Unveiling the Role of Precursors in the Byproduct Formation of AgCl-Replicated Bimetallic Nanostructures and Their Stability-Dependent Photothermal Properties.

AgCl nanomaterials recently attracted scientific interest as useful structural building blocks for producing metallic nanomaterials owing to their facile synthesis, controllable morphology, and ease of removal under ambient conditions. However, their complex chemical reactivity has primarily been studied in association with water solubility or reducibility. This study investigates the pivotal role of precursor ligands in the photochemical synthesis of metallic cubic mesh nanostructures on the AgCl templates. The side reactions between AgCl and Au precursors with different ligands are thoroughly discussed along with their influence on the byproduct formation and the structural stability of the resulting metallic nanostructures. Importantly, we introduce for the first time the partial destruction of AgCl and the formation of undesirable byproducts caused by the presence of highly oxidizing and Cl-containing AuCl4-. In addition, a synthetic route for producing highly pure and stable metallic nanostructures using a halogen-free Au precursor or Pt-priming is proposed. Further, the photothermal properties of these replicated metallic nanostructures are presented as a new evaluation tool for analyzing their overall structural stability. Discovering the role of precursor ligands in the reaction system will prove useful as a guide for the synthesis of functional noble metal nanomaterials using silver halide templates.