Chiral Decomposition of Twisted Graphene Multilayers with Arbitrary Stacking.

We formulate the chiral decomposition rules that govern the electronic structure of a broad family of twisted N + M multilayer graphene configurations that combine arbitrary stacking order and a mutual twist. We show that at the magic angle in the chiral limit the low-energy bands of such systems are composed of chiral pseudospin doublets that are energetically entangled with two flat bands per valley induced by the moiré superlattice potential. The analytic construction is supported by explicit numerical calculations based on realistic parametrization. We further show that vertical displacement fields can open energy gaps between the pseudospin doublets and the two flat bands, such that the flat bands may carry nonzero valley Chern numbers. These results provide guidelines for the rational design of topological and correlated states in generic twisted graphene multilayers.

MoS2 Passivated Multilayer Graphene Membranes for Li-Ion Extraction From Seawater.

Abundant Li resources in the ocean are promising alternatives to refining ore, whose supplies are limited by the total amount and geopolitical imbalance of reserves in Earth's crust. Despite advances in Li+ extraction using porous membranes, they require screening other cations on a large scale due to the lack in precise control of pore size and inborn defects. Herein, MoS2 nanoflakes on a multilayer graphene membrane (MFs-on-MGM) that possess ion channels comprising i) van der Waals interlayer gaps for optimal Li+ extraction and ii) negatively charged vertical inlets for cation attraction, are reported. Ion transport measurements across the membrane reveal ≈6- and 13-fold higher selectivity for Li+ compared to Na+ and Mg2+ , respectively. Furthermore, continuous, stable Li+ extraction from seawater is demonstrated by integrating the membrane into a H2 and Cl2 evolution system, enabling more than 104 -fold decrease in the Na+ concentration and near-complete elimination of other cations.

Microemitter-Based IR Spectroscopy and Imaging with Multilayer Graphene Thermal Emission.

IR analyses such as Fourier transform infrared spectroscopy (FTIR) are widely used in many fields; however, the performance of FTIR is limited by the slow speed (∼10 Hz), large footprint (∼ millimeter), and glass bulb structure of IR light sources. Herein, we present IR spectroscopy and imaging based on multilayer-graphene microemitters, which have distinct features: a planar structure, bright intensity, a small footprint (sub-µm2), and high modulation speed of >50 kHz. We developed an IR analysis system based on the multilayer-graphene microemitter and performed IR absorption spectroscopy. We show two-dimensional IR chemical imaging that visualizes the distribution of the chemical information. In addition, we present high-spatial-resolution IR imaging with a spatial resolution of ∼1 µm, far higher than the diffraction limit. The graphene-based IR spectroscopy and imaging can open new routes for IR applications in chemistry, material science, medicine, biology, electronics, and physics.

Spontaneous Gully-Polarized Quantum Hall States in ABA Trilayer Graphene.

Bernal-stacked multilayer graphene is a versatile platform to explore quantum transport phenomena and interaction physics due to its exceptional tunability via electrostatic gating. For instance, upon applying a perpendicular electric field, its band structure exhibits several off-center Dirac points (so-called Dirac gullies) in each valley. Here, the formation of Dirac gullies and the interaction-induced breakdown of gully coherence is explored via magnetotransport measurements in high-quality Bernal-stacked (ABA) trilayer graphene. At zero magnetic field, multiple Lifshitz transitions indicating the formation of Dirac gullies are identified. In the quantum Hall regime, the emergence of Dirac gullies is evident as an increase in Landau level degeneracy. When tuning both electric and magnetic fields, electron-electron interactions can be controllably enhanced until, beyond critical electric and magnetic fields, the gully degeneracy is eventually lifted. The arising correlated ground state is consistent with a previously predicted nematic phase that spontaneously breaks the rotational gully symmetry.

Mechanical Properties of Graphene Networks under Compression: A Molecular Dynamics Simulation.

