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Crystals
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Synthesis, Structure, and Properties of Inorganic Nanotubes
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Synthesis, Structure, and Properties of Inorganic Nanotubes

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Inorganic Crystalline Materials".

Deadline for manuscript submissions: closed (31 October 2020) | Viewed by 33489

Special Issue Editors

Dr. Erwan Paineau

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Guest Editor
Laboratoire de Physique des Solides, CNRS, Université Paris-Saclay, Orsay, France
Interests: nanotubes; imogolite; synthesis; X-ray scattering; liquid–crystals; molecular confinement
Dr. Pascale Launois

E-Mail Website
Guest Editor
Laboratoire de Physique des Solides, CNRS, Université Paris-Saclay, Orsay, France
Interests: structure; dynamics; nanotubes; molecular nanoconfinement; X-ray and neutron scattering
Dr. Gilberto Teobaldi

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Guest Editor
Theoretical and Computational Physics Group, Scientific Computing Department, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Didcot OX11 0QX, UK
Interests: inorganic nanotubes; functional interfaces; density functional theory; photo-electrocatalysis; energy storage; emergent magnetism

Special Issue Information

Dear Colleagues,

Material scientists, biomedical researchers, and engineers are turning their attention to inorganic nanotubes as hirearchically structured multifunctional nanocontainers for next-generation devices that could outperform current technologies for nanofluidic, molecular sieving, energy storage, and health applications.

Recently developed innovative synthethic approaches open the way for elaboration of a wide variety of inorganic nanotubes of tunable properties. Understanding and control of the structure–property nexus for metal–oxide nanotubes holds the key to application in many areas, such as enhanced chemical separation, photocatalysis, and catalysis, to quote a few. Together with further improvements in the scalabality of inorganic nanotube synthesis, advances along these lines are expected to accelerate the development of industrially viable technologies based on metal–oxide nanotubes.

The proposed Special Issue is intended to be a forum for the latest research in the synthesis, structure, and properties of inorganic nanotubes, including but not limited to sulphide, phosphate, oxyde, hydroxyde, polyoxometalate, and clay nanotubes. Both theoretical and experimental research is invited and welcome.

Potential topics include (but are not limited to):

  • Advances in synthesis of new inorganic nanotubes and growth mechanisms;
  • Development of materials from these nanotubes (membranes, fibers, etc.);
  • Characterization and modelling of structure, dynamics or chemical reactivity;
  • Chemical modifications and functionalization of nanotubes and their relationships to surface properties (mechanical, chemical, electronic, etc);
  • Developments in inorganic nanotubes applications, in particular for nanocomposites functional, molecular confinement, (photo)catalysis, and the environmental field.

Dr. Erwan Paineau
Dr. Pascale Launois
Dr. Gilberto Teobaldi
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 submissions that pass pre-check are 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. Crystals 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 2100 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

  • Metal–oxide nanotubes
  • 1D porous clay minerals
  • Hydrothermal synthesis
  • Sol–gel chemistry
  • Nanotube growth
  • Density functional theory
  • Force field and/or mesoscale modelling
  • Molecular dynamics
  • Nanocomposites
  • Hydrogels
  • Structural resolution, dynamics, diffusion
  • Texture
  • Properties (e.g., mechanical or electrical properties, catalytic activity, etc.)
  • Applications in functional materials

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Further information on MDPI's Special Issue policies can be found here.

Published Papers (7 papers)

