Role of Dopants in Fine-Tuning the Electrical and Catalytic Properties of Barium Niobate Perovskites Towards High-Temperature Electrolyzer Application

Abstract

Perovskite materials are being studied for high temperature electrochemical applications such as solid oxide fuel cells (SOFC) and electrolyzers due to their tunable conductivity and catalytic activity. However, high temperature operation poses significant challenges in both fabrication and durable operation that is further complicated by the operating environment.1 We studied barium niobates with various dopants such as Fe, Ni, Ca, Y, and Mg for B site doping while Sr, K, and La are studied for A site doping. These niobates showed enhanced chemical stability in SOFC relevant conditions and catalytic activity towards methane activation. Nb4+/5+ redox couple seem to be a key reason behind this chemical stability while the size and electronegativity of the dopants affect the electrical properties.2 Catalyst exsolution is explored with dopants such as Fe, Ni, and Co under reducing conditions along with surface bound metallic nanoparticles prepared by an incipient wet synthesis method. Chemical stability of these perovskites was analyzed by an in situ TGA measurements under various gas environments followed by analysis of the powders using PXRD, XPS, SEM, and TEM methodologies.3 Methane activation properties are further analyzed in a temperature programmed reaction setup while Electrochemical properties were evaluated in a home-made setup using different electrolyte materials in the temperature range of 700°C to 900°C. Cyclic voltammetry, impedance spectroscopy, and chronoamperometry measurements coupled with continuous mass spectra analysis was utilized to diagnose any correlation between product distribution and applied potential. Our results demonstrate doped barium niobates as a promising candidate for stable operation in high temperature electrochemical applications. The presentation will discuss these results and provide a correlation between dopants and catalytic activity and chemical stability of doped barium niobate perovskites. References (1) Ramaiyan, K. P.; Denoyer, L. H.; Benavidez, A.; Garzon, F. H. Selective Electrochemical Oxidative Coupling of Methane Mediated by Sr2Fe1.5Mo0.5O6-δ and Its Chemical Stability. Commun. Chem. 2021, 4 (1), 139. https://doi.org/10.1038/s42004-021-00568-1.(2) Denoyer, L. H.; Benavidez, A.; Garzon, F. H.; Ramaiyan, K. P. Highly Stable Doped Barium Niobate Based Electrocatalysts for Effective Electrochemical Coupling of Methane to Ethylene. Adv. Mater. Interfaces 2022, 9 (27), 2200796. https://doi.org/10.1002/admi.202200796.(3) Denoyer, L. H.; Benavidez, A.; Garzon, F. H.; Ramaiyan, K. P. Chemical Stability of BaMg0.33Nb0.67-XFexO3-δ in High Temperature Methane Conversion Environments. under communication - ECS Journal of Solid State Science and Technology.