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Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Physics".

Deadline for manuscript submissions: closed (31 May 2021) | Viewed by 32871

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Prof. Dr. Federico Cesano

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Department of Chemistry, Turin University, 10125 Torino, Italy
Interests: composite/hybrid materials and nanomaterials; surface Science; microscopies and spectroscopies; catalysis and photocatalysis
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Prof. Dr. Domenica Scarano

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Department of Chemistry, University of Torino, Via P. Giuria, 7, 10125 Torino, Italy
Interests: 2D materials; carbons; oxides; polymers and their composite/hybrid materials and nanomaterials; piezoelectric and piezoresistive materials; functional materials; magnetic materials; interface and surface properties; microscopies and spectroscopies; electrical properties
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Special Issue Information

Dear Colleagues,

This Special Issue is dedicated to highlighting significant findings in the field of materials based on two-dimensional/layered systems, their hybrid structures, and composite materials. Graphene, together with a variety of newly developed 2D inorganic systems, have all attracted a remarkable amount of attention due to their unprecedented properties/superior performance encouraging their application in many fields. These two-dimensional systems are known for the fact that they are ultrathin, and hence tend to flexibility, also presenting nearly intrinsic and distinctive characteristics, including electronic, magnetic, optical, thermal conductivity, and superconducting properties. Furthermore, the combination of different structures and synergetic effects may open new and unprecedented perspectives, making these ideally assembled systems multifunctional and advanced materials. On this matter, signiﬁcant examples come from the stacking together of 2D crystals, which can make materials perfectly tuned to the wavelengths of solar light. On the other hand, the ultralow sliding friction resulting from the contact between two crystalline materials or a crystalline material with a more disordered system makes superlubricity possible, which implies a reduction in friction of orders of magnitude compared to that measured for their 3D counterparts.

This Issue is primarily addressed to the two-dimensional (nano)structures and layered materials, from their syntheses/characterizations to their applications. Fundamental findings and theoretical studies contributing to the understanding of their basic principles are also welcomed.

The topics of interest include, but are not limited to, the preparation, properties, and applications of materials containing:

-Few-layered materials;

-Graphene and graphene-like systems (i.e., graphene oxide);

-Transition metal dichalcogenides, carbides, nitrides, carbonitrides;

-Silicene, germanene, stanene, and phosphorene;

-Van der Waals heterostructures, all-inorganic, and organic–inorganic hybrids;

-2D organic framework systems, 2D polymers.

Prof. Dr. Federico Cesano
Prof. Dr. Domenica Scarano
Guest Editors

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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. Materials 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 2600 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

2D systems
graphene
graphene analogues
layered materials
hybrid structures
van der Waals heterostructures
synthesis
properties
characterization
applications

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Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications (Volume II) in Materials (3 articles)

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Editorial

Jump to: Research, Review

5 pages, 1800 KiB

Open AccessEditorial

Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications

by Domenica Scarano and Federico Cesano

Materials 2021, 14(23), 7108; https://doi.org/10.3390/ma14237108 - 23 Nov 2021

Cited by 4 | Viewed by 2252

Abstract

The field of two-dimensional (2D) layered nanomaterials, their hybrid structures, and composite materials has been suddenly increasing since 2004, when graphene—almost certainly the most known 2D material—was successfully obtained from graphite via mechanical exfoliation [...] Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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Research

Jump to: Editorial, Review

12 pages, 2874 KiB

Open AccessArticle

Borocarbonitride Layers on Titanium Dioxide Nanoribbons for Efficient Photoelectrocatalytic Water Splitting

by Nuria Jiménez-Arévalo, Eduardo Flores, Alessio Giampietri, Marco Sbroscia, Maria Grazia Betti, Carlo Mariani, José R. Ares, Isabel J. Ferrer and Fabrice Leardini

Materials 2021, 14(19), 5490; https://doi.org/10.3390/ma14195490 - 23 Sep 2021

Cited by 4 | Viewed by 1723

Abstract

Heterostructures formed by ultrathin borocarbonitride (BCN) layers grown on TiO₂ nanoribbons were investigated as photoanodes for photoelectrochemical water splitting. TiO₂ nanoribbons were obtained by thermal oxidation of TiS₃ samples. Then, BCN layers were successfully grown by plasma enhanced chemical vapour deposition. The structure and the chemical composition of the starting TiS₃, the TiO₂ nanoribbons and the TiO₂-BCN heterostructures were investigated by Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Diffuse reflectance measurements showed a change in the gap from 0.94 eV (TiS₃) to 3.3 eV (TiO₂) after the thermal annealing of the starting material. Morphological characterizations, such as scanning electron microscopy and optical microscopy, show that the morphology of the samples was not affected by the change in the structure and composition. The obtained TiO₂-BCN heterostructures were measured in a photoelectrochemical cell, showing an enhanced density of current under dark conditions and higher photocurrents when compared with TiO₂. Finally, using electrochemical impedance spectroscopy, the flat band potential was determined to be equal in both TiO₂ and TiO₂-BCN samples, whereas the product of the dielectric constant and the density of donors was higher for TiO₂-BCN. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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11 pages, 1653 KiB

