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Advances in Functional Hybrid Materials
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Advances in Functional Hybrid Materials

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

Deadline for manuscript submissions: closed (31 December 2013) | Viewed by 92146

Special Issue Editor

Prof. Dr. Silvia Gross

E-Mail Website
Guest Editor
Department of Chemical Sciences, University of Padova, 35131 Padova, Italy
Interests: wet chemistry & colloid chemistry
Special Issues, Collections and Topics in MDPI journals

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

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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

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Published Papers (8 papers)

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Research

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742 KiB  
Article
Limits of ZnO Electrodeposition in Mesoporous Tin Doped Indium Oxide Films in View of Application in Dye-Sensitized Solar Cells
by Christian Dunkel, Till Von Graberg, Bernd M. Smarsly, Torsten Oekermann and Michael Wark
Materials 2014, 7(4), 3291-3304; https://doi.org/10.3390/ma7043291 - 23 Apr 2014
Cited by 6 | Viewed by 7788
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 improve [...] 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)
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681 KiB  
Article
Interaction and UV-Stability of Various Organic Capping Agents on the Surface of Anatase Nanoparticles
by Mohsin Raza, Angelika Bachinger, Nina Zahn and Guido Kickelbick
Materials 2014, 7(4), 2890-2912; https://doi.org/10.3390/ma7042890 - 10 Apr 2014
Cited by 35 | Viewed by 8653
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 amine). [...] 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)
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814 KiB  
Article
Shape Memory Properties of PBS-Silica Hybrids
by Katia Paderni, Paola Fabbri, Maurizio Toselli and Massimo Messori
Materials 2014, 7(2), 751-768; https://doi.org/10.3390/ma7020751 - 27 Jan 2014
Cited by 3 | Viewed by 6065
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 generation [...] 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)
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998 KiB  
Article
Uniform and Conformal Carbon Nanofilms Produced Based on Molecular Layer Deposition
by Peng Yang, Guizhen Wang, Zhe Gao, He Chen, Yong Wang and Yong Qin
Materials 2013, 6(12), 5602-5612; https://doi.org/10.3390/ma6125602 - 2 Dec 2013
Cited by 24 | Viewed by 7531
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 °C, [...] 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)
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Review

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1422 KiB  
Review
Synthetic Strategies in the Preparation of Polymer/Inorganic Hybrid Nanoparticles
by Matthew A. Hood, Margherita Mari and Rafael Muñoz-Espí
Materials 2014, 7(5), 4057-4087; https://doi.org/10.3390/ma7054057 - 22 May 2014
Cited by 160 | Viewed by 17686 | 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 the [...] 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)
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885 KiB  
Review
Hybrid Materials Based on the Embedding of Organically Modified Transition Metal Oxoclusters or Polyoxometalates into Polymers for Functional Applications: A Review
by Mauro Carraro and Silvia Gross
Materials 2014, 7(5), 3956-3989; https://doi.org/10.3390/ma7053956 - 20 May 2014
Cited by 105 | Viewed by 14583
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) nanoparticles, [...] 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)
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1162 KiB  
Review
Precursor Mediated Synthesis of Nanostructured Silicas: From Precursor-Surfactant Ion Pairs to Structured Materials
by Peter Hesemann, Thy Phung Nguyen and Samir El Hankari
Materials 2014, 7(4), 2978-3001; https://doi.org/10.3390/ma7042978 - 11 Apr 2014
Cited by 24 | Viewed by 8605
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 precursor. [...] 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)
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1792 KiB  
Review
Versatility of Evaporation-Induced Self-Assembly (EISA) Method for Preparation of Mesoporous TiO2 for Energy and Environmental Applications
by Luther Mahoney and Ranjit T. Koodali
Materials 2014, 7(4), 2697-2746; https://doi.org/10.3390/ma7042697 - 31 Mar 2014
Cited by 103 | Viewed by 19282
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 cationic [...] 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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