Functionalized graphene for polymer composites

Tese de Doutoramento (Ciência e Engenharia de Polímeros e Compósitos)Along the past decade graphene has emerged as an exciting material revealing potential applications in various fields. The translation of the graphene outstanding properties observed at lab-scale into real-world applications at industrial scale, however, greatly depends on the capacity to produce good quality graphene at large scale. The typical large scale graphene production processes present disadvantages such as high cost, or the formation of graphene with structural defects, or contaminants which are difficult to remove. Recently, interesting approaches to produce graphene were proposed, based on graphite exfoliation in water using amphiphilic molecules such as pyrene derivatives with a polar moiety. Another approach consists in the production of graphene nanoribbons (GNR) by unzipping of carbon nanotubes. These methods allow the production of graphene sheets (GS) and GNR with negligible structural damage, using low boiling point solvents that are easy to remove. The present work investigated these two graphene production methods. The exfoliation of graphite into GS was achieved by interaction with two different water soluble pyrene derivatives, modified with a carboxylic acid moiety bonded to pyrene through semiflexible side arms of different lengths. The suspensions produced were formed by approximately 80 % of bi-layer and few-layer graphene. The GNR were produced from pyrrolidine-functionalized carbon nanotubes, through application of ultrasounds in ethanol. Multiwall carbon nanotubes of different diameters, namely with approximately 10 and 110 nm, were covalently functionalized using a simple, solvent free method, and the unzipping was observed to occur in both cases. The unzipping process was assigned to the type of functional groups bonded to the nanotubes. The graphene products were extensively characterized, and tested for polymer composite applications. Graphene has the potential to improve the mechanical, electrical, thermal and barrier properties of polymer-based nanocomposites. For that purpose graphene, or graphene derivative, has to be homogeneously distributed and dispersed into the polymer matrix, and establish good interfacial adhesion. Solution mixing is a good method to produce homogeneous graphene/polymer nanocomposites, particularly when using water as a solvent. This method is limited to water soluble polymers, however the development of waterborne polymer suspensions is an area of intense research. Waterborne polyurethane (WPU) is a good example of an eco-friendly synthetic polymer widely used in the coating industry. In this work nanocomposite films were produced incorporating GS formed in aqueous suspension. The composite films presented a large decrease of permeability to water vapor, of the electrical resistivity, and an increase of the mechanical properties. Melt mixing of reinforcing particles in thermoplastic polymers is probably the most environmentally and economically attractive technique, and a scalable method, for composite production. However, the dispersion of nanoparticles in high viscosity polymer melts is a complex process. Several studies reported in the literature used different mixing equipment (extruders, internal mixers, prototype mixers) to disperse carbon black, carbon nanofibers and carbon nanotubes, in polymer melts. They demonstrated that the nanoparticle dispersion varies with factors such as the intensity and type of hydrodynamic stresses, residence time, and interfacial adhesion. Few studies report the dispersion of graphite-derivatives in polymer melts. In the present work the dispersion in polypropylene of graphite nanoplates, with and without functionalization, was studied using a small-scale prototype mixer designed to generate high extensional flow. The dispersion of the nanoparticles was analyzed along the mixer length, demonstrating the initial agglomerated form of the graphite nanoplates and their dispersion into the original nanoplate size along the melt processing.O grafeno tem sido apresentado como um nano material muito interessante com potenciais aplicações em várias áreas. Contudo, a extrapolação das suas excelentes propriedades, que são observadas à escala laboratorial, para uma escala industrial depende amplamente da capacidade de produção de grafeno em grandes quantidades e com boa qualidade. Os processos que normalmente são utilizados para