Open AccessArticle

Highly Water Dispersible Functionalized Graphene by Thermal Thiol-Ene Click Chemistry

by Farzaneh Farivar, Pei Lay Yap, Tran Thanh Tung and Dusan Losic

Materials 2021, 14(11), 2830; https://doi.org/10.3390/ma14112830 - 25 May 2021

Cited by 7 | Viewed by 3668

Abstract

Functionalization of pristine graphene to achieve high water dispersibility remains as a key obstacle owing to the high hydrophobicity and absence of reactive functional groups on the graphene surface. Herein, a green and simple modification approach to prepare highly dispersible functionalized graphene via thermal thiol-ene click reaction was successfully demonstrated on pristine graphene. Specific chemical functionalities (–COO, –NH₂ and –S) on the thiol precursor (L-cysteine ethyl ester) were clicked directly on the sp² carbon of graphene framework with grafting density of 1 unit L-cysteine per 113 carbon atoms on graphene. This functionalized graphene was confirmed with high atomic content of S (4.79 at % S) as well as the presence of C–S–C and N–H species on the L-cysteine functionalized graphene (FG-CYS). Raman spectroscopy evidently corroborated the modification of graphene to FG-CYS with an increased intensity ratio of D and G band, I_D/I_G ratio (0.3 to 0.7), full-width at half-maximum of G band, FWHM [G] (20.3 to 35.5) and FWHM [2D] (64.8 to 90.1). The use of ethanol as the reaction solvent instead of common organic solvents minimizes the chemical hazards exposure to humans and the environment. This direct attachment of multifunctional groups on the surface of pristine graphene is highly demanded for graphene ink formulations, coatings, adsorbents, sensors and supercapacitor applications. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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16 pages, 2516 KiB

Open AccessArticle

Catalyst-Less and Transfer-Less Synthesis of Graphene on Si(100) Using Direct Microwave Plasma Enhanced Chemical Vapor Deposition and Protective Enclosures

by Rimantas Gudaitis, Algirdas Lazauskas, Šarūnas Jankauskas and Šarūnas Meškinis

Materials 2020, 13(24), 5630; https://doi.org/10.3390/ma13245630 - 10 Dec 2020

Cited by 14 | Viewed by 2397

Abstract

In this study, graphene was synthesized on the Si(100) substrates via the use of direct microwave plasma-enhanced chemical vapor deposition (PECVD). Protective enclosures were applied to prevent excessive plasma etching of the growing graphene. The properties of synthesized graphene were investigated using Raman scattering spectroscopy and atomic force microscopy. Synthesis time, methane and hydrogen gas flow ratio, temperature, and plasma power effects were considered. The synthesized graphene exhibited n-type self-doping due to the charge transfer from Si(100). The presence of compressive stress was revealed in the synthesized graphene. It was presumed that induction of thermal stress took place during the synthesis process due to the large lattice mismatch between the growing graphene and the substrate. Importantly, it was demonstrated that continuous horizontal graphene layers can be directly grown on the Si(100) substrates if appropriate configuration of the protective enclosure is used in the microwave PECVD process. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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24 pages, 4522 KiB

Open AccessArticle

LDH-Co-Fe-Acetate: A New Efficient Sorbent for Azoic Dye Removal and Elaboration by Hydrolysis in Polyol, Characterization, Adsorption, and Anionic Exchange of Direct Red 2 as a Model Anionic Dye

