Site-Selective Carving and Co-Deposition: Transformation of Ag Nanocubes into Concave Nanocrystals Encased by Au–Ag Alloy Frames

We report a facile synthesis of Ag nanocubes with concave side faces and Au–Ag alloy frames, namely Ag@Au–Ag concave nanocrystals, by titrating HAuCl4 solution into an aqueous mixture of Ag nanocubes, ascorbic acid (H2Asc), NaOH, and cetyltrimethylammonium chloride (CTAC) at an initial pH of 11.6 under ambient conditions. Different from all previous studies involving poly(vinylpyrrolidine), the use of CTAC at a sufficiently high concentration plays an essential role in carving away Ag atoms from the side faces through galvanic replacement. Concurrent co-deposition of Au and Ag atoms via chemical reduction at orthogonal sites on the surface of Ag nanocubes leads to the generation of Ag@Au–Ag concave nanocrystals with well-defined and controllable structures. Specifically, in the presence of CTAC-derived Cl– ions, the titrated HAuCl4 is maintained in the AuCl4– species, enabling its galvanic replacement with the Ag atoms located on the side faces of nanocubes. The released Ag+ ions can be retained in the soluble form of AgCl2– by complexing with the Cl– ions. Both the AuCl4– and AgCl2– in the solution are then reduced by ascorbate monoanion, a product of the neutralization reaction between H2Asc and NaOH, to Au and Ag atoms for their preferential co-deposition onto the edges and corners of the Ag nanocubes. Compared with Ag nanocubes, the Ag@Au–Ag concave nanocrystals exhibit much stronger SERS activity at an excitation of 785 nm, making it feasible to monitor the Au-catalyzed reduction of 4-nitrothiophenol by NaBH4 in situ. When the Ag cores are removed, the concave nanocrystals evolve into Au–Ag nanoframes with controllable ridge thicknesses.