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Special Issue "Microporous/Mesoporous Inorganic Materials"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: 31 May 2019

Special Issue Editors

Guest Editor
Dr. Bénédicte Lebeau

Institut de Science des Matériaux de Mulhouse, Université de Haute Alsace, CNRS UMR 7361, France
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Fax: +33 389 336885
Interests: mesoporous oxides; materials with hierarchized porosity; sol-gel synthesis; mechanisms of formation; organic and inorganic functionalization; shaping; encapsulation/vectorization; adsorption; catalysis; thermal insulation
Guest Editor
Prof. Dr. T. Jean Daou

Axe Matériaux à Porosité Contrôlée (MPC), Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute Alsace (UHA), CNRS, UMR 7361, 68093 Mulhouse, France
Website | E-Mail
Interests: zeolites; hierarchical materials; synthesis and characterization of porous materials; Textural properties; structural properties; shaping of zeolites; molecular decontamination; energy storage or adsorption; catalysis

Special Issue Information

Dear Colleagues,

Porous materials having inorganic or hybrid frameworks delimiting a regular porous structure are promising candidates for different applications, such as catalysis, separation, ion exchange, gas storage, molecular decontamination, etc. In particular, microporous materials and mesoporous materials have exciting properties due to the size of their pore openings, their large specific surface areas and pore volumes. Recently, another class of porous materials, called hierarchical porous materials, has emerged. These materials contain at least two different types of interconnected porosities (micro/mesopores, etc.), which are known, for example, to improve the performances of the microporous counterpart thanks to an efficient mass transfer kinetics through mesopores. Porous materials are of great scientific importance from a fundamental point of view due to their ability to interact with atoms, ions, and molecules on their sizeable interior surfaces and porosity. This growing interest in porous materials has led to progress in characterization techniques and modelling studies to better understand the structure/property relationships, in order to improve the design of tailor-made porous materials with high performances. This Special Issue proposes a state-of-the-art in recent advances made in the field of inorganic and hybrid porous materials, with a focus on:

  •       New methods for the synthesis of porous materials and the control of particle size and morphology
  •       Methods for textural and structural characterization of porous materials
  •       Shaping of porous materials (films, pellets, beads, extrudates, etc.)
  •       Known applications:
          -Molecular decontamination (water and air treatments)
          -Gas storage
          -Ion-exchange
          -Molecular sieving (molecule separation, gas purification)
          -Catalysis (biomass conversion, etc.)
  •       Emerging applications:
          -Energy storage
          -Sensors
          -Health (biomedical applications)
          -Photovoltaic

Dr. Bénédicte Lebeau
Prof. Dr. T. Jean Daou
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. Molecules is an international peer-reviewed open access semimonthly 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.

Published Papers (6 papers)

