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Special Issue "Advances in Functional Hybrid Materials"

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

Deadline for manuscript submissions: closed (31 December 2013)

Special Issue Editor

Guest Editor
Dr. Silvia Gross (Website)

Istituto per l'Energetica e le Interfasi, IENI-CNR, 35131- Padova, Italy; Dipartimento di Scienze Chimiche, University of Padova, Via Marzolo, 1, 35131- Padova, Italy
Fax: +39 049 8275161
Interests: organic-inorganic hybrid materials; inorganic materials; inorganic coatings; sol-gel; hybrid coatings; surface characterisation

Special Issue Information

Dear Colleagues,

As witnessed by the publication, in the last 20 years, of over 10.000 papers on this wide class of materials, the filing of about 500 patents (source: SciFinder), four dedicated textbooks, several thematic sessions at international conferences and dedicated specialized conferences, organic-inorganic hybrid materials have attracted, in the last decades, a sharply increasing interest, from both the scientific and the technological point of view. The manifold and exciting properties of functional organic-inorganic hybrid materials have to be traced back to the intimate merging, often mediated by the formation of strong chemical bonds, between inorganic and organic building blocks, whose i) chemical nature, ii) structure iii) molar ratios and iv) mutual arrangement of building blocks do remarkably affect the final properties of the resulting materials. Despite the ongoing interest, hybrid materials still present unexplored and challenging issues, deriving from compositional and structural variability. In this framework, the tailoring of their features to achieve enhanced functional (i.e. magnetic, electrical, optical, electrochemical, catalytic, biological etc.) properties represents an intriguing challenge for scientists. In particular, molecularly homogeneous hybrid materials characterized by the formation of strong chemical bonds between the components disclose interesting perspectives in the achievements of new and improved functional performances.
This special issue of Materials will be focused i) on the design and optimization of original synthetic routes for functional inorganic-organic hybrid materials endowed with enhanced functional properties and ii) on their manifold applications. It will further center on the elucidation of structure-property relationships, as well as on the control of organic/inorganic interfaces and on the organization of hybrid building blocks on the micro- and macroscopic scale.

Dr. Silvia Gross
Guest Editor

Submission

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. Papers will be published continuously (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as 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 refereed through a 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 1400 CHF (Swiss Francs).

Keywords

  • organic-inorganic hybrid materials
  • synthesis routes
  • wet chemistry
  • soft chemistry
  • sol-gel
  • polymerization
  • building blocks
  • hierarchical Organization
  • silica-based hybrid Materials
  • porous Structures
  • functional properties

Published Papers (8 papers)

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Research

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Open AccessArticle Limits of ZnO Electrodeposition in Mesoporous Tin Doped Indium Oxide Films in View of Application in Dye-Sensitized Solar Cells
Materials 2014, 7(4), 3291-3304; doi:10.3390/ma7043291
Received: 12 February 2014 / Revised: 24 March 2014 / Accepted: 14 April 2014 / Published: 23 April 2014
PDF Full-text (742 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Well-ordered 3D mesoporous indium tin oxide (ITO) films obtained by a templated sol-gel route are discussed as conductive porous current collectors. This paper explores the use of such films modified by electrochemical deposition of zinc oxide (ZnO) on the pore walls to [...] Read more.
Well-ordered 3D mesoporous indium tin oxide (ITO) films obtained by a templated sol-gel route are discussed as conductive porous current collectors. This paper explores the use of such films modified by electrochemical deposition of zinc oxide (ZnO) on the pore walls to improve the electron transport in dye-sensitized solar cells (DSSCs). Mesoporous ITO film were dip-coated with pore sizes of 20–25 nm and 40–45 nm employing novel poly(isobutylene)-b-poly(ethylene oxide) block copolymers as structure-directors. After electrochemical deposition of ZnO and sensitization with the indoline dye D149 the films were tested as photoanodes in DSSCs. Short ZnO deposition times led to strong back reaction of photogenerated electrons from non-covered ITO to the electrolyte. ITO films with larger pores enabled longer ZnO deposition times before pore blocking occurred, resulting in higher efficiencies, which could be further increased by using thicker ITO films consisting of five layers, but were still lower compared to nanoporous ZnO films electrodeposited on flat ITO. The major factors that currently limit the application are the still low thickness of the mesoporous ITO films, too small pore sizes and non-ideal geometries that do not allow obtaining full coverage of the ITO surface with ZnO before pore blocking occurs. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)
Figures

