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Exploration of glassy state in Prussian blue analogues.

ABSTRACT: Prussian blue analogues (PBAs) are archetypes of microporous coordination polymers/metal-organic frameworks whose versatile composition allows for diverse functionalities. However, developments in PBAs have centred solely on their crystalline state, and the glassy state of PBAs has not been explored. Here we describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties. The preservation of short-range metal-ligand-metal connectivity is confirmed, enabling the framework-based functionality and semiconductivity in the glass. The transformation also generates unconventional CN^- vacancies, followed by the reduction of metal sites. This leads to significant porosity enhancement in recrystallised PBA, enabled by further accessibility of isolated micropores. Finally, mechanical stability under stress for successful vitrification is correlated to defect contents and interstitial water. Our results demonstrate how mechanochemistry provides opportunities to explore glassy states of molecular framework materials in which the stable liquid state is absent.

SUBMITTER: Ma N

PROVIDER: S-EPMC9276687 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Exploration of glassy state in Prussian blue analogues.

Ma Nattapol N Ohtani Ryo R Le Hung M HM Sørensen Søren S SS Ishikawa Ryuta R Kawata Satoshi S Bureekaew Sareeya S Kosasang Soracha S Kawazoe Yoshiyuki Y Ohara Koji K Smedskjaer Morten M MM Horike Satoshi S

Nature communications 20220712 1

Prussian blue analogues (PBAs) are archetypes of microporous coordination polymers/metal-organic frameworks whose versatile composition allows for diverse functionalities. However, developments in PBAs have centred solely on their crystalline state, and the glassy state of PBAs has not been explored. Here we describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties. The preservation of short-range metal-ligand-met ...[more]

PMID: 35821027

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Project description:The elucidation of the ideal coordination environment of a catalytic site has been at the heart of catalytic applications. Herein, we show that the water oxidation activities of catalytic cobalt sites in a Prussian blue (PB) structure could be tuned systematically by decorating its coordination sphere with a combination of cyanide and bidentate pyridyl groups.  K0.1[Co(bpy)]2.9[Fe(CN)6]2 ([Cobpy-Fe]), K0.2[Co(phen)]2.8[Fe(CN)6]2 ([Cophen-Fe]), {[Co(bpy)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 ([Cobpy2-Fe]), and {[Co(phen)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 Cl0.11 ([Cophen2-Fe]) were prepared by introducing bidentate pyridyl groups (phen: 1,10-phenanthroline, bpy: 2,2'-bipyridine) to the common synthetic protocol of Co-Fe Prussian blue analogues. Characterization studies indicate that [Cobpy2-Fe] and [Cophen2-Fe] adopt a pentanuclear molecular structure, while [Cobpy-Fe] and [Cophen-Fe] could be described as cyanide-based coordination polymers with lower-dimensionality and less crystalline nature compared to the regular Co-Fe Prussian blue analogue (PBA), K0.1Co2.9[Fe(CN)6]2 ([Co-Fe]). Photocatalytic studies reveal that the activities of [Cobpy-Fe] and [Cophen-Fe] are significantly enhanced compared to those of [Co-Fe], while molecular [Cobpy2-Fe] and [Cophen2-Fe] are inactive toward water oxidation. [Cobpy-Fe] and [Cophen-Fe] exhibit upper-bound turnover frequencies (TOFs) of 1.3 and 0.7 s-1, respectively, which are ∼50 times higher than that of [Co-Fe] (1.8 × 10-2 s-1). The complete inactivity of [Cobpy2-Fe] and [Cophen2-Fe] confirms the critical role of aqua coordination to the catalytic cobalt sites for oxygen evolution reaction (OER). Computational studies show that bidentate pyridyl groups enhance the susceptibility of the rate-determining Co(IV)-oxo species to the nucleophilic water attack during the critical O-O bond formation. This study opens a new route toward increasing the intrinsic water oxidation activity of the catalytic sites in PB coordination polymers.

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Exploration of glassy state in Prussian blue analogues.

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Exploration of glassy state in Prussian blue analogues.

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