Stability of complex molybdenum(III) ions in molten alkali metal chlorides

Камалов, Р. В.; Volkovich, Vladimir A.; Polovov, Ilya B.; Vasin, B. D.

doi:10.1134/s0036029512020097

Cited by 7 publications

(12 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Earlier reports suggest that Pb-based hybrid layered perovskite iodides − and bromides , show slight band gap increase with increasing spacer length. We also note that the d–d transitions can be seen at 1.91, 2.31, and 2.90 eV in 4 , in agreement with previous work on K 3 MoCl 6 . We did not observe any photoluminescent behavior.…”

mentioning

confidence: 99%

Hybrid Layered Double Perovskite Halides of Transition Metals

Vishnoi

Zuo

et al. 2022

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Hybrid layered double perovskite (HLDP) halides comprise hexa-coordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with Pb II (such as Sb III and Bi III ). Here, we report eight HLDP halides from the A2M I M III X8 family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA) or 1,3propanediammonium (1,3-PDA); M I = Cu or Ag; M III = Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 eV to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)2Ag I Ru III Cl8 and (PPDA)2Ag I Mo III Cl8 show no obvious evidence of a magnetic ordering transition. While the t2g 3 Mo III compound displays Curie-Weiss behavior for a spin-only d 3 ion, the t2g 5 Ru III compound displays marked deviations from the Kotani theory. ASSOCIATED CONTENT Supporting InformationSynthesis and characterization, scXRD refinement details, key bond lengths and bond angles, hydrogen bond interactions, power x-ray diffraction patterns, x-ray photoelectron spectra (XPS), scanning electron microscope (SEM) images, additional single-crystal x-ray structures, octahedral tilting Accession CodesCCDC (2122532 -2122540) contain the supplement crystallographic data for this paper which can be obtained free of charge via www.ccdc.cam.ac.uk

show abstract

mentioning

confidence: 99%

Hybrid Layered Double Perovskite Halides of Transition Metals

Vishnoi

Zuo

et al. 2022

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…Upon changing the melt composition from LiCl to CsCl the value of δ at 1123 K decreases by 13.2 kJ/mol. Previously we found that at 1023 K this decrease was 11.3 kJ/mol (18). Generally contribution of δ into enthalpy of formation of the complex ion, including MoCl 6 3-increases with decreasing mean cationic radius of the solvent melt indicating decreasing stability of the transition metal complex ion due to increasing polarizing effect of the outer sphere cations.…”

Section: Resultsmentioning

confidence: 96%

“…Spectroscopic parameters calculated from electronic absorption spectra of the melts prepared by K 3 MoCl 6 dissolution agree with those obtained previously for the melts prepared by anodic dissolution of molybdenum metal (18). Formal standard electrode potentials of molybdenum were measured in all individual alkali chlorides and some their mixtures between 633-1173 K. As expected E* Mo/Mo(III) increases with decreasing radius of alkali cation although the whole body data taken from the literature and obtained in the present study shows much scatter.…”

Section: Discussionmentioning

confidence: 96%

See 1 more Smart Citation

Electrochemical Properties of Molybdenum in Alkali Chloride Melts

et al. 2014

View full text Add to dashboard Cite

Behavior of molybdenum was studied in individual fused alkali chlorides and their mixtures employing electrochemical and spectroscopic techniques. Formal standard electrode potentials of molybdenum and thermodynamics of molybdenum chloride were obtained in molten LiCl, NaCl, KCl, RbCl, CsCl at 1123 K, NaCl-CsCl eutectic at 793-1023 K, NaCl-KCl equimolar mixture at 973-1123 K, LiCl-KCl-CsCl eutectic at 633-1173 K. Diffusion coefficients of molybdenum ions were determined in LiCl-KCl-CsCl eutectic melt. Electronic absorption spectra of Mo(III) ions were measured in individual salts and their mixtures and spectroscopic parameters of MoCl6 3- complex ions determined.

show abstract

“…The measurements were carried out at 1123 K. Mo(III) ions in chloride melts are sensitive to disproportionation with the formation of metallic molybdenum and volatile MoCl 5 [11]. The rate of this reaction increases in the melts when the cation radius decreases or the temperature increases, which makes it difficult to perform electrochemical measurements at high temperatures [11]. The addition of metallic Fig.…”

Section: Electrode Potentials Of Molybdenum In the Melts Based On Indmentioning

confidence: 99%

Electrochemical properties of molybdenum in individual molten alkali metal chlorides and their mixtures

et al. 2015

Self Cite

View full text Add to dashboard Cite

The behavior of molybdenum in chloride melts is studied, and the standard potentials of Mo are determined in the melts based on eutectic mixtures LiCl-KCl-CsCl (at 633-1173 K) and NaCl-CsCl (at 793-1023 K), an equimolar NaCl-KCl mixture at 973-1123 K, and individual LiCl, NaCl, KCl, RbCl, and CsCl at 1123 K. The change in the conventional standard Gibbs energy of molybdenum trichloride for mation in the NaCl-KCl, NaCl-CsCl, and LiCl-KCl-CsCl melts is calculated. The effect of the cation composition of the salt solvent on the conventional standard electrode potential of molybdenum in the chlo ride melts is considered. The diffusion coefficients of Mo(III) ions in the LiCl-KCl-CsCl melt are deter mined.

show abstract

Stability of complex molybdenum(III) ions in molten alkali metal chlorides

Cited by 7 publications

References 11 publications

Hybrid Layered Double Perovskite Halides of Transition Metals

Hybrid Layered Double Perovskite Halides of Transition Metals

Electrochemical Properties of Molybdenum in Alkali Chloride Melts

Electrochemical properties of molybdenum in individual molten alkali metal chlorides and their mixtures

Contact Info

Product

Resources

About