Special Issue "Functional Organic-Inorganic Interfaces for Enhancing Catalysis"

A special issue of Catalysts (ISSN 2073-4344).

Deadline for manuscript submissions: 30 June 2020.

Special Issue Editors

Prof. Gloria Berlier
Website
Guest Editor
Università di Torino, NIS Centre (Nanostructured Surfaces and Interfaces), Department of Chemistry, Torino, Italy
Interests: heterogeneous catalysis; organic–inorganic interfaces; porous materials; operando/in situ spectroscopy; structure–property correlations
Prof. Enrica Gianotti
Website
Guest Editor
Department of Sciences and Technological Innovation, University of Eastern Piedmont, Alessandria, Italy
Interests: heterogeneous catalysis; organic–inorganic interfaces; synthesis of nanomaterials; in situ physicochemical characterization
Special Issues and Collections in MDPI journals
Dr. Valentina Crocellà
Website
Guest Editor
Università di Torino, NIS Centre (Nanostructured Surfaces and Interfaces), Department of Chemistry, Torino, Italy
Interests: heterogeneous catalysis; organic–inorganic interfaces; operando/in situ spectroscopy; synthesis of multifunctional porous materials

Special Issue Information

Dear Colleagues,

The demand for materials with particular and specific physico-chemical properties is constantly increasing. Thus, new multifunctional hybrid systems (based on inorganic oxides, organic moieties, metallic complexes or polymers) are being synthesised for a wide range of applications. Organic–inorganic hybrids may combine the advantages of inorganic solids (high mechanical, thermal and structural stability) and organic molecules or macromolecules (flexibility and functionality). This is particularly important in the field of catalysis, due to the intrinsic limitations of heterogeneous (nature of active sites and related catalytic performance) and homogeneous catalysts, which can catalyze a larger variety of reactions with high selectivity but suffer from recyclability issues. Moreover, multifunctional hybrid catalysts can be designed for tandem or cascade reactions. This has opened a fascinating field of research, with unprecedented complexity degrees related to the organic–inorganic interface. This Special Issue of Catalysts is aimed at providing an overview on the many aspects of hybrid catalysts, including smart design, advanced synthetic approaches, catalytic activity, physico-chemical characterization (including in situ and operando studies), computational modeling and structure-properties correlations.

We invite you to submit a full paper, communication or review article to this Special Issue, "Functional Organic–Inorganic Interfaces for Enhancing Catalysis ".

Dr. Gloria Berlier
Prof. Enrica Gianotti
Dr. Valentina Crocellà
Guest Editors

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. Catalysts 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 1800 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.

Keywords

  • Heterogeneous Catalysis
  • Hybrid Materials and Processes
  • Functional materials
  • Bifunctional and Cooperative Catalysis
  • Organic-inorganic interfaces
  • Interface characterization
  • Molecular scale characterization
  • In situ studies of surface interactions
  • Operando Spectroscopy
  • Computational modeling

Published Papers (4 papers)

