Concave Gold Nanocubes Exhibit Growth-Etching Behavior: Unexpected Morphological Transformations

Chemical equilibrium stands as a fundamental principle governing the dynamics of chemical systems. However, it may become intricate when it refers to nanomaterials because of their unique properties. Here, we invesitigated concave gold nanocubes (CGNs) subjected to an akaline Au³⁺/H₂O₂ solution, which exhibit both etching and growth in a monotonic solution. When CGNs were subjected to an increasingly alkaline Au³⁺/H₂O₂ solution, their dimensions increased from 107 to 199 nm and then decreased to 125 nm. Transmission electron microscopy (TEM) demonstrated that their morphology undergoes intricate alternations from concave to mutibranch and finally to concave again. Real-time ultraviolet-visible spectroscopy and time-dependent TEM also demonstrated reduction first and then oxidation in one solution. Among the nanomaterials, the obtained carpenterworm-like gold nanoparticles revealed the best catalytic performance in p-nitrophenol reduction by NaBH₄, with a chemical rate that continues to increase until the reaction reaches completion. Growth leading to atomic dislocation, distortion, and exposure on nanoparticles and the redox of H₂O₂ plausibly account for the further etching due to the Ostwald ripening effect. Our study may spur more interest in the tuning of the properties, engineering, investigation, and design of new kinds of nanomaterials.