Speaker
Description
We present a theoretical formulation for studying the pH-dependent interfacial coverage of semiconductor-water interfaces through ab initio electronic-structure calculations, molecular dynamics simulations, and the thermodynamic integration method. The proposed method is applied to study the BiVO4(010)-water interface and yields a pH at the point of zero charge in excellent agreement with the experimental characterization. Furthermore, from the calculated pKa values of the individual adsorption sites, we construct an ab initio concentration diagram of all the adsorbed species at the interface as a function of the pH of the aqueous solution. The achieved results are used in conjunction with the band alignment at the BiVO4(010)-water interface, in order to study the pH-dependent catalytic reaction pathway for water splitting.
