There is still an ongoing effort to search for sustainable, clean and highly efficient energy generation to satisfy the energy needs of modern society. Among various advanced technologies, electrocatalysis for the oxygen evolution reaction (OER) plays a key role and numerous new electrocatalysts have been developed to improve the efficiency of gas evolution. Along the way, enormous effort has been devoted to finding high-performance electrocatalysts, which has also stimulated the invention of new techniques to investigate the properties of materials or the fundamental mechanism of the OER. This accumulated knowledge not only establishes the foundation of the mechanism of the OER, but also points out the important criteria for a good electrocatalyst based on a variety of studies. Even though it may be difficult to include all cases, the aim of this review is to inspect the current progress and offer a comprehensive insight toward the OER. This review begins with examining the theoretical principles of electrode kinetics and some measurement criteria for achieving a fair evaluation among the catalysts. The second part of this review acquaints some materials for performing OER activity, in which the metal oxide materials build the basis of OER mechanism while non-oxide materials exhibit greatly promising performance toward overall water-splitting. Attention of this review is also paid to in situ approaches to electrocatalytic behavior during OER, and this information is crucial and can provide efficient strategies to design perfect electrocatalysts for OER. Finally, the OER mechanism from the perspective of both recent experimental and theoretical investigations is discussed, as well as probable strategies for improving OER performance with regards to future developments.

Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives

Water electrolysis is considered as the most promising technology for hydrogen production. Much research has been devoted to developing efficient electrocatalysts for hydrogen production via the hydrogen evolution reaction (HER) and oxygen production via the oxygen evolution reaction (OER). The optimum electrocatalysts can drive down the energy costs needed for water splitting via lowering the overpotential. A number of cobalt (Co)-based materials have been developed over past years as non-noble-metal heterogeneous electrocatalysts for HER and OER. Recent progress in this field is summarized here, especially highlighting several important bifunctional catalysts. Various approaches to improve or optimize the electrocatalysts are introduced. Finally, the current existing challenges and the future working directions for enhancing the performance of Co-implicated electrocatalysts are proposed.

Recent Progress in Cobalt‐Based Heterogeneous Catalysts for Electrochemical Water Splitting

Remarkable hydrogen evolution reaction (HER) or superior oxygen evolution reaction (OER) catalyst has been applied in water splitting, however, utilizing a bifunctional catalyst for simultaneously generating H2 and O2 is still a challenging issue, which is crucial for improving the overall efficiency of water electrolysis Herein, inspired by the superiority of carbon conductivity, the propitious H atom binding energy of metallic cobalt, and better OER activity of cobalt oxide, we synthesized cobalt–cobalt oxide/N-doped carbon hybrids (CoOx@CN) composed of Co0, CoO, Co3O4 applied to HER and OER by simple one-pot thermal treatment method CoOx@CN exhibited a small onset potential of 85 mV, low charge-transfer resistance (41 Ω), and considerable stability for HER Electrocatalytic experiments further indicated the better performance of CoOx@CN for HER can be attributed to the high conductivity of carbon, the synergistic effect of metallic cobalt and cobalt oxide, the stability of carbon-encapsulated Co nano

In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution.

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. Unlike other polymers, a significant feature of COFs is that they are structurally predesignable, synthetically controllable, and functionally manageable. In principle, the topological design diagram offers geometric guidance for the structural tiling of extended porous polygons, and the polycondensation reactions provide synthetic ways to construct the predesigned primary and high-order structures. Progress over the past decade in the chemistry of these two aspects undoubtedly established the base of the COF field. By virtue of the availability of organic units and the diversity of topologies and linkages, COFs have emerged as a new field of organic materials that offer a powerful molecular platform for complex structural design and tailor-made functional development. Here we target a comprehensive review of the COF field, provide a historic overview of the chemistry of the COF field, survey the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, scrutinize the development and potential of various functions through elucidating structure-function correlations based on interactions with photons, electrons, holes, spins, ions, and molecules, discuss the key fundamental and challenging issues that need to be addressed, and predict the future directions from chemistry, physics, and materials perspectives.

Covalent Organic Frameworks: Design, Synthesis, and Functions.

Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Nickel-iron mixed metal oxyhydroxides have attracted significant attention as an oxygen evolution reaction (OER) catalyst for solar fuel renewable energy applications. Here, we performed surface-selective and time-dependent redox titrations to directly measure the surface OER kinetics of Ni(IV) and Fe(IV) in NiOOH, FeOOH, and Ni(1-x)Fe(x)OOH (0 < x < 0.27) electrodes. Most importantly, two types of surface sites exhibiting "fast" and "slow" kinetics were found, where the fraction of "fast" sites in Ni(1-x)Fe(x)OOH matched the iron atom content in the film. This finding provides experimental support to the theory-proposed model of active sites in Ni(1-x)Fe(x)OOH. The OER rate constant of the "fast" site was 1.70 s(-1) per atom.

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Surface Interrogation Scanning Electrochemical Microscopy of Ni1–xFexOOH (0 < x < 0.27) Oxygen Evolving Catalyst: Kinetics of the “fast” Iron Sites

Cobalt metaphosphate Co(PO3)2 nanoparticles are prepared via the thermolytic molecular precursor (TMP) method. A Ni form electrode decorated with Co(PO3)2 nanoparticles is evaluated as an anode for water oxidation electrocatalysis in pH 6.4 phosphate-buffered water. Catalytic onset occurs at an overpotential of ca. 310 mV, which is 100 mV lower than that observed for Co3O4 nanoparticles, with a comparable surface area under identical conditions. A per-metal turnover frequency (TOF) of 0.10–0.21 s−1 is observed at an overpotential, η, of 440 mV, which is comparable to the highest rate reported for a first-row metal heterogeneous catalyst. Post-catalytic characterization of the catalyst resting state by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy reveals that surface rearrangement occurs, resulting in an oxide-like surface overlayer.

Electrocatalytic Water Oxidation at Neutral pH by a Nanostructured Co(PO3)2 Anode

n-BiVO4 is a promising semiconductor material for photoelectrochemical water oxidation. Although most thin-film syntheses yield discontinuous BiVO4 layers, back reduction of photo-oxidized products on the conductive substrate has never been considered as a possible energy loss mechanism in the material. We report that a 15 s electrodeposition of amorphous TiO2 (a-TiO2) on W:BiVO4/F:SnO2 blocks this undesired back reduction and dramatically improves the photoelectrochemical performance of the electrode. Water oxidation photocurrent increases by up to 5.5 times, and its onset potential shifts negatively by ∼500 mV. In addition to blocking solution-mediated recombination at the substrate, the a-TiO2 film—which is found to lack any photocatalytic activity in itself—is hypothesized to react with surface defects and deactivate them toward surface recombination. The proposed treatment is simple and effective, and it may easily be extended to a wide variety of thin-film photoelectrodes.

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Enhanced Photoelectrochemical Water Oxidation on Bismuth Vanadate by Electrodeposition of Amorphous Titanium Dioxide

The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the “true” cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be t...

A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy

Despite exhaustive spectroscopic investigations on the CoPi oxygen-evolving catalyst over the past several years, little is known about the surface cobalt sites and intermediates in direct contact with water that are responsible for the actual catalysis. Many studies thus far have been limited to ex situ characterizations or bulk film measurements, often in the absence of solvent. Here we describe an investigation of the CoPi catalyst by surface interrogation scanning electrochemical microscopy (SI-SECM). This method should allow us to selectively study surface atoms separately from the bulk in a solvent-filled environment. By SI-SECM, independent titrations of surface CoIII and CoIV were performed, yielding a direct measurement of the surface active-site density of a CoPi electrode (11 Co/nm2). The pseudo-first-order reaction rate constants of CoIII and CoIV with water were determined to be 0.19 and >2 s–1, respectively, through time-dependent titration measurements.

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Hyun S. Ahn

Papers

Surface Interrogation Scanning Electrochemical Microscopy of Ni1–xFexOOH (0 < x < 0.27) Oxygen Evolving Catalyst: Kinetics of the “fast” Iron Sites

Electrocatalytic Water Oxidation at Neutral pH by a Nanostructured Co(PO3)2 Anode

Enhanced Photoelectrochemical Water Oxidation on Bismuth Vanadate by Electrodeposition of Amorphous Titanium Dioxide

A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy

Surface Interrogation of CoPi Water Oxidation Catalyst by Scanning Electrochemical Microscopy