The capacity of current lithium/air cells is severely limited first and foremost by the electrochemical stability of the employed electrolyte and second by the occlusion of the pores of the active cathode surface due to non-uniform deposition of Li2O2 as the discharge product. Here we solve numerically a reaction-diffusion equation to determine the Li2O2 deposition profiles in a model porous cathode in the absence and presence of discrete catalytic sites, considering five commonly used electrolytes. We implement a greedy optimization algorithm to maximize the cathode capacity before pore clogging by optimal positioning of the discrete catalysts along the pore. The results indicate that, under the assumption of equal electrochemical stability, a maximal theoretical capacity is limited by the oxygen solubility and diffusivity in each electrolyte in the absence of catalysts and vary widely in the five cases considered. However, optimal catalyst distributions can effectively compensate for these differences, suggesting a rational way of designing cathode structures with high performances according to the required operation conditions. (C) 2015 The Electrochemical Society. All rights reserved.