Weakly Coordinating Organic Cations Are Intrinsically Capable of Supporting CO2 Reduction Catalysis.

The rates and selectivity of electrochemical CO2 reduction are known to be strongly influenced by the identity of alkali metal cations in the medium. However, experimentally, it remains unclear whether cation effects arise predominantly from coordinative stabilization of surface intermediates or from changes in the mean-field electrostatic environment at the interface. Herein, we show that Au- and Ag-catalyzed CO2 reduction can occur in the presence of weakly coordinating (poly)tetraalkylammonium cations. Through competition experiments in which the catalytic activity of Au was monitored as a function of the ratio of the organic to metal cation, we identify regimes in which the organic cation exclusively controls CO2 reduction selectivity and activity. We observe substantial CO production in this regime, suggesting that CO2 reduction catalysis can occur in the absence of Lewis acidic cations, and thus, coordinative interactions between the electrolyte cations and surface-bound intermediates are not required for CO2 activation. For both Au and Ag, we find that tetraalkylammonium cations support catalytic activity for CO2 reduction on par with alkali metal cations but with distinct cation activity trends between Au and Ag. These findings support a revision in electrolyte design rules to include water-soluble organic cation salts as potential supporting electrolytes for CO2 electrolysis.

Organic Non-Nucleophilic Electrolyte Resists Carbonation during Selective CO2 Electroreduction.

The spontaneous reaction of CO2 with water and hydroxide to form (bi)carbonates in alkaline aqueous electrolytes compromises the energy and carbon efficiency of CO2 electrolyzers. We hypothesized that electrolyte carbonation could be mitigated by operating the reaction in an aprotic solvent with low water content, while also employing an exogenous non-nucleophilic acid as the proton donor to prevent parasitic capture of CO2 by its conjugate base. However, it is unclear whether such an electrolyte design could simultaneously engender high CO2 reduction selectivity and low electrolyte carbonation. We herein report selective CO2 electroreduction with low carbonate formation on a polycrystalline Au catalyst using dimethyl sulfoxide as the solvent and acetic acid/acetate as the proton-donating medium. CO2 is reduced to CO with over 90% faradaic efficiency at potentials relative to the reversible hydrogen electrode that are comparable to those in neutral aqueous electrolytes. 1H and 13C NMR studies demonstrate that only millimolar concentrations of bicarbonates are reversibly formed, that the proton activity of the medium is largely unaffected by exposure to CO2, and that low carbonation is maintained upon addition of 1 M water. This work demonstrates that electrolyte carbonation can be attenuated and decoupled from efficient CO2 reduction in an aprotic solvent, offering new electrolyte design principles for low-temperature CO2 electroreduction systems.

Synthesis and Characterization of Shell-Cross-Linked Glycopolymer Bilayer Vesicles.

Vesicles composed of self-assembled lipids or amphiphilic polymers have significant potential in applications such as delivery of cargo for therapeutics. However, they are fragile under physiological conditions such as inside living cells or the bloodstream, in which a vast number of other molecules are present in high concentrations. This is because vesicles are in dynamic equilibrium between unimers and vesicles. Therefore, the development of more robust vesicles by covalent cross-linking of the shell was focused on. Cross-linked polymer vesicles were prepared by the self-assembly of maltopentaose-b-poly(propylene glycol) followed by the reaction between divinyl sulfone and the hydroxyl group in a maltopentaose unit. It was found that two equivalents of DVS to the polymer is an optimal condition for the cross-linking without changing in size. The bilayer structures were retained after the cross-linking reactions. Importantly, the cross-linked polymer vesicles retained their size and polydispersity even in 50:50 v/v methanol/water solution. This work highlights the potential of the divinyl sulfone shell cross-link as a promising tool for stabilization of glycopolymer vesicles.

Neutralization Short-Circuiting with Weak Electrolytes Erodes the Efficiency of Bipolar Membranes.

Bipolar membranes (BPMs) are critical components of a variety of electrochemical energy technologies. Many electrochemical applications require the use of buffers to maintain stable, nonextreme pH environments, yet the impact of buffers or weak acids/bases on the electrochemical behavior of BPMs remains poorly understood. Our data for a cell containing weak electrolytes is consistent with internal pH gradients within the anion exchange membrane (AEM) or cation exchange membrane (CEM) component of the BPM that form via ionic short-circuiting processes at open-circuit. Short-circuiting results from the coupling of co-ion crossover and parasitic neutralization and leads to buffering of the bipolar interface. This phenomenon, which we term neutralization short-circuiting, serves to erode BPM efficiency by attenuating the open-circuit membrane voltage and introducing parasitic reverse bias currents associated with weak acid/base dissociation at the interface. These findings establish a mechanistic basis for the operation of BPM cells in the presence of weak acid/base electrolytes.