Atomic-scale Mapping Unravel Anisotropic Dissolution Behaviors of Gibbsite Nanosheets

Abstract

This study examines the anisotropic dissolution of the basal plane gibbsite ({\gamma}-Al(OH)3) nanoplates in sodium hydroxide solution using in situ atomic force microscopy (AFM) and density functional theory (DFT) calculations. In the surface-reaction controlled regime, in situ AFM measurements reveal anisotropic dissolution of hillocks and etch pits on the gibbsite basal plane, with preferred dissolution directions alternating between layers. The mirror-symmetric pattern of dissolution preference between adjacent gibbsite aluminum hydroxide sheet, observed along the crystallographic a-c plane, results from the matching symmetry between the structures of the adjacent (001) and (002) crystal planes. Consequently, the overall dissolution rate of gibbsite nanoplates exhibits crystallographic a-c plane symmetry, as the rate of parallel steps is governed by the slower ones. DFT calculations suggest that the anisotropic dissolution is partially due to the orientation and strength of Al-OH-Al linkages pair within gibbsite surface structure. These findings offer a comprehensive understanding of anisotropic dissolution behavior of gibbsite and illuminate the mechanisms behind preferential dissolution.