Surface Site Density of Synthetic Goethites and Its Relationship to Atomic Surface Roughness and Crystal Size

• Published in: Langmuir Vol. 39; no. 1; pp. 556 - 562
• Main Authors: Livi, Kenneth J. T., Villalobos, Mario, Ramasse, Quentin, Brydson, Rik, Salazar-Rivera, Hugo Slavko
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10-01-2023
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/acs.langmuir.2c02818

The capacity for crystals to adsorb elements and molecules is a function of the structures of their crystal faces and the relative proportions of those faces. More importantly, this study shows that the surface structure of crystal faces is affected by their surface roughness and is the dominant factor controlling the absorption site density. In a continuation of the study of synthetic goethites with varying single crystal size distributions, two more synthetic goethites with intermediate sizes were analyzed by Brunauer–Emmett–Teller (BET) and atomic-resolution scanning transmission electron microscopy (STEM) to determine the effects of crystal size on their shape, atomic-scale surface roughness, and ultimately on their total surface site density. Results show that surface roughness scales directly with the size [or inversely with the specific surface area (SSA)] of synthetic goethites in the SSA range of 40–75 m2/g. This surface roughness, in turn, increases the total site density over ideal atomically smooth crystals. The total site density of synthetic goethite increases from a combination of decreasing crystal length/width ratio and increasing surface roughness.