Anisotropic Evolution of Nanoclusters from Ag₄₀ to Ag₄₅: Halogen- and Defect-Induced Epitaxial Growth in Nanoclusters

Abstract

Halogens have widely served as handles for regulating the growth of nanoparticles and the control of their physicochemical properties. However, their regulatory mechanism is poorly understood. Nanoclusters are the early morphology of nanoparticles and play an important role in revealing the formation and growth of nanoparticles due to their precise structures. Here, we report that halogens induce the anisotropic growth of Ag 40 (C 6 H 5 COO) 13 (SR) 19 (CH 3 CN) (Ag 40 -II, where SR = 4-tert-butylbenzylmercaptan) into Ag 4 5 (C 6 H 5 COO) 1 3 (SR) 2 2 Cl 2 ( Ag 4 5 ), where Ag 4 0 -II is converted from Ag 40 (CH 3 COO) 10 (SR) 22 (Ag 40 -I). Experiments and theoretical simulations showed that halogen ions adsorb at both ends of the cluster, forming defect sites. The -SR-Ag-complexes fill the defects and complete the anisotropic transition from Ag 40 -II to Ag 45 . Circular dichroism spectra show that the chirality of Ag 45 decreases 15-fold compared with that of Ag 40 -II. This work provides important insights into the effects of halogens on the growth mechanism and property regulation for nanomaterials at the atomic level and the benefits of further applications of halogen-induced nanomaterials.

NHC-Stabilized Au10 Nanoclusters and Their Conversion to Au25 Nanoclusters

“…These results demonstrate the pivotal role not only of the outer sphere counterions but also of the ligated halide ligands in cluster conversion from Au 10 to Au 25 and the overall stability of the clusters. Our observations agree with the previous reports that halides can affect the growth and conversions of metal nanoclusters. − …”

“…Our observations agree with the previous reports that halides can affect the growth and conversions of metal nanoclusters. 37 − 39 …”

Ag–Ga Bimetallic Nanostructures Ultrasonically Prepared from Silver–Liquid Gallium Core–Shell Systems Engineered for Catalytic Applications

“…In many of the synthesis processes, for the development of 1D Ag nanoalloys, a range of Ag salts as precursors are employed that take advantage of the halogen ions and halide species which are known to assist in the anisotropic development by influencing the surface energies and kinetics at the metal–solvent interface. ,− The role of halides can be complex and synergistic, mediating the morphological development, by means such as by (1) modulating the redox potentials of the metal ions, (2) acting as facet-specific capping agents, and (3) controlling the extent of Ag underpotential deposition at the nanocrystal surface . Given that the control specimens synthesized from pure Ag powder did not produce any 1D nanostructures during the 30 min cycle (Supporting Information Figure S6), in order to provide further insights, the influence of halides was investigated through the comparison of a series of Ag–halides as precursors.…”

Homoleptic Alkynyl‐Protected Ag15 Nanocluster with Atomic Precision: Structural Analysis and Electrocatalytic Performance toward CO2 Reduction

“…Theb inding energy of Ag 3d 5/2 in sole Ag 15 is 367.8 eV (Figure S2 d), which is between the value of Ag foil (368.6 eV) [43] and Ag I (367.3 eV). [44,45] When adsorbed on XC-72, the Ag 3d 5/2 binding energy shows almost no change (367.9 eV) (Figure S2 d). After the catalytic reaction, the Ag 3d 5/2 binding energy shifts to 367.4 eV,close to the Ag 3d 5/2 in Ag 2 CO 3 (367.2 eV).…”