Dual-Role of Polyelectrolyte-Tethered Benzimidazolium Cation in Promoting CO2 /Pure Water Co-Electrolysis to Ethylene.

Electrochemical CO2 reduction reaction (CO2 RR), as a promising route to realize negative carbon emissions, is known to be strongly affected by electrolyte cations (i.e., cation effect). In contrast to the widely-studied alkali cations in liquid electrolytes, the effect of organic cations grafted on alkaline polyelectrolytes (APE) remains unexplored, although APE has already become an essential component of CO2 electrolyzers. Herein, by studying the organic cation effect on CO2 RR, we find that benzimidazolium cation (Beim+ ) significantly outperforms other commonly-used nitrogenous cations (R4 N+ ) in promoting C2+ (mainly C2 H4 ) production over copper electrode. Cyclic voltammetry and in situ spectroscopy studies reveal that the Beim+ can synergistically boost the CO2 to *CO conversion and reduce the proton supply at the electrocatalytic interface, thus facilitating the *CO dimerization toward C2+ formation. By utilizing the homemade APE ionomer, we further realize efficient C2 H4 production at an industrial-scale current density of 331 mA cm-2 from CO2 /pure water co-electrolysis, thanks to the dual-role of Beim+ in synergistic catalysis and ionic conduction. This study provides a new avenue to boost CO2 RR through the structural design of polyelectrolytes.

Conductivity and Stability Properties of Anion Exchange Membranes: Cation Effect and Backbone Effect.

The rise of heterocycle cations, a new class of stable cations, has fueled faster growth of research interest in heterocycle cation-attached anion exchange membranes (AEMs). However, once cations are grafted onto backbones, the effect of backbones on properties of AEMs must also be taken into account. In order to comprehensively study the influence of cations effect and backbones effect on AEMs performance, a series of AEMs were prepared by grafting spacer cations, heterocycles cations, and aromatic cations onto brominated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) or poly(vinylbenzyl chloride) (PVB) backbones, respectively. Spacer cation [trimethylamine (TMA), N,N-dimethylethylamine (DMEA)]-attached AEMs showed general ion transportation and stability behaviors, but exhibited high cationic reaction efficiency. Heterocycle cation [1-methylpyrrolidine (MPY), 1-methylpiperidine (MPrD)]-attached AEMs showed excellent chemical stability, but their ion conduction properties were unimpressive. Aromatic cation [1-methylimidazole (MeIm), N,N-dimethylaniline (DMAni)]-attached AEMs exhibited superior ionic conductivity, while their poor cations stabilities hindered the application of the membranes. Besides, it was found that PVB-based AEMs had excellent backbone stability, but BPPO-based AEMs exhibited higher OH- conductivity and cation stability than those of the same cations grafted PVB-based AEMs due to their higher water uptake (WU). For example, the ionic conductivities (ICs) of BPPO-TMA and PVB-TMA at 80 °C were 53.1 and 38.3 mS cm-1 , and their WU was 152.3 and 95.1 %, respectively. After the stability test, the IC losses of BPPO-TMA and PVB-TMA were 21.4 and 32.2 %, respectively. The result demonstrated that the conductivity and stability properties of the AEMs could be enhanced by increasing the WU of the membranes. These findings allowed the matching of cations to the appropriate backbones and reasonable modification of the AEM structure. In addition, these results helped to fundamentally understand the influence of cation effect and backbone effect on AEM performance.