Vertical heterostructure of graphite-MoS2 for gas sensing.

2D materials, given their form-factor, high surface-to-volume ratio, and chemical functionality have immense use in sensor design. Engineering 2D heterostructures can result in robust combinations of desirable properties but sensor design methodologies require careful considerations about material properties and orientation to maximize sensor response. This study introduces a sensor approach that combines the excellent electrical transport and transduction properties of graphite film with chemical reactivity derived from the edge sites of semiconducting molybdenum disulfide (MoS2) through a two-step chemical vapour deposition method. The resulting vertical heterostructure shows potential for high-performance hybrid chemiresistors for gas sensing. This architecture offers active sensing edge sites across the MoS2 flakes. We detail the growth of vertically oriented MoS2 over a nanoscale graphite film (NGF) cross-section, enhancing the adsorption of analytes such as NO2, NH3, and water vapor. Raman spectroscopy, density functional theory calculations and scanning probe methods elucidate the influence of chemical doping by distinguishing the role of MoS2 edge sites relative to the basal plane. High-resolution imaging techniques confirm the controlled growth of highly crystalline hybrid structures. The MoS2/NGF hybrid structure exhibits exceptional chemiresistive responses at both room and elevated temperatures compared to bare graphitic layers. Quantitative analysis reveals that the sensitivity of this hybrid sensor surpasses other 2D material hybrids, particularly in parts per billion concentrations.

Graphene nanowalls formation investigated by Electron Energy Loss Spectroscopy.

The properties of layered materials are significantly dependent on their lattice orientations. Thus, the growth of graphene nanowalls (GNWs) on Cu through PECVD has been increasingly studied, yet the underlying mechanisms remain unclear. In this study, we examined the GNWs/Cu interface and investigated the evolution of their microstructure using advanced Scanning transmission electron microscopy and Electron Energy Loss Spectroscopy (STEM-EELS). GNWs interface and initial root layers of comprise graphitic carbon with horizontal basal graphene (BG) planes that conform well to the catalyst surface. In the vertical section, the walls show a mix of graphitic and turbostratic carbon, while the latter becomes more noticeable close to the top edges of the GMWs film. Importantly, we identified growth process began with catalysis at Cu interface forming BG, followed by defect induction and bending at 'coalescence points' of neighboring BG, which act as nucleation sites for vertical growth. We reported that although classical thermal CVD mechanism initially dominates, growth of graphene later deviates a few nanometers from the interface to form GNWs. Nascent walls are no longer subjected to the catalytic action of Cu, and their development is dominated by the stitching of charged carbon species originating in the plasma with basal plane edges.

Anisotropic Superconducting Nb2 CTx MXene Processed by Atomic Exchange at the Wafer Scale.

Superconductivty has recently been induced in MXenes through surface modification. However, the previous reports have mostly been based on powders or cold-pressed pellets, with no known reports on the intrinsic superconsucting properties of MXenes at the nanoale. Here, it is developed a high-temperature atomic exchange process in NH3 atmosphere which induces superconductivity in either singleflakes or thin films of Nb2 CTx MXene. The exchange process between nitrogen atoms and fluorine, carbon, and oxygen atoms in the MXene lattice and related structural adjustments are studied using both experiments and density functional theory. Using either single-flake or thin-film devices, an anisotropic magnetic response of the 2D superconducting transformation has been successfully revealed. The anisotropic superconductivity is further demonstrated using superconducting thin films uniformly deposited over a 4 in. wafers, which opens up the possibility of scalable MXene-based superconducting devices.

Graphene nanowalls grown on copper mesh.