Molecular dynamics simulation is used to study and compare the mechanical properties obtained from compression and tension numerical tests of multilayered graphene with an increased interlayer distance. The multilayer graphene with an interlayer distance two-times larger than in graphite is studied first under biaxial compression and then under uniaxial tension along three different axes. The mechanical properties, e.g., the tensile strength and ductility as well as the deformation characteristics due to graphene layer stacking, are studied. The results show that the mechanical properties along different directions are significantly distinguished. Two competitive mechanisms are found both for the compression and tension of multilayer graphene-the crumpling of graphene layers increases the stresses, while the sliding of graphene layers through the surface-to-surface connection lowers it. Multilayer graphene after biaxial compression can sustain high tensile stresses combined with high plasticity. The main outcome of the study of such complex architecture is an important step towards the design of advanced carbon nanomaterials with improved mechanical properties.

Model Approach to Thermal Conductivity in Hybrid Graphene-Polymer Nanocomposites.

The thermal conductivity of epoxy nanocomposites filled with self-assembled hybrid nanoparticles composed of multilayered graphene nanoplatelets and anatase nanoparticles was described using an analytical model based on the effective medium approximation with a reasonable amount of input data. The proposed effective thickness approach allowed for the simplification of the thermal conductivity simulations in hybrid graphene@anatase TiO2 nanosheets by including the phenomenological thermal boundary resistance. The sensitivity of the modeled thermal conductivity to the geometrical and material parameters of filling particles and the host polymer matrix, filler's mass concentration, self-assembling degree, and Kapitza thermal boundary resistances at emerging interfaces was numerically evaluated. A fair agreement of the calculated and measured room-temperature thermal conductivity was obtained.

High-Rate CO2 Electrolysis to Formic Acid over a Wide Potential Window: An Electrocatalyst Comprised of Indium Nanoparticles on Chitosan-Derived Graphene.

Realizing industrial-scale production of HCOOH from the CO2 reduction reaction (CO2 RR) is very important, but the current density as well as the electrochemical potential window are still limited to date. Herein, we achieved this by integration of chemical adsorption and electrocatalytic capabilities for the CO2 RR via anchoring In nanoparticles (NPs) on biomass-derived substrates to create In/X-C (X=N, P, B) bifunctional active centers. The In NPs/chitosan-derived N-doped defective graphene (In/N-dG) catalyst had outstanding performance for the CO2 RR with a nearly 100 % Faradaic efficiency (FE) of HCOOH across a wide potential window. Particularly, at 1.2 A ⋅ cm-2 high current density, the FE of HCOOH was as high as 96.0 %, and the reduction potential was as low as -1.17 V vs RHE. When using a membrane electrode assembly (MEA), a pure HCOOH solution could be obtained at the cathode without further separation and purification. The FE of HCOOH was still up to 93.3 % at 0.52 A ⋅ cm-2 , and the HCOOH production rate could reach 9.051 mmol ⋅ h-1 ⋅ cm-2 . Our results suggested that the defects and multilayer structure in In/N-dG could not only enhance CO2 chemical adsorption capability, but also trigger the formation of an electron-rich catalytic environment around In sites to promote the generation of HCOOH.

Graphene delamination from chemical vapor deposited turbostratic multilayer graphene for TEM analysis.

Turbostratic multilayer graphene (MLG) is of great interest due to its unique electronic properties resulting from a linear band dispersion at the K point, which is similar to that of single-layer graphene. The band structure is derived from the stacking structure of turbostratic MLG where graphene layers have random in-plane rotations with respect to each other. Although wafer-scale growth of turbostratic MLG has been demonstrated, the crystallinity of individual graphene layers is still challenging to investigate. In this study, we present a new approach to reveal the grain structure of turbostratic MLG by transmission electron microscopy (TEM) observation. Mechanical delamination is demonstrated for the chemical vapor deposited MLG to peel off the topmost graphene layers by using a polydimethylsiloxane sheet. Micrometer-scale patterning of the MLG prior to the delamination is found to be effective to obtain graphene films with the designed shape and arrangement. Furthermore, the delaminated graphene films are successfully transferred onto a TEM grid, enabling us to estimate the grain size of the turbostratic MLG. This method is potentially applicable for not only preparing samples but also fabricating vertically stacked heterostructure devices using 2D materials.

