Electricity-driven water splitting can facilitate the storage of electrical energy in the form of hydrogen gas. As a half-reaction of electricity-driven water splitting, the oxygen evolution reaction (OER) is the major bottleneck due to the sluggish kinetics of this four-electron transfer reaction. Developing low-cost and robust OER catalysts is critical to solving this efficiency problem in water splitting. The catalyst design has to be built based on the fundamental understanding of the OER mechanism and the origin of the reaction overpotential. In this article, we summarize the recent progress in understanding OER mechanisms, which include the conventional adsorbate evolution mechanism (AEM) and lattice-oxygen-mediated mechanism (LOM) from both theoretical and experimental aspects. We start with the discussion on the AEM and its linked scaling relations among various reaction intermediates. The strategies to reduce overpotential based on the AEM and its derived descriptors are then introduced. To further reduce the OER overpotential, it is necessary to break the scaling relation of HOO* and HO* intermediates in conventional AEM to go beyond the activity limitation of the volcano relationship. Strategies such as stabilization of HOO*, proton acceptor functionality, and switching the OER pathway to LOM are discussed. The remaining questions on the OER and related perspectives are also presented at the end.

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A review on fundamentals for designing oxygen evolution electrocatalysts

Alkaline water splitting is an attractive method for sustainable hydrogen production. Owing to the sluggish kinetics of alkaline water reduction and oxidation, it is crucial to understand the mechanism of the hydrogen evolution reaction/oxygen evolution reaction (HER/OER) and construct efficient electrocatalysts based on the structure–activity relationship. This review describes the fundamentals of the alkaline HER and OER, the design of noble and nonnoble HER electrocatalysts with low energy barriers, OER electrocatalysts based on binding energy, electronic structure, lattice oxygen, and surface reconstruction as well as the recent developments of bifunctional HER/OER electrocatalysts. Future perspectives towards alkaline water splitting electrocatalysts are also proposed.

Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting

The oxygen evolution reaction (OER) is a key process in electrochemical energy conversion devices. Understanding the origins of the lattice oxygen oxidation mechanism is crucial because OER catalysts operating via this mechanism could bypass certain limitations associated with those operating by the conventional adsorbate evolution mechanism. Transition metal oxyhydroxides are often considered to be the real catalytic species in a variety of OER catalysts and their low-dimensional layered structures readily allow direct formation of the O–O bond. Here, we incorporate catalytically inactive Zn2+ into CoOOH and suggest that the OER mechanism is dependent on the amount of Zn2+ in the catalyst. The inclusion of the Zn2+ ions gives rise to oxygen non-bonding states with different local configurations that depend on the quantity of Zn2+. We propose that the OER proceeds via the lattice oxygen oxidation mechanism pathway on the metal oxyhydroxides only if two neighbouring oxidized oxygens can hybridize their oxygen holes without sacrificing metal–oxygen hybridization significantly, finding that Zn0.2Co0.8OOH has the optimum activity. Oxygen evolution is one half of the overall water splitting reaction to produce hydrogen. Although this reaction is well studied, there remains debate over the particulars of the catalytic mechanism. Here, the authors investigate Co–Zn oxyhydroxide electrocatalysts, and suggest that the mechanism depends on the amount of Zn2+ they contain.

Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts

Transition metal nitrides (TMNs), by virtue of their unique electronic structure, high electrical conductivity, superior chemical stability, and excellent mechanical robustness, have triggered tremendous research interest over the past decade, and showed great potential for electrochemical energy conversion and storage. However, bulk TMNs usually suffer from limited numbers of active sites and sluggish ionic kinetics, and eventually ordinary electrochemical performance. Designing nanostructured TMNs with tailored morphology and good dispersity has proved an effective strategy to address these issues, which provides a larger specific surface area, more abundant active sites, and shorter ion and mass transport distances over the bulk counterparts. Herein, the most up-to-date progress on TMN-based nanomaterials is comprehensively reviewed, focusing on geometric-structure design, electronic-structure engineering, and applications in electrochemical energy conversion and storage, including electrocatalysis, supercapacitors, and rechargeable batteries. Finally, we outline the future challenges of TMN-based nanomaterials and their possible research directions beyond electrochemical energy applications.

Transition metal nitrides for electrochemical energy applications.

Metallic nanostructures with low dimensionality (one-dimension and two-dimension) possess unique structural characteristics and distinctive electronic and physicochemical properties including high aspect ratio, high specific surface area, high density of surface unsaturated atoms and high electron mobility. These distinctive features have rendered them remarkable advantages over their bulk counterparts for surface-related applications, for example, electrochemical water splitting. In this review article, we highlight the recent research progress in low-dimensional metallic nanostructures for electrochemical water splitting including hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Fundamental understanding of the electrochemistry of water splitting including HER and OER is firstly provided from the aspects of catalytic mechanisms, activity descriptors and property evaluation metrics. Generally, it is challenging to obtain low-dimensional metallic nanostructures with desirable characteristics for HER and OER. We hereby introduce several typical methods for synthesizing one-dimensional and two-dimensional metallic nanostructures including organic ligand-assisted synthesis, hydrothermal/solvothermal synthesis, carbon monoxide confined growth, topotactic reduction, and templated growth. We then put emphasis on the strategies adopted for the design and fabrication of high-performance low-dimensional metallic nanostructures for electrochemical water splitting such as alloying, structure design, surface engineering, interface engineering and strain engineering. The underlying structure–property correlation for each strategy is elucidated aiming to facilitate the design of more advanced electrocatalysts for water splitting. The challenges and perspectives for the development of electrochemical water splitting and low-dimensional metallic nanostructures are also proposed.

