Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting.

The growing need to store increasing amounts of renewable energy has recently triggered substantial R&D efforts towards efficient and stable water electrolysis technologies. The oxygen evolution reaction (OER) occurring at the electrolyser anode is central to the development of a clean, reliable and emission-free hydrogen economy. The development of robust and highly active anode materials for OER is therefore a great challenge and has been the main focus of research. Among potential candidates, perovskites have emerged as promising OER electrocatalysts. In this study, by combining a scalable cutting-edge synthesis method with time-resolved X-ray absorption spectroscopy measurements, we were able to capture the dynamic local electronic and geometric structure during realistic operando conditions for highly active OER perovskite nanocatalysts. Ba0.5Sr0.5Co0.8Fe0.2O3-δ as nano-powder displays unique features that allow a dynamic self-reconstruction of the material's surface during OER, that is, the growth of a self-assembled metal oxy(hydroxide) active layer. Therefore, besides showing outstanding performance at both the laboratory and industrial scale, we provide a fundamental understanding of the operando OER mechanism for highly active perovskite catalysts. This understanding significantly differs from design principles based on ex situ characterization techniques.

Design of active and stable Co-Mo-Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction.

Three of the fundamental catalytic limitations that have plagued the electrochemical production of hydrogen for decades still remain: low efficiency, short lifetime of catalysts and a lack of low-cost materials. Here, we address these three challenges by establishing and exploring an intimate functional link between the reactivity and stability of crystalline (CoS2 and MoS2) and amorphous (CoSx and MoSx) hydrogen evolution catalysts. We propose that Co(2+) and Mo(4+) centres promote the initial discharge of water (alkaline solutions) or hydronium ions (acid solutions). We establish that although CoSx materials are more active than MoSx they are also less stable, suggesting that the active sites are defects formed after dissolution of Co and Mo cations. By combining the higher activity of CoSx building blocks with the higher stability of MoSx units into a compact and robust CoMoSx chalcogel structure, we are able to design a low-cost alternative to noble metal catalysts for efficient electrocatalytic production of hydrogen in both alkaline and acidic environments.

Activity-stability relationship in the surface electrochemistry of the oxygen evolution reaction.

Understanding the functional links between the stability and reactivity of oxide materials during the oxygen evolution reaction (OER) is one key to enabling a vibrant hydrogen economy capable of competing with fossil fuel-based technologies. In this work, by focusing on the surface chemistry of monometallic Ru oxide in acidic and alkaline environments, we found that the kinetics of the OER are almost entirely controlled by the stability of the Ru surface atoms. The same activity-stability relationship was found for more complex, polycrystalline and single-crystalline SrRuO(3) thin films in alkaline solutions. We propose that the electrochemical transformation of either water (acidic solutions) or hydroxyl ions (alkaline solutions) to di-oxygen molecules takes place at defect sites that are inherently present on every electrode surface. During the OER, surface defects are also created by the corrosion of the Ru ions. The dissolution is triggered by the potential-dependent change in the valence state (n) of Ru: from stable but inactive Ru(4+) to unstable but active Ru(n>4+). We conclude that if the oxide is stable then it is completely inactive for the OER. A practical consequence is that the best materials for the OER should balance stability and activity in such a way that the dissolution rate of the oxide is neither too fast nor too slow.

Using surface segregation to design stable Ru-Ir oxides for the oxygen evolution reaction in acidic environments.

The methods used to improve catalytic activity are well-established, however elucidating the factors that simultaneously control activity and stability is still lacking, especially for oxygen evolution reaction (OER) catalysts. Here, by studying fundamental links between the activity and stability of well-characterized monometallic and bimetallic oxides, we found that there is generally an inverse relationship between activity and stability. To overcome this limitation, we developed a new synthesis strategy that is based on tuning the near-surface composition of Ru and Ir elements by surface segregation, thereby resulting in the formation of a nanosegregated domain that balances the stability and activity of surface atoms. We demonstrate that a Ru0.5Ir0.5 alloy synthesized by using this method exhibits four-times higher stability than the best Ru-Ir oxygen evolution reaction materials, while still preserving the same activity.

Ionomer-free and recyclable porous-transport electrode for high-performing proton-exchange-membrane water electrolysis.

