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State-of-the-Art 2D and Carbon Nanomaterials in France

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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "2D and Carbon Nanomaterials".

Deadline for manuscript submissions: closed (31 May 2022) | Viewed by 24837

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Prof. Dr. Catherine Journet

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Laboratoire des Multimatériaux et Interfaces (LMI-UMR 5615 CNRS / UCBL), Domaine Scientifique de la Doua, Université Claude Bernard Lyon 1, Bâtiment Chevreul, 6 rue Victor Grignard, CEDEX, 69622 Villeurbanne, France
Interests: carbon nanotubes; hexagonal boron nitride; 2D materials; synthesis of nanomaterials; chemical vapor deposition; electric arc discharge; transmission electron microscopy

Special Issue Information

Dear Colleagues,

Since the discovery of fullerenes in 1985, the appeal of carbon nanomaterials has never wavered. With the start of experiments on nanotubes in 1991 and on graphene in 2004, carbon has now become one of the most widely and extensively studied materials. Although interest in fullerenes has waned over time, research on its one-dimensional (1D) and two-dimensional (2D) counterparts remains very active. Carbon nanomaterials occupy a unique place in science because of their exceptional thermal, electrical, chemical, and mechanical properties. They find applications in areas as diverse as super-strong composite materials, energy storage and conversion, supercapacitors, smart sensors, targeted drug delivery, paints, and nanoelectronics. The study of such nanostructures has, in recent years, become a common theme across many disciplines, where scientists and engineers manipulate and study matter at the atomic and molecular scale to obtain materials and systems with significantly improved properties.

France is in the top ten countries that publish the most on these materials. This Special Issue specifically focuses on “State-of-the-Art 2D and Carbon Nanomaterials in France” and welcomes contributions devoted to the progress in synthesis, processing, characterization, properties, and applications of various types of 2D and carbon nanomaterials.

Prof. Dr. Catherine Journet
Guest Editor

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Keywords

carbon nanomaterials
synthesis
processing
characterization
properties
applications

Published Papers (11 papers)

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Editorial

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3 pages, 185 KiB

Open AccessEditorial

State-of-the-Art 2D and Carbon Nanomaterials in France

by Catherine Journet

Nanomaterials 2023, 13(21), 2826; https://doi.org/10.3390/nano13212826 - 25 Oct 2023

Viewed by 599

Abstract

Nanotechnology has revolutionized various industries by enabling the manipulation and fabrication of materials at the nanoscale [...] Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

Research

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24 pages, 10709 KiB

Open AccessArticle

Critical Role of the Acetylene Content and Fe/C Ratio on the Thickness and Density of Vertically Aligned Carbon Nanotubes Grown at Low Temperature by a One-Step Catalytic Chemical Vapor Deposition Process

by Antoine Combrisson, Emeline Charon, Mathieu Pinault, Cécile Reynaud and Martine Mayne-L’Hermite

Nanomaterials 2022, 12(14), 2338; https://doi.org/10.3390/nano12142338 - 07 Jul 2022

Cited by 3 | Viewed by 1662

Abstract

The present work explores the role of the carbon source content and the Fe/C ratio on the synthesis of vertically aligned carbon nanotubes (VACNTs) by one-step aerosol-assisted CCVD operated at a medium temperature (615 °C) on aluminum substrates. The main objective was to overcome the limitations of VACNT growth, constituting a drawback for applications requiring thick VACNTs. By using acetylene as carbon feedstock and ferrocene as a catalyst precursor, we demonstrate that when acetylene content is reduced to 1.5 vol%, it is possible to grow VACNT carpets up to 700 µm thick while maintaining constant VACNT growth for a long duration (up to 160 min). The carbon conversion yield is significantly improved when the acetylene content reaches 1.5 vol%. The Al surface roughness also influences VACNT growth. An optimum Fe/C ratio of 0.8 wt.% coupled with a low acetylene content gives the highest growth rate (5.4 µm/min) ever reported for a thermal aerosol-assisted CCVD process operated at such a low temperature. The CNT number density can be controlled by varying the Fe/C ratio, enabling high density growth (e.g., 1.3 × 10¹¹ CNT/cm²). Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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11 pages, 2158 KiB

Open AccessEditor’s ChoiceArticle

Chain Formation during Hydrogen Loss and Reconstruction in Carbon Nanobelts

by Yuri Tanuma, Paul Dunk, Toru Maekawa and Chris P. Ewels

Nanomaterials 2022, 12(12), 2073; https://doi.org/10.3390/nano12122073 - 16 Jun 2022

