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Polyoxometalate

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https://www.readbyqxmd.com/read/30325113/strong-solid-state-luminescence-enhancement-in-supramolecular-assemblies-of-polyoxometalate-and-aggregation-induced-emission-active-phospholium
#1
Patricia Bolle, Yohan Chéret, Claire Roiland, Lionel Sanguinet, Eric Faulques, Hélène Serier-Brault, Pierre-Antoine Bouit, Muriel Hissler, Remi Dessapt
Two new supramolecular fluorescent hybrid materials combining for the first time [M6O19]2- (M = Mo, W) polyoxometalates (POMs) and the aggregation-induced emission (AIE)-active 1-methyl-1,2,3,4,5-pentaphenyl-phospholium (1+) were successfully synthesized. This novel molecular self-assembling strategy allows designing efficient solid-state emitters such as (1)2[W6O19] by directing favourably the balance between the AIE and aggregation-caused quenching (ACQ) effects using both anion-π+ and H-bonding interactions in the solid-state...
October 16, 2018: Chemistry, An Asian Journal
https://www.readbyqxmd.com/read/30324961/polyoxometalate-coupled-mxene-nanohybrid-via-poly-ionic-liquid-linkers-and-its-electrode-for-enhanced-supercapacitive-performance
#2
Shu Chen, Yuanfang Xiang, M Katherine Banks, Chang Peng, Weijian Xu, Ruoxi Wu
MXenes are novel 2D transition metal carbides with metallic conductivity and hydrophilic surfaces, which have highly active 2D surfaces and can act as a promising new type of electrode material; however, their low capacity and irreversible self-restacking limit their practicality and development. This paper presents a novel method for preparing an MXene-polyoxometalate (POM) nanohybrid using poly(ionic liquid) (PIL) as the linker. The electrostatic interactions, chemical structure, and morphology of this nanohybrid are systematically characterized and have indicated that the MXene-PIL-POM nanohybrid provides the uniform distribution of POM nanoparticles on the MXene nanosheets and exhibits excellent electrochemical activity and stability due to the use of PIL as the linker and stabilizer...
October 16, 2018: Nanoscale
https://www.readbyqxmd.com/read/30320059/a-multifunctional-dual-luminescent-polyoxometalate-metal-organic-framework-euw-10-uio-67-composite-as-chemical-probe-and-temperature-sensor
#3
William Salomon, Anne Dolbecq, Catherine Roch-Marchal, Grégoire Paille, Rémi Dessapt, Pierre Mialane, Hélène Serier-Brault
The luminescent [EuW10 O36 ]9- polyoxometalate has been introduced into the cavities of the highly porous zirconium luminescent metal-organic framework UiO-67 via a direct synthesis approach, affording the EuW10 @UiO-67 hybrid. Using a combination of techniques (TGA, BET, elemental analysis, EDX mapping,…) this new material has been fully characterized, evidencing that it contains only 0.25% in europium and that the polyoxometalate units are located inside the octahedral cavities and not at the surface of the UiO-67 crystallites...
2018: Frontiers in Chemistry
https://www.readbyqxmd.com/read/30307453/an-unprecedented-cute-core-incorporated-in-a-36-tungsto-4-silicate-polyoxometalate-with-visible-light-driven-catalytic-hydrogen-evolution-activity
#4
Wei-Chao Chen, Si-Tong Wu, Chao Qin, Xin-Long Wang, Kui-Zhan Shao, Zhong-Min Su, En-Bo Wang
We report an unprecedented {CuII14TeIV10} core containing the novel μ,μ-/μ6-TeIVO32- mode and TeIVO44- embedded within a 36-tungsto-4-silicate POT shell, which constitutes the first example of a tellurous copper cluster in POMs. The structure-stabilizing and templating effects of tellurite anions are crucial for this assembly. Moreover, its visible light-driven catalytic H2 evolution activity and related quenching mechanism are demonstrated, and extensive stability studies are presented.
