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Two-dimensional (2D) materials offer exciting potential for applications in many fields including electronics, optics, catalysis and energy storage. Recently, materials such as graphene, boron nitride, molybdenum sulfide and tungsten sulfide have been widely studied due to their availability, easy synthesis and fascinating properties. The combination of two or more of these 2D materials into hybrid assemblies provides a unique way to obtain novel properties different from those of the parent materials. This review examines recent literature on the synthesis and preparation of 2D hybrid material assemblies and some potential applications such as photo-detection, battery performance and efficient catalysis. We also discuss some of the future challenges that need to be addressed in the near future in this emerging field.

Large-area (∼cm2) films of vertical heterostructures formed by alternating graphene and transition-metal dichalcogenide (TMD) alloys are obtained by wet chemical routes followed by a thermal treatment at low temperature. In particular, we synthesized stacked graphene and WxMo1–xS2 alloy phases that were used as hydrogen evolution catalysts. We observed a Tafel slope of 38.7 mV dec–1 and 96 mV onset potential (at current density of 10 mA cm–2) when the heterostructure alloy was annealed at 300 °C. These results indicate that heterostructures formed by graphene and W0.4Mo0.6S2 alloys are far more efficient than WS2 and MoS2 by at least a factor of 2, and they are superior compared to other reported TMD systems. This strategy offers a cheap and low temperature synthesis alternative able to replace Pt in the hydrogen evolution reaction (HER). Furthermore, the catalytic activity of the alloy is stable over time, i.e., the catalytic activity does not experience a significant change even after 1000 cycles. Using...

In recent years tremendous efforts have been made to exploit the exceptional properties of 1-Dimensional carbon nanotubes and 2-Dimensional graphene in order to interconnect those forming 3-Dimensional hybrid systems. Such macroscopic 3-D networks possess several advantages such as highly accessible surface area, minimized agglomeration or re-stacking, enhanced thermal and electrical transport, and robust mechanical properties as compared to their nanoscale 1-D or 2-D building blocks. This review aims to provide a fundamental understanding of state-of-the-art synthesis methodologies for interconnecting these carbon nanostructures, structure-property relationships as well as potential environmental applications related to adsorption, catalysis, sensing, and energy conversion. The technical challenges and future research opportunities are also discussed.

To expand the applications of carbon nanotubes (CNTs) at macroscale, a heteroatom doping technique has been employed to fabricate isotropic 3-D CNT architectures by inducing elbow-like covalent junctions into multiwalled CNTs. As the junctions modify the topology of each CNT by favoring the stable bends in CNTs, junction stiffness and the consequence of junction-related morphology changes in sponge's hyperelasticity remain largely elusive. In this study, two types of 3-D multiwalled CNT sponges were fabricated by inducing boron-doped or nitrogen-doped covalent junctions into CNTs. Hyperelastic properties of the sponges were experimentally quantified as the functions of CNT morphology. A novel microstructure informed continuum constitutive law was developed specifically for such isotropic CNT sponges with junctions. Analyzing the experimental data with the new theory demonstrated that, for the first time, the effective modulus of boron-doped junctions (∼100 GPa) is higher than that of nitrogen-doped junctions (∼20 GPa), and the junction stiffness is a key factor in regulating the hyperelastic compressive modulus of the material. Theoretical analysis further revealed that increased number of junctions and shorter segments on each individual CNT chain would result in stronger hyperelastic 3-D CNT networks. This study has established a fundamental knowledge base to provide guidance for the future design and fabrication of 3-D CNT macrostructures.

3D carbon nanotube (CNT)-based macrostructures are the subject of extensive attention because the outstanding properties of 1D and 2D nanostructures have not been fully translated into key engineering applications. Generation of 3D CNT architectures with covalent junctions could endow the new materials with extraordinary mechanical properties. In this study, detailed experimental characterization and statistical comparison are carried out on 3D boron-doped multiwalled CNT (CBxMWNT) sponges with covalent junctions and undoped multiwalled CNT (undoped-MWNT) sponges without junctions. By investigating the plastic, elastic, viscoelastic, and dynamic viscoelastic properties of both sponges, as well as the dependency of these mechanical properties on material morphology, the CBxMWNT sponge is found to be a more predictable and stable material than the undoped-MWNT sponge. Statistical comparison proves that the excellent properties of the CBxMWNT are attributed to its “elbow-like” junctions inside the 3D networks, which prevent permanent buckling and bundling of the CNTs under extreme loading. Thus, by optimizing the covalent junctions in 3D CNT sponges, their functional behavior can be controlled and regulated. These findings may promote applications of 3D CNT sponges in various fields, including biomedical or high-precision devices in which lightweight, controllable, and reliable mechanical properties are always desirable.

