Bifunctional Pd@RhPd Core–Shell Nanodendrites for Methanol Electrolysis
Yu‐Chuan Jiang, Hui‐Ying Sun, Yanan Li, Jiawei He, Qi Xue, Xinlong Tian, Fumin Li, Shibin Yin, Dong‐Sheng Li, Yu Chen
Abstract
Methanol electrolysis is a promising strategy to achieve energy-saving and efficient electrochemical hydrogen (H2) 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 [email protected] 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 [email protected] NDs as robust bifunctional electrocatalysts, the as-constructed two-electrode methanol electrolysis cell shows a much lower voltage (0.813 V) than that of water electrolysis (1.672 V) to achieve electrochemical H2 production at 10 mA cm–2, demonstrating the application prospect of methanol electrolysis for H2 production.