produção de grafeno em grande quantidade apresentam algumas desvantagens, tais como, elevado custo de produção, a obtenção de grafeno com defeitos estruturais ou com contaminações cuja remoção é difícil. Recentemente foram reportadas abordagens interessantes para a produção de grafeno baseadas na exfoliação da grafite em meio aquoso utilizando moléculas anfifílicas, tais como derivados de pireno com grupos funcionais polares. Outra abordagem consiste na produção de nanofitas de grafeno através da abertura longitudinal de nanotubos de carbono. Estes métodos permitem a produção de folhas de grafeno e nanofitas de grafeno com poucos defeitos estruturais, utilizando solventes com pontos de ebulição baixos que são fáceis de remover. Neste trabalho foram estudadas estas duas abordagens para a produção de grafeno. A exfoliação da grafite para a formação de folhas de grafeno foi obtida através da interação com dois derivados de pireno solúveis em água, modificados com um grupo funcional ácido carboxílico ligado à molécula de pireno formando cadeias semi-flexíveis com comprimentos diferentes. As suspensões produzidas apresentaram cerca de 80% de grafeno bicamada e grafeno com poucas camadas. As nanofitas de grafeno foram produzidas a partir de nanotubos de carbono funcionalizados com um grupo pirrolidina, através da aplicação de ultrassons em etanol. Os nanotubos de carbono multicamada com diferentes diâmetros, nomeadamente, 10 e 110 nm, foram funcionalizados covalentemente através de uma metodologia simples, sem a utilização de solventes, e a abertura longitudinal dos nanotubos de carbono funcionalizados ocorreu em ambos os casos. O processo de abertura dos nanotubos de carbono funcionalizados foi desencadeado devido ao tipo de grupo funcionais ligados à superfície dos nanotubos. As nanofitas de grafeno bem como o grafeno obtido a partir da exfoliação da grafite foram caracterizados extensivamente e testados para aplicações em compósitos poliméricos. O grafeno tem potencial para melhorar as propriedades mecânicas, elétricas bem como propriedades de barreira em nanocompósitos poliméricos. Para tal, o grafeno ou derivados de grafeno têm que estar distribuídos e dispersos homogeneamente na matriz polimérica, e estabelecer uma boa adesão na interface com a matriz. A mistura em solução é uma boa técnica para a produção de nanocompósitos poliméricos com grafeno de uma forma homogénea, especialmente quando o solvente utilizado é a água. Este método é limitado à utilização de polímeros solúveis em água, contudo o desenvolvimento de polímeros que formam suspensões estáveis em água tem vindo a ser extensamente estudado. O poliuretano de base aquosa representa um bom exemplo de um polímero sintético e ecológico que é amplamente usado da industria dos revestimentos. Neste trabalho foram produzidos filmes nanocompósitos com a incorporação de folhas de grafeno produzidas em suspensão aquosa. Os filmes nanocompósitos apresentaram uma diminuição significativa na permeabilidade ao vapor de água, da resistividade elétrica bem como um melhoramento das propriedades mecânicas. A mistura de partículas de reforço em polímeros termoplásticos fundidos é provavelmente a técnica mais atrativa do ponto de vista económico e ecológico, e um método que pode ser utilizado para a produção de compósitos poliméricos em escala industrial. Todavia, a dispersão de nanopartículas em polímeros com viscosidade elevada é um processo complexo. Alguns estudos reportados na literatura usaram diferentes equipamentos de mistura (como por exemplo, extrusoras e misturadores protótipos) para dispersar nanopartículas de carbono, tais como, negro de fumo, nanofibras de carbono e nanotubos de carbono, em polímero fundido. Os estudos demonstraram que a dispersão das nanopartículas varia com fatores como a intensidade e o tipo de tensões hidrodinâmicas, o tempo de residência, e a adesão na interface entre o reforço e a matriz. Poucos estudos reportam a dispersão de derivados de grafite em polímero fundido. Neste trabalho foi estudada a dispersão em polipropileno fundido de nanoplaquetas de grafite, com e sem funcionalização, utilizando um misturador protótipo, que permite o estudo em pequenas quantidades de material, e que foi desenhado para gerar fluxos extensionais elevados. A dispersão das nanopartículas foi analisada ao longo do misturador, demonstrado que os aglomerados de nanoplaquetas de grafite formados evoluíram até às dimensões inicias destas ao longo do processamento em polímero fundido

