An organic proton cage that is ultra-resistant to hydroxide-promoted degradation.

Alkaline polymer membrane electrochemical energy conversion devices offer the prospect of using non-platinum group catalysts. However, their cationic functionalities are currently not sufficiently stable for vapor-phase applications, such as fuel cells. Herein, we report 1,6-diazabicyclo[4.4.4]tetradecan-1,6-ium (in-DBD), a cationic proton cage, that is orders of magnitude more resistant to hydroxide-promoted degradation than state-of-the-art organic cations under ultra-dry conditions and elevated temperature, and the first organic cation-hydroxide to persist at critically low hydration levels ( < 10% RH at 80 °C). This high stability against hydroxide-promoted degradation is due to the unique combination of endohedral protection and intra-bridgehead hydrogen bonding that prevents the removal of the inter-cavity proton and lowers the susceptibility to Hofmann elimination. We anticipate this discovery will facilitate a step-change in the advancement of materials and electrochemical devices utilizing anion-exchange membranes based on in-DBD that will enable stable operation under extreme alkaline conditions.

Effects of Iron Species on Low Temperature CO2 Electrolyzers.

Electrochemical energy conversion devices are considered key in reducing CO2 emissions and significant efforts are being applied to accelerate device development. Unlike other technologies, low temperature electrolyzers have the ability to directly convert CO2 into a range of value-added chemicals. To make them commercially viable, however, device efficiency and durability must be increased. Although their design is similar to more mature water electrolyzers and fuel cells, new cell concepts and components are needed. Due to the complexity of the system, singular component optimization is common. As a result, the component interplay is often overlooked. The influence of Fe-species clearly shows that the cell must be considered holistically during optimization, to avoid future issues due to component interference or cross-contamination. Fe-impurities are ubiquitous, and their influence on single components is well-researched. The activity of non-noble anodes has been increased through the deliberate addition of iron. At the same time, however, Fe-species accelerate cathode and membrane degradation. Here, we interpret literature on single components to gain an understanding of how Fe-species influence low temperature CO2 electrolyzers holistically. The role of Fe-species serves to highlight the need for considerations regarding component interplay in general.

Performance and Stability of Aemion and Aemion+ Membranes in Zero-Gap CO2 Electrolyzers with Mild Anolyte Solutions.

The dependence of performance and stability of a zero-gap CO2 electrolyzer on the properties of the anion exchange membrane (AEM) is examined. This work firstly assesses the influence of the anolyte when using an Aemion membrane and then shows that when using 10 mM KHCO3 , a CO2 electrolyzer using a next-generation Aemion+ membrane can achieve lower cell voltages and longer lifetimes due to increased water permeation. The impact of lower permselectivity of Aemion+ on water transport is also discussed. Using Aemion+, a cell voltage of 3.17 V at 200 mA cm-2 is achieved at room temperature, with a faradaic efficiency of >90 %. Stable CO2 electrolysis at 100 mA cm-2 is demonstrated for 100 h, but with reduced lifetime at 300 mA cm-2 . However, the lifetime of the cell at high current densities is shown to be increased by improving water transport characteristics of the AEM and reducing dimensional swelling, as well as by improving cathode design to reduce localized dehydration of the membrane.

Lectin and E. coli Binding to Carbohydrate-Functionalized Oligo(ethylene glycol)-Based Microgels: Effect of Elastic Modulus, Crosslinker and Carbohydrate Density.

The synthesis of carbohydrate-functionalized biocompatible poly(oligo(ethylene glycol) methacrylate microgels and the analysis of the specific binding to concanavalin A (ConA) and Escherichia coli (E. coli) is shown. By using different crosslinkers, the microgels' size, density and elastic modulus were varied. Given similar mannose (Man) functionalization degrees, the softer microgels show increased ConA uptake, possibly due to increased ConA diffusion in the less dense microgel network. Furthermore, although the microgels did not form clusters with E. coli in solution, surfaces coated with mannose-functionalized microgels are shown to bind the bacteria whereas galactose (Gal) and unfunctionalized microgels show no binding. While ConA binding depends on the overall microgels' density and Man functionalization degree, E. coli binding to microgels' surfaces appears to be largely unresponsive to changes of these parameters, indicating a rather promiscuous surface recognition and sufficiently strong anchoring to few surface-exposed Man units. Overall, these results indicate that carbohydrate-functionalized biocompatible oligo(ethylene glycol)-based microgels are able to immobilize carbohydrate binding pathogens specifically and that the binding of free lectins can be controlled by the network density.