Open AccessArticle Interaction and UV-Stability of Various Organic Capping Agents on the Surface of Anatase Nanoparticles
Materials 2014, 7(4), 2890-2912; doi:10.3390/ma7042890
Received: 29 December 2013 / Revised: 20 March 2014 / Accepted: 25 March 2014 / Published: 10 April 2014
Cited by 8 | PDF Full-text (681 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Anatase nanoparticles synthesized by the sol-gel method were surface-functionalized with long alkyl chain coupling agents as compatibilizers for a nonpolar environment, containing different anchor groups for surface interaction namely phosphonate (dodecyl phosphonate), carboxylate (dodecanoic acid), sulfate (sodium dodecyl sulphate), and amine (dodecyl [...] Read more.
Anatase nanoparticles synthesized by the sol-gel method were surface-functionalized with long alkyl chain coupling agents as compatibilizers for a nonpolar environment, containing different anchor groups for surface interaction namely phosphonate (dodecyl phosphonate), carboxylate (dodecanoic acid), sulfate (sodium dodecyl sulphate), and amine (dodecyl amine). It was shown that the surface of the nanoparticles can be functionalized with the various surface groups applying similar reaction conditions. The kind of surface interaction was analyzed applying FTIR spectroscopy. The phosphonate and the carboxylate groups interact with the surface via quite strong covalent or coordinative interactions, respectively. The sulfate and amine based coupling agents on the other hand exhibit electrostatic interactions. UV stability studies of the surface bound groups revealed different degradation mechanisms for the various functionalities and moreover showed that phosphonates are the most stable among the investigated surface capping groups. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)
Figures

Open AccessArticle Shape Memory Properties of PBS-Silica Hybrids
Materials 2014, 7(2), 751-768; doi:10.3390/ma7020751
Received: 23 December 2013 / Revised: 21 January 2014 / Accepted: 22 January 2014 / Published: 27 January 2014
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Abstract
A series of novel Si–O–Si crosslinked organic/inorganic hybrid semi-crystalline polymers with shape memory properties was prepared from alkoxysilane-terminated poly(butylene succinate) (PBS) by water-induced silane crosslinking under organic solvent-free and catalyst-free conditions. The hydrolyzation and condensation of alkoxysilane end groups allowed for the [...] Read more.
A series of novel Si–O–Si crosslinked organic/inorganic hybrid semi-crystalline polymers with shape memory properties was prepared from alkoxysilane-terminated poly(butylene succinate) (PBS) by water-induced silane crosslinking under organic solvent-free and catalyst-free conditions. The hydrolyzation and condensation of alkoxysilane end groups allowed for the generation of silica-like crosslinking points between the polymeric chains, acting not only as chemical net-points, but also as inorganic filler for a reinforcement effect. The resulting networks were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic-mechanical analysis (DMA) and tensile and shape memory tests to gain insight into the relationship between the polymeric structure, the morphology and the properties. By controlling the molecular weight of the PBS precursor, a fine tuning of the crosslinking density and the inorganic content of the resulting network was possible, leading to different thermal, mechanical and shape memory properties. Thanks to their suitable morphology consisting of crystalline domains, which represent the molecular switches between the temporary and permanent shapes, and chemical net-points, which permit the shape recovery, the synthesized materials showed good shape memory characteristics, being able to fix a significant portion of the applied strain in a temporary shape and to restore their original shape above their melting temperature. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)
Open AccessArticle Uniform and Conformal Carbon Nanofilms Produced Based on Molecular Layer Deposition
Materials 2013, 6(12), 5602-5612; doi:10.3390/ma6125602
Received: 3 November 2013 / Revised: 12 November 2013 / Accepted: 25 November 2013 / Published: 2 December 2013
Cited by 9 | PDF Full-text (998 KB) | HTML Full-text | XML Full-text
Abstract
Continuous and uniform carbon nanofilms (CNFs) are prepared by pyrolysis of polyimide films which are produced by molecular layer deposition (MLD). The film thickness can be easily controlled at nanometer scale by altering the cycle numbers. During the annealing process at 600 [...] Read more.
Continuous and uniform carbon nanofilms (CNFs) are prepared by pyrolysis of polyimide films which are produced by molecular layer deposition (MLD). The film thickness can be easily controlled at nanometer scale by altering the cycle numbers. During the annealing process at 600 °C, the polyimide film is subject to shrinkage of 70% in thickness. The obtained CNFs do not exhibit a well-graphitized structure due to the low calcination temperature. No clear pore structures are observed in the produced films. CNFs grown on a glass substrate with a thickness of about 1.4 nm shows almost 98% optical transmittance in the visible spectrum range. Au nanoparticles coated with CNFs are produced by this method. Carbon nanotubes with uniform wall thickness are obtained using anodic aluminum oxide as a template by depositing polyimide films into its pores. Our results demonstrate that this method is very effective to coat conformal and uniform CNFs on various substrates, such as nanoparticles and porous templates, to produce functional composite nanomaterials. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)