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Research

Open AccessArticle
Incorporation of Brazilian Diatomite in the Synthesis of An MFI Zeolite
Molecules 2019, 24(10), 1980; https://doi.org/10.3390/molecules24101980 (registering DOI)
Received: 1 April 2019 / Revised: 17 April 2019 / Accepted: 23 April 2019 / Published: 23 May 2019
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Abstract
The need for greener procedures is a fact to reduce residues, to decrease industrial costs, and to accomplish the environmental agreements. In an attempt to address this question, we propose the addition of a natural resource, Brazilian diatomite, to an MFI zeolite traditional [...] Read more.
The need for greener procedures is a fact to reduce residues, to decrease industrial costs, and to accomplish the environmental agreements. In an attempt to address this question, we propose the addition of a natural resource, Brazilian diatomite, to an MFI zeolite traditional synthesis. We have characterized the resulting product with different techniques, such as X-ray diffraction, microscopy, and gas sorption, and, afterwards, we evaluate the greenness of the process by the Green Star method. The results were promising: We obtained the desired topology in the form of small crystallites aggregated and a pore diameter of 0.8 nm. In conclusion, the product has the necessary characteristics for an adsorption or catalytic future tests and escalation to industrial production. Full article
(This article belongs to the Special Issue Microporous/Mesoporous Inorganic Materials)
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Open AccessArticle
First-Principles Study of AlPO4-H3, a Hydrated Aluminophosphate Zeotype Containing Two Different Types of Adsorbed Water Molecules
Molecules 2019, 24(5), 922; https://doi.org/10.3390/molecules24050922
Received: 13 February 2019 / Revised: 28 February 2019 / Accepted: 1 March 2019 / Published: 6 March 2019
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Abstract
Porous aluminophosphate zeotypes (AlPOs) are promising materials for heat transformation applications using water as a working fluid. Two “types” of adsorbed water molecules can be distinguished in hydrated AlPOs: Water molecules adsorbed in the direct proximity of framework aluminium atoms form bonds to [...] Read more.
Porous aluminophosphate zeotypes (AlPOs) are promising materials for heat transformation applications using water as a working fluid. Two “types” of adsorbed water molecules can be distinguished in hydrated AlPOs: Water molecules adsorbed in the direct proximity of framework aluminium atoms form bonds to these Al atoms, with the coordination number of Al increasing from four to five or six. The remaining water molecules that are adsorbed in other parts of the accessible pore space are not strongly bonded to any framework atom, they interact with their environment exclusively through hydrogen bonds. The APC-type small-pore aluminophosphate AlPO4-H3 contains both types of H2O molecules. In the present work, this prototypical hydrated AlPO is studied using dispersion-corrected density functional theory (DFT) calculations. After validating the computations against experimental crystal structure and Raman spectroscopy data, three interrelated aspects are addressed: First, calculations for various partially hydrated models are used to establish that such partially hydrated phases are not thermodynamically stable, as the interaction with the adsorbed water molecules is distinctly weaker than in fully hydrated AlPO4-H3. Second, IR and Raman spectra are computed and compared to those of the dehydrated analogue AlPO4-C, leading to the identification of a few “fingerprint” modes that could be used as indicators for the presence of Al-coordinated water molecules. Finally, DFT-based molecular dynamics calculations are employed to study the dynamics of the adsorbed water molecules. All in all, this in-depth computational study of AlPO4-H3 contributes to the fundamental understanding of hydrated AlPOs, and should therefore provide valuable information for future computational and experimental studies of these systems. Full article
(This article belongs to the Special Issue Microporous/Mesoporous Inorganic Materials)
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Open AccessArticle
A Spectroscopic Study of Tautomeric Equilibrium of Salicylideneaniline in ZSM-5 Zeolites
Molecules 2019, 24(4), 795; https://doi.org/10.3390/molecules24040795
Received: 31 January 2019 / Revised: 18 February 2019 / Accepted: 19 February 2019 / Published: 22 February 2019
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Abstract
Salicylideneaniline (SA) sorbed in cation-exchanged M-ZSM-5 (M = H+, Li+, Na+, K+, Rb+, Cs+ and Zn2+) zeolites was studied by spectroscopic techniques assisted by quantum-chemical calculations. The nature of extra-framework [...] Read more.
Salicylideneaniline (SA) sorbed in cation-exchanged M-ZSM-5 (M = H+, Li+, Na+, K+, Rb+, Cs+ and Zn2+) zeolites was studied by spectroscopic techniques assisted by quantum-chemical calculations. The nature of extra-framework cations present in the zeolite void was found to affect the spectral signature of the sorbed SA molecule that points to the shift of tautomeric equilibrium between the enol and keto forms. Small size cations, such as H+ and Li+, stabilize a cis-keto SA tautomer along with a enol one in the zeolite structure. The calculations indicate that the sorbed cis-keto tautomer may have the dipole large enough to be considered as a zwitterion. New features appearing in the spectra with the increase of the cation size were attributed to the presence of trans-keto SA tautomer, which up to now has been observed only in time-resolved spectroscopic experiments. A strong interaction of the molecule with cations in Zn-ZSM-5 zeolite results in the chelation of enol SA with the divalent Zn2+ ions. The results of the study suggest that the tautomeric equilibrium of molecules belonging to the Schiff base family can be tuned by the confinement in the nanoporous materials via a choice of topology of zeolite framework and the nature of extra-framework cations. Full article
