Enhanced Hydrolysis of p‑Nitrophenyl Phosphate by Iron (Hydr)oxide Nanoparticles: Roles of Exposed Facets

Iron (hydr)­oxide nanoparticles are one of the most abundant classes of naturally occurring nanoparticles and are widely used engineered nanomaterials. In the environment these nanoparticles may significantly affect contaminant fate. Using two goethite materials with different contents of exposed {021} facet and two hematite materials with predominantly exposed {001} and {100} facets, respectively, we show that exposed facets, one of the most intrinsic properties of nanocrystals, significantly affect the efficiency of iron (hydr)­oxide nanoparticles in catalyzing acid-promoted hydrolysis of 4-nitrophenyl phosphate (pNPP, selected as a model organophosphorus pollutant). Attenuated total reflectance Fourier-transform infrared spectroscopy analysis and density functional theory calculations indicate that the pNPP hydrolysis reaction on the iron (hydr)­oxide surface involves the inner-sphere complexation between the phosphonate moiety of pNPP and the surface ferric iron (Fe­(III)), through ligand exchange with primarily the singly coordinated surface hydroxyl groups of iron (hydr)­oxides. Both the abundance and affinity of these adsorption sites are facet-dependent. Exposed facets also determine the reaction kinetics of surface-bound pNPP mainly by regulating the Lewis acidity of the surface Fe­(III) atoms. These findings underline the important roles of facets in determining the reactivity of naturally occurring metal-based nanoparticles toward environmental contaminants and may shed light on the development of nanomaterial-based remediation strategies.