Double perovskites are known for their special structures which can be utilized as catalyst electrode materials for electrochemical water splitting to generate carbon-neutral hydrogen energy. In this work, we prepared lanthanide series metal-doped double perovskites at the M site such as M2NiMnO6 (where M = Eu, Gd, Tb) using the solid-state reaction method, and they were investigated for an oxygen evolution reaction (OER) study in an alkaline medium. It is revealed that the catalyst with a configuration of Tb2NiMnO6 has outstanding OER properties such as a low overpotential of 288 mV to achieve a current density of 10 mAcm−2, a lower Tafel slope of 38.76 mVdec−1, and a long cycling stability over 100 h of continuous operation. A-site doping causes an alteration in the oxidation or valence states of the NiMn cations, their porosity, and the oxygen vacancies. This is evidenced in terms of the Mn4+/Mn3+ ratio modifying electronic properties and the surface which facilitates the OER properties of the catalyst. This is discussed using electrochemical impedance spectroscopy (EIS) and electrochemical surface area (ECSA) of the catalysts. The proposed work is promising for the synthesis and utilization of future catalyst electrodes for high-performance electrochemical water splitting.
Layered double hydroxides (LDHs) have gained vast importance as an electrocatalyst for water electrolysis to produce carbon-neutral and clean hydrogen energy. In this work, we demonstrated the fabrication of nano-flake-like NiMn LDH thin film electrodes onto porous membrane-like Ni-foam by using a simple and cost-effective electrodeposition method for oxygen evolution reaction (OER). Various Ni1-xMnx LDH (where x = 0.15, 0.25, 0.35, 0.50 and 0.75) thin film electrodes are utilized to achieve the optimal catalyst for an efficient and sustainable OER process. The various composition-dependent surface morphologies and porous-membrane-like structure provided the high electrochemical surface area along with abundant active sites facilitating the OER. The optimized catalyst referred to as Ni0.65Mn0.35 showed excellent OER properties with an ultralow overpotential of 253 mV at a current density of 50 mAcm−2, which outperforms other state-of-the art catalysts reported in the literature. The relatively low Tafel slope of 130 mV dec−1 indicates faster and more favorable reaction kinetics for OER. Moreover, Ni0.65Mn0.35 exhibits excellent durability over continuous operation of 20 h, indicating the great sustainability of the catalyst in an alkaline medium. This study provides knowledge for the fabrication and optimization of the OER catalyst electrode for water electrolysis.
The development of ternary metal oxide electrocatalysts with optimized electronic structures and surface morphologies has emerged as one of the effective strategies to improve the performance of electrochemical water splitting. In this work, ternary CoMoCe (CMC)-oxide electrocatalysts were successfully synthesized on nickel foam substrates via a hydrothermal technique and employed for their catalytic activity in an alkaline electrolyte. For comparison, binary counterparts (CoMo, CoCe, and MoCe) were also fabricated under similar conditions. The synthesized catalysts’ electrodes exhibited diverse surface architectures, including microporous-flake hybrids, ultrathin flakes, nanoneedle-assembled microspheres, and randomly oriented hexagonal structures. Among them, the ternary CoMoCe-oxide electrode exhibited outstanding bifunctional electrocatalytic activity, delivering low overpotentials of 124 mV for the hydrogen evolution reaction (HER) at −10 mA cm−2, and 340 mV for the oxygen evolution reaction (OER) at 100 mA cm−2, along with excellent durability. Furthermore, in full water-splitting configuration, the CMC||CMC and RuO2||CMC electrolyzers required cell voltages of 1.69 V and 1.57 V, respectively, to reach a current density of 10 mA cm−2. Remarkably, the CMC-based electrolyzer reached an industrially relevant current density of 1000 mA cm−2 at a cell voltage of 2.18 V, maintaining excellent stability over 100 h of continuous operation. These findings underscore the impact of an optimized electronic structure and surface architecture on design strategies for high-performance ternary metal oxide electrocatalysts. Herein, a robust and straightforward approach is comprehensively presented for fabricating highly efficient ternary metal-oxide catalyst electrodes, offering significant potential for scalable water splitting.