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The impact of topological defects associated with grain boundaries (GB defects) on the electrical, optical, magnetic, mechanical and chemical properties of nanocrystalline materials1,2 is well known. However, elucidating this influence experimentally is difficult because grains typically exhibit a large range of sizes, shapes and random relative orientations3-5. Here we demonstrate that precise control of the heteroepitaxy of colloidal polyhedral nanocrystals enables ordered grain growth and can thereby produce material samples with uniform GB defects. We illustrate our approach with a multigrain nanocrystal comprising a Co3O4 nanocube core that carries a Mn3O4 shell on each facet. The individual shells are symmetry-related interconnected grains6, and the large geometric misfit between adjacent tetragonal Mn3O4 grains results in tilt boundaries at the sharp edges of the Co3O4 nanocube core that join via disclinations. We identify four design principles that govern the production of these highly ordered multigrain nanostructures. First, the shape of the substrate nanocrystal must guide the crystallographic orientation of the overgrowth phase7. Second, the size of the substrate must be smaller than the characteristic distance between the dislocations. Third, the incompatible symmetry between the overgrowth phase and the substrate increases the geometric misfit strain between the grains. Fourth, for GB formation under near-equilibrium conditions, the surface energy of the shell needs to be balanced by the increasing elastic energy through ligand passivation8-10. With these principles, we can produce a range of multigrain nanocrystals containing distinct GB defects.

The reconstructed surface structure of Co‐based spinel oxides serves as the active site for oxygen evolution reaction (OER). However, the structural complexity of spinel oxides and surface dynamics during the OER hinder the understanding of the reconstruction mechanism and electronic structure of the active site. In this study, spinel Co3O4@(CoFeV)3O4 nanocube (CoFeV) is reported, a (001) facet‐defined spinel oxide comprising Co, Fe, and V deposited on the Co3O4 nanocube template to exclude facet‐dependent factors. Introducing highly dissoluble V cations accelerates the reconstruction process to enhance the electrocatalytic activity. CoFeV exhibited enhanced electrocatalytic activity (266 mV at 10 mA cm−2 in 1 M KOH) and durability (maintained stable electrocatalytic activity during a 200 h chronopotentiometry (CP) test at 100 mA cm−2) with significantly enlarged electrochemically active surface area (ECSA). The experimental and theoretical results demonstrated that V dissolution during catalysis induced oxygen vacancies, accelerating the surface reconstruction to highly active oxyhydroxide. Consequently, the anion exchange membrane water electrolyzer (AEMWE) of CoFeV as the anode exhibited a remarkable performance of 6.19 A cm−2 at 2.0 Vcell in 1 M KOH and robust durability for 96 h at a constant current density of 500 mA cm−2. [ABSTRACT FROM AUTHOR]