Nanoscale engineering of porous Fe-doped Pd nanosheet assemblies for efficient methanol and ethanol electrocatalyses

Although great successes have been accomplished on the controlled synthesis of 2D and 3D Pd-containing nanomaterials, tapping into the novel Pd-containing electrocatalysts that combined the advantages of both 2D and 3D structures remains a significant challenge. Here, an approach to systematically produce porous Fe-doped Pd nanosheet assemblies (NSAs) with a geometry tuning from PdFe hollow nanospheres (HNSs), PdFe nanocages (NCs), to PdFe nanoplates (NPs) is reported. The inherent ultrathin and porous features endow these PdFe catalysts with excellent electrocatalytic performance. As a result, the optimized 3D PdFe NCs show a much-improved methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) activities in comparison with PdFe HNSs, Pd NPs, and commercial Pd/C catalysts. Moreover, these PdFe nanocatalysts also display greatly enhanced electrocatalytic stability, which can endure 500 cycles with negligible activity loss and structural changes. The mechanism investigations reveal that the introduced Fe atom efficiently modulates the electronic structure of Pd, leading to the downshift of the d-band center of Pd, which is beneficial for the adsorption of reactants. Moreover, the porous nanosheet assembly structure can provide rich mass and electron transfer channels, further boosting the improvement of electrocatalytic performance.