(This article belongs to the Special Issue Microporous/Mesoporous Inorganic Materials)
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Open AccessArticle
Synthesis of Mesoporous TiO2/Boron-Doped Diamond Photocatalyst and Its Photocatalytic Activity under Deep UV Light (λ = 222 nm) Irradiation
Molecules 2018, 23(12), 3095; https://doi.org/10.3390/molecules23123095
Received: 16 October 2018 / Revised: 6 November 2018 / Accepted: 19 November 2018 / Published: 27 November 2018
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Abstract
There is a need for highly efficient photocatalysts, particularly for water purification. In this study, we fabricated a mesoporous TiO2 thin film on a boron-doped diamond (BDD) layer by a surfactant-assisted sol-gel method, in which self-assembled amphiphilic surfactant micelles were used as [...] Read more.
There is a need for highly efficient photocatalysts, particularly for water purification. In this study, we fabricated a mesoporous TiO2 thin film on a boron-doped diamond (BDD) layer by a surfactant-assisted sol-gel method, in which self-assembled amphiphilic surfactant micelles were used as an organic template. Scanning electron microscopy revealed uniform mesopores, approximately 20 nm in diameter, that were hexagonally packed in the TiO2 thin film. Wide-angle X-ray diffraction and Raman spectroscopy clarified that the framework crystallized in the anatase phase. Current–voltage (I–V) measurements showed rectification features at the TiO2/BDD heterojunction, confirming that a p–n hetero-interface formed. The as-synthesized mesoporous TiO2/BDD worked well as a photocatalyst, even with a small volume of TiO2 (15 mm × 15 mm × c.a. 1.5 µm in thickness). The use of deep UV light (λ = 222 nm) as a light source was necessary to enhance photocatalytic activity, due to photo-excitation occurring in both BDD and TiO2. Full article
(This article belongs to the Special Issue Microporous/Mesoporous Inorganic Materials)
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Open AccessFeature PaperArticle
Synthesis of Binderless ZK-4 Zeolite Microspheres at High Temperature
Molecules 2018, 23(10), 2647; https://doi.org/10.3390/molecules23102647
Received: 17 September 2018 / Revised: 9 October 2018 / Accepted: 12 October 2018 / Published: 16 October 2018
Cited by 1 | PDF Full-text (6021 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Binderless zeolite macrostructures in the form of ZK-4 microspheres were prepared using anion-exchange resin beads as shape-directing macrotemplates. The particles were synthesized under hydrothermal conditions at different temperatures and treatment times. The influence of the different synthesis parameters was investigated by X-ray diffraction, [...] Read more.
Binderless zeolite macrostructures in the form of ZK-4 microspheres were prepared using anion-exchange resin beads as shape-directing macrotemplates. The particles were synthesized under hydrothermal conditions at different temperatures and treatment times. The influence of the different synthesis parameters was investigated by X-ray diffraction, scanning electron microscopy, fluorescence X, nitrogen adsorption measurements and 29Si solid-state NMR. Fully crystalline spheres similar in size and shape to the original resin beads were obtained by a hydrothermal treatment at the highest temperatures (150–180 °C) for a short treatment time of 24 h. The synthesized microspheres showed to be promising in the molecular decontamination of volatile organic compounds (VOCs). Full article
(This article belongs to the Special Issue Microporous/Mesoporous Inorganic Materials)
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Open AccessArticle
Influence of Synthesis Method on LTA Time-Dependent Stability
Molecules 2018, 23(9), 2122; https://doi.org/10.3390/molecules23092122
Received: 1 August 2018 / Revised: 21 August 2018 / Accepted: 22 August 2018 / Published: 23 August 2018
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Abstract
Time-stability of LTA zeolite formed by hydrothermal method with or without the action of ultrasonic irradiation was investigated by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The results show that 6 months after the synthesis by hydrothermal process with continuous sonication, [...] Read more.
Time-stability of LTA zeolite formed by hydrothermal method with or without the action of ultrasonic irradiation was investigated by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The results show that 6 months after the synthesis by hydrothermal process with continuous sonication, LTA evolves into a more stable sodalite, whereas no differences are detected 12 months after LTA synthesis by conventional pre-fused hydrothermal process. These data confirm that using the two approaches, different mechanisms control both zeolite crystallization and time-stability of the newly-formed mineral at solid state. The results are particularly important in the light of the synthetic zeolite application. Full article
(This article belongs to the Special Issue Microporous/Mesoporous Inorganic Materials)
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Graphical abstract

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