October 11, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30301551/structures-and-dynamics-of-carbon-black-in-suspension-probed-by-static-and-dynamic-ultrasound-scattering-techniques
#5
Motoki Ozaki, Tomohisa Norisuye, Hideyuki Nakanishi, Qui Tran-Cong-Miyata
Carbon black (CB) suspension exhibits various structures depending on the properties of solvent and dispersant as well as the preparation process of suspension. In most cases, CB particles do not exist as independent nanoparticles but as aggregates or agglomerates. In order to evaluate the size distribution at different level of hierarchal structure, we carried out static/dynamic ultrasound scattering analysis for the CB suspensions in alcohol and/or water with or without Nafion, a perfluorinated polymer. The potential of the dynamic ultrasound scattering technique was demonstrated by discriminating diffusing nanoparticles and micron-sized aggregates/agglomerates without dilution of the sample...
September 29, 2018: Ultrasonics
https://www.readbyqxmd.com/read/30285284/single-source-bismuth-transition-metal-polyoxovanadate-precursors-for-the-scalable-synthesis-of-doped-bivo-4-photoanodes
#6
Haijiao Lu, Virgil Andrei, Kellie J Jenkinson, Anna Regoutz, Ning Li, Charles E Creissen, Andrew E H Wheatley, Hongxun Hao, Erwin Reisner, Dominic S Wright, Sebastian D Pike
Single-source precursors are used to produce nanostructured BiVO4 photoanodes for water oxidation in a straightforward and scalable drop-casting synthetic process. Polyoxometallate precursors, which contain both Bi and V, are produced in a one-step reaction from commercially available starting materials. Simple annealing of the molecular precursor produces nanocrystalline BiVO4 films. The precursor can be designed to incorporate a third metal (Co, Ni, Cu, or Zn), enabling the direct formation of doped BiVO4 films...
October 4, 2018: Advanced Materials
https://www.readbyqxmd.com/read/30264902/hybrid-core-shell-nanoparticles-by-plug-and-play-self-assembly
#7
Benjamin Pacaud, Loïc Leclercq, Jean-François Dechézelles, Véronique Nardello-Rataj
Supramolecular hybrid functional nanoparticles (NPs) can be obtained via the colloidal tectonics approach provided that multiple interactive molecular tectons are used. Herein, the programmable synthesis of novel hybrid core-shell nanoparticles via the following sequential steps is reported: (i) complexation of 1-decanol by the β-cyclodextrin (β-CD), (ii) spontaneous self-assembly into CD NPs, (iii) adsorption of polyoxometalate anions, PW12O403-, on the polar neutral interface of the CD NPs. Such an approach paves the way for the design of novel and original materials and systems...
September 28, 2018: Chemistry: a European Journal
https://www.readbyqxmd.com/read/30261437/a-critical-review-of-the-application-of-chelating-agents-to-enable-fenton-and-fenton-like-reactions-at-high-ph-values
#8
Ying Zhang, Minghua Zhou
To overcome the drawback of low pH requirement of the classical Fenton reaction, researchers have applied chelating agents to form complexes with Fe and enable Fenton reaction at high pHs, which is reviewed in this article. The chelating agents reviewed include humic substances, polycarboxylates, aminopolycarboxylic acids, and polyoxometalates. Ligands affect the reactivity of Fe-complexes by changing their redox potentials, promoting their reaction with H2 O2 , and competing with target contaminants for the oxidative species...
January 15, 2019: Journal of Hazardous Materials
https://www.readbyqxmd.com/read/30259731/polyoxometalates-active-carbon-thin-separator-for-improving-cycle-performance-of-lithium-sulfur-batteries
#9
Wei Yao, Li Liu, Xue-Song Wu, Chao Qin, Haiming Xie, Zhong-Min Su
Lithium-sulfur (Li-S) batteries have great potential for the next generation of energy-storage devices owing to their high theoretical energy density. However, the polysulfides shuttling effect seriously degraded the cycle stability and capacity and hindered their commercial applications. Here, we design and fabricate a bifunctional composite separator including polypropylene (PP) matrix layer and Keggin polyoxometalate [PW12O40]3-/Super P composite retarding layer by utilizing the Coulombic repulsion between polyanion and polysulfides...
