Shape‐Controlled Synthesis of Colloidal Metal Nanocrystals by Replicating the Surface Atomic Structure on the Seed

Abstract Controlling the surface structure of metal nanocrystals while maximizing the utilization efficiency of the atoms is a subject of great importance. An emerging strategy that has captured the attention of many research groups involves the conformal deposition of one metal as an ultrathin shell (typically 1–6 atomic layers) onto the surface of a seed made of another metal and covered by a set of well‐defined facets. This approach forces the deposited metal to faithfully replicate the surface atomic structure of the seed while at the same time serving to minimize the usage of the deposited metal. Here, the recent progress in this area is discussed and analyzed by focusing on the synthetic and mechanistic requisites necessary for achieving surface atomic replication of precious metals. Other related methods are discussed, including the one‐pot synthesis, electrochemical deposition, and skin‐layer formation through thermal annealing. To close, some of the synergies that arise when the thickness of the deposited shell is decreased controllably down to a few atomic layers are highlighted, along with how the control of thickness can be used to uncover the optimal physicochemical properties necessary for boosting the performance toward a range of catalytic reactions.