[Mo12S12O12(OH)12(H2O)6]: A Cyclic Molecular Cluster Based on the [Mo2S2O2]2+ Building Block

Cadot, Emmanuel; Salignac, Bernadette; Halut, Sabine; Sécheresse, Francis

doi:10.1002/(sici)1521-3773(19980316)37:5<611::aid-anie611>3.0.co;2-o

Cited by 71 publications

(14 citation statements)

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“…Based on the Mo–Mo dimer building block of [Mo 2 S 2 O 2 ] 2+ , , the structurally characterized polymeric chain of [Mo 4 O 8 S 4 ] n as a model for the local structure present in the MoO x S y was adopted. This model reproduces the local structure of the amorphous MoO x S y where the bridging O/S atoms are connected to the Ni 3 S 2 support.…”

Section: Methodsmentioning

confidence: 99%

“…Moreover, each Mo is coordinated to terminal double-bonded O and bridging S/O atoms. Based on a broad battery of experimental evidence for the MoO x S y /Ni 3 S 2 hierarchical structure and the known structurally established [Mo 2 S 2 O 2 ] 2+ dimer-based compounds, , we propose a model structure with the repeating unit of [Mo 4 O 8 S 4 ] to represent the key local structural characteristics of amorphous MoO x S y supported on the crystalline Ni 3 S 2 structure. The [Mo 4 O 8 S 4 ] chain-like structure features [Mo 2 O 2 (S,O) 4 ] dimers with MO bonding bridged by S or O atoms (see Figure S1).…”

Section: Introductionmentioning

confidence: 99%

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MoO_xS_y/Ni₃S₂ Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

Yao

Yang

et al. 2022

Chem. Mater.

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Hydrogen energy derived from water splitting is the cleanest renewable energy source, but it is also very challenging to achieve because the hydrogen evolution reaction (HER) requires highly efficient and low-cost electrocatalysts. We have fabricated a novel hierarchical system of amorphous molybdenum oxy/sulfide microspheres with crystalline Ni3S2 intergrown in situ on Ni foam (MoO x S y /Ni3S2/NF) as an outstanding electrocatalyst for HER. The MoO x S y /Ni3S2/NF demonstrates an ultra-low overpotential of 58 mV at a current density of 10 mA cm–2 and extremely durable stability (>200 h), suggesting superior performance comparable to that of Pt-C/NF under acidic conditions. The X-ray absorption fine structure (XAFS) determines the average valence state of Mo to be +(5 + δ), with a coordination motif by O and S. To explain such high HER activity, a [Mo2O2(S,O)4] dimer-based periodic model structure with the average composition of [Mo4O8S4] interfaced with the Ni3S2(101) surface is proposed. The interactions between the Ni of Ni3S2 and bridging S/O of [Mo4O8S4] result in an average formal Mo charge state between +5 and +6, and significant charge transfer from Ni3S2 to [Mo4O8S4] activates the MoO bonds. The calculated |ΔG H*| of less than 50 meV suggests that the double-bonded O is the most active site. This work points to the importance of oxy/sulfides with Mo n+ (+5 < n<+6) as exceptional electrochemical catalysts for HER.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

MoO_xS_y/Ni₃S₂ Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

Yao

Yang

et al. 2022

Chem. Mater.

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“…improving the cohesion of the unit and leading to its excellent stability. The double sulfido bridges and the metal-metal bond confer to these building block specific coordination properties producing a unique class of compounds which are not observed with the full oxo analogue [51]. The coordination requirements are mainly restricted to the equatorial and axial sites of the two equivalent Mo V atoms leading to the highly predictable assembly.…”

Section: Polyoxothiometalatesmentioning

confidence: 99%

“…It is worth noting that the self-condensation process is susceptible to the presence of structure directing agents (e.g. counter ions and metal ions) in a similar fashion to POM chemistry [51,52].…”

Section: Polyoxothiometalatesmentioning

confidence: 99%

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Building Block Libraries and Structural Considerations in the Self-assembly of Polyoxometalate and Polyoxothiometalate Systems

McAllister

Miras

2017

Polyoxometalate-Based Assemblies and Functional Materials

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Inorganic metal-oxide clusters form a class of compounds that are unique in their topological and electronic versatility and are becoming increasingly more important in a variety of applications. Namely, Polyoxometalates (POMs) have shown an unmatched range of physical properties and the ability to form structures that can bridge several length scales. The formation of these molecular clusters is often ambiguous and is governed by self-assembly processes that limit our ability to rationally design such molecules. However, recent years have shown that by considering new building block principles the design and discovery of novel complex clusters is aiding our understanding of this process. Now with current progress in thiometalate chemistry, specifically polyoxothiometalates (POTM), the field of inorganic molecular clusters has further diversified allowing for the targeted development of molecules with specific functionality. This chapter discusses the main differences between POM and POTM systems and how this affects synthetic methodologies and reactivities. We will illustrate how careful structural considerations can lead to the generation of novel building blocks and further deepen our understanding of complex systems.

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[W16S16O16(OH)16(H2O)4(C5H6O4)2]4−: A Flexible, Pillared Oxothiotungstate Wheel

2001

Self Cite

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Wie zwei Schnappschüsse der Dynamik in Lösung können die beiden durch Röntgenstrukturanalyse nachgewiesenen Konformationen (siehe Abbildung) von [W16S16O16(OH)16(H2O)4(C5H6O4)2]4−, dem größten diskreten cyclischen Oxothioanion, aufgefasst werden. Hergestellt wird das Ion durch Kondensation von [W2O2S2]2+‐Ionen in Gegenwart von Glutarat‐Ionen (C5H6O42−). Eine weitere Charakterisierung in wässriger Lösung erfolgte mit 1H‐NMR‐ und Raman‐Spektroskopie.

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[Mo12S12O12(OH)12(H2O)6]: A Cyclic Molecular Cluster Based on the [Mo2S2O2]2+ Building Block

Cited by 71 publications

References 6 publications

MoO_xS_y/Ni₃S₂ Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

MoO_xS_y/Ni₃S₂ Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

Building Block Libraries and Structural Considerations in the Self-assembly of Polyoxometalate and Polyoxothiometalate Systems

[W16S16O16(OH)16(H2O)4(C5H6O4)2]4−: A Flexible, Pillared Oxothiotungstate Wheel

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[Mo12S12O12(OH)12(H2O)6]: A Cyclic Molecular Cluster Based on the [Mo2S2O2]2+ Building Block

Cited by 71 publications

References 6 publications

MoOxSy/Ni3S2 Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

MoOxSy/Ni3S2 Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

Building Block Libraries and Structural Considerations in the Self-assembly of Polyoxometalate and Polyoxothiometalate Systems

[W16S16O16(OH)16(H2O)4(C5H6O4)2]4−: A Flexible, Pillared Oxothiotungstate Wheel

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MoO_xS_y/Ni₃S₂ Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

MoO_xS_y/Ni₃S₂ Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction