Functional Organic-Inorganic Interfaces for Enhancing Catalysis

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

Deadline for manuscript submissions: closed (30 June 2020) | Viewed by 20170

Special Issue Editors


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Guest Editor
NIS Centre (Nanostructured Surfaces and Interfaces), Department of Chemistry, Università di Torino, Torino, Italy
Interests: heterogeneous catalysis; organic–inorganic interfaces; porous materials; operando/in situ spectroscopy; structure–property correlations

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Guest Editor
Department of Sustainable Development and Ecological Transition, University of Eastern Piedmont, Vercelli, Italy
Interests: heterogeneous catalysis; organic–inorganic interfaces; synthesis of nanomaterials; in situ physicochemical characterization
Special Issues, Collections and Topics in MDPI journals

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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

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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

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Published Papers (5 papers)

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Research

16 pages, 6254 KiB  
Article
β-Cyclodextrin-Silica Hybrid: A Spatially Controllable Anchoring Strategy for Cu(II)/Cu(I) Complex Immobilization
by Federica Calsolaro, Katia Martina, Elisa Borfecchia, Fernando Chávez-Rivas, Giancarlo Cravotto and Gloria Berlier
Catalysts 2020, 10(10), 1118; https://doi.org/10.3390/catal10101118 - 27 Sep 2020
Cited by 4 | Viewed by 2602
Abstract
The development of new strategies for spatially controllable immobilization has encouraged the preparation of novel catalysts based on the organic-inorganic hybrid concept. In the present paper, a Cu-based multi-structured silica catalyst has been prepared and fully characterized. The inclusion of Cu(II) in β-cyclodextrins [...] Read more.
The development of new strategies for spatially controllable immobilization has encouraged the preparation of novel catalysts based on the organic-inorganic hybrid concept. In the present paper, a Cu-based multi-structured silica catalyst has been prepared and fully characterized. The inclusion of Cu(II) in β-cyclodextrins has been exploited with the double aim to stabilize the metal and to act as a source of Cu(I) catalytic sites. Multi-technique characterization by infrared, UV-visible, electron microscopy and X-ray absorption spectroscopies of the fresh and exhaust catalysts provided information on the local structure, redox properties and stability of the investigated hybrid systems. The catalytic system showed that copper nanospecies were dispersed on the support and hardly affected by the catalytic tests, confirming the stabilizing effect of β-CD, and likely of the N1-(3-Trimethoxysilylpropyl) diethylenetriamine spacer, as deduced by X-ray absorption spectroscopy analysis. Overall, we demonstrate a feasible approach to efficiently anchor Cu(II) species and to obtain a reusable single-site hybrid catalyst well suited for Cu(I)-catalyzed alkyne-azide cycloaddition. Full article
(This article belongs to the Special Issue Functional Organic-Inorganic Interfaces for Enhancing Catalysis)
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15 pages, 3294 KiB  
Article
Catalytic Activity of Hybrid Iron Oxide Silver Nanoparticles in Methyl Methacrylate Polymerization
by Sanaa M. Solyman, Mohamed S.A. Darwish and Jungwon Yoon
Catalysts 2020, 10(4), 422; https://doi.org/10.3390/catal10040422 - 12 Apr 2020
Cited by 6 | Viewed by 3487
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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21 pages, 3967 KiB  
Article
Influence of the Framework Topology on the Reactivity of Chiral Pyrrolidine Units Inserted in Different Porous Organosilicas
by Sebastián Llopis, Alexandra Velty and Urbano Díaz
Catalysts 2019, 9(8), 654; https://doi.org/10.3390/catal9080654 - 31 Jul 2019
Cited by 1 | Viewed by 2586
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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15 pages, 3092 KiB  
Article
Reduced Graphene Oxide–P25 Nanocomposites as Efficient Photocatalysts for Degradation of Bisphenol A in Water
by Fei Yu, Xueting Bai, Changfu Yang, Lijie Xu and Jie Ma
Catalysts 2019, 9(7), 607; https://doi.org/10.3390/catal9070607 - 17 Jul 2019
Cited by 30 | Viewed by 4490
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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34 pages, 8495 KiB  
Article
Polyaniline-Grafted RuO2-TiO2 Heterostructure for the Catalysed Degradation of Methyl Orange in Darkness
by Fatima Mousli, Ahcène Chaouchi, Mohamed Jouini, François Maurel, Abdelaziz Kadri and Mohamed M. Chehimi
Catalysts 2019, 9(7), 578; https://doi.org/10.3390/catal9070578 - 30 Jun 2019
Cited by 37 | Viewed by 6013
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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