Integrating molecular design and crystal engineering approaches in non-humidified intermediate-temperature proton conductors based on a Dawson-type polyoxometalate and poly(ethylene glycol) derivatives

Abstract

Anionic metal−oxygen clusters known as polyoxometalates (POMs) have been widely researched as components of proton conductors. While proton conduction under non-humidified intermediate-temperature (100−250 °C) conditions is advantageous from the viewpoint...

Controlled Assembly of a Dawson-like Antimoniotungstate-Supported Trefoil-type Trimer with Good Proton Conductivity Performance

“…For example, the following four cases of novel organic–inorganic hybrids, formulated as (H 2 bpe) 3.5 H 2 [SbW 18 O 60 ]·5H 2 O, {Ni(phen) 3 } 3 [SbW 18 O 60 ](H 3 O) 3 ·7H 2 O, [Cu I (phen)(H 2 O) 3 ]{[Cu II 2 (phen) 2 (H 2 O) 2 ] 2 [SbW 18 O 60 ]}·2H 2 O, and [Cu 2 Cl(H 2 O) 3 (phen) 2 ] 2 [H 3 SbW 18 O 60 ]·7H 2 O (phen = 1,10-phenanthroline), all were successfully established by the assembly between an inorganic Dawson-like [SbW 18 O 60 ] 9– polyanion and an organic ligand. − These new Dawson-like compounds not only greatly enrich the library of the Dawson structures but also provide more optional building blocks for further embellishing structures. In addition, in recent years, the development process of proton conductivity materials has drawn great attention owing to their wide application in fuel cells and other electrochemical devices. , As a class of significant materials with great prospect, POMs exhibit great advantages in the proton conduction because of the delocalization of small negative surface charges with low Madelung site potential and oxygen-rich surface. − As one of the typical types in the POM field, the Dawson-type POMs become one of multitudinous candidates owing to their relatively large cluster size and anisotropic shape and also are considered as ideal receptors for forming hydrogen bonding networks with water molecules, which endows the Dawson-type compounds with good proton conductivity property. , However, there are few reports about the application of Dawson-type POMs in proton conduction.…”

Precise modification of poly(aryl ether ketone sulfone) proton exchange membranes with positively charged bismuth oxide clusters for high proton conduction performance

“…29 In order to solve the solubility problem of POMs in water, electrostatic interactions or acid-base pair needs to be introduced to the host-guest hybrid system preventing leaching of the POMs. 30,31 In 2018, Yoo's group introduced phosphotungstic acid into sulfonated fluorinated block copolymer using facile solution casting approach and the proton conductivity of SFBC-50/PWA-30 can reach 105.22 mS⋅cm −1 at 90 ) is an excellent filler candidate not only because of its own good proton conductivity, but also for the high positive charge on the surface of H 6 Bi 12 O 16 clusters, which can form electrostatic interaction with sulfonate in the main chain. This precise molecular-level hybridization will be conducive to good microphase separation of PEMs, improving the proton conductivity of hybrid membranes.…”

Syntheses, Polymorphic Transformations, and Functions of Ionic Crystals Based on Mononuclear Bismuth(III) Complexes and Polyoxometalates

“…As summarized in Figure 1, polymorphs could be readily obtained by controlling the crystallization conditions. Since POM-based compounds are known to show efficient proton conduction, [31][32][33][34][35][36] proton conductivities of the ionic crystals were estimated by alternating current (AC) impedance measurements as a method for sample characterization and exploring functionality. As expected, the compounds with higher porosity, terminal amines (i. e., DMF), or coordination water exhibited high proton conductivity.…”