Advances in electrocatalysis at solid-liquid interfaces are vital for driving the technological innovations that are needed to deliver reliable, affordable and environmentally friendly energy. Here, we highlight the key achievements in the development of new materials for efficient hydrogen and oxygen production in electrolysers and, in reverse, their use in fuel cells. A key issue addressed here is the degree to which the fundamental understanding of the synergy between covalent and non-covalent interactions can form the basis for any predictive ability in tailor-making real-world catalysts. Common descriptors such as the substrate-hydroxide binding energy and the interactions in the double layer between hydroxide-oxides and H---OH are found to control individual parts of the hydrogen and oxygen electrochemistry that govern the efficiency of water-based energy conversion and storage systems. Links between aqueous- and organic-based environments are also established, encouraging the 'fuel cell' and 'battery' communities to move forward together.

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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.

Design and synthesis of active, stable and cost-effective materials for efficient hydrogen production (hydrogen evolution reaction, HER) is of paramount importance for the successful deployment of hydrogen-based alternative energy technologies. The HER, seemingly one of the simplest electrochemical reactions, has served for decades to bridge the gap between fundamental electrocatalysis and practical catalyst design. However, there are still many open questions that need to be answered before it would be possible to claim that design principles of catalyst materials are fully developed for the efficient hydrogen production. In this review, by summarizing key results for the HER on well-characterized electrochemical interfaces in acidic and alkaline media, we have broadened our understanding of the HER in the whole range of pH by considering three main parameters: the nature of the proton donor (H 3 O + in acid and H 2 O in alkaline), the energy of adsorption of H ad and OH ad , and the presence of spectator species. Simply by considering these three parameters we show that great deal has already been learned and new trends are beginning to emerge, giving some predictive ability with respect to the nature of electrochemical interface and electrocatalytic activity of the HER.

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.