The fascinating polyoxometalates

Lunk, Hans‐Joachim; Hartl, Hans

doi:10.1007/s40828-021-00145-y

Cited by 8 publications

(9 citation statements)

References 170 publications

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“…They consist of different metal-oxygen polyhedra MO x (mostly octahedra MO 6 ). [1][2][3][4][5][6][7] Formally, POMs are oxo complexes in which the oxo ligands coordinate the metals in a terminal M=O and bridging MÀ OÀ M bond motif. Normally, POMs are formed with group five and six metals such as tungsten W, molybdenum Mo, vanadium V, niobium Nb, and tantalum Ta in their highest oxidation states.…”

Section: Introductionmentioning

confidence: 99%

“…In recent decades, polyoxometalates (POMs), also called iso‐ or heteropolyanions, have emerged as a fascinating class of molecular metal oxides, that have attracted considerable attention in catalysis due to their remarkable structural diversity and high ability to drive various chemical reactions. They consist of different metal‐oxygen polyhedra MO x (mostly octahedra MO 6 ) [1–7] . Formally, POMs are oxo complexes in which the oxo ligands coordinate the metals in a terminal M=O and bridging M−O−M bond motif.…”

Section: Introductionmentioning

confidence: 99%

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Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Mürtz,

Raabe,

Poller

et al. 2024

ChemCatChem

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Polyoxometalates (POMs) are known for their unique redox properties, making them interesting candidates as redox mediators in electro‐organic transformations. We investigated derivatives of H3[PMo12O40], a classical Keggin‐type POM, as a potential redox mediator in the indirect electrolysis of biobased glyceraldehyde (GLAD), focusing on the effects of double substitution of the Mo framework metal by redox active transition metals (Mo replaced by V, Ni, Co, Mn). By combining electrochemical techniques with HPLC, UV‐Vis spectroscopy, and 31P‐NMR spectroscopy, a comprehensive overview of the reaction pathways, as well as the electronic and structural changes of the POM during the reaction were revealed. This work not only contributes to the fundamental understanding of POMs as redox mediators, but also paves the way for innovative development of sustainable and environmentally friendly electro‐organic transformations.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Mürtz,

Raabe,

Poller

et al. 2024

ChemCatChem

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“…Of the possible strategies to control Co(II) coordination environment, the use of polyoxometalate (POM) anions is one of the explored since several decades. [14][15][16][17][18] Among the large family of these versatile systems, lacunary POMs [19,20] are promising as ligands for designing Co(II) SIMs because various coordination geometries can be formed taking advantage of the unique properties of the coordination sites, such as multiple hydrogen bonding networks and protonation behaviour, as well as a defined and relatively rigid coordination pocket. In addition, undesired intermolecular magnetic interactions can be minimized by the bulkiness of POMs.…”

Section: Introductionmentioning

confidence: 99%

Slow relaxation of magnetization in the Co(II)‐phosphotungstate Keggin polyoxometalate

Martinez,

Alborés

2024

Eur J Inorg Chem

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We are reporting the single crystal structure of the tetrabutylammonium (TBA) salt of the old Co(II) Keggin phosphotungstate anion (Co(II)POM) and a study of the magnetic behaviour of this well‐known POM. This Co(II)POM crystallizes in a cubic cell and this high symmetry obscure a precise characterization of Co(II) coordination sphere metrics due to positional disordered. We employed DFT and SA‐SOC‐CASSCF as auxiliary tools to complement DC and AC magnetic data collected. The studied complex behaves as a fieldinduced single ion magnet (SIM) showing slow relaxing magnetization below 5 K under small DC applied magnetic fields. Raman relaxation mechanisms dominates with different relaxation times observed when switching from the TBA salt to the K salt of the Co(II)POM.

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“…In 2021, the worldwide mine production of tungsten amounted to 79 000 t [1] . Due to its high melting point, density, modulus of elasticity and thermal conductivity as well as its low vapor pressure, compressibility and thermal expansion, it has a broad spectrum of applications [2] . About 60 % of tungsten is processed in cemented carbide parts for wear‐resistant and cutting applications, primarily in the construction, mining, metalworking as well as gas and oil drilling industries.…”

Section: Introductionmentioning

confidence: 99%

In Situ X‐ray Diffraction Studies on the Reduction of V₂O₅ and WO₃ by Using Hydrogen

Keilholz

Dorsch

Kohlmann

2023

Chemistry A European J

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The reduction of metal oxides with hydrogen is widely used for the production of fine chemicals and metals both on the laboratory and industry scale. In situ methods can help to elucidate reaction pathways and to gain control over such synthesis reactions. In this study, the reduction of WO3 and V2O5 with hydrogen was investigated by in situ X‐ray powder diffraction with regard to intermediates and the influence of heating rates and hydrogen flow rates. Mixtures of V4O9, V6O13 and VO2 in two modifications were identified as intermediates on the way to phase‐pure V2O3. None of the intermediates occurs in a single phase and therefore cannot be prepared this way. In contrast, the intermediates of the WO3 reduction, H0.23WO3 and W10O29, appear consecutively and can be isolated. For both reactions, the heating and flow rates have little influence on the formation of intermediates.

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The fascinating polyoxometalates

Cited by 8 publications

References 170 publications

Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Slow relaxation of magnetization in the Co(II)‐phosphotungstate Keggin polyoxometalate

In Situ X‐ray Diffraction Studies on the Reduction of V₂O₅ and WO₃ by Using Hydrogen

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The fascinating polyoxometalates

Cited by 8 publications

References 170 publications

Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Transition‐metal Substituted Polyoxometalates as Soluble RedOx Mediators in Electrocatalytic Biomass Conversion

Slow relaxation of magnetization in the Co(II)‐phosphotungstate Keggin polyoxometalate

In Situ X‐ray Diffraction Studies on the Reduction of V2O5 and WO3 by Using Hydrogen

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In Situ X‐ray Diffraction Studies on the Reduction of V₂O₅ and WO₃ by Using Hydrogen