Review

Jump to: Research

Open AccessReview Synthetic Strategies in the Preparation of Polymer/Inorganic Hybrid Nanoparticles
Materials 2014, 7(5), 4057-4087; doi:10.3390/ma7054057
Received: 24 February 2014 / Revised: 12 April 2014 / Accepted: 9 May 2014 / Published: 22 May 2014
Cited by 23 | PDF Full-text (1422 KB) | HTML Full-text | XML Full-text | Correction
Abstract
This article reviews the recent advances and challenges in the preparation of polymer/inorganic hybrid nanoparticles. We mainly focus on synthetic strategies, basing our classification on whether the inorganic and the polymer components have been formed in situ or ex situ, of [...] Read more.
This article reviews the recent advances and challenges in the preparation of polymer/inorganic hybrid nanoparticles. We mainly focus on synthetic strategies, basing our classification on whether the inorganic and the polymer components have been formed in situ or ex situ, of the hybrid material. Accordingly, four types of strategies are identified and described, referring to recent examples: (i) ex situ formation of the components and subsequent attachment or integration, either by covalent or noncovalent bonding; (ii) in situ polymerization in the presence of ex situ formed inorganic nanoparticles; (iii) in situ precipitation of the inorganic components on or in polymer structures; and (iv) strategies in which both polymer and inorganic component are simultaneously formed in situ. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)
Open AccessReview Hybrid Materials Based on the Embedding of Organically Modified Transition Metal Oxoclusters or Polyoxometalates into Polymers for Functional Applications: A Review
Materials 2014, 7(5), 3956-3989; doi:10.3390/ma7053956
Received: 12 February 2014 / Revised: 22 April 2014 / Accepted: 25 April 2014 / Published: 20 May 2014
Cited by 26 | PDF Full-text (885 KB) | HTML Full-text | XML Full-text
Abstract
The covalent incorporation of inorganic building blocks into a polymer matrix to obtain stable and robust materials is a widely used concept in the field of organic-inorganic hybrid materials, and encompasses the use of different inorganic systems including (but not limited to) [...] Read more.
The covalent incorporation of inorganic building blocks into a polymer matrix to obtain stable and robust materials is a widely used concept in the field of organic-inorganic hybrid materials, and encompasses the use of different inorganic systems including (but not limited to) nanoparticles, mono- and polynuclear metal complexes and clusters, polyhedral oligomeric silsesquioxanes (POSS), polyoxometalates (POM), layered inorganic systems, inorganic fibers, and whiskers. In this paper, we will review the use of two particular kinds of structurally well-defined inorganic building blocks, namely transition metals oxoclusters (TMO) and polyoxometalates (POM), to obtain hybrid materials with enhanced functional (e.g., optical, dielectric, magnetic, catalytic) properties. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)
Open AccessReview Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials
Materials 2014, 7(4), 2978-3001; doi:10.3390/ma7042978
Received: 13 February 2014 / Revised: 19 March 2014 / Accepted: 25 March 2014 / Published: 11 April 2014
Cited by 2 | PDF Full-text (1162 KB) | HTML Full-text | XML Full-text
Abstract
The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS) recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA), mostly a silylated ammonium [...] Read more.
The synthesis of nanostructured anionic-surfactant-templated mesoporous silica (AMS) recently appeared as a new strategy for the formation of nanostructured silica based materials. This method is based on the use of anionic surfactants together with a co-structure-directing agent (CSDA), mostly a silylated ammonium precursor. The presence of this CSDA is necessary in order to create ionic interactions between template and silica forming phases and to ensure sufficient affinity between the two phases. This synthetic strategy was for the first time applied in view of the synthesis of surface functionalized silica bearing ammonium groups and was then extended on the formation of materials functionalized with anionic carboxylate and bifunctional amine-carboxylate groups. In the field of silica hybrid materials, the “anionic templating” strategy has recently been applied for the synthesis of silica hybrid materials from cationic precursors. Starting from di- or oligosilylated imidazolium and ammonium precursors, only template directed hydrolysis-polycondensation reactions involving complementary anionic surfactants allowed accessing structured ionosilica hybrid materials. The mechanistic particularity of this approach resides in the formation of precursor-surfactant ion pairs in the hydrolysis-polycondensation mixture. This review gives a systematic overview over the various types of materials accessed from this cooperative ionic templating approach and highlights the high potential of this original strategy for the formation of nanostructured silica based materials which appears as a complementary strategy to conventional soft templating approaches. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)
Figures

