Figure 1. a) Electrochemical oxide pathway. [13] Copyright 2016, John Wiley and Sons. b) Cationic redox mechanism proposed by Kçtz et al. [21] Copyright 1984, IOP Publishing. c) Scheme of the OER, including the formation of an OOH intermediate, as detected by Sivasankar et al. [24] Copyright 2011, AmericanC hemical Society.d )Schematic representation of O2pbands penetrating into Ir dorbitals and triggering an anionic redox process. [27] Copyright 2016, Springer Nature. e) OER scheme showing the formation of oxyl species, as aresult of hybridization of Ir and O orbitals, which are prone to nucleophilic attack by water and the formation of an OÀObond. [33] Copyright2 019, Elsevier.

The production of hydrogen via a proton-exchange membrane water electrolyzer (PEM-WE) is directly dependent on the rational design of electrocatalysts for the anodic oxygen evolution reaction (OER), which is the bottleneck of the process. Here, we present a smart design strategy for enhancing Ir utilization and stabilization. We showcase it on a catalyst, where Ir nanoparticles are efficiently anchored on a conductive support titanium oxynitride (TiON x ) dispersed over carbon-based Ketjen Black and covered by a thin layer of copper (Ir/CuTiON x /C), which gets removed in the preconditioning step. Electrochemical OER activity, stability, and structural changes were compared to the Ir-based catalyst, where Ir nanoparticles without Cu are deposited on the same support (Ir/TiON x /C). To study the effect of the sacrificial less-noble metal layer on the catalytic performance of the synthesized material, characterization methods, namely X-ray powder diffraction, X-ray photoemission spectroscopy, and identical location transmission electron microscopy were employed and complemented with scanning flow cell coupled to an inductively coupled plasma mass spectrometer, which allowed studying the online dissolution during the catalytic reaction. Utilization of these advanced methods revealed that the sacrificial Cu layer positively affects both Ir OER mass activity and its durability, which was assessed via S-number, a recently reported stability metric. Improved activity of Cu analogue was ascribed to the higher surface area of smaller Ir nanoparticles, which are better stabilized through a strong metal–support interaction (SMSI) effect.

The commercialization of acidic proton exchange membrane water electrolyzers (PEMWE) is heavily hindered by the price and scarcity of oxygen evolution reaction (OER) catalyst, i. e. iridium and its oxides. One of the solutions to enhance the utilization of this precious metal is to use a support to distribute well dispersed Ir nanoparticles. In addition, adequately chosen support can also impact the activity and stability of the catalyst. However, not many materials can sustain the oxidative and acidic conditions of OER in PEMWE. Hereby, we critically and extensively review the different materials proposed as possible supports for OER in acidic media and the effect they have on iridium performances.

More efficient utilization of iridium is of immense importance for the future development of proton exchange membrane electrolyzers. In this study, we introduce a new facile and scalable synthesis of an Ir-based high-performance oxygen evolution reaction (OER) electrocatalytic nanocomposite. The composite consists of Ir nanoparticles with an average size of 3-4 nm, which are effectively anchored on a titanium oxynitride support (TiON x ), which is distributed across high-surface-area Ketjen Black carbon (Ir/TiON x /C). We provide complete structural, morphological and compositional characterization (x-ray diffraction, scanning transmission electron microscopy and energy-dispersive x-ray spectroscopy) and propose a proper benchmark protocol to measure true electrochemical performance. Compared to the state-of-the-art Ir Black electrocatalyst, Ir/TiON x /C exhibits approximately three times higher OER performance.

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Decreasing iridium loading in the electrocatalyst presents a crucial challenge in the implementation of proton exchange membrane (PEM) electrolyzers. In this respect, fine dispersion of Ir on electrically conductive ceramic supports is a promising strategy. However, the supporting material needs to meet the demanding requirements such as structural stability and electrical conductivity under harsh oxygen evolution reaction (OER) conditions. Herein, nanotubular titanium oxynitride (TiON) is studied as a support for iridium nanoparticles. Atomically resolved structural and compositional transformations of TiON during OER were followed using a task-specific advanced characterization platform. This combined the electrochemical treatment under floating electrode configuration and identical location transmission electron microscopy (IL-TEM) analysis of an in-house-prepared Ir-TiON TEM grid. Exhaustive characterization, supported by density functional theory (DFT) calculations, demonstrates and confirms that both the Ir nanoparticles and single atoms induce a stabilizing effect on the ceramic support via marked suppression of the oxidation tendency of TiON under OER conditions.

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A versatile approach to the production of cluster- and single atom-based thin-film electrode composites is presented. The developed TiO x N y –Ir catalyst was prepared from sputtered Ti–Ir alloy constituted of 0.8 ± 0.2 at % Ir in α-Ti solid solution. The Ti–Ir solid solution on the Ti metal foil substrate was anodically oxidized to form amorphous TiO2–Ir and later subjected to heat treatment in air and in ammonia to prepare the final catalyst. Detailed morphological, structural, compositional, and electrochemical characterization revealed a nanoporous film with Ir single atoms and clusters that are present throughout the entire film thickness and concentrated at the Ti/TiO x N y –Ir interface as a result of the anodic oxidation mechanism. The developed TiO x N y –Ir catalyst exhibits very high oxygen evolution reaction activity in 0.1 M HClO4, reaching 1460 A g–1 Ir at 1.6 V vs reference hydrogen electrode. The new preparation concept of single atom- and cluster-based thin-film catalysts has wide potential applications in electrocatalysis and beyond. In the present paper, a detailed description of the new and unique method and a high-performance thin film catalyst are provided along with directions for the future development of high-performance cluster and single-atom catalysts prepared from solid solutions.