Holey Sheets Enhance the Packing and Osmotic Energy Harvesting of Graphene Oxide Membranes.

Layered membranes assembled from two-dimensional (2D) building blocks such as graphene oxide (GO) are of significant interest in desalination and osmotic power generation because of their ability to selectively transport ions through interconnected 2D nanochannels between stacked layers. However, architectural defects in the final assembled membranes (e.g., wrinkles, voids, and folded layers), which are hard to avoid due to mechanical compliant issues of the sheets during the membrane assembly, disrupt the ionic channel pathways and degrade the stacking geometry of the sheets. This leads to degraded ionic transport performance and the overall structural integrity. In this study, we demonstrate that introducing in-plane nanopores on GO sheets is an effective way to suppress the formation of such architectural imperfections, leading to a more homogeneous membrane. Stacking of porous GO sheets becomes significantly more compact, as the presence of nanopores makes the sheets mechanically softer and more compliant. The resulting membranes exhibit ideal lamellar microstructures with well-aligned and uniform nanochannel pathways. The well-defined nanochannels afford excellent ionic conductivity with an effective transport pathway, resulting in fast, selective ion transport. When applied as a nanofluidic membrane in an osmotic power generation system, the holey GO membrane exhibits higher osmotic power density (13.15 W m-2) and conversion efficiency (46.6%) than the pristine GO membrane under a KCl concentration gradient of 1000-fold.

Surface nitrided MXene sheets with outstanding electroconductivity and oxidation stability.

Two-dimensional Ti3C2Tx MXenes are promising candidates for a wide range of film- or fiber-based devices owing to their solution processability, high electrical conductivity, and versatile surface chemistry. The surface terminal groups (Tx) of MXenes can be removed to increase their inherent electrical performance and ensure chemical stability. Therefore, understanding the chemical evolution during the removal of the terminal groups is crucial for guiding the production, processing, and application of MXenes. Herein, we investigate the effect of chemical modification on the electron-transfer behavior during the removal of the terminal groups by annealing Ti3C2Tx MXene single sheets under argon (Ar-MXene) and ammonia gas (NH3-MXene) conditions. Annealing in ammonia gas results in surface nitridation of MXenes and preserves the electron-abundant Ti3C2 structure, whereas annealing MXene single sheets in Ar gas results in the oxidation of the titanium layers. The surface-nitrided MXene film exhibits an electrical conductivity two times higher than that of the Ar-MXene film. The oxidation stability is quantified by calculating the oxidation rate constants for severe reactions with H2O2. The surface-nitrided MXene is 13 times more stable than Ar-MXene. The investigation of MXene single sheets provides fundamental insights that are valuable for designing electrically conductive and chemically stable MXenes.

Microstructure-Controlled Polyacrylonitrile/Graphene Fibers over 1 Gigapascal Strength.

Controlling the microstructures in fibers, such as crystalline structures and microvoids, is a crucial challenge for the development of mechanically strong graphene fibers (GFs). To date, although GFs graphitized at high temperatures have exhibited high tensile strength, GFs still have limited the ultimate mechanical strength owing to the presence due to the structural defects, including the imperfect alignment of graphitic crystallites and the presence of microsized voids. In this study, we significantly enhanced the mechanical strength of GF by controlling microstructures of fibers. GF was hybridized by incorporating polyacrylonitrile (PAN) in the graphene oxide (GO) dope solution. In addition, we controlled the orientation of the inner structure by applying a tensile force at 800 °C. The results suggest that PAN can act as a binder for graphene sheets and can facilitate the rearrangement of the fiber's microstructure. PAN was directionally carbonized between graphene sheets due to the catalytic effect of graphene. The resulting hybrid GFs successfully displayed a high strength of 1.10 GPa without undergoing graphitization at extremely high temperatures. We believe that controlling the alignment of nanoassembled structure is an efficient strategy for achieving the inherent performance characteristics of graphene at the level of multidimensional structures including films and fibers.

