Enhanced electrocatalytic water splitting by Sm and Gd-doped ceria electrocatalysts on Ni foam substrate

Abstract

CeO2 is attractive for water splitting due to its various valence oxidation states, however, its catalytic performance in alkaline medium is challenging. In this study, we synthesized novel ceria-based electrocatalysts: Gd-doped CeO2 nanocrystals (GDC) and Sm-doped CeO2 nanospheres (SDC) on Ni foam using sol–gel and one-step hydrothermal methods, respectively. These ceria-based electrocatalysts, GDC and SDC, depict excellent activity in the OER and HER, respectively. The GDC/NF showed promising OER performance, achieving an exceptional overpotentials of 300 and 420 mV to keep current densities of 10 and 100 mA cm−2, respectively. In addition, SDC/NF exhibited excellent HER activity with overpotentials of 117 and 325 mV to reach current densities of 10 and 100 mA cm-2, respectively. Furthermore, both GDC and SDC were ultra-stable at a fixed current density of 50 mA cm−2 for 25 h. Moreover, the complete anion-exchange membrane (GDC/NF||SDC/NF) demonstrated 1.6 Vcell to accomplish 10 mA cm-2 current density, with ultra-durability for 40 h at 50 mA cm-2. The versatile electrochemical performance of ceria-based catalysts is attributed to diverse-valence Ce3+/Ce4+ redox states and positive entropy contribution of the f0–f1 transition. Notably, doping with Gd and Sm led to an easy and strong reduction owing to the oxygen voids created and hydroxyls. Moreover, dopants stabilized ceria and assisted the generation of metal–H groups, which improved the kinetic activity of ceria for electrochemical water splitting.