Recent progress in transition metal hexacyanometallates: From structure to properties and functionality

Ávila, Y.; Acevedo–Peña, Próspero; Reguera, L.; Reguera, E.

doi:10.1016/j.ccr.2021.214274

Cited by 42 publications

(42 citation statements)

References 448 publications

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“…Then, the redox potential of the PBAs is expected to shift toward more positive values. 16 Fe2p high-resolution spectra show the same tendency but with a smaller displacement in the binding energy value. However, the variation in the ratio of the Co: Zn affected the Fe 3+ /Fe 2+ ratio, reaching a maximum for the solid composed of equivalent molar quantities of Co 2+ and Zn 2+ .…”

Section: Morphological and Structural Characterizations Coznhcf Seriesmentioning

confidence: 70%

“…Then, this material can be easily dissolved in aqueous solutions at temperatures above room temperature by a Jahn Teller effect of Mn 3+, 12 considering A x MnHCF optimal as a template in the formation of hollow structures. Although incorporating Zn in CoHCF hollow structures has not been reported in the specialized literature, our primary motivation was driven by the fast kinetics promoted by Zn in PBAs 16,23 . The main steps for synthesizing the CoZnHCF hollow structures are schematized in Figure 1A.…”

Section: Resultsmentioning

confidence: 99%

“…Although incorporating Zn in CoHCF hollow structures has not been reported in the specialized literature, our primary motivation was driven by the fast kinetics promoted by Zn in PBAs. 16,23 The main steps for synthesizing the CoZnHCF hollow structures are schematized in Figure 1A. Once the cubes of MnHCF are formed, our series of materials are grown over their surface to adopt the cubic shape, creating a layer covering the material by co-precipitation in the same way the template material was synthesized.…”

Section: Morphological and Structural Characterizations Coznhcf Seriesmentioning

confidence: 99%

“…These materials contain vacancies in their structure and can store alkali cations or zeolitic water in the interconnected cavities system 14,15 . For example, the PBA resulting from divalent M 1 and trivalent M 2 will have up to 33% of vacancies of the hexacyanometallate groups due to the octahedral coordination 16 . Consequently, their potential, theoretical capacity, and large interconnected interstitial sites make these materials attractive for energy storage in large‐scale applications 17 .…”

Section: Introductionmentioning

confidence: 99%

“…This behavior is due to the high polarizing power of Zn 2+ ions that favors the charge subtraction from the iron through a pi-back donation in the Zn 2+ -N ≡ C-Fe 2+ chains. 16 ZnHCF is suitable for storing monovalent and divalent ions due to its unique porosity promoted by the tetrahedral coordination of Zn 2+ . Nevertheless, ZnHCF suffers from poor chemical stability in neutral electrolytes.…”

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confidence: 99%

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Mixed cobalt–zinc hexacyanoferrate hollow micro‐cubes for a high‐voltage hybrid supercapacitor

Villalva‐Mejorada

Acevedo–Peña

Leyva‐Porras

et al. 2022

Intl J of Energy Research

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Summary The behavior of Prussian Blue Analogs (PBAs) is determined by the external transition metal coordinated to the N‐end of the hexacyanoferrate block. Combining transition metal ions allows obtaining a material with improved performance for energy‐related applications. A mixed PBA was formed with cobalt hexacyanoferrate (CoHCF) and ZnHCF. The former has two redox processes and easy modulation of its morphology, while the latter exhibits fast kinetics during the charge transfer. The morphology of the solids was controlled by composition, shaping hollow structures at a high concentration of Co2+ in the PBA. Spectroscopic characterization displayed the change in the charge density at the N‐end of the cyanide bridges caused by the polarizing power of Zn2+. XRD showed the formation of more than one crystalline phase. The presence of Co2+ provided larger specific capacity and stability during cycling, while Zn2+ afforded a higher potential and improved rate capability to the solid. The material with the best electrochemical behavior was employed to assemble a hybrid supercapacitor, reaching specific energy of 30 Wh kg−1 at a power of 450 W kg−1 and 7 Wh kg−1 at 5.5 kW kg−1. Additionally, the device retained 85% of its initial capacitance after 5000 galvanostatic charge–discharge cycles.

