Nanofluidic membranes (NFMs) are gaining prominence as alternative ion-exchange membranes, because of their distinct selectivity mechanism, which does not rely on functional groups on a polymeric backbone but rather on charged nanopores that allow straight ion-conductive pathways for efficient ion transport. We measured the conductivity of commercial anodized aluminum oxide membranes with different pore sizes under different current densities and electrolyte concentrations. We also simulated a nanopore channel with charged walls between two electrolyte reservoirs. Our findings indicate that electrolyte concentration is the main parameter that determines NFM conductivity, with a linear dependence at least up to 1 M. Our study shows that the optimal pore length is between 0.5 and 5 μm considering the trade-off between selectivity and conductance. On the other hand, the conductance is not sensitive to the pore diameter. Conical nanopores are a way to increase conductance, but according to our results, this increase comes at the expense of selectivity. Our findings suggest that NFMs can outperform polymeric ion-exchange membranes in certain electrochemical applications, such as reverse electrodialysis, but not in applications that use low electrolyte concentrations on both sides of the membrane.

Electrochemical CO2 reduction offers a promising method of converting renewable electrical energy into valuable hydrocarbon compounds vital to hard-to-abate sectors. Significant progress has been made on the lab scale, but scale-up demonstrations remain limited. Because of the low energy efficiency of CO2 reduction, we suspect that significant thermal gradients may develop in industrially relevant dimensions. We describe here a model prediction for non-isothermal behavior beyond the typical 1D models to illustrate the severity of heating at larger scales. We develop a 2D model for two membrane electrode assembly (MEA) CO2 electrolyzers; a liquid anolyte fed MEA (exchange MEA) and a fully gas fed configuration (full MEA). Our results indicate that full MEA configurations exhibit very poor electrochemical performance at moderately larger scales due to non-isothermal effects. Heating results in severe membrane dehydration, which induces large Ohmic losses in the membrane, resulting in a sharp decline in the current density along the flow direction. In contrast, the anolyte employed in the exchange MEA configuration is effective in preventing large thermal gradients. Membrane dehydration is not a problem for the exchange MEA configuration, leading to a nearly constant current density over the entire length of the modeled domain, and indicating that exchange MEA configurations are well suited for scale-up. Our results additionally indicate that a balance between faster kinetics, higher ionic conductivity, smaller pH gradients and lower CO2 solubility causes an optimum operating temperature between 60 and 70 °C.