Graphene nanowalls (GNWs) can be described as extended nanosheets of graphitic carbon where the basal planes are perpendicular to a substrate. Generally, existing techniques to grow films of GNWsare based on plasma-enhanced chemical vapor deposition (PECVD) and the use of diverse substrate materials (Cu, Ni, C, etc) shaped as foils or filaments. Usually, patterned films rely on substrates priorly modified by costly cleanroom procedures. Hence, we report here the characterization, transfer and application of wafer-scale patterned GNWsfilms that were grown on Cu meshes using low-power direct-current PECVD. Reaching wall heights of ∼300 nm, mats of vertically-aligned carbon nanosheets covered square centimeter wire meshes substrates, replicating well the thread dimensions and the tens of micrometer-wide openings of the meshes. Contrastingly, the same growth conditions applied to Cu foils resulted in limited carbon deposition, mostly confined to the substrate edges. Based on the wet transfer procedure turbostratic and graphitic carbon domains co-exist in the GNWsmicrostructure. Interestingly, these nanoscaled patterned films were quite hydrophobic, being able to reverse the wetting behavior of SiO2surfaces. Finally, we show that the GNWscan also be used as the active material for C-on-Cu anodes of Li-ion battery systems.

Flexible, Air-Stable, High-Performance Heaters Based on Nanoscale-Thick Graphite Films.

Graphite sheets are known to exhibit remarkable performance in applications such as heating panels and critical elements of thermal management systems. Industrial-scale production of graphite films relies on high-temperature treatment of polymers or calendering of graphite flakes; however, these methods are limited to obtaining micrometer-scale thicknesses. Herein, we report the fabrication of a flexible and power-efficient cm2-scaled heater based on a polycrystalline nanoscale-thick graphite film (NGF, ∼100 nm thick) grown by chemical vapor deposition. The stability of these NGF heaters (operational in air over the range 30-300 °C) is demonstrated by a 12-day continuous heating test, at 215 °C. The NGF exhibits a fast switching response and attains a steady peak temperature of 300 °C at a driving bias of 7.8 V (power density of 1.1 W/cm2). This excellent heating performance is attributed to the structural characteristics of the NGF, which contains well-distributed wrinkles and micrometer-wide few-layer graphene domains (characterized using conductive imaging and finite element methods, respectively). The efficiency and flexibility of the NGF device are exemplified by externally heating a 2000 µm-thick Pyrex glass vial and bringing 5 mL of water to a temperature of 96 °C (at 2.4 W/cm2). Overall, the NGF could become an excellent active material for ultrathin, flexible, and sustainable heating panels that operate at low power.

Investigating the thermal stability of metallic and non-metallic nanoparticles using a novel graphene oxide-based transmission electron microscopy heating-membrane.

In recent years, graphene has been explored as a heating membrane for studying high-temperature dynamics inside the transmission electron microscope (TEM) due to several limitations with the existing silicon nitride-based membrane. However, the transfer of monolayer graphene films for TEM experiments is challenging and requires many complicated steps with a minimum success rate. This work developed a novelin situheating platform by combining the graphene oxide (GO) flakes in the pre-patterned chips. The isolated GO flake was self-suspended between the metal electrodes by a simple drop-casting process. The GO was reduced and characterized using Raman and electron energy-loss spectroscopy. Furthermore, a GO-based heater was used to investigate the thermal stability of gold and silica nanoparticles. The gold nanoparticles evaporated non-uniformly and left an empty carbon shell, while silica disappeared uniformly by etching carbon support. We successfully demonstrated a GO flake as a heating membrane to study high temperature thermal dynamic reactions: melting/evaporation, agglomeration, Rayleigh instability, and formation/or removal of carbon in the nanoparticles.

Lattice Orientation Heredity in the Transformation of 2D Epitaxial Films.

The ability to control lattice orientation is often an essential requirement in the growth of both 2D van der Waals (vdW) layered and nonlayered thin films. Here, a unique and universal phenomenon termed "lattice orientation heredity" (LOH) is reported. LOH enables product films (including 2D-layered materials) to inherit the lattice orientation from reactant films in a chemical conversion process, excluding the requirement on the substrate lattice order. The process universality is demonstrated by investigating the lattice transformations in the carbonization, nitridation, and sulfurization of epitaxial MoO2 , ZnO, and In2 O3 thin films. Their resultant compounds all inherit the mono-oriented crystal feature from their precursor oxides, including 2D vdW-layered semiconductors (e.g., MoS2 ), metallic films (e.g., MXene-like Mo2 C and MoN), wide-bandgap semiconductors (e.g., hexagonal ZnS), and ferroelectric semiconductors (e.g., In2 S3 ). Using LOH-grown MoN as a seeding layer, mono-oriented GaN is achieved on an amorphous quartz substrate. The LOH process presents a universal strategy capable of growing epitaxial thin films (including 2D vdW-layered materials) not only on single-crystalline but also on noncrystalline substrates.