by Nawal Drici-Setti, Paolo Lelli and Noureddine Jouini

Materials 2020, 13(14), 3183; https://doi.org/10.3390/ma13143183 - 16 Jul 2020

Cited by 6 | Viewed by 2191

Abstract

A new, double hydroxide based on Co and Fe was elaborated on by forced hydrolysis in a polyol medium. Complementary characterization techniques show that this new phase belongs to the layered double hydroxide family (LDH) with Co²⁺ and Fe³⁺ ions located in the octahedral sites of the bucite-like structure. The acetate anions occupy interlayer space with an interlamellar distance of 12.70 Å. This large distance likely facilitates the exchange reaction. Acetates were exchanged by carbonates. The as-obtained compound Co-Fe-Ac/_Ex shows an interlamellar distance of 7.67 Å. The adsorption of direct red 2 by Co-Fe-Ac-LDH has been examined in order to measure the capability of this new LDH to eliminate highly toxic azoic anionic dyes from waste water and was compared with that of Co-Fe-Ac/_Ex and Co-Fe-CO₃/_A (synthesized in an aqueous medium). The adsorption capacity was found to depend on contact time, pH, initial dye concentration, and heating temperature. Concerning CoFeAc-LDH, the dye uptake reaches a high level (588 mg/g) due to the occurrence of both adsorption processes: physisorption on the external surface and chemical sorption due to the intercalation of dye by exchange with an acetate anion. The study enables us to quantify the uptake amount of each effect in which the intercalation has the most important amount (418 mg/g). Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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13 pages, 3262 KiB

Open AccessArticle

Electrochemically Exfoliated Graphene-Like Nanosheets for Use in Ceramic Nanocomposites

by Rosalía Poyato, Reyes Verdugo, Carmen Muñoz-Ferreiro and Ángela Gallardo-López

Materials 2020, 13(11), 2656; https://doi.org/10.3390/ma13112656 - 11 Jun 2020

Cited by 8 | Viewed by 2872

Abstract

In this work, the synthesis of graphene-like nanosheets (GNS) by an electrochemical exfoliation method, their microstructural characterization and their performance as fillers in a ceramic matrix composite have been assessed. To fabricate the composites, 3 mol % yttria tetragonal zirconia (3YTZP) powders with 1 vol % GNS were processed by planetary ball milling in tert-butanol to enhance the GNS distribution throughout the matrix, and densified by spark plasma sintering (SPS). According to a thorough Raman analysis and SEM observations, the electrochemically exfoliated GNS possessed less than 10 graphene layers and a lateral size lower than 1 μm. However, they contained amorphous carbon and vacancy-like defects. In contrast the GNS in the sintered composite exhibited enhanced quality with a lower number of defects, and they were wavy, semi-transparent and with very low thickness. The obtained nanocomposite was fully dense with a homogeneous distribution of GNS into the matrix. The Vickers hardness of the nanocomposite showed similar values to those of a monolithic 3YTZP ceramic sintered in the same conditions, and to the reported ones for a 3YTZP composite with the same content of commercial graphene nanosheets. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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11 pages, 5113 KiB

Open AccessFeature PaperArticle

Controlling the Electronic Properties of a Nanoporous Carbon Surface by Modifying the Pores with Alkali Metal Atoms

by Michael M. Slepchenkov, Igor S. Nefedov and Olga E. Glukhova

Materials 2020, 13(3), 610; https://doi.org/10.3390/ma13030610 - 30 Jan 2020

Cited by 3 | Viewed by 2113

Abstract

We investigate a process of controlling the electronic properties of a surface of nanoporous carbon glass-like thin films when the surface pores are filled with potassium atoms. The presence of impurities on the surface in the form of chemically adsorbed hydrogen and oxygen atoms, and also in the form of hydroxyl (OH) groups, is taken into account. It is found that even in the presence of impurities, the work function of a carbon nanoporous glass-like film can be reduced by several tenths of an electron volt when the nanopores are filled with potassium atoms. At the same time, almost all potassium atoms are ionized, losing one electron, which passes to the carbon framework of the film. This is due to the nanosizes of the pores in which the electron clouds of the potassium atom interact maximally with the electrons of the carbon framework. As a result, this leads to an improvement in the electrical conductivity and an increase in the electron density at the Fermi level. Thus, we conclude that an increase in the number of nanosized pores on the film surface makes it possible to effectively modify it, providing an effective control of the electronic structure and emission properties. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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11 pages, 3756 KiB

Open AccessArticle

A Strategy to Synthesize Multilayer Graphene in Arc-Discharge Plasma in a Semi-Opened Environment

by Hai Tan, Deguo Wang and Yanbao Guo

Materials 2019, 12(14), 2279; https://doi.org/10.3390/ma12142279 - 16 Jul 2019

Cited by 20 | Viewed by 2705

Abstract

Graphene, as the earliest discovered two-dimensional (2D) material, possesses excellently physical and chemical properties. Vast synthetic strategies, including chemical vapor deposition, mechanical exfoliation, and chemical reduction, are proposed. In this paper, a method to synthesize multilayer graphene in a semi-opened environment is presented by introducing arc-discharge plasma technology. Compared with previous technologies, the toxic gases and hazardous chemical components are not generated in the whole process. The synthesized carbon materials were characterized by transmission electron microscopy, atomic force microscopy, X-ray diffraction, and Raman spectra technologies. The paper offers an idea to synthesize multilayer graphene in a semi-opened environment, which is a development to produce graphene with arc-discharge plasma. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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8 pages, 3697 KiB