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Research

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15 pages, 4661 KiB  
Article
Influence of the Al/Ge Ratio on the Structure and Self-Organization of Anisometric Imogolite Nanotubes
by Erwan Paineau and Pascale Launois
Crystals 2020, 10(12), 1094; https://doi.org/10.3390/cryst10121094 - 28 Nov 2020
Cited by 5 | Viewed by 2847
Abstract
Synthetic imogolite-like nanotubes (INT) with well-defined diameters represent a considerable opportunity for the development of advanced functional materials. Recent progress has made it possible to increase their aspect ratio and unique self-organization properties were evidenced. We suggest that slight modification of the synthesis [...] Read more.
Synthetic imogolite-like nanotubes (INT) with well-defined diameters represent a considerable opportunity for the development of advanced functional materials. Recent progress has made it possible to increase their aspect ratio and unique self-organization properties were evidenced. We suggest that slight modification of the synthesis conditions may drastically affect the resulting liquid-crystalline properties. In this work, we investigate how the precursor’s [Al]/[Ge] molar ratio (R’) impacts the morphology and the colloidal properties of aluminogermanate INTs by combining a multi-scale characterization. While only double-walled nanotubes are found for R’ ≥ 1.8, the presence of single-walled nanotubes occurs when the ratio is lowered. Except for the lowest R’ ratio investigated (R’ = 0.66), all synthetic products present one-dimensional shapes with a high aspect ratio. Small-angle X-ray scattering experiments allow us to comprehensively investigate the colloidal properties of the final products. Our results reveal that a liquid-crystalline hexagonal columnar phase is detected down to R’ = 1.33 and that it turns into a nematic arrested phase for R’ = 0.90. These results could be useful for the development of novel stimuli-responsive nanocomposites based-on synthetic imogolite nanotubes. Full article
(This article belongs to the Special Issue Synthesis, Structure, and Properties of Inorganic Nanotubes)
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17 pages, 7090 KiB  
Article
Termination Effects in Aluminosilicate and Aluminogermanate Imogolite Nanotubes: A Density Functional Theory Study
by Emiliano Poli, Joshua D. Elliott, Ziwei Chai and Gilberto Teobaldi
Crystals 2020, 10(11), 1051; https://doi.org/10.3390/cryst10111051 - 19 Nov 2020
Cited by 7 | Viewed by 2438
Abstract
We investigate termination effects in aluminosilicate (AlSi) and aluminogermanate (AlGe) imogolite nanotubes (NTs) by means of semi-local and range-corrected hybrid Density Functional Theory (DFT) simulations. Following screening and identification of the smallest finite model capable of accommodating full relaxation of the NT terminations [...] Read more.
We investigate termination effects in aluminosilicate (AlSi) and aluminogermanate (AlGe) imogolite nanotubes (NTs) by means of semi-local and range-corrected hybrid Density Functional Theory (DFT) simulations. Following screening and identification of the smallest finite model capable of accommodating full relaxation of the NT terminations around an otherwise geometrically and electrostatically unperturbed core region, we quantify and discuss the effects of physical truncation on the structure, relative energy, electrostatics and electronic properties of differently terminated, finite-size models of the NTs. In addition to composition-dependent changes in the valence (VB) and conduction band (CB) edges and resultant band gap (BG), the DFT simulations uncover longitudinal band bending and separation in the finite AlSi and AlGe models. Depending on the given termination of the NTs, such longitudinal effects manifest in conjunction with the radial band separation typical of fully periodic AlSi and AlGe NTs. The strong composition dependence of the longitudinal and radial band bending in AlSi and AlGe NTs suggests different mechanisms for the generation, relaxation and separation of photo-generated holes in AlSi and AlGe NTs, inviting further research in the untapped potential of imogolite compositional and structural flexibility for photo-catalytic applications. Full article
(This article belongs to the Special Issue Synthesis, Structure, and Properties of Inorganic Nanotubes)
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23 pages, 7821 KiB  
Article
Water Based Synthesis of ZIF-8 Assisted by Hydrogen Bond Acceptors and Enhancement of CO2 Uptake by Solvent Assisted Ligand Exchange
by Kasama Kenyotha, Kingkaew Chayakul Chanapattharapol, Sirirath McCloskey and Phongphan Jantaharn
Crystals 2020, 10(7), 599; https://doi.org/10.3390/cryst10070599 - 10 Jul 2020
Cited by 23 | Viewed by 4881
Abstract
The aim of this work was to synthesize zeolitic imidazolate framework-8 (ZIF-8) by an alternative method and then modify the surface properties for enhancing the CO2 adsorption performance. The ZIF-8 was synthesized by a water based synthesis method using 2-methyl imidazole (2-MeIM) [...] Read more.