Clean hydrogen production requires large-scale deployment of water-electrolysis technologies, particularly proton-exchange-membrane water electrolyzers (PEMWEs). However, as iridium-based electrocatalysts remain the only practical option for PEMWEs, their low abundance will become a bottleneck for a sustainable hydrogen economy. Herein, we propose high-performing and durable ionomer-free porous transport electrodes (PTEs) with facile recycling features enabling Ir thrifting and reclamation. The ionomer-free porous transport electrodes offer a practical pathway to investigate the role of ionomer in the catalyst layer and, from microelectrode measurements, point to an ionomer poisoning effect for the oxygen evolution reaction. The ionomer-free porous transport electrodes demonstrate a voltage reduction of > 600 mV compared to conventional ionomer-coated porous transport electrodes at 1.8 A cm-2 and <0.1 mgIr cm-2, and a voltage degradation of 29 mV at average rate of 0.58 mV per 1000-cycles after 50k cycles of accelerated-stress tests at 4 A cm-2. Moreover, the ionomer-free feature enables facile recycling of multiple components of PEMWEs, which is critical to a circular clean hydrogen economy.

Insights into Interfacial and Bulk Transport Phenomena Affecting Proton Exchange Membrane Water Electrolyzer Performance at Ultra-Low Iridium Loadings.

Interfacial and bulk properties between the catalyst layer and the porous transport layer (PTL) restrict the iridium loading reduction for proton exchange membrane water electrolyzers (PEMWEs), by limiting their mass and charge transport. Using titanium fiber PTLs of varying thickness and porosity, the bulk and interface transport properties are investigated, correlating them to PEMWEs cell performance at ultra-low Ir loadings of ≈0.05 mgIr cm-2 . Electrochemical experiments, tomography, and modeling are combined to study the bulk and interfacial impacts of PTLs on PEMWE performance. It is found that the PEMWE performance is largely dependent on the PTL properties at ultra-low Ir loadings; bulk structural properties are critical to determine the mass transport and Ohmic resistance of PEMWEs while the surface properties of PTLs are critical to govern the catalyst layer utilization and electrode kinetics. The PTL-induced variation in kinetic and mass transport overpotential are on the order of ≈40 and 60 mV (at 80 A mgIr -1 ), respectively, while a nonnegligible 35 mV (at 3 A cm-2 ) difference in Ohmic overpotential. Thus at least 150 mV improvement in PEMWE performance can be achieved through PTL structural optimization without membrane thickness reduction or advent of new electrocatalysts.

Pathway to Complete Energy Sector Decarbonization with Available Iridium Resources using Ultralow Loaded Water Electrolyzers.

We present ultralow Ir-loaded (ULL) proton exchange membrane water electrolyzer (PEMWE) cells that can produce enough hydrogen to largely decarbonize the global natural gas, transportation, and electrical storage sectors by 2050, using only half of the annual global Ir production for PEMWE deployment. This represents a significant improvement in PEMWE's global potential, enabled by careful control of the anode catalyst layer (CL), including its mesostructure and catalyst dispersion. Using commercially relevant membranes (Nafion 117), cell materials, electrocatalysts, and fabrication techniques, we achieve at peak a 250× improvement in Ir mass activity over commercial PEMWEs. An optimal Ir loading of 0.011 mgIr cm-2 operated at an Ir-specific power of ∼100 MW kgIr-1 at a cell potential of ∼1.66 V versus RHE (85% higher heating value efficiency). We further evaluate the performance limitations within the ULL regime and offer new insights and guidance in CL design relevant to the broader energy conversion field.

Observation of Preferential Pathways for Oxygen Removal through Porous Transport Layers of Polymer Electrolyte Water Electrolyzers.

Understanding the relationships between porous transport layer (PTL) morphology and oxygen removal is essential to improve the polymer electrolyte water electrolyzer (PEWE) performance. Operando X-ray computed tomography and machine learning were performed on a model electrolyzer at different water flow rates and current densities to determine how these operating conditions alter oxygen transport in the PTLs. We report a direct observation of oxygen taking preferential pathways through the PTL, regardless of the water flow rate or current density (1-4 A/cm2). Oxygen distribution in the PTL had a periodic behavior with period of 400 µm. A computational fluid dynamics model was used to predict oxygen distribution in the PTL showing periodic oxygen front. Observed oxygen distribution is due to low in-plane PTL tortuosity and high porosity enabling merging of oxygen bubbles in the middle of the PTL and also due to aerophobicity of the layer.

Perspectives on Low-Temperature Electrolysis and Potential for Renewable Hydrogen at Scale.

