The Perfect Imperfections in Electrocatalysts

Modern day electrochemical devices find applications in a wide range of industrial sectors, from consumer electronics, renewable energy management to pollution control by electric vehicles and reduction of greenhouse gas. There has been a surge of diverse electrochemical systems which are to be scaled up from the lab‐scale to industry sectors. To achieve the targets, the electrocatalysts are continuously upgraded to meet the required device efficiency at a low cost, increased lifetime and performance. An atomic scale understanding is however important for meeting the objectives. Transitioning from the bulk to the nanoscale regime of the electrocatalysts, the existence of defects and interfaces is almost inevitable, significantly impacting (augmenting) the material properties and the catalytic performance. The intrinsic defects alter the electronic structure of the nanostructured catalysts, thereby boosting the performance of metal‐ion batteries, metal‐air batteries, supercapacitors, fuel cells, water electrolyzers etc. This account presents our findings on the methods to introduce measured imperfections in the nanomaterials and the impact of these atomic‐scale irregularities on the activity for three major reactions, oxygen evolution reaction (OER), oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Grain boundary (GB) modulation of the (ABO3)n type perovskite oxide by noble metal doping is a propitious route to enhance the OER/ORR bifunctionality for zinc‐air battery (ZAB). The perovskite oxides can be tuned by calcination at different temperatures to alter the oxygen vacancy, GB fraction and overall reactivity. The oxygen defects, unsaturated coordination environment and GBs can turn a relatively less active nanostructure into an efficient redox active catalyst by imbibing plenty of electrochemically active sites. Obviously, the crystalline GB interface is a prerequisite for effective electron flow, which is also applicable for the crystalline surface oxide shell on metal alloy core of the nanoparticles (NPs). The oxygen vacancy of two‐dimensional (2D) perovskite oxide can be made reversible by the A‐site termination of the nanosheets, facilitating the reversible entry and exit of a secondary phase during the redox processes. In several instances, the secondary phases have been observed to introduce the right proportion of structural defects and orbital occupancies for adsorption and desorption of reaction intermediates. Also, heterogeneous interfaces can be created by wrapping the perovskite oxide with negatively charged surface by layered double hydroxide (LDH) can promote the OER process. In another approach, ion intercalation at the 2D heterointerfaces steers the interlayer spacing that can influence the mass diffusion. Similar to anion vacancy, controlled formation of the cation vacancies can be achieved by exsolving the B‐site cations of perovskite oxides to surface anchored catalytically active metal/alloy NPs. In case of the alloy electrocatalysts, incomplete solid solution by two or more mutually immiscible metals results in heterogeneous alloys having differently exposed facets with complementary functionalities. From the future perspective, new categories of defect structures including the 2D empty spaces or voids leading to undercoordinated sites, the multiple interfaces in heterogeneous alloys, antisite defects between anions and cations, and the defect induced inverse charge transfer should bring new dimensionalities to this riveting area of research.