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Although the term 'confinement' regularly appears in electrochemical literature, elevated by continuous progression in the research of nanomaterials and nanostructures, up until today the various aspects of confinement considered in electrochemistry are rather scattered individual contributions outside the established disciplines in this field. Thanks to a number of highly original publications and the growing appreciation of confinement as an overarching link between different exciting new research strategies, 'electrochemistry under confinement' is the process of forming a research discipline of its own. To aid the development a coherent terminology and joint basic concepts, as crucial factors for this transformation, this review provides an overview on the different effects on electrochemical processes known to date that can be caused by confinement. It also suggests where boundaries to other effects, such as nano-effects could be drawn. To conceptualize the vast amount of research activities revolving around the main concepts of confinement, we define six types of confinement and select two of them to discuss the state of the art and anticipated future developments in more detail. The first type concerns nanochannel environments and their applications for electrodeposition and for electrochemical sensing. The second type covers the rather newly emerging field of colloidal single entity confinement in electrochemistry. In these contexts, we will for instance address the influence of confinement on the mass transport and electric field distributions and will link the associated changes in local species concentration or in the local driving force to altered reaction kinetics and product selectivity. Highlighting pioneering works and exciting recent developments, this educational review does not only aim at surveying and categorizing the state-of-the-art, but seeks to specifically point out future perspectives in the field of confinement-controlled electrochemistry. [ABSTRACT FROM AUTHOR]

The effect of surface orientations on the formation of iridium oxide species during the oxygen evolution reaction (OER) remains yet unknown. Herein, we use a needle‐shaped iridium atom probe specimen as a nanosized working electrode to ascertain the role of the surface orientations in the formation of oxide species during OER. At the beginning of electrolysis, the top 2–3 nm of (024), (026), (113), and (115) planes are covered by IrO−OH, which activates all surfaces towards OER. A thick subsurface oxide layer consisting of sub‐stoichiometric Ir−O species is formed on the open (024) planes as OER proceeds. Such metastable Ir−O species are thought to provide an additional contribution to the OER activity. Overall, this study sheds light on the importance of the morphological effects of iridium electrocatalysts for OER. It also provides an innovative approach that can directly reveal surface species on electrocatalysts at atomic scale. [ABSTRACT FROM AUTHOR]

Metal‐rich chalcogenides composed of highly abundant elements recently emerged as promising catalysts for the electrocatalytic hydrogen evolution reaction (HER). Many of these materials benefit from a high intrinsic conductivity as compared to their chalcogen‐rich congeners, greatly reducing the necessity for conductive additives or sophisticated nanostructuring. Herein, we showcase the high potential of metal‐rich transition‐metal chalcogenides for the electrocatalytic hydrogen formation by summarizing the recent progress achieved with M9S8 (pentlandite type) and M3S2 (heazlewoodite type) based materials, which represent the most frequently applied compositions for this purpose. By a detailed electrochemical comparison of bulk as well as pellet electrodes of metal‐rich Fe4.5Ni4.5S8, we also aim at raising awareness in the community for the inherent differences in catalytic properties of the materials themselves and those of the fabricated electrodes, a point that is often disregarded in reports on HER‐catalyst systems. [ABSTRACT FROM AUTHOR]

Single-entity electrochemistry allows for assessing electrocatalytic activities of individual material entities such as nanoparticles (NPs). Thus, it becomes possible to consider intrinsic electrochemical properties of nanocatalysts when researching how activity relates to physical and structural material properties. Conversely, conventional electrochemical techniques provide a normalized sum current referring to a huge ensemble of NPs constituting, along with additives (e.g., binders), a complete catalyst-coated electrode. Accordingly, recording electrocatalytic responses of single NPs avoids interferences of ensemble effects and reduces the complexity of electrocatalytic processes, thus enabling detailed description and modelling. Herein, we present insights into the oxygen evolution catalysis at individual cubic Co3O4 NPs impacting microelectrodes of different support materials. Simulating diffusion at supported nanocubes, measured step current signals can be analyzed, providing edge lengths, corresponding size distributions, and interference-free turnover frequencies. The provided nano-impact investigation of (electro-)catalyst-support effects contradicts assumptions on a low number of highly active sites. [ABSTRACT FROM AUTHOR]

Identifying the intrinsic electrocatalytic activity of nanomaterials is challenging, as their characterization usually requires additives and binders whose contributions are difficult to dissect. Herein, we use nano impact electrochemistry as an additive-free method to overcome this problem. Due to the efficient mass transport at individual catalyst nanoparticles, high current densities can be realized. High-resolution bright-field transmission electron microscopy and selected area diffraction studies of the catalyst particles before and after the experiments provide valuable insights in the transformation of the nanomaterials during harsh oxygen evolution reaction (OER) conditions. We demonstrate this for 4 nm sized CoFe 2 O 4 spinel nanoparticles. It is revealed that these particles retain their size and crystal structure even after OER at current densities as high as several kA·m -2 . The steady-state current scales with the particle size distribution and is limited by the diffusion of produced oxygen away from the particle. This versatilely applicable method provides new insights into intrinsic nanocatalyst activities, which is key to the efficient development of improved and precious metal-free catalysts for renewable energy technologies.