The influence of edge sites on the development of surface charge on goethite nanoparticles: A molecular dynamics investigation

Large-scale molecular simulation of proton accumulations were carried out on (i) (110) and (021) slabs immersed in aqueous solution and (ii) a series of model goethite nanoparticles of dimension 2 to 8 nm with systematically varying acicularity and (110)/(021) surface areas. In the slab systems, the (021) surface exhibits 15% more proton charge per unit area than the (110) surface. In the particulate systems, the acicular particles having the highest (110)/(021) ratio accumulate the most charge, opposite to the trend expected from the slab simulations, indicating that, at length scales on the order of 10 nm, the slab results are not a good indicator of the overall charging behavior of the particles. The primary reason for the discrepancy between the particulate systems and slab systems is the preferential accumulation of protons at acute (110)-(110) intersections. Charge accumulates preferentially in this region because excess proton charge at an asperity is more effectively solvated than at a flat interface.