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Special Issue "Polyoxometalate and Nanohybrid Materials"

A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (16 March 2018)

Special Issue Editor

Guest Editor
Assoc. Prof. Rudy Luck

Department of Chemistry, Michigan Technological University, Houghton, MI, USA
Website | E-Mail
Interests: low-valent molybdenum complexes capable of activating dinitrogen; heteronuclear quadruply bonded metal-metal complexes; molecular dihydrogen compounds; catalytic applications of metal-oxo/peroxo systems in the area of epoxidation of olefins; construction of metallo-framework cluster materials

Special Issue Information

Dear Colleagues,

Following a seminal publication [1] on polyoxometalate (POM) complexes, research over the years has branched into combinations of inorganic–organic hybrid nanomaterials. More recently, this research has been extended to the combination of POMs into various nanohybrid materials ranging from carbon nanotubules and functionalized graphene to inorganic platforms including MCM-41-type compounds or metal nanoparticles themselves. These compounds have recently been suggested to have scope and application to a wide diversity of areas including nonlinear optics, magnetism, catalysis and health.

Various novel uses have been proposed for such materials including SWCNT–POM nanohybrid materials as electrodes for electrochemical supercapacitors/batteries; Keggin-type POM and Cd(II) semicarbazone Schiff base complexes for excellent adsorption properties for the removal of cationic dye pollutants; efficient visible light-induced O2 generation by self-assembled nanohybrids of inorganic nanosheets and POM nanoclusters; energy storage devices using POM/Graphene nanohybrid materials; water purification by POM-supported ionic liquid phases and micro-encapsulation of POMs inside MCM-41 mesoporous molecular sieve materials which display photoluminescent (incorporating rare earth elements) activity.

As the fields of both polyoxmetalate and nanohybrid material are rapidly advancing, it is our pleasure to invite you to submit a manuscript for this Special Issue. Full papers, communications, and reviews are welcome. The main theme can be either on the synthesis and characterization of polyoxometalate nanohybrid materials or on the applications of these compounds, or (ideally) the manuscript can cover both aspects simultaneously.

Assoc. Prof. Rudy Luck
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Reference:

  1. Pope, M.T.; Mueller, A. (Eds.) Polyoxometalate Chemistry from Topology via Self-Assembly to Applications; Kluwer Academic Publishers: Dordrecht, The Netherlands, 2001; p. 427.

Keywords

  • nanohybrid

  • polyoxometallate

  • supercapacitors

  • batteries

  • water purification

  • energy storage

  • photoluminescent

  • catalysis

  • medicine

Published Papers (5 papers)