The aim of this work was to synthesize zeolitic imidazolate framework-8 (ZIF-8) by an alternative method and then modify the surface properties for enhancing the CO2 adsorption performance. The ZIF-8 was synthesized by a water based synthesis method using 2-methyl imidazole (2-MeIM) as a hydrogen bond donor and quaternary ammonium salts (QAS) as a hydrogen bond acceptor. The optimal synthesis conditions were investigated by varying (i) the order of precursor mixing during the synthesis process (ii) different QAS (tetrabutyl ammonium bromide (TBAB), tetraethyl ammonium bromide (TEAB) and trimethyl phenyl ammonium bromide (TMPAB)) and (iii) the ratio between 2-MeIM and QAS. The results show that the optimal synthesis condition was using TMPAB as the hydrogen bond acceptor with the ratio between 2-MeIM and TMPAB of 8:2 and in the order of first mixing both hydrogen bond donor and acceptor before adding Zn(NO3)2⋅6H2O solution. TMPAB can provide uniform size distribution with the smallest particle sizes of ZIF-8. This can be explained by the higher hydrogen bond strength between hydrogen bond donor (2-MeIM) and hydrogen bond acceptor (TMPAB) when compared with that of the rest of two QAS. The synthesized ZIF-8 was modified by solvent-assisted ligand exchange methods. The organic linker of ZIF-8 (2-MeIM) was exchanged by 2-aminobenzimidazole (2-NH2bZIM) and 2-phenylimidazole (2-PhIM). The CO2 uptake of modified ZIF-8 was enhanced upon exchanging with 2-NH2bZIM. The increase in CO2 uptake was due to an additional interaction between CO2 and exchanged imidazole linker and an increase in surface properties (higher surface area, pore size and pore volume). Full article
(This article belongs to the Special Issue Synthesis, Structure, and Properties of Inorganic Nanotubes)
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17 pages, 4135 KiB  
Article
A Comparative Study of Theoretical Methods to Estimate Semiconductor Nanoparticles’ Size
by Fernando Rodríguez-Mas, Juan Carlos Ferrer, José Luis Alonso, David Valiente and Susana Fernández de Ávila
Crystals 2020, 10(3), 226; https://doi.org/10.3390/cryst10030226 - 21 Mar 2020
Cited by 34 | Viewed by 4644
Abstract
In this paper, we compare four different methods to estimate nanoparticle diameters from optical absorption measurements, using transmission electron microscopy (TEM) images as a reference for the nanoparticle size. Three solutions of colloidal nanoparticles coated with thiophenol with different diameters were synthesized by [...] Read more.
In this paper, we compare four different methods to estimate nanoparticle diameters from optical absorption measurements, using transmission electron microscopy (TEM) images as a reference for the nanoparticle size. Three solutions of colloidal nanoparticles coated with thiophenol with different diameters were synthesized by thiolate decomposition. The nanoparticle sizes were controlled by the addition of a certain volume of a 1% sulphur solution in toluene. TEM measurements showed that the average diameter for each type of these nanoparticles was 2.8 nm, 3.2 nm, and 4.0 nm. The methods studied for the calculation of the nanoparticles diameter were: The Brus model, the hyperbolic band model (HBM), the Henglein model, and the Yu equation. We evaluated the importance of a good knowledge of the nanoparticle bandgap energy, and the nature of electronic transitions in the semiconductor. We studied the effects that small variations in the electron and hole effective mass values produced in the Brus equation and in the HBM model for CdS, PbS, and ZnS nanoparticles. Finally, a comparison was performed between the data provided by these models and the experimental results obtained with TEM images. In conclusion, we observed that the best approximation to the experimental results with TEM images was the Brus equation. However, when the bandgap energy was close to the bulk bandgap energy, the theoretical models did not adjust correctly to the size measured from the TEM images. Full article
(This article belongs to the Special Issue Synthesis, Structure, and Properties of Inorganic Nanotubes)
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12 pages, 4463 KiB  
Article
Controlled Synthesis of Magnetic Iron Oxide Nanoparticles: Magnetite or Maghemite?
by Sebastian P. Schwaminger, Christopher Syhr and Sonja Berensmeier
Crystals 2020, 10(3), 214; https://doi.org/10.3390/cryst10030214 - 19 Mar 2020
Cited by 86 | Viewed by 10319
Abstract
Today, magnetic nanoparticles are present in multiple medical and industrial applications. We take a closer look at the synthesis of magnetic iron oxide nanoparticles through the co-precipitation of iron salts in an alkaline environment. The variation of the synthesis parameters (ion concentration, temperature, [...] Read more.
Today, magnetic nanoparticles are present in multiple medical and industrial applications. We take a closer look at the synthesis of magnetic iron oxide nanoparticles through the co-precipitation of iron salts in an alkaline environment. The variation of the synthesis parameters (ion concentration, temperature, stirring rate, reaction time and dosing rate) change the structure and diameter of the nanoparticles. Magnetic iron oxide nanoparticles are characterized by X-ray diffraction (XRD), Raman spectroscopy and transmission electron microscopy (TEM). Magnetic nanoparticles ranging from 5 to 16 nm in diameter were synthesized and their chemical structure was identified. Due to the evaluation of Raman spectra, TEM and XRD, the magnetite and maghemite nanoparticles can be observed and the proportion of phases and the particle size can be related to the synthesis conditions. We want to highlight the use of Raman active modes A1g of spinel structured iron oxides to determine the content of magnetite and maghemite in our samples. Magnetite nanoparticles can be derived from highly alkaline conditions even without establishing an inert atmosphere during the synthesis. The correlation between the particle properties and the various parameters of the synthesis was modelled with linear mixture models. The two models can predict the particle size and the oxidation state of the synthesized nanoparticles, respectively. The modeling of synthesis parameters not only helps to improve synthesis conditions for iron oxide nanoparticles but to understand crystallization of nanomaterials. Full article
(This article belongs to the Special Issue Synthesis, Structure, and Properties of Inorganic Nanotubes)
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Review

