With the increase in renewable energy usage comes the need for energy storage systems due to intermittency issues. Hydrogen storage systems have been identified as one solution. Unitized regenerative fuel cells (URFC) combine electrolyzers and fuel cells in one device, allowing electricity to be stored and used easily. However, the oxygen electrodes are still affected by high overpotentials and slow kinetics. Perovskite oxides have been identified as a class of materials, which are low-cost, tunable, and active for the oxygen reduction (ORR) and evolution (OER) reactions. Here, we investigate perovskites as bifunctional catalysts for ORR and OER in alkaline solution. We examine and compare two strategies for bifunctional catalysts: using one catalyst, which is able to perform OER and ORR vs. a combination of two catalysts, one active for ORR and one active for OER. Frequently, the catalysts’ performances for these two reactions are measured separately.^1,2,3 Here, we investigate how these bifunctional catalysts respond to cycling between the OER and ORR regions.

Ba_0.5Sr_0.5Co_0.8Fe_0.2O₃ (BSCF) is known to be a promising OER catalyst.^4,5,6 However, without carbon, it lacks ORR activity.⁴ La_(1-x)Sr_xMnO₃ (LSM) is a promising ORR catalyst.^3,7 However, without modification, it has been shown to have limited OER activity.³ Separately, these catalysts lack high performance for both reactions. Here, we combine the two catalysts into a BSCF/LSM/Carbon composite electrode and compare to electrodes prepared from the constituent single material components. In addition, we have synthesized single material perovskites containing both Co and Mn that to the best of our knowledge have never been tested as electrodes for ORR/OER. In order to understand the catalysts’ behaviors under OER and ORR conditions, X-ray adsorption spectroscopy (XAS) was measured continuously while performing cyclic voltammetry. We were able to monitor the continuous changes of the Co, Mn, and Fe oxidation states and local environment during OER and ORR with remarkably high time/applied potential resolution. Our findings illustrate the reversible and irreversible changes that can occur during OER and ORR and provide strategies for future bifunctional catalyst design.

References

1. Kirsanova, M. A.; Okatenko, V. D.; Aksyonov, D. A.; Forslund, R. P.; Mefford, J. T.; Stevenson, K. J.; Abakumov, A. M. Bifunctional OER/ORR Catalytic Activity in the Tetrahedral YBaCo 4 O 7.3 Oxide. Mater. Chem. A 2019, 7 (1), 330–341.
2. Elumeeva, K.; Masa, J.; Sierau, J.; Tietz, F.; Muhler, M.; Schuhmann, W. Perovskite-Based Bifunctional Electrocatalysts for Oxygen Evolution and Oxygen Reduction in Alkaline Electrolytes. Acta 2016, 208, 25–32.
3. Xu, W.; Apodaca, N.; Wang, H.; Yan, L.; Chen, G.; Zhou, M.; Ding, D.; Choudhury, P.; Luo, H. A-Site Excessive (La0.8Sr0.2)1+ XMnO3 Perovskite Oxides for Bifunctional Oxygen Catalyst in Alkaline Media. ACS Catal. 2019, 9 (6), 5074–5083.
4. Fabbri, E.; Nachtegaal, M.; Cheng, X.; Schmidt, T. J. Superior Bifunctional Electrocatalytic Activity of Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ /Carbon Composite Electrodes: Insight into the Local Electronic Structure. Energy Mater. 2015, 5 (17), 1402033.
5. Fabbri, E.; Nachtegaal, M.; Binninger, T.; Cheng, X.; Kim, B.-J.; Durst, J.; Bozza, F.; Graule, T.; Schäublin, R.; Wiles, L.; Pertoso, M.; Danilovic, N.; Ayers, K. E.; Schmidt, T. J. Dynamic Surface Self-Reconstruction Is the Key of Highly Active Perovskite Nano-Electrocatalysts for Water Splitting. Mater. 2017, 16 (9), 925–931.
6. Kim, B. J.; Fabbri, E.; Abbott, D. F.; Cheng, X.; Clark, A. H.; Nachtegaal, M.; Borlaf, M.; Castelli, I. E.; Graule, T.; Schmidt, T. J. Functional Role of Fe-Doping in Co-Based Perovskite Oxide Catalysts for Oxygen Evolution Reaction. Am. Chem. Soc. 2019, 141 (13), 5231–5240.
7. Tulloch, J.; Donne, S. W. Activity of Perovskite La1−xSrxMnO3 Catalysts towards Oxygen Reduction in Alkaline Electrolytes. Power Sources 2009, 188 (2), 359–366.