Highly Dispersed Molybdenum Oxycarbide Clusters Supported on Multilayer Graphene for the Selective Reduction of Carbon Dioxide.

Molybdenum oxycarbide clusters are novel nanomaterials that exhibit attractive catalytic activity; however, the methods for their production are currently very restrictive. This work represents a new strategy for the creation of near-subnanometer size molybdenum oxycarbide clusters on multilayer graphene. To adsorb Mo-based polyoxometalates of the type [PMo12 O40 ]3- as a precursor for Mo oxycarbide clusters, the novel tripodal-phenyl cation N,N,N-tri(4-phenylbutyl)-N-methylammonium ([TPBMA]+ ) is synthesized. [TPBMA]+ exhibits superior adsorption on multilayer graphene compared to commercially available cations such as tetrabutylammonium ([nBu4 N]+ ) and tetraphenylphosphonium ([PPh4 ]+ ). Using [TPBMA]+ as an anchor, highly dispersed precursor clusters (diameter: 1.0 ± 0.2 nm) supported on multilayer graphene are obtained, as confirmed by high-resolution scanning transmission electron microscopy. Remarkably, this new material achieves the catalytic reduction of CO2 to selectively produce CO (≈99.9%) via the reverse water-gas-shift reaction, by applying carbothermal hydrogen reduction to generate Mo oxycarbide clusters in situ.

Sensing mechanism of the nano-confined space constructed by graphene.

Multilayer graphene with dense interlayer space is the most explored two-dimensional material (2DMs) in high performance gas sensor. Herein, the insertion and the diffusion behaviors of NO, NO2, NH3and H2S in the nano-confined space of graphene are investigated using density functional theory calculations. The optimum interlayer distance is found to be 6-7 Å, in which the interaction strength is enhanced by 2 -3 times compared to monolayer graphene. Based on the optimum interlayer spacing, a barrierless diffusion process is observed due to the negligible influence of adsorption sites on the adsorption energy. Besides, an enhanced adsorption of NO2is found at the edge, which leads to a small barrier (<0.15 eV) during the its inserting into graphene layers, while the barrierless process is observed for NO, NH3and H2S. As for sensing performance, an increased sensitivity is observed for NO and NO2at the edge because of the significant energy level shift and charge transfer. Meanwhile, multilayer graphene shows good selectivity towards NO2gas. Therefore, modulating the interlayer spacing of graphene layers is a promising strategy for fabricating practical low-cost gas sensors, which may facilitate future exploration of high performance gas sensor using multilayer 2DMs.

Layer exchange synthesis of multilayer graphene.

Low-temperature synthesis of multilayer graphene (MLG) on arbitrary substrates is the key to incorporating MLG-based functional thin films, including transparent electrodes, low-resistance wiring, heat spreaders, and battery anodes in advanced electronic devices. This paper reviews the synthesis of MLG via the layer exchange (LE) phenomenon between carbon and metal from its mechanism to the possibility of device applications. The mechanism of LE is completely different from that of conventional MLG precipitation methods using metals, and the resulting MLG exhibits unique features. Modulation of metal species and growth conditions enables synthesis of high-quality MLG over a wide range of growth temperatures (350 °C-1000 °C) and MLG thicknesses (5-500 nm). Device applications are discussed based on the high electrical conductivity (2700 S cm-1) of MLG and anode operation in Li-ion batteries. Finally, we discuss the future challenges of LE for MLG and its application to flexible devices.

Comparative Electroanalytical Studies of Graphite Flake and Multilayer Graphene Paste Electrodes.

In this paper, the fabrication, surface characterisation and electrochemical properties of graphite flake (GFPE) and multilayer graphene (MLGPE) paste electrodes are described. The Raman investigations and scanning electron microscopy were used to analyze and compare structure of both carbon materials. The electroanalytical performance of both electrodes was examined and compared on the basis of the square-wave and cyclic voltammetric behavior of acetaminophen and model redox systems. Results of those studies revealed that GFPE has a larger electroactive surface area and better conductive properties, whilst MLGPE demonstrate better analytical characteristic in case of acetaminophen (AC) determination. AC determination was developed using square wave voltammetry (SWV) and square wave stripping voltammetry (SWSV). For both working electrodes, the process of accumulation enabled us to obtain an extended linear range and to lower the detection limit. In pharmaceutical formulations, AC was determined with good recovery.