Electrode-Electrolyte Interactions in an Aqueous Aluminum-Carbon Rechargeable Battery System.

Being environmentally friendly, safe and easy to handle, aqueous electrolytes are of particular interest for next-generation electrochemical energy storage devices. When coupled with an abundant, recyclable and low-cost electrode material such as aluminum, the promise of a green and economically sustainable battery system has extraordinary appeal. In this work, we study the interaction of an aqueous electrolyte with an aluminum plate anode and various graphitic cathodes. Upon establishing the boundary conditions for optimal electrolyte performance, we find that a mesoporous reduced graphene oxide powder constitutes a better cathode material option than graphite flakes.

Activated Carbon from Palm Date Seeds for CO2 Capture.

The process of carbon dioxide capture and storage is seen as a critical strategy to mitigate the so-called greenhouse effect and the planetary climate changes associated with it. In this study, we investigated the CO2 adsorption capacity of various microporous carbon materials originating from palm date seeds (PDS) using green chemistry synthesis. The PDS was used as a precursor for the hydrochar and activated carbon (AC). Typically, by using the hydrothermal carbonization (HTC) process, we obtained a powder that was then subjected to an activation step using KOH, H3PO4 or CO2, thereby producing the activated HTC-PDS samples. Beyond their morphological and textural characteristics, we investigated the chemical composition and lattice ordering. Most PDS-derived powders have a high surface area (>1000 m2 g-1) and large micropore volume (>0.5 cm3 g-1). However, the defining characteristic for the maximal CO2 uptake (5.44 mmol g-1, by one of the alkaline activated samples) was the lattice restructuring that occurred. This work highlights the need to conduct structural and elemental analysis of carbon powders used as gas adsorbents and activated with chemicals that can produce graphite intercalation compounds.

CVD-Grown Monolayer Graphene-Based Geometric Diode for THz Rectennas.

For THz rectennas, ultra-fast diodes are required. While the metal-insulator-metal (MIM) diode has been investigated in recent years, it suffers from large resistance and capacitance, as well as a low cut-off frequency. Alternatively, a geometric diode can be used, which is more suitable due to its planar structure. However, there is only one report of a THz geometric diode based on a monolayer graphene. It is based on exfoliated graphene, and thus, it is not suitable for mass production. In this work, we demonstrate chemical vapor deposition (CVD)-grown monolayer graphene based geometric diodes, which are mass-producible. The diode's performance has been studied experimentally by varying the neck widths from 250-50 nm, the latter being the smallest reported neck width for a graphene geometric diode. It was observed that by decreasing the neck widths, the diode parameters such as asymmetry, nonlinearity, zero-bias resistance, and responsivity increased within the range studied. For the 50 nm neck width diode, the asymmetry ratio was 1.40 for an applied voltage ranging from -2 V to 2 V, and the zero-bias responsivity was 0.0628 A/W. The performance of the diode was also verified through particle-in-cell Monte Carlo simulations, which showed that the simulated current-voltage characteristics were consistent with our experimental results.

Can a Procedure for the Growth of Single-layer Graphene on Copper be used in Different Chemical Vapor Deposition Reactors?

In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a "showerhead" cold-wall type, whereas the other represented the popular "tubular" hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm2 -scale SLG growth that differed only by the carrier gas flow rate used in the two reactors.

A Cyclized Polyacrylonitrile Anode for Alkali Metal Ion Batteries.

Organic anodes have attracted increasing attention for alkali metal ion batteries. In this work, we discovered that cyclized polyacrylonitrile (cPAN) can serve as an excellent anode for alkali metal ion batteries. Upon activation cycling, as an anode of lithium-ion battery, cPAN exhibits a reversible capacity as high as 1238 mAh g-1 under a current density of 50 mA g-1 . Based on electrochemical experiments and first-principles calculations, it is demonstrated that the hexagonal carbon ring, piperidine ring, and pyridine nitrogen in ladder cPAN are the main active sites for lithium-ion storage. cPAN displays a unique potential-dependent solid electrolyte interphase formation from 0.1 to 0.01 V vs. Li/Li+ . It also displays decent performance as an anode in SIBs and PIBs.

