Solid-State Magnetic Switching Triggered by Proton-Coupled Electron-Transfer Assisted by Long-Distance Proton-Alkali Cation Transport

Abstract

Acidity of water molecules coordinated to Co ions in CoFe Prussian blue analogues (PBA) has been used to reversibly activate the Co(III)Fe(II) ↔ Co(II)Fe(III) electron transfer. The study of the structure and the electronic structure shows that the process implies an original PCET reaction between a solid-state porous coordination polymer and hydroxide ions in solution. The PCET reaction spreads throughout the solid network thanks to a long-range H(+) and Rb(+) transport within the pore channels of PBA taking advantage of the hydrogen-bonding network of zeolitic water molecules acting as proton wires.

Ordered colloidal clusters constructed by nanocrystals with valence for efficient CO 2 photoreduction

“…This result confirms that the molecular frameworks of PBAs could provide open channels for the migration of the CO 2 to access more Co sites within the materials (54) rather than just on the surface as those for the oxides (56). Besides, the active Co sites are usually coordinated by water ligands in PBAs and may facilitate a proton-coupled electron transfer process (13,64), which could accelerate the CO 2 -to-CO conversion kinetics (58). After the thermal annealing, the molecular frameworks within the PBAs would be destroyed completely, thus greatly reducing the amounts of the open active sites, which may be another reason for the relatively poor photoactivity of the oxides.…”

Hollow Structures Based on Prussian Blue and Its Analogs for Electrochemical Energy Storage and Conversion

“…[2][3][4][5][6][7][8][9] Motivated by the discovery of carbon nanotubes and fullerenes, scientists have devoted many efforts in exploiting nanomaterials with a hollow interior, for example hollow polyhedra and spheres, tubes, open cages, and frames, which has become an intriguing research topic over the past two decades. [44,45] As a result, PB and PBA materials find promising applications in catalysis, [46,47] photothermal therapy, [48] information storage, [37] sensor, [38] and energy storage and conversion. [17,[22][23][24][25][26][28][29][30][31][32] Nowadays, www.advmat.de www.advancedsciencenews.com structural traits and diverse chemical compositions, the electronic properties of the PB and PBA materials can be tailored by external stimulus, e.g., magnetic/electric field, [39,40] photoradiation, [41] temperature, [42] pressure, [43] and chemical modifications.…”

“…structural traits and diverse chemical compositions, the electronic properties of the PB and PBA materials can be tailored by external stimulus, e.g., magnetic/electric field, [39,40] photoradiation, [41] temperature, [42] pressure, [43] and chemical modifications. [44,45] As a result, PB and PBA materials find promising applications in catalysis, [46,47] photothermal therapy, [48] information storage, [37] sensor, [38] and energy storage and conversion. [49][50][51][52][53][54][55][56][57] For example, when applied in rechargeable batteries, the available channels and rigid structure of the open framework make PBA materials a kind of excellent cathode materials with fast charge transfer kinetics and long cycle life.…”

Magnetism and Photomagnetism of Prussian Blue Analogue Nanoparticles Embedded in Porous Metal Oxide Ordered Nanostructures

“…ing to the mechanism involved in the switching properties, which can be a spin state change of a metal ion, [15][16][17][18][19] a metalto-metal charge transfer [20][21][22][23][24][25] or a metal-to-ligand charge transfer. [26] Prussian blue analogues (PBAs) are also significant in this field, with the photomagnetic effect due to a metal-to-metal charge transfer having first been evidenced in a CoFe PBA.…”