Influence of particle size on the phase behavior associated with the thermal spin transition of the Prussian blue analogue K0.4Co1.3[Fe(CN)6]·4.4H2O

Andrus, Matthew J.; Calm, Yitzi M.; Knowles, Elisabeth S.; Dumont, Matthieu; Abboud, Khalil A.; Meisel, Mark W.; Talham, Daniel R.

doi:10.1016/j.poly.2013.05.031

Cited by 9 publications

(14 citation statements)

References 18 publications

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“…26,28 Similar effects were observed when coupling the same materials in core−shell particles. 24,25,27,29 The concept has been extended to heterostructures with other magnetic components and with other light-switchable components, 30 including Hofmann-like spin crossover networks. 31 It was postulated that the light-induced magnetism changes are magnetomechanical in origin.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Our groups recently reported a new mechanism for changing magnetism with light based on mesoscale coordination polymer heterostructures that couple a magnetic component with a light-switchable component. − For example, a thin film of the CTIST material Rb 0.7 Co 4.0 [Fe(CN) 6 ] 3.0 · n H 2 O (CoFe-PBA) sandwiched between two layers of the ferromagnetic Rb 0.8 Ni 4.0 [Cr(CN) 6 ] 2.9 · n H 2 O (NiCr-PBA) enables light-induced changes in the magnetization of NiCr-PBA, which is not light-switchable on its own. , Similar effects were observed when coupling the same materials in core–shell particles. ,,, The concept has been extended to heterostructures with other magnetic components and with other light-switchable components, including Hofmann-like spin crossover networks …”

Section: Introductionmentioning

confidence: 99%

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Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, Rb_aCo_b[Fe(CN)₆]_c·mH₂O@K_jNi_k[Cr(CN)₆]_l·nH₂O

et al. 2016

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A series of photomagnetic coordination polymer core–shell heterostructures, based on the light-switchable Prussian blue analogue Rb a Co b [Fe(CN)6] c ·mH2O (RbCoFe-PBA) as the core and the ferromagnetic K j Ni k [Cr(CN)6] l ·nH2O (KNiCr-PBA) as the shell, was studied using powder X-ray diffraction, down to 100 K, and magnetometry, down to 2 K, to investigate the influence of the shell thickness on light-induced magnetization changes and gain insight into the mechanism. The core material is known to undergo a charge-transfer-induced spin transition (CTIST), and synchrotron powder diffraction was used to monitor structural changes in both the core and the shell associated with the thermally and optically induced CTIST of the core. Significant lattice contraction in the RbCoFe-PBA core upon cooling through the high-spin to the low-spin state transition near ∼260 K induces strain on the KNiCr-PBA shells. This lattice strain in the shell can be relieved either by thermal cycling back to high temperature or by using light to access the metastable high-spin state of the core at low temperature. The different extents of strain in the KNiCr-PBA shell are reflected in low-temperature, low-field magnetization versus temperature data in the light and dark states. A broader magnetic transition at T c ≈ 70 K in the dark state relative to the light state reflects the greater dispersion of nearest-neighbor contacts and exchange energies induced by the structural distortions of the strained state. Analyses for different shell thicknesses, coupled with high-field magnetization data, support a mechanism whereby the light-induced magnetization changes in the KNiCr-PBA shell are due to realignment of the local magnetic anisotropy as a result of the structural changes in the shell associated with the optical CTIST of the core. Through magnetization and structural analyses, the depth to which the properties of the shell are influenced by the core–shell architecture was estimated to be between 40 and 50 nm.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, Rb_aCo_b[Fe(CN)₆]_c·mH₂O@K_jNi_k[Cr(CN)₆]_l·nH₂O

et al. 2016

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“…Relative to the bulk properties, changes in magnetic response, rates of linkage isomerism, oxidation states and counter ion content have previously been observed for particles in the 30 nm size regime and smaller. [39][40][41] These changes have been attributed to the many more degrees of freedom available to coordination polymer networks to reduce surface energies, including stabilizing different oxidation states and changing metal ion coordination environments. A signicant peak at 2102 cm À1 in the infrared spectrum associated with the cyanide stretch of Fe 2+ -CN-Ni 2+ pairs in the NiFe-PBA becomes more prominent with decreasing particle size (Fig.…”

Section: Discussionmentioning

confidence: 99%

Li-ion and Na-ion insertion into size-controlled nickel hexacyanoferrate nanoparticles

Asakura

Okubo

et al. 2014

RSC Adv.

