A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

Mukhopadhyay, Subhabrata; Debgupta, Joyashish; Singh, Chandani; Kar, Aranya; Das, Samar K.

doi:10.1002/anie.201711920

Cited by 156 publications

(182 citation statements)

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“…[1][2][3][4][5][6][7][8] However, a loss of these functionalities in aqueous electrolytes (strong acid or alkali) severely limits application of MOFs in energy-related electrocatalysis. [1][2][3][4][5][6][7][8] However, a loss of these functionalities in aqueous electrolytes (strong acid or alkali) severely limits application of MOFs in energy-related electrocatalysis.…”

Section: Oxygen Evolution Reactionmentioning

confidence: 99%

“…[13][14][15] This is because transition-metal-based MOFs readily collapse in these relative harsh environments. [1][2][3][4][5][6][7][8] However, a loss of these functionalities in aqueous electrolytes (strong acid or alkali) severely limits application of MOFs in energy-related electrocatalysis. Therefore, designing new MOFs with intrinsic stability is important for their applications in electrocatalysis field.…”

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confidence: 99%

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Co (II) Boron Imidazolate Framework with Rigid Auxiliary Linkers for Stable Electrocatalytic Oxygen Evolution Reaction

et al. 2019

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Metal–organic frameworks (MOFs) have significant potential for practical application in catalysis. However, many MOFs are shown to be sensitive to aqueous solution. This severely limits application of MOFs in electrocatalytic operations for energy production and storage. Here, a Co (II) boron imidazolate framework CoB(im) 4 (ndc) 0.5 ( BIF‐91 , im = imidazolate, ndc = 2,6‐naphthalenedicarboxylate) that is rationally designed and successfully tested for electrocatalytic application in strong alkaline (pH ≈ 14) solution is reported. In such a BIF system, the inherent carboxylate species segment large channel spaces into multiple domains in which each single channel is filled with ndc ligands through the effect of zeolite channel confinement. These ligands, with strong C—H···π interaction, act as a rigid auxiliary linker to significantly enhance the structural stability of the BIF‐91 framework. Additionally, the π‐conjugated effect in BIF‐91 stabilizes dopant Fe (III) at the atomic scale to construct Fe‐immobilized BIF‐91 ( Fe@BIF‐91 ). Due to the synergistic effect between Fe (III) guest and Co (II) in the framework, the Fe@BIF‐91 acts as an active and stable electrocatalyst for the oxygen evolution reaction in alkaline solution.

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Section: Oxygen Evolution Reactionmentioning

confidence: 99%

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confidence: 99%

Co (II) Boron Imidazolate Framework with Rigid Auxiliary Linkers for Stable Electrocatalytic Oxygen Evolution Reaction

et al. 2019

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“…[5,6] Porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) are 3D periodic arrays of metal ions and organic/inorganic ligands connected by coordination bonds and even weaker supramolecular interactions. [2,8] Some MOFs,e specially those with 2D coordination networks,h ave been used for making 2D materials or ultrathin nanosheets. [2,8] Some MOFs,e specially those with 2D coordination networks,h ave been used for making 2D materials or ultrathin nanosheets.…”

Section: Understandingthestructure-propertyrelationshipiscrucialmentioning

confidence: 99%

“…[7] With diversified and designable structures,M OFs have been widely studied in various fields such as storage,s eparation, and heterogeneous catalysis. [2,8] Some MOFs,e specially those with 2D coordination networks,h ave been used for making 2D materials or ultrathin nanosheets. [9] Them ajor obstacles for preparation of 2D materials or ultrathin nanosheets from MOFs are their relatively weak intralayer bonding (coordination bonds) and relatively strong interlayer interactions (hydrogen bonds, p-p stacking,multiple interactions between the wrinkle surface,etc.).…”

Section: Understandingthestructure-propertyrelationshipiscrucialmentioning

confidence: 99%

Electrochemical Exfoliation of Pillared‐Layer Metal–Organic Framework to Boost the Oxygen Evolution Reaction

Huang

et al. 2018

Angewandte Chemie

108

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Tw o-dimensional (2D) materials and ultrathin nanosheets are advantageous for elevating the catalysis performance and elucidating the catalysis mechanism of heterogeneous catalysts,but they are mostly restricted to inorganic or organic materials based on covalent bonds.W er eport an electrochemical/chemical exfoliation strategy for synthesizing metal-organic 2D materials based on coordination bonds.A catechol functionalizedligand is used as the redox active pillar to construct apillared-layer framework. When the 3D pillaredlayer MOF serves as an electrocatalyst for water oxidation (pH 13), the pillar ligands can be oxidized in situ and removed. The remaining ultrathin (2 nm) nanosheets of the metalorganic layers are an efficient catalyst with overpotentials as low as 211 mV at 10 mA cm À2 and aturnover frequency as high as 30 s À1 at an overpotential of 300 mV.