Cited by 4 | Viewed by 1266

Abstract

Using laser-induced vaporisation to evaporate and ionise a source of curved polyaromatic hydrocarbons (carbon nanobelts), we show collision impacts between species cause mass loss and the resultant ions are catalogued via mass-spectrometry. These data are interpreted via a series of “in-silico”-simulated systematic hydrogen-loss studies using density functional theory modelling, sequentially removing hydrogen atoms using thermodynamic stability as a selection for subsequent dehydrogenation. Initial hydrogen loss results in the formation of carbyne chains and pentagon-chains while the nanobelt rings are maintained, giving rise to new circular strained dehydrobenzoannulene species. The chains subsequently break, releasing CH and C₂. Alternative routes towards the formation of closed-cages (fullerenes) are identified but shown to be less stable than chain formation, and are not observed experimentally. The results provide important information on collision degradation routes of curved molecular carbon species, and notably serve as a useful guide to high-energy impact conditions observed in some astrochemical environments. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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10 pages, 19524 KiB

Open AccessArticle

Transport Properties of Methyl-Terminated Germanane Microcrystallites

by Davide Sciacca, Maxime Berthe, Bradley J. Ryan, Nemanja Peric, Dominique Deresmes, Louis Biadala, Christophe Boyaval, Ahmed Addad, Ophélie Lancry, Raghda Makarem, Sébastien Legendre, Didier Hocrelle, Matthew G. Panthani, Geoffroy Prévot, Emmanuel Lhuillier, Pascale Diener and Bruno Grandidier

Nanomaterials 2022, 12(7), 1128; https://doi.org/10.3390/nano12071128 - 29 Mar 2022

Cited by 2 | Viewed by 1880

Abstract

Germanane is a two-dimensional material consisting of stacks of atomically thin germanium sheets. It’s easy and low-cost synthesis holds promise for the development of atomic-scale devices. However, to become an electronic-grade material, high-quality layered crystals with good chemical purity and stability are needed. To this end, we studied the electrical transport of annealed methyl-terminated germanane microcrystallites in both high vacuum and ultrahigh vacuum. Scanning electron microscopy of crystallites revealed two types of behavior which arise from the difference in the crystallite chemistry. While some crystallites are hydrated and oxidized, preventing the formation of good electrical contact, the four-point resistance of oxygen-free crystallites was measured with multiple tips scanning tunneling microscopy, yielding a bulk transport with resistivity smaller than 1 Ω·cm. When normalized by the crystallite thickness, the resistance compares well with the resistance of hydrogen-passivated germanane flakes found in the literature. Along with the high purity of the crystallites, a thermal stability of the resistance at 280 °C makes methyl-terminated germanane suitable for complementary metal oxide semiconductor back-end-of-line processes. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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10 pages, 3389 KiB

Open AccessArticle

Analysis of the Continuous Feeding of Catalyst Particles during the Growth of Vertically Aligned Carbon Nanotubes by Aerosol-Assisted CCVD

by Celia Castro, Rodrigo Fernández-Pacheco, Mathieu Pinault, Odile Stephan, Cécile Reynaud and Martine Mayne-L’Hermite

Nanomaterials 2022, 12(3), 449; https://doi.org/10.3390/nano12030449 - 28 Jan 2022

Cited by 4 | Viewed by 1666

Abstract

Aerosol-assisted catalytic chemical vapor deposition (AACCVD) is a powerful one-step process to produce vertically aligned carbon nanotubes (VACNTs), characterized by the continuous supply of the catalyst precursor (metallocene). The behavior of catalyst species all along the synthesis is essential for the continuous growth of VACNTs. It is there investigated through detailed observations and elemental analyses at scales of VACNT carpets and of individual CNTs. Our approach is based on two complementary experiments: quenching of the sample cooling, and sequential injection of two distinct metallocenes. Metal-based nanoparticles nucleated in the gas-phase during the whole synthesis duration are shown to diffuse in between the growing VACNTs from the top of the CNT carpet towards the substrate. They are much smaller than the catalyst particles formed on the substrate in the initial steps of the process and evidences are given that they continuously feed these catalyst particles at the VACNT roots. Particularly, the electron energy-loss spectroscopy (EELS) analyses of metal-based segments found into a single CNT show that the second injected metal is very gradually incorporated in the particle initially formed from the metal firstly injected. The feeding of the catalyst particles by the nanoparticles continuously nucleated in the gas-phase is therefore an essential feature of the base-growth of CNTs by AACCVD. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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12 pages, 1894 KiB

Open AccessArticle

Strain and Spin-Orbit Coupling Engineering in Twisted WS₂/Graphene Heterobilayer

by Cyrine Ernandes, Lama Khalil, Hugo Henck, Meng-Qiang Zhao, Julien Chaste, Fabrice Oehler, Alan T. Charlie Johnson, Maria C. Asensio, Debora Pierucci, Marco Pala, José Avila and Abdelkarim Ouerghi