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The influence of particle size on the electrochemical properties of guest-ion storage materials has attracted much attention because of the extensive need for long cycle-life, high energy density, and high power batteries. The present work describes a systematic study of the effect of particle size on the guest-ion storage capabilities of a cyanide-bridged coordination polymer. A series of nickel hexacyanoferrate particles ranging from approximately 40 to 400 nm were synthesized by a co-precipitation method and were used as the cathode material for both Li-ion and Na-ion insertion/extraction experiments using organic electrolyte. A large polarization was observed for the largest particles during Li-ion cycling, indicating a heterogeneous ion concentration within the lattice. As a consequence, the available capacity of Li-ion intercalation at high rates is significantly improved by reducing the particle size. On the other hand, Na-ion intercalation shows excellent rate capability regardless of the particle size.Scheme 1 Schematic depiction of alkali ion insertion mechanism in the cubic Prussian blue analogue structure. The cyanometallate vacancies and coordinated and zeolitic water molecules are omitted for clarity.

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“…Spin-transition materials are known to be sensitive to particle size − and interface quality, − variables that can be well controlled using the PBA platform. PBAs are coordination polymers that form extended networks of metal ions bridged by cyanide ligands, and core@shell heterostructures of PBAs can routinely be synthesized with polydispersities of 5–6% without the use of surfactants, which might compromise the heterostructure interface. ,− Charge-stabilized colloidal suspensions of PBA particles allow for the controlled addition of a shell, composed of another structurally similar but chemically different PBA, with epitaxy determined by the lattice mismatch between the core and shell . In this study, Rb x Co[Fe(CN) 6 ] y · n H 2 O (RbCoFe-PBA) is used as the spin-transition-active core, capable of undergoing a charge-transfer induced spin transition (CTIST) in response to light, temperature, or pressure changes.…”

Section: Introductionmentioning

confidence: 98%

Crafting Spin-State Switchable Strain Profiles within Rb_xCo[Fe(CN)₆]_y@K_jNi[Cr(CN)₆]_k Heterostructures

et al. 2020

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Spin-transition heterostructures have shown promise for inducing large switchable stresses at the nanoscale with a volumetric work density similar to piezoelectrics, but before practical applications are feasible, how heterostructure interfaces and geometry influence the transmission of stress and, in return, how they affect the spin-transition actuator itself, must be better understood. Here, four series of cubic spin-transition Prussian blue analogue (PBA) core–shell heterostructures were developed in order to probe the scaling behavior of the strain induced in the shell by the spin transition of the core. Cubic Rb x Co[Fe(CN)6] y·nH2O (RbCoFe-PBA) particles ranging 100–600 nm were used to prepare separate series of Rb x Co[Fe(CN)6] y ·nH2O@KjNi[Cr(CN)6] k ·mH2O (RbCoFe@KNiCr-PBA) core–shell particles with magnetic KNiCr-PBA shells ranging from 15 to 130 nm. A model fit to the strain-modified magnetization extracts the “strained volume” of the shell, and the results are compared with structural changes observed with powder X-ray diffraction. A linear relationship is found between the strained volume of the shell and the volume of the core for thicker shells, where the magnetic KNiCr-PBA shell is influenced to depths greater than 100 nm in response to the spin transition of the RbCoFe-PBA core. For thin shells, the relationship is more complicated, as the volume change in the actuating core and the strain it induces in the shell become interdependent and a function of shell thickness.

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Influence of particle size on the phase behavior associated with the thermal spin transition of the Prussian blue analogue K0.4Co1.3[Fe(CN)6]·4.4H2O

Cited by 9 publications

References 18 publications

Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, Rb_aCo_b[Fe(CN)₆]_c·mH₂O@K_jNi_k[Cr(CN)₆]_l·nH₂O

Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, Rb_aCo_b[Fe(CN)₆]_c·mH₂O@K_jNi_k[Cr(CN)₆]_l·nH₂O

Li-ion and Na-ion insertion into size-controlled nickel hexacyanoferrate nanoparticles

Crafting Spin-State Switchable Strain Profiles within Rb_xCo[Fe(CN)₆]_y@K_jNi[Cr(CN)₆]_k Heterostructures

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Influence of particle size on the phase behavior associated with the thermal spin transition of the Prussian blue analogue K0.4Co1.3[Fe(CN)6]·4.4H2O

Cited by 9 publications

References 18 publications

Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, RbaCob[Fe(CN)6]c·mH2O@KjNik[Cr(CN)6]l·nH2O

Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, RbaCob[Fe(CN)6]c·mH2O@KjNik[Cr(CN)6]l·nH2O

Li-ion and Na-ion insertion into size-controlled nickel hexacyanoferrate nanoparticles

Crafting Spin-State Switchable Strain Profiles within RbxCo[Fe(CN)6]y@KjNi[Cr(CN)6]k Heterostructures

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Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, Rb_aCo_b[Fe(CN)₆]_c·mH₂O@K_jNi_k[Cr(CN)₆]_l·nH₂O

Evidence for Interface-Induced Strain and Its Influence on Photomagnetism in Prussian Blue Analogue Core–Shell Heterostructures, Rb_aCo_b[Fe(CN)₆]_c·mH₂O@K_jNi_k[Cr(CN)₆]_l·nH₂O

Crafting Spin-State Switchable Strain Profiles within Rb_xCo[Fe(CN)₆]_y@K_jNi[Cr(CN)₆]_k Heterostructures