To compare the performance of carbonate-based electrolytes on various Ag facets, we considered K + based buffers on Ag(100), Ag(111), and Ag(110). Results are given for Ag(100) and Ag(110) up to the potential where convergence of the multiscale loop is possible. As shown in Figure (a), for a given starting ion concentration, in agreement with experimental evidence , we predict better performance for the (110) facet, where the reaction intermediates are relatively more stabilized (Figure ), followed by (100) and (111). From a transport perspective, the distinguishing factor among these crystalline planes is their potential of zero charge (PZC). In the gmPNP model, the PZC corresponds to the potential at which there is no surplus charge at the working electrode surface . Ag(110) has the lowest PZC (Table ), leading to reduced [K + ] OHP because of the reduced ∆ϕ OHP (see Figure ); the current densities are still high for Ag(110) due to the large stabilization of the adsorbates (Figure ). On the other hand, Ag(111) produces the strongest electric field gradient in the set due to the high PZC, thus favoring the cation accumulation and surface activation, but the atomic scale energetics are unfavorable properties . In this electrolyte, the water content is regulated by the membrane's properties and the water activity a H 2 O ̸ = 1. Therefore, we adapted the gmPNP model to account for both the reduced water content and the fixed background charge. The microenvironments formed by both the TMA + positive moiety and the inorganic cation K + present in the buffer solution were considered. We kept a 50 µm geometrical domain for the transport model for consistency, and we maintained a water coordination of 3 for TMA + in the DFT simulations, consistent with the inorganic cations. We assume the density of TMA + ions at the surface to be same as the bulk (surface coverage ≈ 1.6% -see the Supporting Information Section 1.1.5 for further details). We considered the parameter λ, defined as the number of H 2 O molecules per each positive moiety .