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.
Tao et al. (Thu,) studied this question.