Graphene-Based Adaptive Thermal Camouflage.

In nature, adaptive coloration has been effectively utilized for concealment and signaling. Various biological mechanisms have evolved to tune the reflectivity for visible and ultraviolet light. These examples inspire many artificial systems for mimicking adaptive coloration to match the visual appearance to their surroundings. Thermal camouflage, however, has been an outstanding challenge which requires an ability to control the emitted thermal radiation from the surface. Here we report a new class of active thermal surfaces capable of efficient real-time electrical-control of thermal emission over the full infrared (IR) spectrum without changing the temperature of the surface. Our approach relies on electro-modulation of IR absorptivity and emissivity of multilayer graphene via reversible intercalation of nonvolatile ionic liquids. The demonstrated devices are light (30 g/m2), thin (<50 µm), and ultraflexible, which can conformably coat their environment. In addition, by combining active thermal surfaces with a feedback mechanism, we demonstrate realization of an adaptive thermal camouflage system which can reconfigure its thermal appearance and blend itself with the varying thermal background in a few seconds. Furthermore, we show that these devices can disguise hot objects as cold and cold ones as hot in a thermal imaging system. We anticipate that, the electrical control of thermal radiation would impact on a variety of new technologies ranging from adaptive IR optics to heat management for outer space applications.

Enantioselective Molecular Transport in Multilayer Graphene Nanopores.

Multilayer superstructures based on stacked layered nanomaterials offer the possibility to design three-dimensional (3D) nanopores with highly specific properties analogous to protein channels. In a layer-by-layer design and stacking, analogous to molecular printing, superstructures with lock-and-key molecular nesting and transport characteristics could be prepared. To examine this possibility, we use molecular dynamics simulations to study electric field-driven transport of ions through stacked porous graphene flakes. First, highly selective, tunable, and correlated passage rates of monovalent atomic ions through these superstructures are observed in dependence on the ion type, nanopore type, and relative position and dynamics of neighboring porous flakes. Next, enantioselective molecular transport of ionized l- and d-leucine is observed in graphene stacks with helical nanopores. The outlined approach provides a general scheme for synthesis of functional 3D superstructures.

Molecular Beam Epitaxy of GaN Nanowires on Epitaxial Graphene.

We demonstrate an all-epitaxial and scalable growth approach to fabricate single-crystalline GaN nanowires on graphene by plasma-assisted molecular beam epitaxy. As substrate, we explore several types of epitaxial graphene layer structures synthesized on SiC. The different structures differ mainly in their total number of graphene layers. Because graphene is found to be etched under active N exposure, the direct growth of GaN nanowires on graphene is only achieved on multilayer graphene structures. The analysis of the nanowire ensembles prepared on multilayer graphene by Raman spectroscopy and transmission electron microscopy reveals the presence of graphene underneath as well as in between nanowires, as desired for the use of this material as contact layer in nanowire-based devices. The nanowires nucleate preferentially at step edges, are vertical, well aligned, epitaxial, and of comparable structural quality as similar structures fabricated on conventional substrates.

Effects of Electrode Layer Band Structure on the Performance of Multilayer Graphene-hBN-Graphene Interlayer Tunnel Field Effect Transistors.

Interlayer tunnel field-effect transistors based on graphene and hexagonal boron nitride (hBN) have recently attracted much interest for their potential as beyond-CMOS devices. Using a recently developed method for fabricating rotationally aligned two-dimensional heterostructures, we show experimental results for devices with varying thicknesses and stacking order of the graphene electrode layers and also model the current-voltage behavior. We show that an increase in the graphene layer thickness results in narrower resonance. However, due to a simultaneous increase in the number of sub-bands and decrease of sub-band separation with an increase in thickness, the negative differential resistance peaks becomes less prominent and do not appear for certain conditions at room temperature. Also, we show that due to the unique band structure of odd number of layer Bernal-stacked graphene, the number of closely spaced resonance conditions increase, causing interference between neighboring resonance peaks. Although this can be avoided with even number of layer graphene, we find that in this case the bandgap opening present at high biases tend to broaden the resonance peaks.

