Nickel’s Surface Secrets: Three Species Steer Hydrogen Production in Alkaline Water

Hydrogen has long been heralded as the backbone of a decarbonized energy system, a clean fuel that can store renewable electricity and feed heavy industry without a whiff of carbon dioxide. Yet the most scalable way to make it—splitting water with electricity—still leans heavily on precious metals such as platinum to drive the hydrogen evolution reaction, the cathodic half of electrolysis that stitches protons and water molecules into molecular hydrogen. In alkaline electrolytes, where many commercial electrolysers operate, that reaction becomes stubbornly sluggish on most cheap alternatives. A new study published in Nature Catalysis now dissects, species by species, what actually happens on the surface of nickel, the most promising precious-metal-free candidate, and in doing so offers a roadmap for designing cheaper, more efficient water electrolysers.

The research team set out to answer a deceptively simple question: when hydrogen gas bubbles off a nickel electrode in an alkaline solution, which of the surface species that form on nickel is actually doing the catalytic work? Nickel electrodes in alkaline media are never chemically naked. Depending on the applied potential and local conditions, their surfaces can host nickel oxide, nickel hydroxide, and nickel hydride phases, each with distinct electronic structures and bonding geometries. For decades, researchers have debated whether these species are innocent bystanders, harmful blockers, or hidden active sites. Because real electrodes present a patchwork of all three, isolating their individual contributions has been extraordinarily difficult.

The breakthrough of the new work lies in its systematic approach to well-defined nickel surfaces. Rather than studying polycrystalline foams or nanoparticles, where grain boundaries and defects confound interpretation, the researchers prepared carefully controlled nickel surfaces and deliberately generated each candidate species under known conditions. By systematically varying the presence and coverage of nickel oxide, nickel hydride, and nickel hydroxide, and then measuring the hydrogen evolution activity of each configuration, they could assign catalytic roles with a clarity that previous ensemble measurements could not achieve. The strategy echoes a classic theme in surface electrochemistry: only when a surface is well defined can the link between structure and function be drawn unambiguously.

What emerged is a picture in which no single species can claim sole credit. Nickel oxide species, the team found, contribute to the reaction in ways that depend sensitively on their exact chemical state and distribution on the metallic surface. Nickel hydroxide, which forms readily in alkaline environments and has often been invoked as the key promoter of alkaline hydrogen evolution, plays a role that must be carefully separated from the contributions of the oxide and hydride phases. Meanwhile, nickel hydride, the species formed when adsorbed hydrogen penetrates the metal lattice or binds in hydride-like configurations, emerges as a central participant in the hydrogen formation chemistry itself. The study’s central achievement is showing how these three species interact and divide the labor of the reaction rather than acting in isolation.

The distinction matters enormously for the alkaline hydrogen evolution reaction because its mechanism differs fundamentally from the one that operates in acid. In acidic media, the reaction proceeds through adsorbed hydrogen atoms that form directly on the metal surface and combine into hydrogen molecules. In alkaline electrolytes, however, water itself is the proton source, so every hydrogen molecule produced requires a water molecule to dissociate on the surface, cleaving an O-H bond and liberating a hydroxide ion. This initial water dissociation step is widely regarded as the kinetic bottleneck on pure metals, and it is precisely where adjacent oxide or hydroxide species have been proposed to help, by offering oxygen-affine sites that cleave water while neighboring metallic sites assemble the hydrogen. The new results put this bifunctional picture on a much firmer experimental footing for nickel.

For the electrolyser industry, the implications are immediate. Alkaline water electrolysis is the most mature and lowest-cost electrolysis technology on the market, but its cathodes and anodes still trail the performance achievable with platinum-group catalysts. Nickel is already the workhorse electrode material in commercial alkaline electrolysers, prized for its corrosion resistance in concentrated potassium hydroxide and its reasonable activity. If engineers can now identify which surface species to stabilize—and in what proportion—they can rationally tune electrode preparation protocols, whether through surface oxidation treatments, controlled potential cycling, or the deliberate engineering of oxide-hydride interfaces, instead of relying on empirical trial and error. The study effectively converts a long-standing controversy into an engineering design principle.

The findings also carry weight for the broader search for precious-metal-free catalysts. Earth-abundant transition metals such as nickel, cobalt, iron, and molybdenum have all been explored as hydrogen evolution catalysts, and many of the most successful candidates are not pure metals at all but composites in which metallic domains coexist with oxide or hydroxide phases. The nickel study provides a conceptual template for deconvoluting such systems: prepare well-defined versions of each phase, measure their individual kinetics, and then interrogate their combinations. Applied across the periodic table, this methodology could accelerate the discovery of catalysts that match platinum’s performance at a fraction of the cost, a goal that would ripple through green hydrogen production, fuel cells, and carbon-neutral synthesis of fuels and chemicals.

There are also cautionary lessons in the results. Because nickel hydride participates directly in the reaction, the subsurface and bulk hydride chemistry of nickel electrodes deserves renewed attention, particularly under the strongly reducing potentials of cathodic operation where hydride formation is thermodynamically favored. Hydride formation can induce lattice strain, alter electronic properties, and even degrade electrode morphology over time, so understanding its catalytic role may simultaneously illuminate pathways to more durable electrodes. Similarly, the finding that oxide and hydroxide species make separable, state-dependent contributions suggests that the dynamic potential-dependent evolution of surface chemistry during electrolyser start-up, shutdown, and fluctuating renewable power input could shift which species dominates, with consequences for both efficiency and lifetime.

The study arrives at a moment when green hydrogen is scaling from demonstration projects to gigawatt deployments, and every millivolt saved at the cathode translates into real energy and cost savings at industrial scale. By systematically dissecting the individual roles of nickel oxide, nickel hydride, and nickel hydroxide on well-defined nickel surfaces, the researchers have replaced a murky, contested narrative with a mechanistically grounded one. The work does not end the search for better alkaline hydrogen evolution catalysts, but it decisively sharpens it: the target is no longer simply nickel, or nickel oxide, or nickel hydroxide, but the precisely engineered coexistence of all three. For a field racing to strip precious metals out of the hydrogen economy, that clarity may prove as valuable as any single catalyst.

Subject of Research: The individual roles of nickel oxide, nickel hydride, and nickel hydroxide surface species in the alkaline hydrogen evolution reaction on nickel electrodes.

Article Title: The role of individual nickel surface species in the hydrogen evolution reaction on nickel in alkaline electrolytes

Article References: Kozlica, D. K., Finšgar, M., Farinazzo Bergamo Dias Martins, P., Huš, M., Genorio, B., Connell, J. G., Martins, M., Hývl, M., Žibert, T., Andrina Varda, K., Osmić, A., Bele, M., Likozar, B., Tomc, B., Gaberšček, M., & Strmčnik, D. (2026). The role of individual nickel surface species in the hydrogen evolution reaction on nickel in alkaline electrolytes. Nature Catalysis. https://doi.org/10.1038/s41929-026-01605-9

Image Credits: AI Generated

DOI: 10.1038/s41929-026-01605-9

Keywords: hydrogen evolution reaction, nickel, alkaline electrolytes, water electrolysis, nickel oxide, nickel hydride, nickel hydroxide, electrocatalysis, green hydrogen, surface chemistry, precious-metal-free catalysts, Nature Catalysis