Carbon nanotube-reduced graphene oxide fiber with high torsional strength from rheological hierarchy control.

High torsional strength fibers are of practical interest for applications such as artificial muscles, electric generators, and actuators. Herein, we maximize torsional strength by understanding, measuring, and overcoming rheological thresholds of nanocarbon (nanotube/graphene oxide) dopes. The formed fibers show enhanced structure across multiple length scales, modified hierarchy, and improved mechanical properties. In particular, the torsional properties were examined, with high shear strength (914 MPa) attributed to nanotubes but magnified by their structure, intercalating graphene sheets. This design approach has the potential to realize the hierarchical dimensional hybrids, and may also be useful to build the effective network structure of heterogeneous materials.

Highly Electroconductive and Mechanically Strong Ti3C2Tx MXene Fibers Using a Deformable MXene Gel.

Self-assembly of two-dimensional MXene sheets is used in various fields to create multiscale structures due to their electrical, mechanical, and chemical properties. In principle, MXene nanosheets are assembled by molecular interactions, including hydrogen bonds, electrostatic interactions, and van der Waals forces. This study describes how MXene colloid nanosheets can form self-supporting MXene hydrogels. Three-dimensional network structures of MXene gels are strengthened by reinforced electrostatic interactions between nanosheets. Stable gel networks are beneficial for fabricating highly aligned fibers because MXene gel can endure structural deformation. During wet spinning of highly concentrated MXene colloids in a coagulation bath, MXene sheets can be transformed into perfectly aligned fibers under a mechanical drawing force. Oriented MXene fibers exhibit a 1.5-fold increase in electrical conductivity (12 504 S cm-1) and Young's modulus (122 GPa) compared with other fibers. The oriented MXene fibers are expected to have widespread applications, including electrical wiring and signal transmission.

Large-scale wet-spinning of highly electroconductive MXene fibers.

Ti3C2Tx MXene is an emerging class of two-dimensional nanomaterials with exceptional electroconductivity and electrochemical properties, and is promising in the manufacturing of multifunctional macroscopic materials and nanomaterials. Herein, we develop a straightforward, continuously controlled, additive/binder-free method to fabricate pure MXene fibers via a large-scale wet-spinning assembly. Our MXene sheets (with an average lateral size of 5.11 µm2) are highly concentrated in water and do not form aggregates or undergo phase separation. Introducing ammonium ions during the coagulation process successfully assembles MXene sheets into flexible, meter-long fibers with very high electrical conductivity (7,713 S cm-1). The fabricated MXene fibers are comprehensively integrated by using them in electrical wires to switch on a light-emitting diode light and transmit electrical signals to earphones to demonstrate their application in electrical devices. Our wet-spinning strategy provides an approach for continuous mass production of MXene fibers for high-performance, next-generation, and wearable electronic devices.

Super-Expansion of Assembled Reduced Graphene Oxide Interlayers by Segregation of Al Nanoparticle Pillars for High-Capacity Na-Ion Battery Anodes.

The applicability of Na-ion batteries is contingent on breakthroughs in alternative electrode materials that have high capacities and which are economically viable. Unfortunately, conventional graphite anodes for Li-ion battery systems do not allow Na-ion accommodation into their interlayer space owing to the large ionic radius and low stabilizing energy of Na in graphite. Here, we suggest a promising strategy for significantly increasing Na capacity by expanding the axial slab space of graphite. We successfully synthesized reconstructed graphite materials via self-assembly of negative graphite oxide (GO) flakes and Al cation (positive) pillars and by subsequent chemical reaction of the obtained Al-GO materials. Al pillars, atomically distributed in graphite interlayers, can extend the slab space by up to ∼7 Å, which is a 2-fold interlayer distance of pristine graphite. An exceptionally high capacity of 780 mAh/g is demonstrated for reconstructed graphite anodes with Al pillars, compared with rGO materials (210 mAh/g). We investigated the electrochemical reaction mechanism and structural changes associated with discharge and charge to emphasize the benefit of using reconstructed graphite as anodes in Na-ion batteries. Our strategy of modifying the interlayer distance by introducing metallic pillars between the layers can help address the low capacity of carbonaceous anodes.