Unusual Enhancement in Intrinsic Thermal Conductivity of Multilayer Graphene by Tensile Strains.

Using the Boltzmann-Peierls equation for phonon transport approach with the inputs of interatomic force constants from the self-consistent charge density functional tight binding method, we calculate the room-temperature in-plane lattice thermal conductivities k of multilayer graphene (up to four layers) and graphite under different isotropic tensile strains. The calculated in-plane k of graphite, finite monolayer graphene and 3-layer graphene agree well with previous experiments. For unstrained graphene systems, both the intrinsic k and the extent of the diffusive transport regime present a drastic dimensional transition in going from monolayer to 2-layer graphene and thereafter a gradual transition to the graphite limit. We find a peak enhancement of intrinsic k for multilayer graphene and graphite with increasing strain with the largest enhancement amplitude ∼40%. Competition between the decreased mode heat capacities and the increased lifetimes of flexural phonons with increasing strain contribute to this k behavior. Similar k behavior is observed for 2-layer hexagonal boron nitride systems. This study provides insights into engineering k of multilayer graphene and boron nitride by strain and into the nature of thermal transport in quasi-two-dimensional and highly anisotropic systems.

Direct Observation of Wet Biological Samples by Graphene Liquid Cell Transmission Electron Microscopy.

Recent development of liquid phase transmission electron microscopy (TEM) enables the study of specimens in wet ambient conditions within a liquid cell; however, direct structural observation of biological samples in their native solution using TEM is challenging since low-mass biomaterials embedded in a thick liquid layer of the host cell demonstrate low contrast. Furthermore, the integrity of delicate wet samples is easily compromised during typical sample preparation and TEM imaging. To overcome these limitations, we introduce a graphene liquid cell (GLC) using multilayer graphene sheets to reliably encapsulate and preserve biological samples in a liquid for TEM observation. We achieve nanometer scale spatial resolution with high contrast using low-dose TEM at room temperature, and we use the GLC to directly observe the structure of influenza viruses in their native buffer solution at room temperature. The GLC is further extended to investigate whole cells in wet conditions using TEM. We also demonstrate the potential of the GLC for correlative studies by TEM and fluorescence light microscopy imaging.

High-performance graphene-based hole conductor-free perovskite solar cells: Schottky junction enhanced hole extraction and electron blocking.

Multilayered graphene and single-layered graphene are assembled onto perovskite films in the form of Schottky junctions and ohmic contacts, respectively, for the production of a graphene-based hole transporting material-free perovskite solar cell. Multilayered graphene extracts charge selectively and efficiently, delivering a higher efficiency of 11.5% than single-layered graphene (6.7%).

Graphene multilayer as nanosized optical strain gauge for polymer surface relief gratings.

In this paper, we show how graphene can be utilized as a nanoscopic probe in order to characterize local opto-mechanical forces generated within photosensitive azobenzene containing polymer films. Upon irradiation with light interference patterns, photosensitive films deform according to the spatial intensity variation, leading to the formation of periodic topographies such as surface relief gratings (SRG). The mechanical driving forces inscribing a pattern into the films are supposedly fairly large, because the deformation takes place without photofluidization; the polymer is in a glassy state throughout. However, until now there has been no attempt to characterize these forces by any means. The challenge here is that the forces vary locally on a nanometer scale. Here, we propose to use Raman analysis of the stretching of the graphene layer adsorbed on top of polymer film under deformation in order to probe the strength of the material transport spatially resolved. With the well-known mechanical properties of graphene, we can obtain lower bounds on the forces acting within the film. Upon the basis of our experimental results, we can deduce that the internal pressure in the film due to grating formation can exceed 1 GPa. The graphene-based nanoscopic gauge opens new possibilities to characterize opto-mechanical forces generated within photosensitive polymer films.