High Proton‐Conductivity in Covalently Linked Polyoxometalate‐Organoboronic Acid‐Polymers

Abstract

The controlled bottom-up design of polymers with metal oxide backbones is a grand challenge in materials design, as it could give unique control over the resulting chemical properties. Herein, we report a 1D-organo-functionalized polyoxometalate polymer featuring a purely inorganic backbone. The polymer is self-assembled from two types of monomers, inorganic Wells-Dawson-type polyoxometalates, and aromatic organo-boronates. Their covalent linkage results in 1D polymer strands, which combine an inorganic oxide backbone (based on BÀO and NbÀO linkages) with functional organic side-chains. The polymer shows high bulk proton conductivity of up to 1.59 10 À1 S cm À1 at 90 8C and 98 % relative humidity. This synthetic approach could lead to a new class of organic-inorganic polymers where function can be designed by controlled tuning of the monomer units.

Superprotonic conduction of intrinsically zwitterionic microporous polymers based on easy-to-make squaraine, croconaine and rhodizaine dyes

“…As a result, the greatest proton conductivity of 5.4 × 10 −1 S cm −1 for LiCl@PRH was obtained at 90 °C and 90% relative humidity. 51 In addition, the activation energy ( E a ) of the proton conduction in three POPs were estimated from Arrhenius plots to be 0.26–0.40 eV (Fig. S30c–S35c † ).…”

Highly Effective Proton-Conduction Matrix-Mixed Membrane Derived from an -SO3H Functionalized Polyamide

“…Great efforts have been dedicated to this mission, and numerous materials such as polyoxometalates [10,11], graphynes [12,13], recently developed porous materials [14][15][16][17], and so on have been constructed and studied thus far as proton-conductive electrolytes for application in PEM fuel cells. Among these functional materials, Nafion, a perfluorinated sulfonated polymer that shows an excellent proton conductivity and durability has gradually become a commercially accessible PEM electrolyte, although many issues in its fabrication and application still need to be overcome [18][19][20].…”

Facile construction of a highly proton-conductive matrix-mixed membrane based on a –SO3H functionalized polyamide

“…Diverse materials, which include polyoxometalates, 10,11 graphynes, 12,13 and even recently developed porous materials, 14–17 have been synthesized and investigated as proton-conductive electrolytes so far. Among these functional materials, a perfluorinated sulfonated polymeric electrolyte, i.e.…”