Journal
INORGANIC CHEMISTRY
Volume 52, Issue 8, Pages 4494-4501Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic302764k
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Funding
- National Science Foundation (NSF) [DMR-1005581, DMR-1202033]
- National High Magnetic Field Laboratory (NHMFL) via NSF [DMR-1157490]
- State of Florida
- UF DSR Research Opportunity Fund
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [1005581, 1202033] Funding Source: National Science Foundation
- Grants-in-Aid for Scientific Research [24108736] Funding Source: KAKEN
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The controlled synthesis of monodisperse nano-particles of the cubic Prussian blue analogue iron(II) hexacyanochromate(III) is reported along with a kinetic study, using cyanide stretching frequencies, showing the variations of the activation energy (E-a) of the linkage isomerism as a function of the particle size. Highly reproducible, cubic-shaped iron(11) hexacyanochromate(110 nanocrystals, with sizes ranging from 2 to 50 nm, are synthesized using a microemulsion technique, whereas a bulk synthesis yields nonuniform less monodisperse particles with sizes greater than 100 nm. Monitoring the cyanide stretching frequency with FTIR spectroscopy shows that the rate of isomerization is faster for smaller particles. Moreover, a kinetic analysis at different temperatures (255 K <= T <= 321 K) gives insight into the evolution of E-a with the particle size. Finally, time-dependent powder X-ray diffraction and net magnetization confirm the FTIR observations. The data are interpreted within the concept of a simple two-component model with different activation energies for structures near the surface of the solid and within the bulk.
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