Heteroatom-doped carbon materials are widely used to improve the electrocatalytic oxidation of methanol; however, the underlying mechanisms driving this enhancement remain poorly understood. A major challenge lies in developing non-doped carbon supports with tunable intrinsic defect types tailored for metal-based catalysts. In this study, we synthesize a series of ordered mesoporous carbon (OMC) supports with adjustable edge defect densities by varying roasting temperatures and employing a zinc (Zn) evaporation strategy to systematically investigate the impact of edge defects on methanol oxidation reaction (MOR) performance. Theoretical calculations and structural characterizations confirm that the electron metal-support interaction (EMSI) between OMC edge defects and palladium nanoparticles (Pd NPs) effectively modulates the electronic structure of Pd NPs. This modulation not only enhances overall reaction activity and selectivity for the non-CO pathway but also strengthens the anchoring of Pd NPs, leading to superior activity and stability of the Pd/OMC-Zn0.55 catalyst in methanol electrocatalytic oxidation. Notably, after rigorously excluding the influence of various physicochemical properties of the carbon supports, the crucial role of edge defects in improving MOR performance is established. This work provides essential insights into the controlled synthesis of carbon-based catalysts with edge defects and introduces promising strategies for the development of high-performance anode catalysts for direct methanol fuel cells.
Keywords: Edge defect; Electronic metal–support interaction; Methanol oxidation reaction; Porous carbon carrier.
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