(Digital Presentation) The New 2H Hexagonal Double Perovskite Ba2CoMnO6 As a Superior OER Catalyst in Alkaline Media
Authors: Erdil Tuncay , Toparli Cigdem 
Published: July 2022

Climate change has stimulated great interest in developing clean and renewable energy conversion and storage solutions. Emerging technologies for solutions, like unitized regenerative fuel cells, metal-air batteries, and water electrolyzers, depend on the reliable catalyst materials suited for long-term application in alkaline environments[1]. In particular, the demanding reaction in these systems is the oxygen evolution reaction involving complex multielectron/proton transfer processes and thus sluggish kinetic.[2] At present, the state-of-the-art OER catalysts are IrO2 and RuO2. However, the high cost and scarcity of these materials severely prevent the wide-scale application of these systems.[3] Perovskite oxide (e.g., single perovskite expressed as ABO3) electrocatalysts are particularly considered next-generation OER catalysts due to their adjustable physicochemical properties and, as a consequence, their catalytic properties by substitution of ions in the A and B sites.[4] Via doping both at A and B site, double perovskite oxides structure can form (AA′B2O5+δ), which were shown to have stable structure during the OER due to proper O p-band center position relative to the Fermi level. The previous research shows that hexagonal perovskites exhibit enhanced catalytic activity rather than cubic or tetragonal perovskites, which is associated with the face-sharing octahedral unit. [5,6]

In this work, we systematically investigate doping of parent La2CoMnO6 with Ba to tune the crystal structure and electronic structure. A series of the double perovskites with the chemical formula of La2-xBaxCoMnO6 (x = 0, 0.5, 1.5, 2) were fabricated via the modified Sol-Gel Pechini method. According to Goldschmidt tolerance factor, it is expected that when Ba amount increases in the A site, the crystal structure changes from cubic to hexagonal, which can contribute to electrocatalytic OER activity based above discussions. Furthermore, it is anticipated that increasing Ba content at the A site should result in higher valence state of transition metals due to stabilizing charge balance of the structure. It is widely reported that presence of higher valence state of transition metals is beneficial for OER.
The crystal structure was confirmed by combining powder X-ray diffraction (XRD) patterns and selected area electron diffraction (SAED) patterns. The two-layer hexagonal structure of Ba2CoMnO6 (BCM) was further characterized by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The results show doping of Ba into parent La2CoMnO6 resulted in the hexagonal phase formation and BCM achieves a current density of 10 mA cm–2 at a low overpotential of 288 mV and has the highest intrinsic activity in the series of BaxLa2-xCoMnO6 (x = 0, 0.5, 1, 1.5, 2). Furthermore, BCM exhibits outstanding stability of 12 h in a 0.1 M KOH electrolyte. The electronic structure and surface work function values of the catalysts were examined with X-ray photoelectron spectroscopy (XPS). XPS analysis revealed that valence state of Co and Mn increases through Ba amount in the structure, indicating the double perovskite oxide charge balance is maintained. In addition to valence state analysis, we performed work function analysis of the catalysts tested in this work. The result shows work function of the series of BaxLa2-xCoMnO6 (x = 0, 0.5, 1, 1.5, 2) substantially decreases with Ba content. Here, we show that the high intrinsic activity of BCM is not only related with the hexagonal structure and also may be related with exhibiting lower work function value in the series. In addition, our approach presents a new strategy, air quenching method, to synthesize a phase pure 2H-hexagonal double perovskite oxide.
[1] Y. Zhou, X. Guan, H. Zhou, K. Ramadoss, S. Adam, H. Liu, S. Lee, H. Shi, M. Tsuchiya, D. Fong and S. Ramanathan, Nature, 534, 231-234 (2016).
[2] X. Cui, P. Ren, D. Deng, J. Deng and X. Bao, Energy & Environmental Science, 9, 123-129 (2016).
[3] X. Qiu, Y. Zhang, Y. Zhu, C. Long, L. Su, S. Liu and Z. Tang, Advanced Materials, 33, 2001731 (2020).
[4] W. Yin, B. Weng, J. Ge, Q. Sun, Z. Li and Y. Yan, Energy & Environmental Science, 12, 442-462 (2019).
[5] L. Tang, W. Zhang, D. Lin, Y. Ren, H. Zheng, Q. Luo, L. Wei, H. Liu, J. Chen and K. Tang, Inorganic Chemistry Frontiers, 7, 4488-4497 (2020).
[6] C. Chen, G. King, R. M. Dickerson, P. A. Papin, S. Gupta, W. R. Kellogg and G. Wu, Nano Energy, 13, 423-432 (2015).