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Research

Open AccessArticle
Catalytic Activity of Hybrid Iron Oxide Silver Nanoparticles in Methyl Methacrylate Polymerization
Catalysts 2020, 10(4), 422; https://doi.org/10.3390/catal10040422 - 12 Apr 2020
Abstract
One of the challenges in the preparation of poly(methyl methacrylate) (PMMA) is to develop new catalytic systems with improved efficiency. A hybrid iron oxide silver catalyst holds promise in solving this issue. Catalysts were prepared at room temperature by a two-step technique. First, [...] Read more.
One of the challenges in the preparation of poly(methyl methacrylate) (PMMA) is to develop new catalytic systems with improved efficiency. A hybrid iron oxide silver catalyst holds promise in solving this issue. Catalysts were prepared at room temperature by a two-step technique. First, iron oxide nanoparticles were prepared by the reduction of FeCl3 using sodium borohydride (NaBH4) at room temperature. Second, magnetic nanoparticles doped with a series of Ag nanoparticles (Ag, Ag/3 –amino propyltriethoxysilane (APTES) and Ag/poly(ethyleneimine) (PEI)). The prepared catalysts were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic light scattering (DLS), scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), and Fourier-transform infrared spectroscopy (FTIR). The catalytic activity of Fe, Ag/Fe, PEI–Ag/Fe, and APTES–Ag/Fe in methyl methacrylate (MMA) polymerization was investigated in the presence of O2, N2, NaHSO3, and benzoyl peroxide in bulk or solution conditions. The produced polymer was characterized by gel permeation chromatography (GPC) and proton nuclear magnetic resonance spectroscopy (1HNMR). The structures of PEI–Ag/Fe and APTES–Ag/Fe are assumed. The conversion efficiency was 100%, 100%, 97.6%, and 99.1% using Fe, Ag/Fe, PEI–Ag/Fe, and APTES–Ag/Fe catalysts at the optimum conditions, respectively. Hybrid iron oxide silver nanoparticles are promising catalysts for PMMA preparation. Full article
(This article belongs to the Special Issue Functional Organic-Inorganic Interfaces for Enhancing Catalysis)
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Open AccessArticle
Influence of the Framework Topology on the Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas
Catalysts 2019, 9(8), 654; https://doi.org/10.3390/catal9080654 - 31 Jul 2019
Abstract
Three families of organosiliceous materials with different structuration level, order, and textural properties (non-ordered, M41S, and SBA-15 type materials) were prepared incorporating in their structural framework chiral pyrrolidine units with variable content. Likewise, non-ordered mesoporous hybrid solids were obtained through a sol-gel process [...] Read more.
Three families of organosiliceous materials with different structuration level, order, and textural properties (non-ordered, M41S, and SBA-15 type materials) were prepared incorporating in their structural framework chiral pyrrolidine units with variable content. Likewise, non-ordered mesoporous hybrid solids were obtained through a sol-gel process in a fluoride medium, while M41S and SBA-15 type materials were obtained through micellar routes in the presence of long-chain neutral surfactants or block copolymers. Thanks to appropriate characterization studies and catalytic tests for the Michael addition between butyraldehyde and β-nitrostyrene, we showed how the void shapes and sizes present in the structure of hybrid materials control the diffusion of reactants and products, as well as confine transition states and reactive intermediates. The best catalytic results, considering activity and enantioselectivity, were achieved in the presence of a non-ordered material, NOH-Pyr-5%, which exhibited the highest Brunauer-Emmett-Teller (BET) area, with a 96% yield and a 82% ee for the Michael adduct. Full article
(This article belongs to the Special Issue Functional Organic-Inorganic Interfaces for Enhancing Catalysis)
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Open AccessArticle
Reduced Graphene Oxide–P25 Nanocomposites as Efficient Photocatalysts for Degradation of Bisphenol A in Water
Catalysts 2019, 9(7), 607; https://doi.org/10.3390/catal9070607 - 17 Jul 2019
Cited by 4
Abstract
Reduced graphene oxide–titanium dioxide photocatalyst (rGO–TiO2) was successfully synthesized by the hydrothermal method. The rGO–TiO2 was used as photocatalyst for the degradation of bisphenol A (BPA), which is a typical endocrine disruptor of the environment. Characterization of photocatalysts and photocatalytic [...] Read more.
Reduced graphene oxide–titanium dioxide photocatalyst (rGO–TiO2) was successfully synthesized by the hydrothermal method. The rGO–TiO2 was used as photocatalyst for the degradation of bisphenol A (BPA), which is a typical endocrine disruptor of the environment. Characterization of photocatalysts and photocatalytic experiments under different conditions were performed for studying the structure and properties of photocatalysts. The characterization results showed that part of the anatase type TiO2 was converted into rutile type TiO2 after hydrothermal treatment and 1% rGO–P25 had the largest specific surface area (52.174 m2/g). Photocatalytic experiments indicated that 1% rGO–P25 had the best catalytic effect, and the most suitable concentration was 0.5 g/L. When the solution pH was 5.98, the catalyst was the most active. Under visible light, the three photocatalytic mechanisms were ranked as follows: O2•− > •OH > h+. 1% rGO–P25 also had strong photocatalytic activity in the photocatalytic degradation of BPA under sunlight irradiation. 1% rGO–P25 with 0.5 g/L may be a very promising photocatalyst with a variety of light sources, especially under sunlight for practical applications. Full article
(This article belongs to the Special Issue Functional Organic-Inorganic Interfaces for Enhancing Catalysis)
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Open AccessArticle
Polyaniline-Grafted RuO2-TiO2 Heterostructure for the Catalysed Degradation of Methyl Orange in Darkness
Catalysts 2019, 9(7), 578; https://doi.org/10.3390/catal9070578 - 30 Jun 2019
Cited by 3
Abstract
Massive industrial and agricultural developments have led to adverse effects of environmental pollution resisting conventional treatment processes. The issue can be addressed via heterogeneous photocatalysis as witnessed recently. Herein, we have developed novel metal/semi-conductor/polymer nanocomposite for the catalyzed degradation and mineralization of a [...] Read more.
Massive industrial and agricultural developments have led to adverse effects of environmental pollution resisting conventional treatment processes. The issue can be addressed via heterogeneous photocatalysis as witnessed recently. Herein, we have developed novel metal/semi-conductor/polymer nanocomposite for the catalyzed degradation and mineralization of a model organic dye pollutant in darkness. RuO2-TiO2 mixed oxide nanoparticles (NPs) were modified with diphenyl amino (DPA) groups from the 4-diphenylamine diazonium salt precursor. The latter was reduced with ascorbic acid to provide radicals that modified the NPs and further served for in situ synthesis of polyaniline (PANI) that resulted in RuO2/TiO2-DPA-PANI nanocomposite catalyst. Excellent adhesion of PANI to RuO2/TiO2-DPA was noted but not in the case of the bare mixed oxide. This stresses the central role of diazonium compounds to tether PANI to the underlying mixed oxide. RuO2-TiO2/DPA/PANI nanocomposite revealed superior catalytic properties in the degradation of Methyl Orange (MO) compared to RuO2-TiO2/PANI and RuO2-TiO2. Interestingly, it is active even in the darkness due to high PANI mass loading. In addition, PANI constitutes a protective layer of RuO2-TiO2 NPs that permitted us to reuse the RuO2-TiO2/DPA/PANI nanocomposite nine times, whereas RuO2-TiO2/PANI and RuO2-TiO2 were reused seven and five times only, respectively. The electronic displacements at the interface of the heterojunction metal/semi-conductor under visible light and the synergistic effects between PANI and RuO2 result in the separation of electron-hole pairs and a reduction of its recombination rate as well as a significant catalytic activity of RuO2-TiO2/DPA/PANI under simulated sunlight and in the dark, respectively. Full article
(This article belongs to the Special Issue Functional Organic-Inorganic Interfaces for Enhancing Catalysis)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Investigating the role of silica-anchored cyclodextrin derivatives to stabilize catalytically active copper and palladium species
Authors: Berlier, E. Borfecchia F. Calsolaro, G. Cravotto, K. Martina, J. Menzio, M. J. Moran Plata, C. Negri
Affiliation: Dipartimento di Scienza e Tecnologia del Farmaco, University of Turin, Italy
Department of Chemistry and NIS centre, University of Turin, Italy
Abstract: Supported metallic species have appeared as valuable catalysts in green chemistry because their high efficiency enable a wide applicability even at industrial scale. Silica is a versatile support capable to host metals enhancing stability and reactivity. Organic-inorganic hybrid materials have been widely used in this field and an efficient grafting of cyclodextrin onto the inorganic silica surface has been recently object of our study. In the present work we report the preparation of new solid supported copper and palladium catalysts mono or bimetallic. With the aim to effectively immobilize and stabilize the catalyst we exploited the features of β-CD derivative. The prepared catalysts were characterized about their physico-chemical properties by means of structural, textural and spectroscopic techniques, with the aim to investigate the structure of the β-CD stabilized metal species and to correlate their properties (dispersion, nuclearity, coordination and oxidation state) to their activity. To this aim, the catalyst were tested in coupling and in CH activation reactions, as well as in Cu(II) catalysed procedures.

