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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]

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]

The rational design of the electronic structure and elemental compositions of anode electrocatalysts for formic acid electrooxidation reaction (FAOR) is paramount for realizing high‐performance direct formic acid fuel cells. Herein, palladium‐boride nanoflowers (Pd‐B NFs) with controllable boron content are rationally designed via a simple wet chemical reduction method, utilizing PdII‐dimethylglyoxime as precursor and NaBH4 as both reductant and boron source. The boron content of Pd‐B NFs can be regulated through manipulation of reaction time, accompanying with the crystal phase transition from face‐centered cubic to hexagonal close‐packed within the parent Pd lattice. The obtained Pd‐B NFs exhibit increased FAOR mass and specific activity with increasing boron content, showcasing remarkable inherent stability and anti‐poisoning capability compare to commercial Pd and platinum (Pt) nanocrystals. Notably, the sample reacted for 12 h reveals high FAOR specific activity (31.5 A m−2), which is approximately two times higher than the commercial Pd nanocrystals. Density functional theory calculations disclose that the d‐sp orbital hybridization between Pd and B modifies surface d‐band properties of Pd, thereby optimizing the adsorption of key intermediates and facilitating FAOR kinetics on the Pd surface. This study paves the way toward the utilization of metal boride‐based materials with simple synthesis methods for various electrocatalysis applications. [ABSTRACT FROM AUTHOR]