Lawrence Berkeley National Laboratory

The function of nanoporous electrodes involves chemical reactions coupled to transport of reactants and products into and out of the solid matrix. To understand how this coupling can depend on electrode structure and chemistry, a general multiscale, molecular-level computational framework is introduced and applied to a model system containing a nanoporous photoanode, the dye-sensitized solar cell. The pore structure and electrolyte composition are systematically varied to probe this coupling, revealing that in most cases the photocurrent density depends on dye coverage within the anode matrix, the specific architecture of an individual pore, and electrolyte gradients in between the anode and cathode. The large electrolyte gradients that develop in the anode are not kinetically controlling. The computational framework demonstrated is general and can be applied to other electrochemical, photochemical, and thermally driven nanoporous systems to evaluate the fundamental characteristics of their function.