This work demonstrated a robust, scalable cell architecture for electroreduction of CO2 (CO2R). An up to 90% faradaic efficiency for the conversion of CO2R to formate at 500 mA/cm2 was realized at a 25 cm2 gas diffusion electrode (GDE) with a carbon-supported SnO2 electrocatalyst. A 1.27 mm thick catholyte was used between the bipolar membrane and cathode GDE, which could be further reduced to tens of micrometers upon refinement. The deconvolution of the potential drop from each individual component/process guides the pathways to higher energy efficiencies of CO2R at this platform. Significant changes in the agglomerate size and aspect ratio on the electrode before and after an 11 h test were revealed by nano-CT, suggesting reduced CO2 accessibility from electrode degradation. The versatility of this CO2R testing platform enables the ability to assess materials, components, and interactions at scales more in line with future devices.

The acids and bases used for ion exchange regeneration contribute significantly to the increasing salinity of potable water supplies. This research investigated the use of bipolar membrane electrodialysis (BMED) for producing acids and bases from dilute salt solutions that are produced during reverse osmosis or evaporative cooling. Using single pass BMED, acids and bases were produced with concentrations equal to ∼75% of the feed salt concentration with current utilizations >75%. Current utilization increased with increasing feed salt concentrations due to decreased leakage current through the monopolar membranes. The maximum current density at which the BMED stack could be operated depended on the feed salt concentration and the flow velocity and was limited by water dissociation at the interface between the diluate solutions and the monopolar membranes. The stack resistance was dominated by the bipolar membranes, even for the most dilute feed solutions. The energy required per mole of acid or base produced increased linearly with increasing current density. The energy costs for producing acids and bases were significantly less than costs for purchasing bulk HCl and NaOH, and the process is scalable to large systems.

Bipolar membranes (BPMs) have proven useful in numerous electrochemical energy conversion and storage applications, including fuel cells and electrolyzers. However, water dissociation in bipolar membrane electrolysis cells (BPMECs) is a complicated phenomenon that occurs via several different pathways. In this work, we develop a model based on the Poisson-Nernst-Planck system that includes a multistep water-dissociation mechanism to observe the fundamental processes that contribute to BPMEC performance. The model, which is validated to in-house experimental data, demonstrates that the junction potential is the most significant contributor to the total electrolysis voltage. We investigated the effects of water-dissociation catalysts and found that the optimal catalyst pK a depends on how the catalyst is integrated into the BPM (although values near 7 are typically best, in accordance with conventional wisdom). We also simulated the water content across the BPM and found that dry-out is not a significant issue when the membrane is in contact with liquid water on both sides. The species conservation approach taken here leads to a physical understanding of the system without using any fitting parameters.

This research investigated the use of an electrochemical system for regenerating ion-exchange media and for promoting the crystallization of hardness minerals in a fluidized bed crystallization reactor (FBCR). The closed-loop process eliminates the creation of waste brine solutions that are normally produced when regenerating ion-exchange media. A bipolar membrane electrodialysis stack was used to generate acids and bases from 100 mM salt solutions. The acid was used to regenerate weak acid cation (WAC) ion-exchange media used for water softening. The base solutions were used to absorb CO2 gas and to provide a source of alkalinity for removing noncarbonate hardness by WAC media operated in H(+) form. The base solutions were also used to promote the crystallization of CaCO3 and Mg(OH)2 in a FBCR. The overall process removes hardness ions from the water being softened and replaces them with H(+) ions, slightly decreasing the pH value of the softened water. The current utilization efficiency for acid and base production was ∼75% over the operational range of interest, and the energy costs for producing acids and bases were an order of magnitude lower than the costs for purchasing acid and base in bulk quantities. Ion balances indicate that the closed-loop system will accumulate SO4(2-), Cl(-), and alkali metal ions. Acid and base balances indicate that for a typical water, small amounts of base will be accumulated.