Nanomaterials 2021, 11(11), 2921; https://doi.org/10.3390/nano11112921 - 31 Oct 2021

Cited by 12 | Viewed by 3121

Abstract

The strain in hybrid van der Waals heterostructures, made of two distinct two-dimensional van der Waals materials, offers an interesting handle on their corresponding electronic band structure. Such strain can be engineered by changing the relative crystallographic orientation between the constitutive monolayers, notably, the angular misorientation, also known as the “twist angle”. By combining angle-resolved photoemission spectroscopy with density functional theory calculations, we investigate here the band structure of the WS₂/graphene heterobilayer for various twist angles. Despite the relatively weak coupling between WS₂ and graphene, we demonstrate that the resulting strain quantitatively affects many electronic features of the WS₂ monolayers, including the spin-orbit coupling strength. In particular, we show that the WS₂ spin-orbit splitting of the valence band maximum at K can be tuned from 430 to 460 meV. Our findings open perspectives in controlling the band dispersion of van der Waals materials. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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11 pages, 4661 KiB

Open AccessArticle

Physical and Electrical Characterization of Synthesized Millimeter Size Single Crystal Graphene, Using Controlled Bubbling Transfer

by Soukaina Ben Salk, Reetu Raj Pandey, Phi H. Q. Pham, Di Zhou, Wei Wei, Guillaume Cochez, Dominique Vignaud, Emiliano Pallecchi, Peter J. Burke and Henri Happy

Nanomaterials 2021, 11(10), 2528; https://doi.org/10.3390/nano11102528 - 27 Sep 2021

Cited by 2 | Viewed by 1885

Abstract

In this work, we have investigated the influence of the transfer process on the monocrystalline graphene in terms of quality, morphology and electrical properties by analyzing the data obtained from optical microscopy, scanning electron microscopy, Raman spectroscopy and electrical characterizations. The influence of Cu oxidation on graphene prior to the transfer is also discussed. Our results show that the controlled bubbling electrochemical delamination transfer is an easy and fast transfer technique suitable for transferring large single crystals graphene without degrading the graphene quality. Moreover, Raman spectroscopy investigation reveals that the Cu surface oxidation modifies the strain of the graphene film. We have observed that graphene laying on unoxidized Cu is subject to a biaxial strain in compression, while graphene on Cu oxide is subject to a biaxial strain in tension. However, after graphene was transferred to a host substrate, these strain effects were strongly reduced, leaving a homogeneous graphene on the substrate. The transferred single crystal graphene on silicon oxide substrate was used to fabricate transmission line method (TLM) devices. Electrical measurements show low contact resistance ~150 Ω·µm, which confirms the homogeneity and high quality of transferred graphene. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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14 pages, 3938 KiB

Open AccessArticle

Physical and Chemical Activation of Graphene-Derived Porous Nanomaterials for Post-Combustion Carbon Dioxide Capture

by Rabita Mohd Firdaus, Alexandre Desforges, Mélanie Emo, Abdul Rahman Mohamed and Brigitte Vigolo

Nanomaterials 2021, 11(9), 2419; https://doi.org/10.3390/nano11092419 - 17 Sep 2021

Cited by 9 | Viewed by 2679

Abstract

Activation is commonly used to improve the surface and porosity of different kinds of carbon nanomaterials: activated carbon, carbon nanotubes, graphene, and carbon black. In this study, both physical and chemical activations are applied to graphene oxide by using CO₂ and KOH-based approaches, respectively. The structural and the chemical properties of the prepared activated graphene are deeply characterized by means of scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectrometry and nitrogen adsorption. Temperature activation is shown to be a key parameter leading to enhanced CO₂ adsorption capacity of the graphene oxide-based materials. The specific surface area is increased from 219.3 m² g⁻¹ for starting graphene oxide to 762.5 and 1060.5 m² g⁻¹ after physical and chemical activation, respectively. The performance of CO₂ adsorption is gradually enhanced with the activation temperature for both approaches: for the best performances of a factor of 6.5 and 9 for physical and chemical activation, respectively. The measured CO₂ capacities are of 27.2 mg g⁻¹ and 38.9 mg g⁻¹ for the physically and chemically activated graphene, respectively, at 25 °C and 1 bar. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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15 pages, 3014 KiB

Open AccessArticle

Hydrogen Storage in Pure and Boron-Substituted Nanoporous Carbons—Numerical and Experimental Perspective

by Lucyna Firlej, Bogdan Kuchta, Katarzyna Walczak and Catherine Journet

Nanomaterials 2021, 11(9), 2173; https://doi.org/10.3390/nano11092173 - 25 Aug 2021