September 27, 2018: ACS Applied Materials & Interfaces
https://www.readbyqxmd.com/read/30256617/a-novel-tetrameric-polyoxotantalate-aggregate-co-8-ta-24-featuring-a-high-nuclearity-co-8-cluster
#10
Zhijie Liang, Shufang Zhao, Pengtao Ma, Chao Zhang, Junjun Sun, Tingting Song, Jingyang Niu, Jingping Wang
The first Co-containing polyoxotantalate cluster, [H5 Co8 Ta24 O80 ]15- , has been obtained. The tetramer has by far the highest degree of polymerization of any polyoxotantalate based on {Ta6 O19 } and is the largest high-nuclearity Co-cluster-containing polyoxotantalate obtained thus far. The synthesis of new polyoxotantalates has long been a challenging subject in polyoxotantalate chemistry. The findings of this study show the possibility of using Ta-based polyoxometalates as ligands to construct large aggregated structures analogous to the related Nb compounds...
September 26, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30254260/skin-color-specific-and-spectrally-selective-naked-eye-dosimetry-of-uva-b-and-c-radiations
#11
Wenyue Zou, Ana González, Deshetti Jampaiah, Rajesh Ramanathan, Mohammad Taha, Sumeet Walia, Sharath Sriram, Madhu Bhaskaran, José M Dominguez-Vera, Vipul Bansal
Spectrally-selective monitoring of ultraviolet radiations (UVR) is of paramount importance across diverse fields, including effective monitoring of excessive solar exposure. Current UV sensors cannot differentiate between UVA, B, and C, each of which has a remarkably different impact on human health. Here we show spectrally selective colorimetric monitoring of UVR by developing a photoelectrochromic ink that consists of a multi-redox polyoxometalate and an e- donor. We combine this ink with simple components such as filter paper and transparency sheets to fabricate low-cost sensors that provide naked-eye monitoring of UVR, even at low doses typically encountered during solar exposure...
September 25, 2018: Nature Communications
https://www.readbyqxmd.com/read/30250000/thermochemical-measurements-of-alkali-cation-association-to-hexatantalate
#12
Dylan J Sures, G P Nagabhushana, Alexandra Navrotsky, May Nyman
Ion association is an important process in aqueous dissolution, precipitation, and crystallization of ionic inorganic, organic, and biological materials. Polyoxometalates (POMs) are good model compounds for understanding the complex relationships between lattice energy, ion-pairing in solution, and salt solubility. Here we perform calorimetric measurements to elucidate trends in cluster stability, lattice energy, and ion-pairing behavior studies of simple hexatantalate salts in neat water, parent hydroxide solutions, and molybdate melts, extending previous studies on the isostructural hexaniobates...
September 24, 2018: Molecules: a Journal of Synthetic Chemistry and Natural Product Chemistry
https://www.readbyqxmd.com/read/30238478/hydrolysis-of-chemically-distinct-sites-of-human-serum-albumin-by-polyoxometalate-a-hybrid-qm-mm-oniom-study
#13
Vindi M Jayasinghe-Arachchige, Qiaoyu Hu, Gaurav Sharma, Thomas J Paul, Marcus Lundberg, David Quinonero, Tatjana N Parac-Vogt, Rajeev Prabhakar
In this study, mechanisms of hydrolysis of all four chemically diverse cleavage sites of human serum albumin (HSA) by [Zr(OH)(PW11 O39 )]4- (ZrK) have been investigated using the hybrid two-layer QM/MM (ONIOM) method. These reactions have been proposed to occur through the following two mechanisms: internal attack (IA) and water assisted (WA). In both mechanisms, the cleavage of the peptide bond in the Cys392-Glu393 site of HSA is predicted to occur in the rate-limiting step of the mechanism. With the barrier of 27...
