We demonstrate the translation of a low cost, non-precious metal cobalt phosphide (CoP) catalyst from 1 cm 2 lab-scale experiments to a commercial-scale 86 cm 2 polymer electrolyte membrane (PEM) electrolyser. A 2-step bulk synthesis was adopted to produce CoP on a high surface area carbon support that was readily integrated into an industrial PEM electrolyser fabrication process. The performance of the CoP was compared head-to-head with a platinum-based PEM under the same operating conditions (400 psi, 50 °C). CoP was found to be active and stable, operating at 1.86 A.cm-2 for >1700 hours of continuous hydrogen production while providing substantial material cost savings relative to platinum. This work illustrates a potential pathway for non-precious hydrogen evolution catalysts developed in past decades to translate to commercial applications.
Ru-based oxygen evolution reaction (OER) catalysts show significant promise for efficient water electrolysis, but rapid degradation poses a major challenge for commercial applications. In this work, we explore several Ru-based pyrochlores (A 2 Ru 2 O 7 , A = Y, Nd, Gd, Bi) as OER catalysts and demonstrate improved activity and stability of catalytic Ru sites relative to RuO 2 . Furthermore, we combine complementary experimental and theoretical analysis to understand how the A-site element impacts activity and stability under acidic OER conditions. Amongst the A 2 Ru 2 O 7 studied herein, we find that a longer Ru-O bond and a weaker interaction of the Ru 4d and O 2p orbitals compared to RuO 2 results in enhanced initial activity. We observe that the OER activity of the catalysts changes over time and is accompanied by both A-site and Ru dissolution at different relative rates depending on the identity of the A-site. Pourbaix diagrams constructed using density functional theory (DFT) calculations reveal a driving force for this experimentally observed dissolution, indicating that all compositions studied herein are thermodynamically unstable in acidic OER conditions. Theoretical activity predictions show consistent trends between A-site cation leaching and OER activity. These trends coupled with Bader charge analysis suggest that dissolution exposes highly oxidized Ru sites that exhibit enhanced activity. Overall, using the stability number (mol O 2 evolved /mol Ru dissolved ) as a comparative metric, the A 2 Ru 2 O 7 materials studied in this work show substantially greater stability than a standard RuO 2 and commensurate stability to some Ir mixed metal oxides. The insights described herein provide a path to further enhance Ru catalyst activity and durability, ultimately improving the efficiency of water electrolyzers.
Developing materials, interfaces, and devices with improved stability remains one of the key challenges in the field of photoelectrochemical water splitting. As a barrier to corrosion, molybdenum disulfide is a particularly attractive protection layer for photocathodes due to its inherent stability in acid, the low permeability of its basal planes, and the excellent hydrogen evolution reaction (HER) activity the MoS edge. Here, we demonstrate a stable silicon photocathode containing a protecting layer consisting of molybdenum disulfide, molybdenum silicide, and silicon oxide which operates continuously for two months. We make comparisons between this system and another molybdenum sulfide-silicon photocathode embodiment, taking both systems to catastrophic failure during photoelectrochemical stability measurements and exploring mechanisms of degradation. X-ray photoelectron spectroscopy and transmission electron microscopy provide key insights into the origins of stability.
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