Cited by 3 | Viewed by 2673

Abstract

Nanoporous carbons remain the most promising candidates for effective hydrogen storage by physisorption in currently foreseen hydrogen-based scenarios of the world’s energy future. An optimal sorbent meeting the current technological requirement has not been developed yet. Here we first review the storage limitations of currently available nanoporous carbons, then we discuss possible ways to improve their storage performance. We focus on two fundamental parameters determining the storage (the surface accessible for adsorption and hydrogen adsorption energy). We define numerically the values nanoporous carbons have to show to satisfy mobile application requirements at pressures lower than 120 bar. Possible necessary modifications of the topology and chemical compositions of carbon nanostructures are proposed and discussed. We indicate that pore wall fragmentation (nano-size graphene scaffolds) is a partial solution only, and chemical modifications of the carbon pore walls are required. The positive effects (and their limits) of the carbon substitutions by B and Be atoms are described. The experimental ‘proof of concept’ of the proposed strategies is also presented. We show that boron substituted nanoporous carbons prepared by a simple arc-discharge technique show a hydrogen adsorption energy twice as high as their pure carbon analogs. These preliminary results justify the continuation of the joint experimental and numerical research effort in this field. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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Review

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49 pages, 31242 KiB

Open AccessFeature PaperReview

Conducting Interface for Efficient Growth of Vertically Aligned Carbon Nanotubes: Towards Nano-Engineered Carbon Composite

by Blagoj Karakashov, Martine Mayne-L’Hermite and Mathieu Pinault

Nanomaterials 2022, 12(13), 2300; https://doi.org/10.3390/nano12132300 - 04 Jul 2022

Cited by 4 | Viewed by 2366

Abstract

Vertically aligned carbon nanotubes (VACNT) are manufactured nanomaterials with excellent properties and great potential for numerous applications. Recently, research has intensified toward achieving VACNT synthesis on different planar and non-planar substrates of various natures, mainly dependent on the user-defined application. Indeed, VACNT growth has to be adjusted and optimized according to the substrate nature and shape to reach the requirements for the application envisaged. To date, different substrates have been decorated with VACNT, involving the use of diffusion barrier layers (DBLs) that are often insulating, such as SiO₂ or Al₂O₃. These commonly used DBLs limit the conducting and other vital physico-chemical properties of the final nanomaterial composite. One interesting route to improve the contact resistance of VACNT on a substrate surface and the deficient composite properties is the development of semi-/conducting interlayers. The present review summarizes different methods and techniques for the deposition of suitable conducting interfaces and controlled growth of VACNT on diverse flat and 3-D fibrous substrates. Apart from exhibiting a catalytic efficiency, the DBL can generate a conducting and adhesive interface involving performance enhancements in VACNT composites. The abilities of different conducting interlayers are compared for VACNT growth and subsequent composite properties. A conducting interface is also emphasized for the synthesis of VACNT on carbonaceous substrates in order to produce cost-effective and high-performance nano-engineered carbon composites. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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40 pages, 13062 KiB

Open AccessReview

Vitreous Carbon, Geometry and Topology: A Hollistic Approach

by Patrice Mélinon

Nanomaterials 2021, 11(7), 1694; https://doi.org/10.3390/nano11071694 - 28 Jun 2021

Cited by 18 | Viewed by 3862

Abstract

Glass-like carbon (GLC) is a complex structure with astonishing properties: isotropic

s p^{2}

structure, low density and chemical robustness. Despite the expanded efforts to understand the structure, it remains little known. We review the different models and a physical route [...] Read more.

Glass-like carbon (GLC) is a complex structure with astonishing properties: isotropic

s p^{2}

structure, low density and chemical robustness. Despite the expanded efforts to understand the structure, it remains little known. We review the different models and a physical route (pulsed laser deposition) based on a well controlled annealing of the native 2D/3D amorphous films. The many models all have compromises: neither all bad nor entirely satisfactory. Properties are understood in a single framework given by topological and geometrical properties. To do this, we present the basic tools of topology and geometry at a ground level for 2D surface, graphene being the best candidate to do this. With this in mind, special attention is paid to the hyperbolic geometry giving birth to triply periodic minimal surfaces. Such surfaces are the basic tools to understand the GLC network architecture. Using two theorems (the classification and the uniformisation), most of the GLC properties can be tackled at least at a heuristic level. All the properties presented can be extended to 2D materials. It is hoped that some researchers may find it useful for their experiments. Full article

(This article belongs to the Special Issue State-of-the-Art 2D and Carbon Nanomaterials in France)

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