In Situ Liquid Cell TEM Studies on Etching and Growth Mechanisms of Gold Nanoparticles at a Solid–Liquid–Gas Interface

Etching and growth of gold nanoparticles at a solid–liquid–gas interface are investigated via in situ liquid cell transmission electron microscopy. For this purpose, the gold precursor tetrachloroauric acid is enclosed in the wells of a free‐standing, locally thinned silicon nitride film covered by few‐layer graphene. Etching of gold is attributed to hydroxide radicals generated by radiolysis and gaseous species which are located within a gas bubble. The etching mechanism comprises two distinct cases. In one case, the gas bubble is in direct contact with the gold particle, separated only by a thin liquid membrane. In the other case, the gold particle is thoroughly immersed in liquid in the vicinity of the particle. In the latter, etching molecules diffuse from the bubble through the liquid toward the surface of the nanoparticle and subsequently etch the gold platelet. During the particle etching process, concurrent nucleation and ripening of gold nanoparticles are observed. This growth is induced by local supersaturation of the solution with gold ions. Experimental results show that the growth process is limited by diffusion, even though the diffusivity of reactants is very low due to narrow‐channel effects compared against the diffusivity of solvated ions in bulk liquids. Etching of gold at a solid–liquid–gas interface is observed in situ by liquid cell transmission electron microscopy. A dedicated reaction mechanism involving the interaction between particle and nanobubble is proposed. The dissolution exponent is found to strongly increase with decreasing particle size. Subsequent growth of gold nanoparticles is observed and modeled. Monitoring their total volume suggests a remarkable similarity to the initially etched volume.