pH dependent reactivity of boehmite surfaces from first principles molecular dynamics

William Smith; Maxime Pouvreau; Kevin Rosso; Aurora E Clark

doi:10.1039/d2cp00534d

pH dependent reactivity of boehmite surfaces from first principles molecular dynamics

Phys Chem Chem Phys. 2022 Jun 15;24(23):14177-14186. doi: 10.1039/d2cp00534d.

Authors

William Smith¹, Maxime Pouvreau¹, Kevin Rosso², Aurora E Clark^{1

2

3}

Affiliations

¹ Department of Chemistry, Washington State University, Pullman, WA 99164, USA. william.t.smith@wsu.edu.
² Pacific Northwest National Laboratory, Richland, WA 99354, USA.
³ Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA 99164, USA.

PMID: 35583197
DOI: 10.1039/d2cp00534d

Abstract

pH dependent interfacial chemistry depends upon the distribution and respective pK_a values of different surface active sites. This is highly relevant to the chemistry of nanoparticle morphologies that expose faces with varying surface termination. Recent synthetic advances for nanoparticles of various minerals, including AlO(OH) (boehmite), present an excellent opportunity to compare and contrast predicted surface pK_a on low Miller index planes so as to reinterpret reported interfacial properties (i.e., point of zero charge - PZC) and reactivity. This work employs ab initio molecular dynamics and empirical models to predict site-specific pK_a values of accurate (benchmarked) surface models of boehmite. Using the different surface site populations, the PZC is determined and the influence this has upon reported interfacial chemistry is described.