Summary Monolayers of transition metal dichalcogenides (TMDs), such as MoS2 and WS2, have recently triggered worldwide research interest due to their remarkable optical and electronic properties. More fascinatingly is the fact that these monolayers could also adopt various morphologies with exposed edges that include triangular, hexagonal or star-shaped clusters, in addition to nanoribbons. Exciting progress has been recently achieved in the synthesis, characterization, device fabrication and functionalization of these monolayer and few-layer TMDs. This article firstly reviews the properties of bulk and monolayer/few-layer TMDs. The “top-down” and “bottom-up” synthesis routes for different TMDs are then summarized. Raman spectroscopy is now becoming a key tool used to characterize atomically thin TMDs, and this review will show the latest advances using this spectroscopic technique. Here we also summarize the most relevant characterization techniques, optical/electronic device fabrication, functionalization and defect engineering of TMDs. There are numerous opportunities for applications and multiple challenges to overcome, and this review will be instructive and useful to researchers working in the area of 2-dimensional materials, as well as scientists and engineers interested in their applications in electronics, optics, catalysis, energy and many others.

Synthesizing 3D carbon nanotube (CNT) networks with multifunctional characteristics has stimulated the interest from the scientific community since the 1990s. Here, the fabrication of a novel composite material consisting of 3D covalently interconnected multiwalled CNT with silicon carbide (SiC) nano and microparticles is reported. The material is synthesized by a two-step process involving the coating of CNT with silicon oxide (SiO x ) via chemical routes, followed by spark plasma sintering (SPS). SPS enables carbothermal reduction of SiOx and subsequent densification of the material into 3D composite blocks. Covalent interconnections of CNT are facilitated by a carbon diffusion process resulting in SiC formation as SiOx coated CNT are subjected to high temperatures. The presence of SiC in the sintered composite has been confirmed by Raman spectroscopy, as well as through energy filtered transmission electron microscopy maps. Interestingly, the 3D CNT composite exhibits high thermal conductivity (16.72 W m−1 K−1); and also a semiconducting behavior with an electron hopping mechanism associated to a 3D variable range hopping model. These findings demonstrate that it is indeed possible to fabricate SiC–CNT composites with enhanced physical properties that can be used as multifunctional materials.

Three types of multi-walled carbon nanotubes are investigated as electrodes in the positive half-cell of a vanadium redox flow battery (VRFB). Pure (MWCNTs), nitrogen-doped (CNxMWNTs) and oxygen functionalized (MWCNT-Cs) carbon nanotubes exhibit significant structural differences at the nanoscale, as well as different chemical and physical properties. The influence of such different characteristics on the electrochemical behavior towards the VO2+/VO2+ redox reactions is investigated by cyclic voltammetry, electrochemical impedance spectroscopy and charge/discharge experiments. MWCNT-Cs exhibit the best performance despite not having the largest specific surface area, neither the greatest amount of oxygen nor nitrogen functional groups on their surface. Therefore, their enhanced performance in terms of electrochemical activity and kinetic reversibility towards the vanadium reactions and energy efficiency of the corresponding static battery, are attributed to the highest sp2 carbon content, which brings the highest electrical conductivity. These results represent a significant advance in the fundamental understanding and design of effective electrode materials that will lead to more efficient batteries.

Elucidating the origin of carbon nanotube chirality is key for realizing their untapped potential. Currently, prevalent theories suggest that catalyst structure originates chirality via an epitaxial relationship. Here we studied chirality abundances of carbon nanotubes grown on floating liquid Ga droplets, which excludes the influence of catalyst features, and compared them with abundances grown on solid Ru nanoparticles. Results of growth on liquid droplets bolsters the intrinsic preference of carbon nuclei toward certain chiralities. Specifically, the abundance of the (11,1)/χ = 4.31° tube can reach up to 95% relative to (9,4)/χ = 17.48°, although they have exactly the same diameter, (9.156 A). However, the comparative abundances for the pair, (19,3)/χ = 7.2° and (17,6)/χ = 14.5°, with bigger diameter, (16.405 A), fluctuate depending on synthesis temperature. The abundances of the same pairs of tubes grown on floating solid polyhedral Ru nanoparticles show completely different trends. Analysis of abundances in relation to nucleation probability, represented by a product of the Zeldovich factor and the deviation interval of a growing nuclei from equilibrium critical size, explain the findings. We suggest that the chirality in the nanotube in general is a result of interplay between intrinsic preference of carbon cluster and induction by catalyst structure. This finding can help to build the comprehensive theory of nanotube growth and offers a prospect for chirality-preferential synthesis of carbon nanotubes by the exploitation of liquid catalyst droplets.