Article Type: Article
Title: Hybrid catalysts based on carbene anchored on inorganic supports with hierarchical porosity
Authors:
Enrica Gianotti1*, Ivana Miletto1, Chiara Ivaldi1, Geo Paul1, Leonardo Marchese1, Marta Meazza2, Ramon Rios2 and Robert Raja2
Affiliations:
1   Dipartimento di Scienze e Innovazione Tecnologica, Università del Piemonte Orientale, V. T. Michel 11, I-15100 Alessandria, Italy.
2   School of Chemistry, University of Southampton, University Road, Southampton, SO17 1BJ, U.K.
*   Correspondence: [email protected]
Abstract:
Hybrid organic-inorganic catalysts have been synthesized by anchoring N-heterocyclic carbene (NHC) on different inorganic supports with hierarchical porosity, in particular hierarchical HZSM-5 and SAPO-5. Hierarchical inorganic supports have been obtained both by top-down and bottom-up approaches and the role of hierarchical porosity has been evaluated. A detailed physico-chemical characterization has been performed on the hybrid organic-inorganic catalysts using a multi-techniques approach (XRD, volumetric analysis, ss-NMR and FTIR) in order to establish structure-properties relationship. Preliminary catalytic tests for benzoin condensation reactions were also performed.

Title: Influence of the Framework Topology on Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas
Authors: Sebastián Llopis, Alexandra Velty and Urbano Díaz *
Affiliation: Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, Avenida de los Naranjos s/n, E-46022 Valencia, Spain
*Correspondence: [email protected]; Tel.: +34963877811
Abstract: Three families of organosiliceous materials with different structuration level, order and textural properties (non-ordered, M41S and SBA-15 type materials) were prepared incorporating in their structural framework chiral pyrrolidine units with variable content. Likewise non-ordered mesoporous hybrid solids were obtained through a sol-gel process in fluoride medium while M41S and SBA-15 type materials were obtained through micellar routes with the presence of long chain neutral surfactants or block copolymers. Thanks to appropriate characterization studies and catalytic tests for the Michael addition between butyraldehyde and b-nitrostyrene, we showed how the void shapes and sizes present in the structure of hybrid materials control the diffusion of reactants and products as well as confine transition states and reactive intermediates. The best catalytic results, considering activity and enantioselectivity, were achieved in the presence of non-ordered material, NOH-Pyr-5%, that exhibited the highest BET area, with 96% yield and of 82% ee for the Michael adduct.

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