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Section: Morphological and Structural Characterizations Coznhcf Seriesmentioning

confidence: 70%

Section: Resultsmentioning

confidence: 99%

Section: Morphological and Structural Characterizations Coznhcf Seriesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Mixed cobalt–zinc hexacyanoferrate hollow micro‐cubes for a high‐voltage hybrid supercapacitor

Villalva‐Mejorada

Acevedo–Peña

Leyva‐Porras

et al. 2022

Intl J of Energy Research

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Tunable Intervalence Charge Transfer in Ruthenium Prussian Blue Analog Enables Stable and Efficient Biocompatible Artificial Synapses

et al. 2022

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Emerging concepts for neuromorphic computing, bioelectronics, and brain‐computer interfacing inspire new research avenues aimed at understanding the relationship between oxidation state and conductivity in unexplored materials. This report expands the materials playground for neuromorphic devices to include a mixed valence inorganic 3D coordination framework, a ruthenium Prussian blue analog (RuPBA), for flexible and biocompatible artificial synapses that reversibly switch conductance by more than four orders of magnitude based on electrochemically tunable oxidation state. The electrochemically tunable degree of mixed valency and electronic coupling between N‐coordinated Ru sites controls the carrier concentration and mobility, as supported by density functional theory computations and application of electron transfer theory to in situ spectroscopy of intervalence charge transfer. Retention of programmed states is improved by nearly two orders of magnitude compared to extensively studied organic polymers, thus reducing the frequency, complexity, and energy costs associated with error correction schemes. This report demonstrates dopamine‐mediated plasticity of RuPBA synapses and biocompatibility of RuPBA with neuronal cells, evoking prospective application for brain‐computer interfacing.

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Atypical Metal‐Center Coordination in Two Cyanide‐Based Coordination Polymers

Vázquez,

Avila,

Mojica

et al. 2023

ChemistrySelect

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This contribution reports the crystal structure, solved and refined from single crystal XRD data, of two cyanide‐based coordination polymers, with K[Cu2(CN)3] ⋅ H2O (1) and [Cd(H2O)]2Cd(H2O)2[Cu(CN)3Cu(CN)2]2 ⋅ 8H2O (2) as formula units. These coordination polymers are characterized by metal‐metal bonds between copper atoms. In 1, the framework is formed by Cu−Cu(CN)3 pseudo tetrahedral blocks linked by planar Cu2(CN)3 units. In this material, a defined Cu−Cu bond was identified, which is congruent with the corresponding Raman spectrum. The K atom and water molecule occupy the framework cavities. In 2, the Cu−Cu bond is observed in Cu2(CN)6 blocks which remain linked to Cd(NC)2(H2O)4 and Cd(NC)4(H2O)2 units occupying their axial and equatorial coordination positions, respectively. The solid framework is completed by the −N=C−Cu−C=N− chains linked to Cd(NC)4(H2O)2 moieties. The crystal structure for 2 contains two different sites for the metal centers. The structural study was complemented by recording IR, Raman, and UV/Vis spectra. These two coordination polymers behave as semiconductor materials with a band gap of 2.79 and 3.43 eV, respectively, as derived from the Tauc plot of the corresponding UV/Vis spectrum. Band structure calculations properly supported these values. 1 is a material of an indirect band gap, while 2 has a direct band gap.

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Recent progress in transition metal hexacyanometallates: From structure to properties and functionality

Cited by 42 publications

References 448 publications

Mixed cobalt–zinc hexacyanoferrate hollow micro‐cubes for a high‐voltage hybrid supercapacitor

Mixed cobalt–zinc hexacyanoferrate hollow micro‐cubes for a high‐voltage hybrid supercapacitor

Tunable Intervalence Charge Transfer in Ruthenium Prussian Blue Analog Enables Stable and Efficient Biocompatible Artificial Synapses

Atypical Metal‐Center Coordination in Two Cyanide‐Based Coordination Polymers

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