Kinetic Modulation of Carbon Nanotube Growth in Direct Spinning for High-Strength Carbon Nanotube Fibers.

With impressive individual properties, carbon nanotubes (CNTs) show great potential in constructing high-performance fibers. However, the tensile strength of as-prepared carbon nanotube fibers (CNTFs) by floating catalyst chemical vapor deposition (FCCVD) is plagued by the weak intertube interaction between the essential CNTs. Here, we developed a chlorine (Cl)/water (H2O)-assisted length furtherance FCCVD (CALF-FCCVD) method to modulate the intertube interaction of CNTs and enhance the mechanical strength of macroscopic fibers. The CNTs acquired by the CALF-FCCVD method show an improvement of 731% in length compared to that by the conventional iron-based FCCVD system. Moreover, CNTFs prepared by CALF-FCCVD spinning exhibit a high tensile strength of 5.27 ± 0.27 GPa (4.62 ± 0.24 N/tex) and reach up to 5.61 GPa (4.92 N/tex), which outperforms most previously reported results. Experimental measurements and density functional theory calculations show that Cl and H2O play a crucial role in the furtherance of CNT growth. Cl released from the decomposition of methylene dichloride greatly accelerates the growth of the CNTs; H2O can remove amorphous carbon on the floating catalysts to extend their lifetime, which further modulates the growth kinetics and improves the purity of the as-prepared fibers. Our design of the CALF-FCCVD platform offers a powerful way to tune CNT growth kinetics in direct spinning toward high-strength CNTFs.

High Moisture-Barrier Performance of Double-Layer Graphene Enabled by Conformal and Clean Transfer.

Graphene films that can theoretically block almost all molecules have emerged as promising candidate materials for moisture barrier films in the applications of organic photonic devices and gas storage. However, the current barrier performance of graphene films does not reach the ideal value. Here, we reveal that the interlayer distance of the large-area stacked multilayer graphene is the key factor that suppresses water permeation. We show that by minimizing the gap between the two monolayers, the water vapor transmission rate of double-layer graphene can be as low as 5 × 10-3 g/(m2 d) over an A4-sized region. The high barrier performance was achieved by the absence of interfacial contamination and conformal contact between graphene layers during layer-by-layer transfer. Our work reveals the moisture permeation mechanism through graphene layers, and with this approach, we can tailor the interlayer coupling of manually stacked two-dimensional materials for new physics and applications.

Intrinsic Properties of Macroscopically Tuned Gallium Nitride Single-Crystalline Facets for Electrocatalytic Hydrogen Evolution.

The anisotropy of crystalline materials results in different physical and chemical properties on different facets, which warrants an in-depth investigation. Macroscopically facet-tuned, high-purity gallium nitride (GaN) single crystals were synthesised and machined, and the electrocatalytic hydrogen evolution reaction (HER) was used as the model reaction to show the differences among the facets. DFT calculations revealed that the Ga and N sites of GaN (100) had a considerably smaller ΔGH* value than those of the metal Ga site of GaN (001) or N site of GaN (00-1), thereby indicating that GaN (100) should be more catalytically active for the HER on account of its nonpolar facet. Subsequent experiments testified that the electrocatalytic performance of GaN (100) was considerably more efficient than that of other facets for both acidic and alkaline HERs. Moreover, the GaN crystal with a preferentially (100) active facet had an excellently durable alkaline electrocatalytic HER for more than 10 days. This work provides fundamental insights into the exploration of the intrinsic properties of materials and designing advanced materials for physicochemical applications.

Multispecies-coadsorption-induced rapid preparation of graphene glass fiber fabric and applications in flexible pressure sensor.

Direct chemical vapor deposition (CVD) growth of graphene on dielectric/insulating materials is a promising strategy for subsequent transfer-free applications of graphene. However, graphene growth on noncatalytic substrates is faced with thorny issues, especially the limited growth rate, which severely hinders mass production and practical applications. Herein, graphene glass fiber fabric (GGFF) is developed by graphene CVD growth on glass fiber fabric. Dichloromethane is applied as a carbon precursor to accelerate graphene growth, which has a low decomposition energy barrier, and more importantly, the produced high-electronegativity Cl radical can enhance adsorption of active carbon species by Cl-CH2 coadsorption and facilitate H detachment from graphene edges. Consequently, the growth rate is increased by ~3 orders of magnitude and carbon utilization by ~960-fold, compared with conventional methane precursor. The advantageous hierarchical conductive configuration of lightweight, flexible GGFF makes it an ultrasensitive pressure sensor for human motion and physiological monitoring, such as pulse and vocal signals.

Fast synthesis of large-area bilayer graphene film on Cu.

Bilayer graphene (BLG) is intriguing for its unique properties and potential applications in electronics, photonics, and mechanics. However, the chemical vapor deposition synthesis of large-area high-quality bilayer graphene on Cu is suffering from a low growth rate and limited bilayer coverage. Herein, we demonstrate the fast synthesis of meter-sized bilayer graphene film on commercial polycrystalline Cu foils by introducing trace CO2 during high-temperature growth. Continuous bilayer graphene with a high ratio of AB-stacking structure can be obtained within 20 min, which exhibits enhanced mechanical strength, uniform transmittance, and low sheet resistance in large area. Moreover, 96 and 100% AB-stacking structures were achieved in bilayer graphene grown on single-crystal Cu(111) foil and ultraflat single-crystal Cu(111)/sapphire substrates, respectively. The AB-stacking bilayer graphene exhibits tunable bandgap and performs well in photodetection. This work provides important insights into the growth mechanism and the mass production of large-area high-quality BLG on Cu.