September 20, 2018: Journal of Computational Chemistry
https://www.readbyqxmd.com/read/30230484/supramolecular-self-assembly-for-designing-non-centrosymmetric-crystals-based-on-keggin-polyoxometallates-and-crown-ether
#14
Jun Xiong, Kazuya Kubo, Shao-Fang Lü, Ming Li, Takayoshi Nakamura
We report the synthesis of five novel crystals [(4-BrAni+)(DB[18]crown-6)]2[SMo12O402-]·2CH3CN (1), [(4-BrAni+)(B[18]crown-6)]2[SMo12O402-]·CH3CN (2), [(4-BrAni+)(B[18]crown-6)]3[PMo12O402-]·2CH3CN (3), [(3-AP+)3(B[18]crown-6)2][PMo12O403-] (4) and [NBu4+][(3-AP2+)(DB[30]crown-10)][PMo12O403-]·CH3CN (5) (4-BrAni+ = 4-bromoanilinium; B[18]crown-6 = benzo[18]-crown-6; DB[18]crown-6 = dibenzo[18]-crown-6; DB[30]crown-10 = dibenzo[30]-crown-10; 3-AP+ = 3-aminopyridinium; 3-AP2+ = 3-ammoniumpyridinium; NBu4+ = tetrabutylammonium)...
October 9, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30229254/elucidating-white-light-emissions-in-tm-3-dy-3-codoped-polyoxometalates-a-color-tuning-and-energy-transfer-mechanism-study
#15
Hechen Wu, Minna Zhi, Vikram Singh, Huafeng Li, Pengtao Ma, Jingyang Niu, Jingping Wang
The double-tartaric bridging Tm-substituted POM derivative [N(CH3)4]6K3H7[Tm(C4H2O6)(α-PW11O39)]2·27H2O (1) was successfully synthesized and well characterized by various physico-chemical analyses. Furthermore, the mixed Dy3+/Tm3+ ion-based POM derivatives [N(CH3)4]6K3H7[DyxTm1-x(C4H2O6)(α-PW11O39)]2·27H2O (3-8) were first synthesized and confirmed by PXRD and IR spectra, indicating compounds 3-8 are isomorphic with 1. The detailed analyses of Ln-O-W bond angle and coordinated aqua ligands around emitting Ln3+ ions have revealed that the mentioned negative factors do not effectively affect the luminescence of emitting Ln3+ ions in 1-8...
October 9, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30226797/catalytic-oxidative-desulphurization-of-gasoline-using-amphiphilic-polyoxometalate-polymer-nanocomposite-as-an-efficient-reusable-and-green-organic-inorganic-hybrid-catalyst
#16
Mohammad Ali Rezvani, Maryam Shaterian, Masomeh Aghmasheh
To preparation of ultra-clean gasoline fuel, a new amphiphilic nanocomposite (TBA-SiWMn@PVA) has been successfully synthesized by supporting sandwich-type silicotungstate polyoxometalate ((n-C4 H9 )4 N)7 H5 Si2 W18 Mn4 O68 (TBA-SiWMn) on polyvinylalcohol (PVA) as an efficient catalyst for catalytic oxidative desulphurization (CODS) of gasoline. The synthesized materials were characterized by means of elemental analysis, 113 Mn NMR, 29 Si NMR, XRD, SEM, FT-IR and UV-vis techniques. The catalytic activity of TBA-SiWMn@PVA nanocomposite was tested on real gasoline in the presence of CH3 COOH/H2 O2 as an oxidant and the results were compared with model sulphur compounds at the same conditions...