GRAPHENE-BASED SEMICONDUCTOR AND METALLIC NANOSTRUCTURED MATERIALS

Exciting periods of scientific research are often associated with discoveries of novel materials. Such period was brought about by the successful preparation of graphene which is a 2D allotrope of carbon with remarkable electronic, optical and mechanical properties. Functional graphene-based nanocomposites have great promise for applications in various fields such as energy conversion, opteoelectronics, solar cells, sensing, catalysis and biomedicine. Herein, microwave and laser-assisted synthetic approaches were developed for decorating graphene with various semiconductor, metallic or magnetic nanostructures of controlled size and shape. We developed a scalable microwave irradiation method for the synthesis of graphene decorated with CdSe nanocrystals of controlled size, shape and crystalline structure. The efficient quenching of photoluminescence from the CdSe nanocrystals by graphene has been explored. The results provide a new approach for exploring the size-tunable optical properties of CdSe nanocrystals supported on graphene which could have important implications for energy conversion applications. We also extended this approach to the synthesis of Au-ceria-graphene nanocomposites. The synthesis is facilely conducted at mild conditions using ethylenediamine as a solvent. Results reveal significant CO conversion percentages between 60-70% at ambient temperatures. Au nanostructures have received significant attention because of the feasibility to tune their optical properties by changing size or shape. The coupling of the photothermal effects of these Au nanostructures of controlled size and shape with GO nanosheets dispersed in water is demonstrated. Our results indicate that the enhanced photothermal energy conversion of the Au-GO suspensions could to lead to a remarkable increase in the heating efficiency of the laser-induced melting and size reduction of Au nanostructures. The Au-graphene nanocomposites are potential materials for photothermolysis, thermochemical and thermomechanical applications. We developed a facile method for decorating graphene with magnetite nanocrystals of various shapes (namely, spheres, cubes and prisms) by the microwave-assisted-reduction of iron acetylacetonate in benzyl ether. The shape control was achieved by tuning the mole ratio between the oleic acid and the oleyamine. The structural, morphological and physical properties of graphene-based nanocomposites described herein were studied using standard characterization tools such as TEM, SEM, UV-Vis and PL spectroscopy, powder X-ray diffraction, XPS and Raman spectroscopy

Metal-free N-doped ultrafine carbon fibers from electrospun Polymers of Intrinsic Microporosity (PIM-1) based fibers for oxygen reduction reaction

Synthesis of nitrogen-doped carbon fibers (CF) has been proved to be one of the most promising oxygen reduction reaction (ORR) catalysts which can replace the state-of-art Pt catalyst for non-noble metal-free light-weight devices. Polymers of Intrinsic Microporosity (PIM-1) is soluble in common organic solvents and can be tailored by functionalization owing to nitrile groups in the backbone. PIM-1 was functionalized to amide (hydrolyzed PIM-1), amine and amidoxime groups. The modified PIM-1s were electrospun into ultrafine fibers and pyrolyzed to obtain CF. The present article investigates the influence of different functional groups on the properties of PIM-1 based CF and their nitrogen-doping. Particularly, their ORR performance has been evaluated. Interestingly, CF from hydrolyzed PIM-1 have the highest pore volume with small pore size among the CF based on PIM-1, amine and amidoxime PIM-1. The amount of nitrogen-doping in these CF shows the trend according to the functional groups as PIM-1 > amine > amidoxime > amide. Among all these PIM-1 based CF; CF from hydrolyzed PIM-1 has the highest percentage of pyridinic and graphitic nitrogen, furthermore, electrocatalysis revealed that ORR processed through four-electron with the onset potential 985 mV vs. reversible hydrogen electrode (RHE) which is comparable with the standard Pt/C catalysts. © 2020 Elsevier B.V

