The development of an efficient catalyst for formic acid electrocatalytic oxidation reaction (FAEOR) is of great significance to accelerate the commercial application of direct formic acid fuel cells (DFAFC). Herein, palladium phosphide (Pd x P y ) porous nanotubes (PNTs) with different phosphide content (i.e., Pd 3 P and Pd 5 P 2 ) are prepared by combining the self-template reduction method of dimethylglyoxime-Pd(II) complex nanorods and succedent phosphating treatment.During the reduction process, the self-removal of the template and the continual inside-outside Ostwald ripening phenomenon are responsible for the generation of the one-dimensional hollow and porous architecture. On the basis of the unique synthetic procedure and structural advantages, Pd 3 P PNTs with optimized phosphide content show outstanding electroactivity and stability for FAEOR. Importantly, the strong electronic effect between Pd and P promotes the direct pathway of FAEOR and inhibits the occurrence of the formic acid decomposition reaction, which effectively enhances the FAEOR electroactivity of Pd 3 P PNTs. In view of the facial synthesis, excellent electroactivity, high stability, and unordinary selectivity, Pd 3 P PNTs have the potential to be an efficient anode electrocatalyst for DFAFC.

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.

Methanol electrolysis is a promising strategy to achieve energysaving and efficient electrochemical hydrogen (H 2 ) production. In this system, the advanced electrocatalysts with high catalytic performance for both the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) are highly desirable. Inspired by the complementary catalytic properties of rhodium (Rh) and palladium (Pd) for MOR and HER, herein, several Pd core−RhPd alloy shell nanodendrites (Pd@RhPd NDs) are synthesized through the galvanic replacement reaction between Pd nanodendrites (Pd NDs) and rhodium trichloride. For MOR, Pd@RhPd NDs exhibit Rh content-determined catalytic activity, in which Pd@ Rh 0.07 Pd NDs have an optimal combination of oxidation potential and oxidation current due to the synergistic catalytic process of Pd/Rh double active sites. For HER, the introduction of Rh greatly improves the catalytic activity of Pd@RhPd NDs compared to that of Pd NDs, suggesting that Rh is the main activity site for HER. Unlike MOR, however, the HER activity of Pd@RhPd NDs is not sensitive to the Rh content. Using Pd@Rh 0.07 Pd NDs as robust bifunctional electrocatalysts, the asconstructed two-electrode methanol electrolysis cell shows a much lower voltage (0.813 V) than that of water electrolysis (1.672 V) to achieve electrochemical H 2 production at 10 mA cm −2 , demonstrating the application prospect of methanol electrolysis for H 2 production.

The intrinsically sluggish kinetics of Pt towards formate oxidation reaction (FOR) severely impedes its application in direct formate fuel cells (DFFCs). This study reports the synthesis of ultrafine Pd@PdPt nanowires...

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