September 18, 2018: Environmental Technology
https://www.readbyqxmd.com/read/30226372/two-keggin-based-isostructural-pomof-hybrids-synthesis-crystal-structure-and-catalytic-properties
#17
Soumyabrata Roy, Vamseedhara Vemuri, Sthitadhi Maiti, Kaja Sai Manoj, Udumula Subbarao, Sebastian C Peter
In this work we synthesized two novel isostructural twin hybrids Comp1: [H(C10 H10 N2 )Cu2 ][PMo12 O40 ] & Comp2: [H(C10 H10 N2 )Cu2 ][PW12 O40 ], based on the Keggin ions (PMo12 O40 -3 & PW12 O40 -3 ), Cu(I) cation, and 4,4'-bipyridine, by in situ hydrothermal reduction of Cu, facilitated through extensive standardizations of synthetic pH conditions. Both compounds crystallized in monoclinic P21 / c space group with similar lattice parameters and crystal structures. The structural similarity prompted us to explore comparative catalytic properties of the hybrids, to understand the relative role of the POM species in the activity...
October 1, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30225474/a-comprehensive-approach-providing-a-new-synthetic-route-for-bimetallic-electrocatalysts-via-isopoms-m-rh-cp-4-w-8-o-32-m-rh-1-and-ir-2
#18
Vikram Singh, Pengtao Ma, Michael G B Drew, Jingping Wang, Jingyang Niu
Polyoxometalates (POMs) are highly versatile materials if paired with various conducting supports. We here present a new prospective approach for obtaining advanced electrocatalytic systems via POMs (1 and 2) nanostructured on Ni foam (NF) to give bimetallic nanohybrid composite materials M0.4Ni0.6/WO3 (M = Rh (3) or Ir (4)). By this pathway, two rare isopolyoctatungstate-based organometallic clusters [Hx(MCp*)4W8O32]·yH2O (in 1, M = Rh, x = 8, y = 23; in 2, M = Ir, x = 4, y = 17.33) have been synthesized via one-pot reactions using [Cp*MCl2]2 (Cp* = pentamethylcyclopentadienyl, M = Rh or Ir) and Na2WO4·2H2O in basic conditions...
October 9, 2018: Dalton Transactions: An International Journal of Inorganic Chemistry
https://www.readbyqxmd.com/read/30224696/polyoxometalate-based-microcrystal-arrays-patterned-on-air-grid-superwettable-surface
#19
Tianzhan Zhang, Yuefeng Wang, Jun-Bing Fan, Jingxin Meng, Yangguang Li, Enbo Wang, Shutao Wang
Surface patterning of polyoxometalates (POMs) is an important step to gain functional materials and devices. However, some special requirements such as complex operation steps or strict synthesis environment greatly limit their further applications. Herein, we have employed a simple and universal strategy for patterning POM-based microcrystal arrays on air-grid superwettable surfaces. The size and distribution of POM crystals were precisely adjusted by varying the pillar parameter of superwettable surface and concentration of POM mother liquid...
September 17, 2018: Scientific Reports
https://www.readbyqxmd.com/read/30211153/selectivity-and-reactivity-of-zr-iv-and-ce-iv-substituted-keggin-type-polyoxometalates-toward-cytochrome-c-in-surfactant-solutions
#20
Thomas Quanten, Tessa De Mayaer, Pavletta Shestakova, Tatjana N Parac-Vogt
In this paper we investigate the effect of three different types of surfactants, on the hydrolysis of Cytochrome c (Cyt c), a predominantly α helical protein containing a heme group, promoted by [Ce(α PW11 O 39 )2]10- (CeK) and [Zr(α PW11 O 39 )2]10- (ZrK) polyoxometalates. In the presence of SDS, Zw3 12, or CHAPS surfactants, which are commonly used for solubilizing hydrophobic proteins, the specificity of CeK or ZrK toward hydrolysis of Cyt c does not change. However, the hydrolysis rate of Cyt c by CeK was increased in the presence of SDS, but decreased in the presence of CHAPS, and was nearly inhibited in the presence of Zw3 12...
2018: Frontiers in Chemistry
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