Design of Noble-Metal-Free Membrane Electrode Assemblies Based on Metal Chalcogenides for Electrochemical Hydrogen Production Via Alkaline Seawater Electrolysis

The production of large amounts of green hydrogen (H 2 ) by electrochemical water splitting represents one of the key pillars to reach net-zero by 2050. As one of the major drawbacks, both low-temperature proton-exchange membrane (PEM) as well as anion-exchange membrane (AEM) electrolysis still rely on the utilization of noble metals in the catalyst layers driving the evolution of H 2 and oxygen (O 2 ) on the cathode (HER) and on the anode (OER), respectively. Beyond that, the requirement for highly pure water feeds to prevent degradation of the cell performance over time was previously addressed as one of the main concerns. In particular, this holds true for arid regions located close to the ocean. Advantageously, these coastal arid zones provide essentially unlimited access to seawater, coupled with ample solar irradiation and wind throughout the entire year.[1] One of the major challenges for direct seawater electrolysis lies in the development of selective catalysts, especially for the anode due to the inherently faster reaction kinetics of the competing two-electron chlorine evolution reaction (ClER). Nickel-iron layered double hydroxides (NiFe-LDH) were identified as active and selective OER electrocatalysts in a previous study[2] by our group. Dionigi et al.[3] recently reported a general design principle for selective seawater electrolysis, in which alkaline pH values > 7.5 are claimed to favor OER over ClER for overpotentials < 480 mV. At the cathode, state-of-the-art electrolyzers utilize Pt-based catalysts for an efficient HER.[2] For direct seawater electrolysis, however, not only the high cost but also the weak stability due to chloride-induced corrosion restrict the applicability of Pt-based electrodes. In our contribution, we thus present noble-metal free catalyst materials based on metal chalcogenides with high HER activity and improved stability in alkaline seawater electrolyte in a single-cell electrolyzer setup. Membrane-electrode assemblies (MEAs) with superior corrosion-resistance by a modification of the porous transport layers (PTLs) for both cathode and anode will be presented, which outperform reference MEAs containing Pt-based cathodes in alkaline seawater electrolysis. The optimized noble-metal-free electrode design (fig. 1) combined with well-controlled electrolyte feeding enables alkaline seawater electrolysis operating at industrially relevant current densities. References [1] S. Dresp, F. Dionigi, M. Klingenhof, P. Strasser, ACS Energy Lett. 2019 , 4 , 933. [2] S. Dresp, T. N. Thanh, M. Klingenhof, S. Brückner, P. Hauke, P. Strasser, Energy Environ. Sci. 2020 , 13 , 1725. [3] F. Dionigi, T. Reier, Z. Pawolek, M. Gliech, P. Strasser, ChemSusChem 2016 , 9 , 962. Figure 1