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41 pages, 18944 KiB  
Review
Cation Doping Approach for Nanotubular Hydrosilicates Curvature Control and Related Applications
by Andrei A. Krasilin, Ekaterina K. Khrapova and Tatiana P. Maslennikova
Crystals 2020, 10(8), 654; https://doi.org/10.3390/cryst10080654 - 30 Jul 2020
Cited by 22 | Viewed by 3415
Abstract
The past two decades have been marked by an increased interest in the synthesis and the properties of geoinspired hydrosilicate nanoscrolls and nanotubes. The present review considers three main representatives of this group: halloysite, imogolite and chrysotile. These hydrosilicates have the ability of [...] Read more.
The past two decades have been marked by an increased interest in the synthesis and the properties of geoinspired hydrosilicate nanoscrolls and nanotubes. The present review considers three main representatives of this group: halloysite, imogolite and chrysotile. These hydrosilicates have the ability of spontaneous curling (scrolling) due to a number of crystal structure features, including the size and chemical composition differences between the sheets, (or the void in the gibbsite sheet and SiO2 tetrahedron, in the case of imogolite). Mineral nanoscrolls and nanotubes consist of the most abundant elements, like magnesium, aluminium and silicon, accompanied by uncontrollable amounts of impurities (other elements and phases), which hinder their high technology applications. The development of a synthetic approach makes it possible to not only to overcome the purity issues, but also to enhance the chemical composition of the nanotubular particles by controllable cation doping. The first part of the review covers some principles of the cation doping approach and proposes joint criteria for the semiquantitative prediction of morphological changes that occur. The second part focuses on some doping-related properties and applications, such as morphological control, uptake and release, magnetic and mechanical properties, and catalysis. Full article
(This article belongs to the Special Issue Synthesis, Structure, and Properties of Inorganic Nanotubes)
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21 pages, 4242 KiB  
Review
Quaternary Misfit Compounds—A Concise Review
by Sokhrab B. Aliev and Reshef Tenne
Crystals 2020, 10(6), 468; https://doi.org/10.3390/cryst10060468 - 1 Jun 2020
Cited by 8 | Viewed by 4061
Abstract
Misfit layered compounds (MLCs) have been studied in the literature for the last 40 years. They are generally made of an alternating sequence of two monolayers, a distorted rocksalt structure, and a hexagonal layered compound. In a typical MLC, the c-axis is [...] Read more.
Misfit layered compounds (MLCs) have been studied in the literature for the last 40 years. They are generally made of an alternating sequence of two monolayers, a distorted rocksalt structure, and a hexagonal layered compound. In a typical MLC, the c-axis is common to the two monolayers and so is one of the axes in the layer plan. However, the two compounds are non-commensurate along at least one axis, and the ratio between the two axes is an irrational number making the MLC a non-stoichiometric compound. The two main families of MLC are those based on metal dichalcogenides and CoO2 as the hexagonal layered compound. Traditionally, ternary MLCs were prepared and studied, but some quaternary and multinary MLC minerals have been known for many years. Over the last few years, interest in MLCs with four and even larger number of atoms has grown. Doping or alloying of a ternary MLC permits precise control of the charge carrier density and hence the electrical, thermoelectric, catalytic, and optical properties of such compounds. In this short review, some of these developments will be discussed with the main emphasis put on quaternary MLC nanotubes belonging to the chalcogenide series. The synthesis, structural characterization, and some of their properties are considered. Some recent developments in quaternary cobaltite MLCs and recent studies on exfoliated MLCs are discussed as well. Full article
(This article belongs to the Special Issue Synthesis, Structure, and Properties of Inorganic Nanotubes)
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