Open AccessArticle

ZnO-Controlled Growth of Monolayer WS₂ through Chemical Vapor Deposition

by Zhuhua Xu, Yanfei Lv, Feng Huang, Cong Zhao, Shichao Zhao and Guodan Wei

Materials 2019, 12(12), 1883; https://doi.org/10.3390/ma12121883 - 12 Jun 2019

Cited by 5 | Viewed by 3678

Abstract

Monolayer tungsten disulfide (2D WS₂) films have attracted tremendous interest due to their unique electronic and optoelectronic properties. However, the controlled growth of monolayer WS₂ is still challenging. In this paper, we report a novel method to grow WS₂ through chemical vapor deposition (CVD) with ZnO crystalline whisker as a growth promoter, where partially evaporated WS₂ reacts with ZnO to form ZnWO₄ by-product. As a result, a depletion region of W atoms and S-rich region is formed which is favorable for subsequent monolayer growth of WS₂, selectively positioned on the silicon oxide substrate after the CVD growth. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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Review

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30 pages, 3365 KiB

Open AccessReview

Graphene-Based Materials Immobilized within Chitosan: Applications as Adsorbents for the Removal of Aquatic Pollutants

by Daniele C. da Silva Alves, Bronach Healy, Tian Yu and Carmel B. Breslin

Materials 2021, 14(13), 3655; https://doi.org/10.3390/ma14133655 - 30 Jun 2021

Cited by 31 | Viewed by 2925

Abstract

Graphene and its derivatives, especially graphene oxide (GO), are attracting considerable interest in the fabrication of new adsorbents that have the potential to remove various pollutants that have escaped into the aquatic environment. Herein, the development of GO/chitosan (GO/CS) composites as adsorbent materials is described and reviewed. This combination is interesting as the addition of graphene to chitosan enhances its mechanical properties, while the chitosan hydrogel serves as an immobilization matrix for graphene. Following a brief description of both graphene and chitosan as independent adsorbent materials, the emerging GO/CS composites are introduced. The additional materials that have been added to the GO/CS composites, including magnetic iron oxides, chelating agents, cyclodextrins, additional adsorbents and polymeric blends, are then described and discussed. The performance of these materials in the removal of heavy metal ions, dyes and other organic molecules are discussed followed by the introduction of strategies employed in the regeneration of the GO/CS adsorbents. It is clear that, while some challenges exist, including cost, regeneration and selectivity in the adsorption process, the GO/CS composites are emerging as promising adsorbent materials. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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24 pages, 1367 KiB

Open AccessReview

Graphene-Modified Composites and Electrodes and Their Potential Applications in the Electro-Fenton Process

by Tian Yu and Carmel B. Breslin

Materials 2020, 13(10), 2254; https://doi.org/10.3390/ma13102254 - 14 May 2020

Cited by 27 | Viewed by 4905

Abstract

In recent years, graphene-based materials have been identified as an emerging and promising new material in electro-Fenton, with the potential to form highly efficient metal-free catalysts that can be employed in the removal of contaminants from water, conserving precious water resources. In this review, the recent applications of graphene-based materials in electro-Fenton are described and discussed. Initially, homogenous and heterogenous electro-Fenton methods are briefly introduced, highlighting the importance of the generation of H₂O₂ from the two-electron reduction of dissolved oxygen and its catalysed decomposition to produce reactive and oxidising hydroxy radicals. Next, the promising applications of graphene-based electrodes in promoting this two-electron oxygen reduction reaction are considered and this is followed by an account of the various graphene-based materials that have been used successfully to give highly efficient graphene-based cathodes in electro-Fenton. In particular, graphene-based composites that have been combined with other carbonaceous materials, doped with nitrogen, formed as highly porous aerogels, three-dimensional materials and porous gas diffusion electrodes, used as supports for iron oxides and functionalised with ferrocene and employed in the more effective heterogeneous electro-Fenton, are all reviewed. It is perfectly clear that graphene-based materials have the potential to degrade and mineralise dyes, pharmaceutical compounds, antibiotics, phenolic compounds and show tremendous potential in electro-Fenton and other advanced oxidation processes. Full article

(This article belongs to the Special Issue Graphene and Other 2D Layered Nanomaterials and Hybrid Structures: Synthesis, Properties and Applications)

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