Abstract:A new 12-tungstovanadate-templated 3D nanocage framework, Ag 10 (μ 4 -ttz) 4 (H 2 O) 4 (VW 12 O 40 ) (VW 12 @MOCF), was designed based on a "molecular library", hydrothermally synthesized, structurally characterized, and explored as anode material for lithium-ion batteries (LIBs). Combination of the structural superiority of VW 12 @MOCF with the good electrical conductivity of the single-walled carbon nanotubes (SWNTs) renders the VW 12 @MOCF/SWNT-2 nanocomposite reasonable electrochemical performance and stab… Show more
“…Recent reports indicate that tungstovanadates can exhibit special structural features and properties. − Herein, we provide a new method for the preparation of a novel TRIS-substituted Lindqvist-type hexatungstovanadates [V x W 6– x O 16 (CH 2 O) 3 CR] ( x −1)– [ x = 3 or 4; R = CH 3 ( 1 ; CCDC 2027592) or CH 2 OH ( 2 ; CCDC 2027593)]. These compounds were synthesized by a simple one-pot reaction in an aqueous solution with simple vanadate, tungstate salts, and TRIS ligands under mild conditions.…”
We successfully designed and obtained
a new family of polyoxometalates
(POMs) containing mixed-metal elements and a trialkoxyl (TRIS) ligand
via a very simple one-pot process under mild condition. Single-crystal
X-ray diffraction revealed that this family belongs to compact Lindqvist-type
hexatungstovanadates. In particular, the hydroxyl-containing product
can be further functionalized through esterification. Not only does
this work open a broad door for unusual POM clusters involving vanadium
and tungsten atoms in the future, but also the design concept of this
work also provides new insight for the synthesis and further exploration
of POMs.
“…Recent reports indicate that tungstovanadates can exhibit special structural features and properties. − Herein, we provide a new method for the preparation of a novel TRIS-substituted Lindqvist-type hexatungstovanadates [V x W 6– x O 16 (CH 2 O) 3 CR] ( x −1)– [ x = 3 or 4; R = CH 3 ( 1 ; CCDC 2027592) or CH 2 OH ( 2 ; CCDC 2027593)]. These compounds were synthesized by a simple one-pot reaction in an aqueous solution with simple vanadate, tungstate salts, and TRIS ligands under mild conditions.…”
We successfully designed and obtained
a new family of polyoxometalates
(POMs) containing mixed-metal elements and a trialkoxyl (TRIS) ligand
via a very simple one-pot process under mild condition. Single-crystal
X-ray diffraction revealed that this family belongs to compact Lindqvist-type
hexatungstovanadates. In particular, the hydroxyl-containing product
can be further functionalized through esterification. Not only does
this work open a broad door for unusual POM clusters involving vanadium
and tungsten atoms in the future, but also the design concept of this
work also provides new insight for the synthesis and further exploration
of POMs.
“…As we know, POM‐based materials show extraordinary advantages for LIBs [65–67] . However, many factors (such as different chemical components) that might influence electrochemical performance still need to be verified [68] .…”
Section: Resultsmentioning
confidence: 99%
“…As we know, POM-based materials show extraordinary advantages for LIBs. [65][66][67] However, many factors (such as different chemical components) that might influence electrochemical performance still need to be verified. [68] In this respect, the design of specifically targeted compounds often plays an important role in the in-depth study of this issue.…”
With their adjustable structures and diverse functions, polyoxometalate (POM)‐resorcin[4]arene‐based inorganic–organic complexes are a kind of potential multifunctional material. They have potential applications for lithium ion batteries (LIBs). However, the relationship between different coordinated metal ions and electrochemical performance has rarely been investigated. Here, three functionalized POM‐resorcin[4]arene‐based inorganic–organic materials, [Co2(TMR4 A)2(H2O)10][SiW12O40]⋅2 EtOH⋅4.5 H2O (1), [Ni2(TMR4 A)2(H2O)10][SiW12O40]⋅4 EtOH⋅13 H2O (2), and [Zn2(TMR4 A)2(H2O)10][SiW12O40]⋅2 EtOH⋅2 H2O (3), have been synthesized. Furthermore, to enhance the conductivities of these compounds, 1–3 were doped with reduced graphene oxide (RGO) to give composites 1@RGO‐3@RGO, respectively. As anode materials for LIBs, 1@RGO‐3@RGO can deliver very high discharge capacities (1445.9, 1285.0 and 1095.3 mAh g−1, respectively) in the initial run, and show discharge capacities of 898, 665 and 651 mAh g−1, respectively, at a current density of 0.1 A g−1 over 100 runs. More importantly, the discharge capacities of 319, 283 and 329 mAh g−1 were maintained for 1@RGO‐3@RGO even after 400 cycles at large current density (1 A g−1).
“…38−42 For example, Sha et al reported a 12-tungstovanadate framework combined singlewalled carbon nanotube (SWNT) composite (VW12@MOCF/ SWNT-2), which featured the outstanding electrochemical performance. 43 The reduced graphene oxide (RGO)/conducting polymers could interact with POMOFs via hydrogen bonds and π−π interactions to effectively enhance the POMOF conductivity. 44,45 On the other hand, the sizes of the resulting composites could affect the rate performance of LIBs.…”
Section: ■ Introductionmentioning
confidence: 99%
“…In this facet, the most popular method is to combine POMOFs with a conducting substrate. − For example, Sha et al reported a 12-tungstovanadate framework combined single-walled carbon nanotube (SWNT) composite (VW12@MOCF/SWNT-2), which featured the outstanding electrochemical performance . The reduced graphene oxide (RGO)/conducting polymers could interact with POMOFs via hydrogen bonds and π–π interactions to effectively enhance the POMOF conductivity. , On the other hand, the sizes of the resulting composites could affect the rate performance of LIBs. − The nanoscale samples provided a large amount of specific surfaces for the interactions with active sites of Li + , which thus improved their electrochemical behaviors for LIBs. , However, the size-controlled syntheses for the POMOFs are difficult and essential for anode materials. , …”
By employing a bowl-like tetra(benzimidazole)resorcin[4]arene
(TBR4A)
ligand, two new polyoxometalate-templated metal–organic frameworks
(POMOFs), [Co8Cl14(TBR4A)6]·3[H3.3SiW12O40]·10DMF·11EtOH·20H2O (1) and [Co3Cl2(TBR4A)2(DMF)4]·[SiW12O40]·2EtOH·3H2O (2), have been prepared under solvothermal
conditions (DMF = N,N′-dimethylformamide). 1 shows a 2D cationic layer, whereas 2 exhibits
a 3D framework. Remarkably, the Keggin POMs in 1 and 2 were located in the cavities formed by two bowl-like resorcin[4]arenes
in sandwich fashions. Their framework structures were highly dependent
on the coordination modes of the TBR4A ligands. To increase the conductivity
of POMOFs, the samples of 1 and 2 were loaded
on the conductive polypyrrole-reduced graphene oxide (PPy-RGO) via ball milling (1@PG and 2@PG). Then, the obtained composites experienced calcination at a proper
temperature to produce 1@PG-A and 2@PG-A. The resulting 1@PG-A and 2@PG-A composites,
with improved conductivities, uniform sizes and micropores, exhibited
promising electrochemical performance for lithium-ion batteries. We
herein proposed a size-controlled route for the rational fabrication
of functional POMOFs and their usage in energy fields.
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