Partial Chemicalization of Nanoscale Metals: An Intra-Material Transformative Approach for the Synthesis of Functional Colloidal Metal-Semiconductor Nanoheterostructures

Heterostructuring colloidal nanocrystals into multicomponent modular constructs, where domains of distinct metal and semiconductor phases are interconnected through bonding interfaces, is a consolidated approach to advanced breeds of solution-processable hybrid nanomaterials capable to express richly tunable and even entirely novel physical-chemical properties and functionalities. To meet the challenges posed by the wet-chemical synthesis of metal-semiconductor nanoheterostructures, and to overcome some intrinsic limitations of available protocols, innovative transformative routes, based on the paradigm of partial chemicalization, have recently been devised within the framework of the standard seeded-growth scheme. These techniques involve regiospecific replacement reactions on preformed nanocrystal substrates, thus holding great synthetic potential for programmable configurational diversification. This Review article illustrates achievements so far made in the elaboration of metal-semiconductor nanoheterostructures with tailored arrangements of their component modules by means of conversion pathways that leverage on spatially controlled partial chemicalization of mono- and bi-metallic seeds. Advantages and limitations of these approaches are discussed within the context of the most plausible mechanisms underlying the evolution of the nanoheterostructures in liquid media. Representative physical-chemical properties and applications of chemicalization-derived metal-semiconductor nanoheterostructures are emphasized. Finally, prospects for developments in the field are outlined.