Paper-Based In-Situ Gold Nanoparticle Synthesis for Colorimetric, Non-Enzymatic Glucose Level Determination.

Due to its properties, paper represents an alternative to perform point-of-care tests for colorimetric determination of glucose levels, providing simple, rapid, and inexpensive means of diagnosis. In this work, we report the development of a novel, rapid, disposable, inexpensive, enzyme-free, and colorimetric paper-based assay for glucose level determination. This sensing strategy is based on the synthesis of gold nanoparticles (AuNPs) by reduction of a gold salt precursor, in which glucose acts simultaneously as reducing and capping agent. This leads to a direct measurement of glucose without any enzymes or depending on the detection of intermediate products as in conventional enzymatic colorimetric methods. Firstly, we modelled the synthesis reaction of AuNPs to determine the optical, morphological, and kinetic properties and their manipulation for glucose sensing, by determining the influence of each of the reaction precursors towards the produced AuNPs, providing a guide for the manipulation of nucleation and growth. The adaptation of this synthesis into the developed paper platform was tested and calibrated using different standard solutions with physiological concentrations of glucose. The response of the colorimetric signals obtained with this paper-based platform showed a linear behavior until 20 mM, required for glycemic control in diabetes, using the Red × Value/Grey feature combination as a calibration metric, to describe the variations in color intensity and hue in the spot test zone. The colorimetric sensor revealed a detection limit of 0.65 mM, depending on calibration metric and sensitivity of 0.013 AU/mM for a linear sensitivity range from 1.25 to 20 mM, with high specificity for the determination of glucose in complex standards with other common reducing interferents and human serum.

Publisher Correction: Semi-transparent graphite films growth on Ni and their double-sided polymer-free transfer.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Semi-transparent graphite films growth on Ni and their double-sided polymer-free transfer.

Nanorange thickness graphite films (NGFs) are robust nanomaterials that can be produced via catalytic chemical vapour deposition but questions remain regarding their facile transfer and how surface topography may affect their application in next-generation devices. Here, we report the growth of NGFs (with an area of 55 cm2 and thickness of ~ 100 nm) on both sides of a polycrystalline Ni foil and their polymer-free transfer (front- and back-side, in areas up to 6 cm2). Due to the catalyst foil topography, the two carbon films differed in physical properties and other characteristics such as surface roughness. We demonstrate that the coarser back-side NGF is well-suited for NO2 sensing, whereas the smoother and more electrically conductive front-side NGF (2000 S/cm, sheet resistance - 50 Ω/sq) could be a viable conducting channel or counter electrode in solar cells (as it transmits 62% of visible light). Overall, the growth and transfer processes described could help realizing NGFs as an alternative carbon material for those technological applications where graphene and micrometer-thick graphite films are not an option.

Fast, wafer-scale growth of a nanometer-thick graphite film on Ni foil and its structural analysis.

The growth of graphite on polycrystalline Ni by chemical vapor deposition (CVD) and the microstructural relation of the graphitic films and the metallic substrate continues to puzzle the scientific community. Here, we report the wafer-scale growth of a nanometer-thick graphite film (∼100 nm, NGF) on Ni foil via a fast-thermal CVD approach (5 min growth). Moreover, we shed light on how localized thickness variations of the NGF relate to the Ni surface topography and grain characteristics. While on a macro-scale (mm2), the NGF film looks uniform-with a few hundred highly ordered graphene layers (d0002 = 0.335 nm), when studied at the micro- and nano-scales, few-layer graphene sections can be identified. These are present at a density of 0.1%-3% areas in 100 µ m2, can be as thin as two layers, and follow an epitaxial relation with the {111} fcc-Ni planes. Throughout the 50 cm2 NGF, the sharp graphite/substrate interfaces are either composed of a couple of NiCx layers or a graphene layer. Moreover, the NGF was successfully transferred on SiO2/Si substrate by a wet chemical etching method. The as-produced NGFs could complement or offer an alternative to the mm-thick films produced from natural graphite flakes or polymer sheets.