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Research

Open AccessFeature PaperArticle Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite
Materials 2018, 11(7), 1196; https://doi.org/10.3390/ma11071196
Received: 16 April 2018 / Revised: 28 June 2018 / Accepted: 2 July 2018 / Published: 12 July 2018
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Abstract
Different methodologies were used to increase the oxidative desulfurization efficiency of the Keggin phosphotungstate [PW12O40]3− (PW12). One possibility was to replace the acid proton by three different ionic liquid cations, forming the novel hybrid polyoxometalates: [BMIM]
[...] Read more.
Different methodologies were used to increase the oxidative desulfurization efficiency of the Keggin phosphotungstate [PW12O40]3− (PW12). One possibility was to replace the acid proton by three different ionic liquid cations, forming the novel hybrid polyoxometalates: [BMIM]3PW12 (BMIM as 1-butyl-3-methylimidazolium), [BPy]3PW12 (BPy as 1-butylpyridinium) and [HDPy]3PW12 (HDPy as hexadecylpyridinium. These hybrid Keggin compounds showed high oxidative desulfurization efficiency in the presence of [BMIM]PF6 solvent, achieving complete desulfurization of multicomponent model diesel (2000 ppm of S) after only 1 h, using a low excess of oxidant (H2O2/S = 8) at 70 °C. However, their stability and activity showed some weakness in continuous reused oxidative desulfurization cycles. An improvement of stability in continuous reused cycles was reached by the immobilization of the Keggin polyanion in a strategic positively-charged functionalized-SBA-15 support. The PW12@TM–SBA-15 composite (TM is the trimethylammonium functional group) presented similar oxidative desulfurization efficiency to the homogeneous IL–PW12 compounds, having the advantage of a high recycling capability in continuous cycles, increasing its activity from the first to the consecutive cycles. Therefore, the oxidative desulfurization system catalyzed by the Keggin-type composite has high performance under sustainable operational conditions, avoids waste production during recycling and allows catalyst recovery. Full article
(This article belongs to the Special Issue Polyoxometalate and Nanohybrid Materials)
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Open AccessArticle Synthesis and Characterization of a Heterometallic Extended Architecture Based on a Manganese(II)-Substituted Sandwich-Type Polyoxotungstate
Materials 2018, 11(1), 155; https://doi.org/10.3390/ma11010155
Received: 21 December 2017 / Revised: 11 January 2018 / Accepted: 13 January 2018 / Published: 17 January 2018
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Abstract
The reaction of [α-P2W15O56]12− with MnII and DyIII in an aqueous basic solution led to the isolation of an all inorganic heterometallic aggregate Na10(OH2)42[{Dy(H2O)
[...] Read more.
The reaction of [α-P2W15O56]12− with MnII and DyIII in an aqueous basic solution led to the isolation of an all inorganic heterometallic aggregate Na10(OH2)42[{Dy(H2O)6}2Mn4P4W30O112(H2O)2]·17H2O (Dy2Mn4-P2W15). Single-crystal X-ray diffraction revealed that Dy2Mn4-P2W15 crystallizes in the triclinic system with space group P 1 ¯ , and consists of a tetranuclear manganese(II)-substituted sandwich-type phosphotungstate [Mn4(H2O)2(P2W15O56)2]16− (Mn4-P2W15), Na, and DyIII cations. Compound Dy2Mn4-P2W15 exhibits a 1D ladder-like chain structure based on sandwich-type segments and dysprosium cations as linkers, which are further connected into a three-dimensional open framework by sodium cations. The title compound was structurally and compositionally characterized in solid state by single-crystal XRD, powder X-ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric (TGA), and elemental analyses. Further, the absorption and emission electronic spectra in aqueous solutions of Dy2Mn4-P2W15 and Mn4-P2W15 were studied. Also, magnetic properties were studied and compared with the magnetic behavior of [Mn4(H2O)2(P2W15O56)2]16−. Full article
(This article belongs to the Special Issue Polyoxometalate and Nanohybrid Materials)
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Open AccessArticle Analogies between Vanadoborates and Planar Aromatic Hydrocarbons: A High-Spin Analogue of Aromaticity
Materials 2018, 11(1), 15; https://doi.org/10.3390/ma11010015
Received: 8 December 2017 / Revised: 19 December 2017 / Accepted: 22 December 2017 / Published: 23 December 2017
PDF Full-text (930 KB) | HTML Full-text | XML Full-text
Abstract
The vanadium-vanadium interactions in the polygonal aggregates of d1 vanadium(IV) atoms, with a total of 4k + 2 vanadium electrons (k an integer) imbedded in an electronically inactive borate matrix in certain vanadoborate structures are analogous to the ring carbon-carbon
[...] Read more.
The vanadium-vanadium interactions in the polygonal aggregates of d1 vanadium(IV) atoms, with a total of 4k + 2 vanadium electrons (k an integer) imbedded in an electronically inactive borate matrix in certain vanadoborate structures are analogous to the ring carbon-carbon interactions in diamagnetic planar cyclic hydrocarbons. They thus represent a high-spin analogue of aromaticity. Thus, the vanadoborate anion [V6B20O50H8]8− with six V(IV) electrons (i.e., 4k + 2 for k = 1) contains a macrohexagon of d1 V(IV) atoms with four unpaired electrons. This high-spin system is related to the low-spin aromaticity in the diamagnetic benzene having six π electrons. Similarly, the vanadoborate anion [V10B28O74H8]16− with ten V(IV) electrons (i.e., 4k + 2 for k = 2) contains a macrodecagon of d1 V(IV) atoms with eight unpaired electrons. Again, this high-spin system is related to the aromaticity in the diamagnetic 1,6-methanol[10]annulene, having ten π electrons. Full article
(This article belongs to the Special Issue Polyoxometalate and Nanohybrid Materials)
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Open AccessArticle Enhanced Activity of Au/NiO Nanohybrids for the Reductive Amination of Benzyl Alcohol
Materials 2017, 10(12), 1435; https://doi.org/10.3390/ma10121435
Received: 16 November 2017 / Revised: 14 December 2017 / Accepted: 15 December 2017 / Published: 16 December 2017
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Abstract
Gold nanoparticles were prepared by sol immobilization (AuSI) or deposition precipitation (AuDP), then deposited on NiO and commercial TiO2 (P25). The Au/NiO catalysts showed higher activity and yield to the secondary amine, compared to Au/TiO2 catalysts, when
[...] Read more.
Gold nanoparticles were prepared by sol immobilization (AuSI) or deposition precipitation (AuDP), then deposited on NiO and commercial TiO2 (P25). The Au/NiO catalysts showed higher activity and yield to the secondary amine, compared to Au/TiO2 catalysts, when tested for the reductive amination of benzyl alcohol with isopropylamine. We attribute this result to a synergistic effect between Au and NiO. Moreover, as a result of the protective effect of the polyvinyl alcohol used in the sol immobilization synthesis, the gold nanoparticles on NiO demonstrate an increased resistance to structural changes during the reaction. This effect results in enhanced catalytic efficiency in terms of activity, and better stability against deactivation. Full article
(This article belongs to the Special Issue Polyoxometalate and Nanohybrid Materials)
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Open AccessArticle An Investigation of Polyoxometalate Hybrid Materials as Patternable Dielectrics and Lithographic Resists
Materials 2017, 10(11), 1309; https://doi.org/10.3390/ma10111309
Received: 1 November 2017 / Revised: 8 November 2017 / Accepted: 9 November 2017 / Published: 15 November 2017
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Abstract
Polyoxometalate (POM) hybrid materials have shown potential as spin-coatable, patternable dielectric thin-films and components for lithographic resists. In particular, the octamolybdate cluster has been shown to possess good spin-coating properties and the patterning capabilities of hybrid octamolybdate thin-films were explored using a combination
[...] Read more.
Polyoxometalate (POM) hybrid materials have shown potential as spin-coatable, patternable dielectric thin-films and components for lithographic resists. In particular, the octamolybdate cluster has been shown to possess good spin-coating properties and the patterning capabilities of hybrid octamolybdate thin-films were explored using a combination of broadband UV and electron beam lithography (EBL) techiniques. Dielectric properties of these films were determined by ellipsometry, and octamolybdate clusters were subsequently investigated as negative resists in various blends for potential uses in next-generation photolithography, where contrast, sensitivity, and line edge roughness characteristics were determined. Preliminary evidence for the suppression of the diffusion of photo-generated acids is presented. Full article
(This article belongs to the Special Issue Polyoxometalate and Nanohybrid Materials)
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