Hydrogen is an important part of any discussion on sustainability and reduction in emissions across major energy sectors. In addition to being a feedstock and process gas for many industrial processes, hydrogen is emerging as a fuel alternative for transportation applications. Renewable sources of hydrogen are therefore required to increase in capacity. Low-temperature electrolysis of water is currently the most mature method for carbon-free hydrogen generation and is reaching relevant scales to impact the energy landscape. However, costs still need to be reduced to be economical with traditional hydrogen sources. Operating cost reductions are enabled by the recent availability of low-cost sources of renewable energy, and the potential exists for a large reduction in capital cost withmaterial and manufacturing optimization. This article focuses on the current status and development needs by component for the low-temperature electrolysis options.

A non-precious metal hydrogen catalyst in a commercial polymer electrolyte membrane electrolyser.

We demonstrate the translation of a low-cost, non-precious metal cobalt phosphide (CoP) catalyst from 1 cm2 lab-scale experiments to a commercial-scale 86 cm2 polymer electrolyte membrane (PEM) electrolyser. A two-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 >1,700 h 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.

Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts.

The selection of oxide materials for catalyzing the oxygen evolution reaction in acid-based electrolyzers must be guided by the proper balance between activity, stability and conductivity-a challenging mission of great importance for delivering affordable and environmentally friendly hydrogen. Here we report that the highly conductive nanoporous architecture of an iridium oxide shell on a metallic iridium core, formed through the fast dealloying of osmium from an Ir25Os75 alloy, exhibits an exceptional balance between oxygen evolution activity and stability as quantified by the activity-stability factor. On the basis of this metric, the nanoporous Ir/IrO2 morphology of dealloyed Ir25Os75 shows a factor of ~30 improvement in activity-stability factor relative to conventional iridium-based oxide materials, and an ~8 times improvement over dealloyed Ir25Os75 nanoparticles due to optimized stability and conductivity, respectively. We propose that the activity-stability factor is a key "metric" for determining the technological relevance of oxide-based anodic water electrolyzer catalysts.

Activity-Stability Trends for the Oxygen Evolution Reaction on Monometallic Oxides in Acidic Environments.

In the present study, we used a surface-science approach to establish a functional link between activity and stability of monometallic oxides during the OER in acidic media. We found that the most active oxides (Au ≪ Pt < Ir < Ru ≪ Os) are, in fact, the least stable (Au ≫ Pt > Ir > Ru ≫ Os) materials. We suggest that the relationships between stability and activity are controlled by both the nobility of oxides as well as by the density of surface defects. This functionality is governed by the nature of metal cations and the potential transformation of a stable metal cation with a valence state of n = +4 to unstable metal cation with n > +4. A practical consequence of such a close relationship between activity and stability is that the best materials for the OER should balance stability and activity in such a way that the dissolution rate is neither too fast nor too slow.

Functional links between stability and reactivity of strontium ruthenate single crystals during oxygen evolution.

In developing cost-effective complex oxide materials for the oxygen evolution reaction, it is critical to establish the missing links between structure and function at the atomic level. The fundamental and practical implications of the relationship on any oxide surface are prerequisite to the design of new stable and active materials. Here we report an intimate relationship between the stability and reactivity of oxide catalysts in exploring the reaction on strontium ruthenate single-crystal thin films in alkaline environments. We determine that for strontium ruthenate films with the same conductance, the degree of stability, decreasing in the order (001)>(110)>(111), is inversely proportional to the activity. Both stability and reactivity are governed by the potential-induced transformation of stable Ru(4+) to unstable Ru(n>4+). This ordered(Ru(4+))-to-disordered(Ru(n>4+)) transition and the development of active sites for the reaction are determined by a synergy between electronic and morphological effects.

Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption.

The development of hydrogen-based energy sources as viable alternatives to fossil-fuel technologies has revolutionized clean energy production using fuel cells. However, to date, the slow rate of the hydrogen oxidation reaction (HOR) in alkaline environments has hindered advances in alkaline fuel cell systems. Here, we address this by studying the trends in the activity of the HOR in alkaline environments. We demonstrate that it can be enhanced more than fivefold compared to state-of-the-art platinum catalysts. The maximum activity is found for materials (Ir and Pt0.1Ru0.9) with an optimal balance between the active sites that are required for the adsorption/dissociation of H2 and for the adsorption of hydroxyl species (OHad). We propose that the more oxophilic sites on Ir (defects) and PtRu material (Ru atoms) electrodes facilitate the adsorption of OHad species. Those then react with the hydrogen intermediates (Had) that are adsorbed on more noble surface sites.

An integral proton conducting SOFC for simultaneous production of ethylene and power from ethane.

A novel, integral, tri-layered, proton conducting membrane SOFC was readily fabricated for simultaneous conversion of ethane at 650-700 degrees C to electrical power and ethylene with high selectivity.