Properties and Applications of Graphene and Its Derivatives

Graphene is a two-dimensional, one-atom-thick material made entirely of carbon atoms, arranged in a honeycomb lattice. Because of its distinctive mechanical (e.g., high strength and flexibility) and electronic (great electrical and thermal conductivities) properties, graphene is an ideal candidate in myriad applications. Thus, it has just begun to be engineered in electronics, photonics, biomedicine, and polymer-based composites, to name a few. The broad family of graphene nanomaterials (including graphene nanoplatelets, graphene oxide, graphene quantum dots, and many more) go beyond and aim higher than mere single-layer (‘pristine’) graphene, and thus, their potential has sparked the current Special Issue. In it, 18 contributions (comprising 14 research articles and 4 reviews) have portrayed probably the most interesting lines as regards future and tangible uses of graphene derivatives. Ultimately, understanding the properties of the graphene family of nanomaterials is crucial for developing advanced applications to solve important challenges in critical areas such as energy and health

Production and processing of graphene and related materials

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown

Production and processing of graphene and related materials

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown

Production and processing of graphene and related materials

We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV–VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resource-consuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown. Section VIII discusses advances in GRM functionalization. A broad range of organic molecules can be anchored to the sp2 basal plane by reductive functionalization. Negatively charged graphene can be prepared in liquid phase (e.g. via intercalation chemistry or electrochemically) and can react with electrophiles. This can be achieved both in dispersion or on substrate. The functional groups of GO can be further derivatized. Graphene can also be noncovalently functionalized, in particular with polycyclic aromatic hydrocarbons that assemble on the sp2 carbon network by π–π stacking. In the liquid phase, this can enhance the colloidal stability of SLG/FLG. Approaches to achieve noncovalent on-substrate functionalization are also discussed, which can chemically dope graphene. Research efforts to derivatize CNMs are also summarized, as well as novel routes to selectively address defect sites. In dispersion, edges are the most dominant defects and can be covalently modified. This enhances colloidal stability without modifying the graphene basal plane. Basal plane point defects can also be modified, passivated and healed in ultra-high vacuum. The decoration of graphene with metal nanoparticles (NPs) has also received considerable attention, as it allows to exploit synergistic effects between NPs and graphene. Decoration can be either achieved chemically or in the gas phase. All LMs, can be functionalized and we summarize emerging approaches to covalently and noncovalently functionalize MoS2 both in the liquid and on substrate. Section IX describes some of the most popular characterization techniques, ranging from optical detection to the measurement of the electronic structure. Microscopies play an important role, although macroscopic techniques are also used for the measurement of the properties of these materials and their devices. Raman spectroscopy is paramount for GRMs, while PL is more adequate for non-graphene LMs (see section IX.2). Liquid based methods result in flakes with different thicknesses and dimensions. The qualification of size and thickness can be achieved using imaging techniques, like scanning probe microscopy (SPM) or transmission electron microscopy (TEM) or spectroscopic techniques. Optical microscopy enables the detection of flakes on suitable surfaces as well as the measurement of optical properties. Characterization of exfoliated materials is essential to improve the GRM metrology for applications and quality control. For grown GRMs, SPM can be used to probe morphological properties, as well as to study growth mechanisms and quality of transfer. More generally, SPM combined with smart measurement protocols in various modes allows one to get obtain information on mechanical properties, surface potential, work functions, electrical properties, or effectiveness of functionalization. Some of the techniques described are suitable for 'in situ' characterization, and can be hosted within the growth chambers. If the diagnosis is made 'ex situ', consideration should be given to the preparation of the samples to avoid contamination. Occasionally cleaning methods have to be used prior to measurement

Carbon Nanotubes

Since their discovery in 1991, carbon nanotubes have been considered as one of the most promising materials for a wide range of applications, in virtue of their outstanding properties. During the last two decades, both single-walled and multi-walled CNTs probably represented the hottest research topic concerning materials science, equally from a fundamental and from an applicative point of view. There is a prevailing opinion among the research community that CNTs are now ready for application in everyday world. This book provides an (obviously not exhaustive) overview on some of the amazing possible applications of CNT-based materials in the near future