Investigating the Reaction Mechanism of Iridium Oxides for PEM Water Electrolysis by Operando Soft X-Ray Absorption Spectroscopy

Abstract

With the increase in fossil energy consumption and the attendant pronounced climate changes, the call for sustainable energy forms has become urgent and has attracted more and more attention.1 Hydrogen (H2), generated by the electricity-derived water electrolysis, is now considered the promising energy carrier for conversion between electricity and chemical energy.2 The most developed water electrolysis technology up to date is the proton-exchange membrane (PEM) water electrolysis, where commercial Pt/C works as the cathodic catalyst for hydrogen evolution reaction (HER) and noble metal-based materials serve as the anodic catalyst for oxygen evolution reaction (OER).3 Considering the sluggish four-electron reaction kinetics of OER and the harsh acidic environment of PEM water electrolysis, the selectivity of high-efficient OER catalysts is narrowed down to Ir-based catalysts because of their superior activity, long-term stability and corrosion resistance against acidic environment.4 However, the scarcity of Ir on earth has impeded the wide application of PEM water electrolysis and has driven the research of cost-efficient OER catalysts. In this study, we thoroughly investigated several amorphous IrOx catalysts with different degree of crystallinity (SA103, SA58, SA14.6 and SA58) and revealed the relation between their structures and OER activities. Besides, BET surface areas, X-ray diffraction (XRD), Transmission electron microscopy (TEM), scanning TEM (STEM), PDF, and XAS were measured to thoroughly understand the catalytic properties.XRD patterns in Figure 1(a) showed that compared with the well-crystallized IrO2, SA58 sample showed slightly broad peak, while the diffraction peaks were much broad of other samples, indicating their amorphous structures. The amorphous structure of IrOx was characterized through atomic pair distribution function (PDF) analyses as shown in Figure 1(b). Different from the typical tetragonal symmetry of crystal IrO2, the combination of orthorhombic symmetry and monoclinic symmetry was found in the amorphous IrOx. Further, OER activities of all samples were investigated in 0.1 M HClO4 and the current density was calculated against the BET surface areas to examine the intrinsic catalytic activity (Figure 1(c)). The crystallized SA58 sample showed the lowest activity, while SA3.5 sample outperformed all other amorphous oxides. From PDF, it was found that the highest OER active SA3.5 sample exhibited the highest monoclinic phase ratio content. The catalytic structure properties were further evidenced by the XAS results. EXAFS results showed different electronic environment of monoclinic phase samples and further fitting results were in good agreement with the PDF analyses. Moreover, O K-edge results showed the formation of µ2-O (O-O) bond at around 528.7 eV, which was previously observed by Nong, H. N. et. al. through operando O-K edge measurements during OER process.5 It was concluded that that the low symmetry of monoclinic phase in amorphous samples resulted in the structure defection, and thus lead to large amount of active electrophilic OI - species, which boosting the OER activity. This finding provided fundamental understanding of the amorphous iridium oxides and could promisingly shed light on the future OER catalyst design. Acknowledgements This work is based on results obtained from a project (JPNP14021) commissioned by the New Energy and Industrial Technology Development Organization (NEDO) of Japan. References Götz, M.; Lefebvre, J.; Mörs, F.; McDaniel Koch, A.; Graf, F.; Bajohr, S.; Reimert, R.; Kolb, T., Renewable Power-to-Gas: A technological and economic review. Renew. Energy 2016, 85, 1371-1390.Dincer, I.; Acar, C., Review and evaluation of hydrogen production methods for better sustainability. Int. J. Hydrogen Energy 2015, 40 (34), 11094-11111.Carmo, M.; Fritz, D. L.; Merge, J.; Stolten, D., A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 2013, 38 (12), 4901-4934.An, L.; Wei, C.; Lu, M.; Liu, H.; Chen, Y.; Scherer, G. G.; Fisher, A. C.; Xi, P.; Xu, Z. J.; Yan, C.-H., Recent Development of Oxygen Evolution Electrocatalysts in Acidic Environment. Adv. Mater. 2021, 33 (20), 2006328.Nong, H. N.; Falling, L. J.; Bergmann, A.; Klingenhof, M.; Tran, H. P.; Spöri, C.; Mom, R.; Timoshenko, J.; Zichittella, G.; Knop-Gericke, A.; Piccinin, S.; Pérez-Ramírez, J.; Cuenya, B. R.; Schlögl, R.; Strasser, P.; Teschner, D.; Jones, T. E., Key role of chemistry versus bias in electrocatalytic oxygen evolution. Nature 2020, 587 (7834), 408-413. Figure 1