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Comprehensive Summary: We present a strategy that effectively modulate the d‐band electronic structure of the active center by strain effect and interatomic orbital hybridization. This strategy efficiently promotes the kinetic process of the ethanol oxidation reaction (EOR) in alkaline media. In the intermetallic Pd3Pb nanowires, the introduction of Pb not only causes the lattice expansion of Pd but also achieves the interatomic orbital hybridization bonding with Pd. Such interatomic orbital hybridization effect and tensile strain effect can effectively achieve a co‐regulation of the d‐band electronic structure of Pd, which directly affects the adsorption behavior of intermediate on Pd for EOR. Hence, the intermetallic Pd3Pb nanowires demonstrate enhanced EOR activity and anti‐poisoning ability against COads. Theoretical calculations show that the enhanced OH* adsorption ability and the low energy barrier for the oxidative dehydrogenation of ethanol are the keys to high EOR activity and stability of the intermetallic Pd3Pb nanowires. [ABSTRACT FROM AUTHOR]

Small‐molecule electrooxidation‐boosted water electrolysis (WE) is an energy‐saving method for hydrogen (H2) production. Herein, PdPt bimetallenes (PdPt BMLs) are obtained through the simple galvanic replacement reaction. PdPt BMLs reveal 2.93‐fold enhancement in intrinsic electroactivity and 4.53‐fold enhancement in mass electroactivity for the formate oxidation reaction (FOR) with respect to Pd metallenes (Pd MLs) at 0.50 V potential due to the synergistic effect. Meanwhile, the introduction of Pt atoms also considerably increases the electroactivity of PdPt BMLs for hydrogen evolution reaction (HER) with respect to Pd MLs in an alkaline medium, which even exceeds that with the use of commercial Pt nanocrystals. Inspired by the outstanding FOR and HER electroactivity of bifunctional PdPt BMLs, a two‐electrode FOR‐boosted WE system (FOR‐WE) is constructed by using PdPt BMLs as the cathode and the anode. The FOR‐WE system only requires an operational voltage of 0.31 V to achieve H2 production, which is 1.48 V lower than that (ca. 1.79 V) with the use of the traditional WE system. [ABSTRACT FROM AUTHOR]

Palladium (Pd) nanostructures are highly active non‐platinum anodic electrocatalysts in alkaline direct methanol fuel cells (ADMFCs) and their electrocatalytic performance relies highly on their morphology and composition. Herein, a facile high‐temperature pyrolysis method to synthesize high‐quality Pd‐palladium oxide (PdO) porous nanotubes (PNTs) by using Pd(II)‐dimethylglyoxime complex (Pd(II)‐DMG) nanorods as a self‐template is reported. The chemical component of pyrolysis products highly correlates with pyrolysis temperature. The electrochemical measurements and density functional theory calculations show the existence of PdO enhances the electroactivity of metallic Pd for both methanol oxidation reaction (MOR) and carbon monoxide oxidation reaction in alkaline media. Benefiting from its one‐dimensionally porous architecture and evident synergistic effect between PdO and Pd (e.g., electronic effect and bifunctional mechanism), Pd‐PdO PNTs achieve a 3.7‐fold mass activity enhancement and improved durability for MOR compared to commercial Pd nanocrystals. Considering the simple synthesis, excellent activity, and long‐term stability, Pd‐PdO PNTs may be highly promising anodic electrocatalysts in ADMFCs. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: We present a strategy that effectively modulate the d‐band electronic structure of the active center by strain effect and interatomic orbital hybridization. This strategy efficiently promotes the kinetic process of the ethanol oxidation reaction (EOR) in alkaline media. In the intermetallic Pd3Pb nanowires, the introduction of Pb not only causes the lattice expansion of Pd but also achieves the interatomic orbital hybridization bonding with Pd. Such interatomic orbital hybridization effect and tensile strain effect can effectively achieve a co‐regulation of the d‐band electronic structure of Pd, which directly affects the adsorption behavior of intermediate on Pd for EOR. Hence, the intermetallic Pd3Pb nanowires demonstrate enhanced EOR activity and anti‐poisoning ability against COads. Theoretical calculations show that the enhanced OH* adsorption ability and the low energy barrier for the oxidative dehydrogenation of ethanol are the keys to high EOR activity and stability of the intermetallic Pd3Pb nanowires. [ABSTRACT FROM AUTHOR]