Open AccessReview Versatility of Evaporation-Induced Self-Assembly (EISA) Method for Preparation of Mesoporous TiO2 for Energy and Environmental Applications
Materials 2014, 7(4), 2697-2746; doi:10.3390/ma7042697
Received: 30 December 2013 / Revised: 25 February 2014 / Accepted: 24 March 2014 / Published: 31 March 2014
Cited by 14 | PDF Full-text (1792 KB) | HTML Full-text | XML Full-text
Abstract
Evaporation-Induced Self-Assembly (EISA) method for the preparation of mesoporous titanium dioxide materials is reviewed. The versatility of EISA method for the rapid and facile synthesis of TiO2 thin films and powders is highlighted. Non-ionic surfactants such as Pluronic P123, F127 and [...] Read more.
Evaporation-Induced Self-Assembly (EISA) method for the preparation of mesoporous titanium dioxide materials is reviewed. The versatility of EISA method for the rapid and facile synthesis of TiO2 thin films and powders is highlighted. Non-ionic surfactants such as Pluronic P123, F127 and cationic surfactants such as cetyltrimethylammonium bromide have been extensively employed for the preparation of mesoporous TiO2. In particular, EISA method allows for fabrication of highly uniform, robust, crack-free films with controllable thickness. Eleven characterization techniques for elucidating the structure of the EISA prepared mesoporous TiO2 are discussed in this paper. These many characterization methods provide a holistic picture of the structure of mesoporous TiO2. Mesoporous titanium dioxide materials have been employed in several applications that include Dye Sensitized Solar Cells (DSSCs), photocatalytic degradation of organics and splitting of water, and batteries. Full article
(This article belongs to the Special Issue Advances in Functional Hybrid Materials)

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