Room-Temperature, Highly Durable Ti3C2Tx MXene/Graphene Hybrid Fibers for NH3 Gas Sensing.

Graphene-based fibers (GFs) have aroused enormous interest in portable, wearable electronics because of their excellent mechanical flexibility, electrical conductivity, and weavability, which make them advantageous for wearable electronic devices. Herein, we report the development of metal binder-free Ti3C2Tx MXene/graphene hybrid fibers by a scalable wet-spinning process. These hybrid fibers exhibit excellent mechanical and electrical properties for applications in flexible wearable gas sensors. The synergistic effects of electronic properties and gas-adsorption capabilities of MXene/graphene allow the created fibers to show high NH3 gas sensitivity at room temperature. The hybrid fibers exhibited significantly improved NH3 sensing response (ΔR/R0 = 6.77%) compared with individual MXene and graphene. The hybrid fibers also showed excellent mechanical flexibility with a minimal fluctuation of resistance of ±0.2% and low noise resistance even after bending over 2000 cycles, enabling gas sensing during deformation. Furthermore, flexible MXene/graphene hybrid fibers were woven into a lab coat, demonstrating their high potential for wearable devices. We envisage that these exciting features of 2D hybrid materials will provide a novel pathway for designing next-generation portable wearable gas sensors.

Graphene Foam Cantilever Produced via Simultaneous Foaming and Doping Effect of an Organic Coagulant.

Inspired by the role of cellular structures, which give three-dimensional robustness to graphene structures, a new type of graphene cantilever with mechanical resilience is introduced. Here, NH4SCN is incorporated into graphene oxide (GO) gel using it as a coagulant for GO fiber self-assembly, a foaming agent, and a dopant. Subsequent thermal treatment of the GO fiber at 600 °C results in the evolution of gaseous species from NH4SCN, yielding internally porous graphene cantilevers (NS-GF cantilevers). The results reveal that NS-GF cantilevers are doped with N and S and thus exhibit higher electrical conductivity (150 S cm-1) than that of their nonporous counterparts (38.4 S cm-1). Unlike conventional fibers, the NS-GF cantilevers exhibit mechanical resilience by bending under applied mechanical force but reverting to the original position upon release. The tip of the NS-GF cantilevers is coated with magnetic Fe3O4 particles, and fast mechanical movement is achieved by applying the magnetic field. Since the NS-GF cantilevers are highly conductive and elastic, they are employed as bendable, magnetodriven electrical switches that could precisely read on/off signals for >10 000 cycles. Our approach suggests a robust fabrication strategy to prepare highly electroconductive and mechanically elastic foam structures by introducing unique organic foaming agents.

The effect of diverse metal oxides in graphene composites on the adsorption isotherm of gaseous benzene.