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“…The modern chemical research on polyoxometalates (POMs)-based solid state materials fascinates synthetic chemists because of their potential applications in diverse research areas, such as, catalysis (Vazylyev et al, 2005; Hill, 2007; Zhou et al, 2014; Lechner et al, 2016; Mukhopadhyay et al, 2018), medicinal chemistry (Pope and Müller, 1991; Liu et al, 2012; Xie et al, 2018), and materials science (Guo et al, 2000; Rao et al, 2011; Kulikov and Meyer, 2013; Omwoma et al, 2015; Walsh et al, 2016). Among these, the area of polyoxovanadate (henceforth, POV) based materials have received special attention due to not only their diverse topologies (Miiller et al, 1990; Klemperer et al, 1992; Chen et al, 2005), structural (Miiller et al, 1987; Koene et al, 1999) and electronic properties (Müller et al, 1997) but also their fascinating versatile industrial applications, e.g., catalysis (Gao and Hua, 2006) and materials applications (Khan et al, 2003; Arumuganathan and Das, 2009; Chen et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

A Versatile Polyoxovanadate in Diverse Cation Matrices: A Supramolecular Perspective

Amanchi

Das

2018

Front. Chem.

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A series of decavanadate based compounds, formulated as [Co(H2O)6][{Na4(H2O)14}{V10O28}]·4H2O (1), [Zn(H2O)6][Na3(H2O)14] [HV10O28]·4H2O (2), [HMTAH]2 [{Zn(H2O)4}2{V10O28}]·2H2O (3), [{Co(3-amp)(H2O)5}]2 [3-ampH]2 [V10O28] · 6H2O (4), [4-ampH]10[{Na(H2O)6}{HV10O28}][V10O28]·15H2O (5), [{4-ampH}6 {Co(H2O)6}3][V10O28]2·14H2O (6), and [{4-ampH}10{Zn(H2O)6}][V10O28]2·10H2O (7), have been synthesized (where HMTAH = mono-protonated hexamethylenetetramine, 3-ampH = protonated 3-amino pyridine and 4-ampH= protonated 4-aminopyridine) from the relevant aqueous sodium-vanadate solution, by varying the pH of the solution and amino pyridine/hexamine derivatives as well as transition metal salts (Co(II)- and Zn(II)-salts). In this series of compounds 1–7, the polyoxovanadate (POV) cluster [V10O28]6− is the common cluster anion, stabilized by diverse cations. The diverse supramolecular patterns around the decavanadate cluster anion in different cationic matrices have been described to understand the microenvironment in the decavanadate-based minerals. All of these compounds have solvent water molecules in their respective crystal lattices. Since water can interact directly with cations and anions, providing an additional stability and structural diversity, we have analyzed supramolecular water structures in all these compounds to comprehend the role of the lattice water in the formation of natural decavanadate containing minerals. Compounds 1–7, that are isolated at an ambient condition from aqueous solution, are characterized by routine spectral analysis, elemental analyses and finally unambiguously by single crystal X-ray crystallography.

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A Keggin Polyoxometalate Shows Water Oxidation Activity at Neutral pH: POM@ZIF‐8, an Efficient and Robust Electrocatalyst

Cited by 156 publications

References 70 publications

Co (II) Boron Imidazolate Framework with Rigid Auxiliary Linkers for Stable Electrocatalytic Oxygen Evolution Reaction

Co (II) Boron Imidazolate Framework with Rigid Auxiliary Linkers for Stable Electrocatalytic Oxygen Evolution Reaction

Electrochemical Exfoliation of Pillared‐Layer Metal–Organic Framework to Boost the Oxygen Evolution Reaction

A Versatile Polyoxovanadate in Diverse Cation Matrices: A Supramolecular Perspective

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