Durable poly(binaphthyl-co-p-terphenyl piperidinium)-based anion exchange membranes with dual side chains

Building well-developed ion-conductive highways is highly desirable for anion exchange membranes(AEMs).Grafting side chain is a highly effective approach for constructing a well-defined phaseseparated morphological structure and forming unblocked ion pathways in AEMs for fast ion transport.Fluorination of side chains can further enhance phase separation due to the superhydrophobic nature of fluorine groups.However,their electronic effect on the alkaline stability of side chains and membranes is rarely reported.Here,fluorine-containing and fluorine-free side chains are introduced into the polyaromatic backbone in proper configuration to investigate the impact of the fluorine terminal group on the stability of the side chains and membrane properties.The poly(binaphthyl-co-p-terphenyl piperidinium)AEM(QBNp TP)has the highest molecular weight and most dimensional stability due to its favorable backbone arrangement among ortho-and meta-terphenyl based AEMs.Importantly,by introducing both a fluorinated piperidinium side chain and a hexane chain into the p-terphenyl-based backbone,the prepared AEM(QBNp TP-QFC)presents an enhanced conductivity(150.6 m S cm^(-1))and a constrained swelling at 80℃.The electronic effect of fluorinated side chains is contemplated by experiments and simulations.The results demonstrate that the presence of strong electro-withdrawing fluorine groups weakens the electronic cloud of adjacent C atoms,increasing OH^(-)attack on the C atom and improving the stability of piperidinium cations.Hence QBNp TP-QFC possesses a robust alkaline stability at 80℃(95.3%conductivity retention after testing in 2 M Na OH for 2160 h).An excellent peak power density of 1.44 W cm^(-2)and a remarkable durability at 80℃(4.5%voltage loss after 100 h)can be observed.

Copper and zinc isotope variations in ferromanganese crusts and their isotopic fractionation mechanism

Ferromanganese(Fe-Mn)crusts are potential archives of the Cu and Zn isotope compositions of seawater through time.In this study,the Cu and Zn isotopes of the top surface of 28 Fe-Mn crusts and 2 Fe-Mn nodules were analysed by MC-ICP-MS using combined sample-standard bracketing for mass bias correction.The Zn isotope compositions of the top surface of Fe-Mn crusts are in the range of 0.71‰to 1.08‰,with a mean δ^(66)Zn value of 0.94‰±0.21‰(2 SD,n=28).The δ^(65)Cu values of the top surface of Fe-Mn crusts range from 0.33‰to0.73‰,with a mean value of 0.58‰±0.20‰(2 SD,n=28).The Cu isotope compositions of Fe-Mn crusts are isotopically lighter than that of dissolved Cu in deep seawater(0.58‰vs.0.9‰).In contrast,the δ^(66)Zn values of Fe-Mn crusts appear to be isotopically heavy compared to deep seawater(0.94‰±0.21‰vs.0.51‰±0.14‰).The isotope fractionation between Fe-Mn crusts and seawater is attributed to equilibrium partitioning between the sorption to crusts and the organic-ligand-bound Cu and Zn in seawater.The Cu and Zn isotopes in the top surface of Fe-Mn crusts are not a direct reflection of the Cu and Zn isotopes,but a function of Cu and Zn isotopes in modern seawater.This study proposes that Fe-Mn crusts have the potential to be archives for paleoceanography through Cu and Zn isotope analysis.