The effective removal technique is necessary for the real world treatment of a hazardous pollutant (e.g., gaseous benzene). In an effort to develop such technique, the adsorption efficiency of benzene in a nitrogen stream (5 Pa (50 ppm) at 50 mL atm min-1 flow rate and 298 K) was assessed against 10 different metal oxide/GO composite materials (i.e., 1: graphene oxide Co (GO-Co (OH)2), 2: graphene oxide Cu (GO-Cu(OH)2), 3: graphene oxide Mn (GO-MnO), 4: graphene oxide Ni (GO-Ni(OH)2), 5: graphene oxide Sn (GO-SnO2), 6: reduced graphene oxide Co (rGO-Co(OH)2), 7: reduced graphene oxide Cu (rGO-Cu(OH)2), 8: reduced graphene oxide Mn (rGO-MnO), 9: reduced graphene oxide Ni (rGO-Ni(OH)2), and 10: reduced graphene oxide Sn (rGO-SnO2)) in reference to their pristine forms of graphene oxide (GO) and reduced graphene oxide (rGO). The highest adsorption capacities (at 100% breakthrough) were observed as ~23 mg g-1 for both GO-Ni(OH)2 and rGO-SnO2, followed by GO (~19.1 mg g-1) and GO-Co(OH)2 (~18.8 mg g-1). Therefore, the GO-Ni(OH)2 and rGO-SnO2 composites exhibited considerably high capacities to treat streams containing >5 Pa of benzene. However, the lowest adsorption capacity was found for GO-MnO (0.05 mg g-1). Alternately, if expressed in terms of the 10% breakthrough volume (BTV), the five aforementioned materials showed values of 0.50, 0.46, 0.40, 0.44, and 0.39 L g-1, respectively. The experimental data of target sorbents were fitted to linearized Langmuir, Freundlich, Elovich, and Dubinin-Radushkevich isotherm models. Accordingly, the non-linear Langmuir isotherm model revealed the presence of two or more distinct sorption profiles for several of the tested sorbents. Most of the sorbents showed type-III isotherm profiles where the sorption capacity proportional to the loaded volume.

Porous Graphene-Carbon Nanotube Scaffolds for Fiber Supercapacitors.

Fiber nanomaterials can become fundamental devices that can be woven into smart textiles, for example, miniaturized fiber-based supercapacitors (FSCs). They can be utilized for portable, wearable electronics and energy storage devices, which are highly prospective areas of research in the future. Herein, we developed porous carbon nanotube-graphene hybrid fibers (CNT-GFs) for all-solid-state symmetric FSCs, which were assembled through wet-spinning followed by a hydrothermal activation process using environmentally benign chemicals (i.e., H2O2 and NH4OH in deionized water). The barriers that limited effective ion accessibility in GFs were overcome by the intercalation of CNTs in the GFs which enhanced their electrical conductivity and mechanical properties as well. The all-solid-state symmetric FSCs of a precisely controlled activated hybrid fiber (a-CNT-GF) electrode exhibited an enhanced volumetric capacitance of 60.75 F cm-3 compared with those of a pristine CNT-GF electrode (19.80 F cm-3). They also showed a volumetric energy density (4.83 mWh cm-3) roughly 3 times higher than that of untreated CNT-GFs (1.50 mWh cm-3). The excellent mechanical flexibility and structural stability of a miniaturized a-CNT-GF are highlighted by the demonstration of negligible differences in capacitance upon bending and twisting. The mechanism of developing porous, large-scale, low-cost electrodes using an environmentally benign activation method presented in this work provides a promising route for designing a new generation of wearable, portable miniaturized energy storage devices.

High-Temperature Stable Anatase Titanium Oxide Nanofibers for Lithium-Ion Battery Anodes.

Control of the crystal structure of electrochemically active materials is an important approach to fabricating high-performance electrodes for lithium-ion batteries (LIBs). Here, we report a methodology for controlling the crystal structure of TiO2 nanofibers by adding aluminum isopropoxide to a common sol-gel precursor solution utilized to create TiO2 nanofibers. The introduction of aluminum cations impedes the phase transformation of electrospun TiO2 nanofibers from the anatase to the rutile phase, which inevitably occurs in the typical annealing process utilized for the formation of TiO2 crystals. As a result, high-temperature stable anatase TiO2 nanofibers were created in which the crystal structure was well-maintained even at high annealing temperatures of up to 700 °C. Finally, the resulting anatase TiO2 nanofibers were utilized to prepare LIB anodes, and their electrochemical performance was compared to pristine TiO2 nanofibers that contain both anatase and rutile phases. Compared to the electrode prepared with pristine TiO2 nanofibers, the electrode prepared with anatase TiO2 nanofibers exhibited excellent electrochemical performances such as an initial Coulombic efficiency of 83.9%, a capacity retention of 89.5% after 100 cycles, and a rate capability of 48.5% at a current density of 10 C (1 C = 200 mA g-1).