Metallic nanostructures with low dimensionality for electrochemical water splitting

Water splitting is the essential chemical reaction to enable the storage of intermittent energies such as solar and wind in the form of hydrogen fuel. The oxygen evolution reaction (OER) is often considered as the bottleneck in water splitting. Though metal oxides had been reported as OER electrocatalysts more than half a century ago, the recent interest in renewable energy storage has spurred a renaissance of the studies of transition metal oxides as Earth-abundant and nonprecious OER catalysts. This Perspective presents major progress in several key areas of the field such as theoretical understanding, activity trend, in situ and operando characterization, active site determination, and novel materials. A personal overview of the past achievements and future challenges is also provided.

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Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance

The oxygen evolution reaction (OER) is the performance-limiting half reaction of water splitting, which can be used to produce hydrogen fuel using renewable energies. Whereas a number of transition metal oxides and oxyhydroxides have been developed as promising OER catalysts in alkaline medium, the mechanisms of OER on these catalysts are not well understood. Here we combine electrochemical and in situ spectroscopic methods, particularly operando X-ray absorption and Raman spectroscopy, to study the mechanism of OER on cobalt oxyhydroxide (CoOOH), an archetypical unary OER catalyst. We find the dominating resting state of the catalyst as a Co(IV) species CoO2. Through oxygen isotope exchange experiments, we discover a cobalt superoxide species as an active intermediate in the OER. This intermediate is formed concurrently to the oxidation of CoOOH to CoO2. Combing spectroscopic and electrokinetic data, we identify the rate-determining step of the OER as the release of dioxygen from the superoxide intermediate. The work provides important experimental fingerprints and new mechanistic perspectives for OER catalysts.

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Mechanism of Oxygen Evolution Catalyzed by Cobalt Oxyhydroxide: Cobalt Superoxide Species as a Key Intermediate and Dioxygen Release as a Rate-Determining Step

The electrochemical water splitting reaction can convert renewable electricity into clean hydrogen fuel. The efficiency of water splitting is limited to a large extent by the sluggish oxygen evolution reaction (OER). Numerous transition metal oxides have been developed as electrocatalysts for the OER in alkaline medium. However, in-depth studies of the stability of these catalysts have rarely been performed. Here we report a systematic investigation of the stability profiles of five archetypical OER catalysts including CoOx, CoFeOx, CoFeNiOx, NiOx, and NiFeOx. We combine measurements of electrochemical activity, electrochemical quartz crystal microbalance (eQCM), inductively coupled plasma optical emission spectrometry (ICP-OES), and electrochemical impedance spectroscopy (EIS). We find that the eQCM analysis gives incorrect information about the mass change during the OER due to a non-ideal response, and confirms that activity is not a valid descriptor of stability. Of the five oxides, CoOx and CoFeOx lose some mass during the initial period of the OER while CoFeNiOx, NiOx, and NiFeOx maintain their mass. However, all five catalysts undergo noticeable compositional changes due to a dynamic exchange of metal ions with the electrolyte solutions. Partial dissolution of CoOx and incorporation of Fe ions are the main processes of this exchange. The dynamic exchange reaches equilibrium after 6 h, and the catalysts are stable afterwards.

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Stability profiles of transition metal oxides in the oxygen evolution reaction in alkaline medium

The oxygen evolution reaction (OER) is the bottleneck reaction of water splitting, which can be used to generate green hydrogen from renewable electricity. Cobalt iron oxyhydroxides (CoFeOxHy) are among the most active OER catalysts in alkaline medium. However, the active sites of these catalysts remain unclear. Here we use operando ultraviolet-visible (UV-Vis), X-ray absorption, and Raman spectroscopy to reveal oxidations of both Fe and Co ions in CoFeOxHy during the OER. By analyzing samples with different Fe contents and thickness, we find that the concentration of Fe4+ species at the surface, but not the concentration of Co4+ in the bulk, scales with the catalytic activity. These results indicate an Fe4+-containing active site in CoFeOxHy.

Aliki Moysiadou

Papers

Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance

Mechanism of Oxygen Evolution Catalyzed by Cobalt Oxyhydroxide: Cobalt Superoxide Species as a Key Intermediate and Dioxygen Release as a Rate-Determining Step

Stability profiles of transition metal oxides in the oxygen evolution reaction in alkaline medium

Tracking high-valent surface iron species in the oxygen evolution reaction on cobalt iron (oxy)hydroxides