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 PdO_x clusters on defect-rich ceria. Advanced structural and electronic characterization verified the formation of electron-deficient Pd_n clusters with optimized metal-support interactions. The Pd_n/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 Pd_1/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.