A Site-Selective Doping Strategy of Carbon Anodes with Remarkable K-Ion Storage Capacity.

The limited potassium-ion intercalation capacity of graphite hampers development of potassium-ion batteries (PIB). Edge-nitrogen doping is an effective approach to enhance K-ion storage in carbonaceous materials. One shortcoming is the lack of precise control over producing the edge-nitrogen configuration. Here, a molecular-scale copolymer pyrolysis strategy is used to precisely control edge-nitrogen doping in carbonaceous materials. This process results in defect-rich, edge-nitrogen doped carbons (ENDC) with a high nitrogen-doping level (up to 10.5 at %) and a high edge-nitrogen ratio (87.6 %). The optimized ENDC exhibits a high reversible capacity of 423 mAh g-1 , a high initial Coulombic efficiency of 65 %, superior rate capability, and long cycle life (93.8 % retention after three months). This strategy can be extended to design other edge-heteroatom-rich carbons through pyrolysis of copolymers for efficient storage of various mobile ions.

Current-Induced Helicity Reversal of a Single Skyrmionic Bubble Chain in a Nanostructured Frustrated Magnet.

Helicity indicates the in-plane magnetic-moment swirling direction of a skyrmionic configuration. The ability to reverse the helicity of a skyrmionic bubble via purely electrical means has been predicted in frustrated magnetic systems; however, it has been challenging to observe this experimentally. The current-driven helicity reversal of the skyrmionic bubble in a nanostructured frustrated Fe3 Sn2 magnet is experimentally demonstrated. The critical current density required to trigger the helicity reversal is 109 -1010 A m-2 , with a corresponding pulse-width varying from 1 µs to 100 ns. Computational simulations reveal that both the pinning effect and dipole-dipole interaction play a crucial role in the helicity reversal process.

Biofuel powered glucose detection in bodily fluids with an n-type conjugated polymer.

A promising class of materials for applications that rely on electron transfer for signal generation are the n-type semiconducting polymers. Here we demonstrate the integration of an n-type conjugated polymer with a redox enzyme for the autonomous detection of glucose and power generation from bodily fluids. The reversible, mediator-free, miniaturized glucose sensor is an enzyme-coupled organic electrochemical transistor with a detection range of six orders of magnitude. This n-type polymer is also used as an anode and paired with a polymeric cathode in an enzymatic fuel cell to convert the chemical energy of glucose and oxygen into electrical power. The all-polymer biofuel cell shows a performance that scales with the glucose content in the solution and a stability that exceeds 30 days. Moreover, at physiologically relevant glucose concentrations and from fluids such as human saliva, it generates enough power to operate an organic electrochemical transistor, thus contributes to the technological advancement of self-powered micrometre-scale sensors and actuators that run on metabolites produced in the body.

Chemical and Structural Analysis of Carbon Materials Subjected to Alkaline Oxidation.

Redox species such as transition metals may, unknowingly, integrate carbon materials that are produced (or supplied) for the assembling of electrodes in batteries, supercapacitors, and fuel cells. The extent to which these species alter the electrochemical profile of carbons and affect the performance and/or degradation of energy storage systems is still not fully appreciated. Alkaline oxidation (or fusion) is a promising approach to disintegrate nanocarbons for the subsequent study of their chemical composition by routine analytical tools. In this work, three commercial carbon powders, relevant for electrochemical applications and bearing varied textural orientation (point, radial, and planar), were selected to evaluate the versatility of fusion as a pretreatment process for elemental analysis. Additionally, the interaction of the flux, a lithium borate salt, with the carbons was elucidated by examining their post-fusion residues. The degree of structural degradation varied and, generally, the doping with Li and/or B (whether substitutional or interstitial) was low to nonexistent. With future developments, fusion could become a relevant pretreatment method to analyze the composition of carbon materials, even when complex mixtures (e.g., cycled battery electrodes) and larger batch scales are considered.