Flexible Full-Surface Conformal Encapsulation for Each Fiber in Graphene Glass Fiber Fabric against Thermal Oxidation.

Encapsulation for carbon-based electronic devices against oxidation can enhance their long-term working stability. Graphene glass fiber fabric (GGFF), as an advanced flexible electrothermal material, also struggles with graphene oxidation. The flexible, full-surface, conformal encapsulation for each fiber in the large-area fabric puts forward high requirements for encapsulating materials and techniques. Herein, the nanometer-thick h-BN layer was in situ grown on cambered surfaces of each fiber in GGFF with the chemical vapor deposition method. Stable heating duration (500 °C) of h-BN-encapsulated GGFF (h-BN/GGFF) was increased by 1 order of magnitude without compromising the electrothermal performances and flexibility. Theoretical simulations revealed that the enhanced oxidation resistance of h-BN/GGFF was attributed to the decreased interaction and adsorption life of oxygen. The proposed flexible, full-surface, conformal encapsulation technique targeting the fiber-shaped graphene electrothermal device is scalable and can be extended to the other carbon materials, even devices with intricate shapes, which will promote the development of flexible electronics.

Boron Carbonitride Lithium-Ion Capacitors with an Electrostatically Expanded Operating Voltage Window.

Lithium-ion capacitors (LICs) have emerged as attractive energy storage devices to bridge the gap between lithium-ion batteries and supercapacitors. While the distinct charge storage kinetics between the anode and the cathode is still a challenge to the widespread application of LICs, the key to improving the energy density of these devices is to widen the operating voltage window and balance the mismatch of the electrode kinetics. To this end, we propose a strategy based on electrostatic attraction by adjusting the B and N atom contents of boron carbonitride (BCN) electrode materials to alter their electronegativities and successfully prepared B-rich and N-rich BCN nanotubes (BCNNTs) via a facile solid-phase synthesis approach. The B-rich BCN (B-BCN) cathode and N-rich BCN (N-BCN) anode noticeably enhance the adsorption of anions and cations, promoting a matching degree between the anode and cathode. In particular, the rationally designed B-BCN//N-BCN LIC achieves a maximum voltage range of 4.8 V, setting a new record for LICs. Furthermore, the energy density reaches up to 200 Wh kg-1 (based on the total mass of cathodic and anodic active materials). Density functional theory calculations provided insight into the mechanism underlying our strategy of widening the voltage range. Our philosophy provides new design guidelines and alternatives for identifying and optimizing high-performance electrodes for energy storage devices.

A Strategy To Prepare High-Quality Monocrystalline Graphene: Inducing Graphene Growth with Seeding Chemical Vapor Deposition and Its Mechanism.

High-quality monocrystalline graphene has gained considerable attention in fundamental physics, materials science, and nanoelectronics. However, the performance of the graphene obtained by chemical synthesis methods is currently significantly restricted by the crystal quality. Herein, a seeding chemical vapor deposition (SCVD) method is designed to cultivate high-quality monocrystalline graphene on a Cu(111) substrate with hexagonal boron nitride (h-BN) as the seed crystal. Combining the experimental and theoretical research, the nucleation behavior of the growth-induced graphene on the h-BN seed crystal is investigated, and the induced growth mechanism on the Cu(111) substrate is studied. The results show that the h-BN seed crystal can dramatically reduce the adsorption energy of active carbon atoms and the energy barrier for C-C aggregation at the BN/Cu(111) step, thus promoting graphene growth around the h-BN seed. Large monocrystalline graphene domains are obtained by the proposed SCVD method. Further study shows that the growth-induced graphene has good crystal quality and could maintain high structural integrity. This new strategy can be applied for growing high-quality graphene and other two-dimensional materials.

Graphene Nucleation Preference at CuO Defects Rather Than Cu2O on Cu(111): A Combination of DFT Calculation and Experiment.

It is well-known that reducing the nucleation density is an effective way to enhance the growth quality of graphene. In this work, we explore the mechanism of graphene nucleation and growth around CuO defects on a Cu(111) substrate by using density functional theory combined with the nudged elastic band method. The defect formation mechanism at the initial nucleation stage is also studied. Our calculation results of the C adsorption energy and the reaction barrier of C-C dimer formation illustrate that the initial nucleation of graphene could be promoted by artificially introducing CuO defects on a Cu(111) surface and the nucleation on the clean Cu(111) substrate could thus be suppressed. These conclusions have been verified by graphene growth experiments using a chemical vapor deposition method. Further studies showed that graphene grown around CuO "seed crystals" could maintain its structural integrity without significantly producing defective carbon rings. This work provides a fundamental understanding and theoretical guidance for the controllable preparation of large-dimension and high-quality graphene by artificially introducing CuO seeds.