Large-area (∼cm

CVD synthesised CNT flexible sponge with density lower than 0.02 g cm–3 has been found to serve as high performance EMI shielding material without the aid of any polymer infiltration or impregnation. Due to its extreme lightweight, the specific SE of the CNT-sponge was found to be as high as 1100 dB cm3 g–1, having a total SE above 20 dB in the whole 1–18 GHz range, and being able to shield by absorption. The material is the best of our knowledge this specific SE value appears to be the highest reported hitherto. Improved EM absorbers should fulfil the synergic requirements of being low reflective and highly absorptive. In our CNT-sponges this condition is not satisfied because, although their net absorption ability is strongly remarkable, their high electrical conductivity favours the wave to be reflected at the input interface. Therefore, this sponge material would have a great potential for microwave-frequency applications that need negligible reflection and great absorption when combined in a multilayered structure that could prevent the wave to be reflected at the input interface. (© 2014 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

Graphene oxide (GO) has recently become an attractive building block for fabricating graphene-based functional materials. GO films and fibers have been prepared mainly by vacuum filtration and wet spinning. These materials exhibit relatively high Young's moduli but low toughness and a high tendency to tear or break. Here, we report an alternative method, using bar coating and drying of water/GO dispersions, for preparing large-area GO thin films (e.g., 800-1200 cm(2) or larger) with an outstanding mechanical behavior and excellent tear resistance. These dried films were subsequently scrolled to prepare GO fibers with extremely large elongation to fracture (up to 76%), high toughness (up to 17 J/m(3)), and attractive macroscopic properties, such as uniform circular cross section, smooth surface, and great knotability. This method is simple, and after thermal reduction of the GO material, it can render highly electrically conducting graphene-based fibers with values up to 416 S/cm at room temperature. In this context, GO fibers annealed at 2000 °C were also successfully used as electron field emitters operating at low turn on voltages of ca. 0.48 V/μm and high current densities (5.3 A/cm(2)). Robust GO fibers and large-area films with fascinating architectures and outstanding mechanical and electrical properties were prepared with bar coating followed by dry film scrolling.

The metastable 1T′ polymorph of molybdenum disulfide (MoS2) has shown excellent catalytic activity toward the hydrogen evolution reaction (HER) in water‐splitting applications. Its basal plane exhi ...

High pressure/temperature was applied on samples of pristine multi-walled carbon nanotubes (MWCNT), functionalized nanotubes (f-MWCNT), and nanotubes doped with nitrogen (CN x MWNT). Cylindrical compact pellets of f-MWCNT with diameters of about 6 mm were obtained under pressure of 4.0 GPa at room temperature and at 400 °C, using graphite as pressure transmitting medium. The best pellet samples were produced using nitric and sulfuric acids for the functionalization of MWCNT. The effect of high pressure/temperature on CNT was investigated by several spectroscopy and characterization techniques, such as Raman spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, N2 adsorption/desorption isotherms, and transmission electron microscopy. It was found that MWCNT maintain their main features in the compacted pellets, such as integrity, original morphology, and structure, demonstrating that high-pressure/temperature compaction can indeed be used to fabricate novel CNT self-supported materials. Additionally, the specific surface area and porosity are unchanged, which is important when using bulk CNT in adsorption processes. Raman analysis of the G’-band showed a shift to lower wavenumbers when f-MWCNT were processed under high pressure, suggesting that CNT are under tensile stress.

It is a challenge to fabricate graphene bulk materials with properties arising from the nature of individual graphene sheets, and which assemble into monolithic three-dimensional structures. Here we report the scalable self-assembly of randomly oriented graphene sheets into additive-free, essentially homogenous graphene sponge materials that provide a combination of both cork-like and rubber-like properties. These graphene sponges, with densities similar to air, display Poisson's ratios in all directions that are near-zero and largely strain-independent during reversible compression to giant strains. And at the same time, they function as enthalpic rubbers, which can recover up to 98% compression in air and 90% in liquids, and operate between -196 and 900 °C. Furthermore, these sponges provide reversible liquid absorption for hundreds of cycles and then discharge it within seconds, while still providing an effective near-zero Poisson's ratio.