Single-Crystal Electrochemistry Uncovers the Role of Citrate in the Anisotropic Growth of Ag Nanostructures

Abstract

Shape-controlled synthesis of metal nanocrystals is usually achieved by the addition of capping agents and serves an important approach to endowing metal nanomaterials with desired properties.1 A widely accepted hypothesis in the role of capping agents is they suppress the atomic deposition on the facets they selectively adsorb to, which leads to anisotropic growth.2 However, the roles of capping agents are often qualitatively deduced from the shape of metal nanocrystals formed, making it difficult to rationally design a synthetic condition for a certain shape or aspect ratio. Single-crystal electrochemical measurements have been used to uncover the facet-selective roles of a wide range of capping agents, such as chloride in the synthesis of Cu nanowires, bromide in the synthesis of Au nanorods, and iodide in the synthesis of Cu microplates.3-6 However, the anisotropic growth revealed by the growth of these nanocrystals is 10 times higher than that predicted by the single-crystal electrochemical measurements, indicating planar defects, such as twin planes and stacking faults, can also cause anisotropic growth.To elucidate the effects surface capping and defects in the anisotropic growth of metal nanocrystals, the work presented here combines synthetic methods and electrochemical measurements to reveal the roles of citrate in the growth of seeds with different structures.7 The single-crystal Ag seeds (Figure 1A) grow into cuboctahedra in the absence of citrate (Figure 1B) and octahedra in the presence of citrate (Figure 1C), which closely matches the shape prediction from the electrochemical measurements. Linear sweep voltammetry (LSV) measurements under the synthetic conditions demonstrate the anisotropic growth with citrate is a result of citrate selectively suppressing the oxidation of a reducing agent, ascorbic acid, and citrate does not affect silver ion reduction. The Ag nanoplate seeds with planar defects (Figure 1D) undergo isotropic growth in the absence of citrate (Figure 1E), but exhibit 30~100 times more anisotropic growth in the presence of citrate than the single-crystal seeds and electrochemical prediction (Figure 1F). Further investigation suggests planar defects can catalyze silver atom deposition to the nanoplate side planes and citrate suppresses surface diffusion to the nanoplate basal planes.(1) Yang, T.-H.; Shi, Y.; Janssen, A.; Xia, Y., Surface Capping Agents and Their Roles in Shape-Controlled Synthesis of Colloidal Metal Nanocrystals. Angew. Chem., Int. Ed. 2020, 59, 15378-15401.(2) Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E., Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics? Angew. Chem., Int. Ed. 2009, 48, 60-103.(3) Kim, M. J.; Brown, M.; Wiley, B. J., Electrochemical investigations of metal nanostructure growth with single crystals. Nanoscale 2019, 11, 21709-21723.(4) Kim, M. J.; Alvarez, S.; Chen, Z.; Fichthorn, K. A.; Wiley, B. J., Single-Crystal Electrochemistry Reveals Why Metal Nanowires Grow. J. Am. Chem. Soc. 2018, 140, 14740-14746.(5) Brown, M.; Wiley, B. J., Bromide Causes Facet-Selective Atomic Addition in Gold Nanorod Syntheses. Chem. Mater. 2020, 32, 6410-6415.(6) Kim, M. J.; Cruz, M. A.; Chen, Z.; Xu, H.; Brown, M.; Fichthorn, K. A.; Wiley, B. J., Isotropic Iodide Adsorption Causes Anisotropic Growth of Copper Microplates. Chem. Mater. 2021, 33, 881-891.(7) Xu, H.; Wiley, B. J., The Roles of Citrate and Defects in the Anisotropic Growth of Ag Nanostructures. Chem. Mater. 2021, 33, 8301-8311. Figure 1