Considerable efforts have been devoted to developing oxygen evolution reaction (OER) catalysts based on transition metal oxides. Polyoxometalates (POMs) can be regarded as model compounds of transition metal oxides, and cobalt-containing POMs (Co-POMs) have received significant interest as candidates. Nanocomposites based on Co-POMs have been reported to show high OER activities due to synergistic effects among the components; however, the role of each component is unclear due to its complex structure. Herein, we utilize porous ionic crystals (PICs) based on Co-POMs, which enable a composition–structure–function relationship to be established to understand the origin of the synergistic catalysis. Specifically, a Keggin-type POM [α-CoW12O40]6– and a Cr complex [Cr3O­(OOCCH2CN)6(H2O)3]+ are implemented as PIC building blocks for the OER under nonbasic conditions. The potentially OER-active but highly soluble [α-CoW12O40]6– was successfully anchored in the crystalline PIC matrix via Coulomb interactions and hydrogen bonding induced by polar cyano groups of the Cr complex. The PIC exhibits efficient and sustained OER catalytic activity, while each building block is inactive. The Tafel slope of the linear sweep voltammetry curve and the relatively large kinetic isotope effect value suggest that elementary steps closely related to the OER rate involve single-electron and proton transfer reactions. Electrochemical and spectroscopic studies clearly show that the synergistic catalysis originates from the charge transfer from the Cr complex to [α-CoW12O40]6–; the increased electron density of [α-CoW12O40]6– may increase its basicity and accelerate proton abstraction as well as enhance electron transfer to stabilize the reaction intermediates adsorbed on [α-CoW12O40]6–.

We demonstrate a facile synthesis method of a porous ionic crystal (PIC) composed of the little-known δ-Keggin-type cationic polyoxoaluminum cluster ([δ-Al13O4(OH)24(H2O)12]7+, δ-Al13) with an oppositely-charged polyoxometalate, which enabled us to...

Polyoxometalates (POMs) are oxide cluster anions composed of high-valence early transition metals and widely used as catalysts. Yet base catalysis of POMs remains an ongoing challenge; group V (V, Nb,...

The catalytic activities are highly dependent on the components of meso-PICS.

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...