stabilization strategy, offering different perspectives into optimizing catalysts for methane abatement.