Open Access

Qamar Abbas, Bernhard Gollas, Volker Presser

• The Faradaic processes related to electrochemical water reduction at the nanoporous carbon electrode under negative polarization are reduced when the concentration of aqueous sodium nitrate (NaNO3) is increased or the temperature is decreased. This effect enhances the relative contribution of ion electrosorption to the total charge storage process. Hydrogen chemisorption is reduced in aqueous 8.0 m NaNO3 due to the low degree of hydration of the Na+ cation; consequently, less free water is available for redox contributions, driving the system to exhibit electrical double-layer capacitive characteristics. Hydrogen adsorption/desorption is facilitated in 1.0 m NaNO3 due to the high molar ratio. The excess of water shifts the local pH in carbon nanopores to neutral values, giving rise to a high overpotential for dihydrogen evolution in the latter. The dilution effect on local pH shift in 1.0 m NaNO3 can be reduced by decreasing the temperature. A symmetric activated carbon cell assembled with 8.0 m NaNO3 exhibits a high capacitance and coulombic efficiency, a larger contribution of ion electrosorption to the overall charge storage process, and a stable capacitance performance at 1.6 V.