MXene (e.g., Ti3C2) represents an important class of two‐dimensional (2D) materials owing to its unique metallic conductivity and tunable surface chemistry. However, the mainstream synthetic methods rely on the chemical etching of MAX powders (e.g., Ti3AlC2) using hazardous HF or alike, leading to MXene sheets with fluorine termination and poor ambient stability in colloidal dispersions. Here, we demonstrate a fluoride‐free, iodine (I2) assisted etching route for preparing 2D MXene (Ti3C2Tx, T=O, OH) with oxygen‐rich terminal groups and intact lattice structure. More than 71 % of sheets are thinner than 5 nm with an average size of 1.8 μm. They present excellent thin‐film conductivity of 1250 S cm−1 and great ambient stability in water for at least 2 weeks. 2D MXene sheets with abundant oxygen surface groups are excellent electrode materials for supercapacitors, delivering a high gravimetric capacitance of 293 F g−1 at a scan rate of 1 mV s−1, superior to those made from fluoride‐based etchants (<290 F g−1 at 1 mV s−1). Our strategy provides a promising pathway for the facile and sustainable production of highly stable MXene materials.
Overcoming the intrinsic instability and preserving unique electronic properties are key challenges for the practical applications of black phosphorus (BP) under ambient conditions. Here, it is demonstrated that molecular heterostructures of BP and hexaazatriphenylene derivatives (BP/HATs) enable improved environmental stability and charge transport properties. The strong interfacial coupling and charge transfer between the HATs and the BP lattice decrease the surface electron density and protect BP sheets from oxidation, resulting in an excellent ambient lifetime of up to 21 d. Importantly, HATs increase the charge scattering time of BP, contributing to an improved carrier mobility of 97 cm2 V‐1 s‐1, almost three times of the pristine BP films, based on noninvasive THz spectroscopic studies. The film mobility is an order of magnitude larger than previously reported values in exfoliated 2D materials. The strategy opens up new avenues for versatile applications of BP sheets and provides an effective method for tuning the physicochemical properties of other air‐sensitive 2D semiconductors.
Graphene oxide (GO) is a promising material for bone tissue engineering, but the validation of its molecular biological effects, especially in the context of clinically applied materials, is still limited. In this study, we compare the effects of graphene oxide framework structures (F-GO) and reduced graphene oxide-based framework structures (F-rGO) as scaffold material with a special focus on vascularization associated processes and mechanisms in the bone. Highly porous networks of zinc oxide tetrapods serving as sacrificial templates were used to create F-GO and F-rGO with porosities >99% consisting of hollow interconnected microtubes. Framework materials were seeded with human mesenchymal stem cells (MSC), and the cell response was evaluated by confocal laser scanning microscopy (CLSM), deoxyribonucleic acid (DNA) quantification, real-time polymerase chain reaction (RT-PCR), enzyme-linked immunosorbent assay (ELISA), and alkaline phosphatase activity (ALP) to define their impact on cellular adhesion, osteogenic differentiation, and secretion of vascular growth factors. F-GO based scaffolds improved adhesion and growth of MSC as indicated by CLSM and DNA quantification. Further, F-GO showed a better vascular endothelial growth factor (VEGF) binding capacity and improved cell growth as well as the formation of microvascular capillary-like structures in co-cultures with outgrowth endothelial cells (OEC). These results clearly favored non-reduced graphene oxide in the form of F-GO for bone regeneration applications. To study GO in the context of a clinically used implant material, we coated a commercially available xenograft (Bio-Oss® block) with GO and compared the growth of MSC in monoculture and in coculture with OEC to the native scaffold. We observed a significantly improved growth of MSC and formation of prevascular structures on coated Bio-Oss®, again associated with a higher VEGF binding capacity. We conclude that graphene oxide coating of this clinically used, but highly debiologized bone graft improves MSC cell adhesion and vascularization.
Graphene hydrophobic coatings paved the way towards a new generation of optoelectronic and fluidic devices. Nevertheless, such hydrophobic thin films rely only on graphene non-polar surface, rather than taking advantage of its surface roughness. Furthermore, graphene is typically not self-standing. Differently, carbon aerogels have high porosity, large effective surface area due to their surface roughness, and very low mass density, which make them a promising candidate as a super-hydrophobic material for novel technological applications. However, despite a few works reporting the general super-hydrophobic and lipophilic behavior of the carbon aerogels, a detailed characterization of their wetting properties is still missing, to date. Here, the wetting properties of graphene aerogels are demonstrated in detail. Without any chemical functionalization or patterning of their surface, the samples exhibit a super-lipophilic state and a stationary super-hydrophobic state with a contact angle up to 150 ± 15° and low contact angle hysteresis ≈ 15°, owing to the fakir effect. In addition, the adhesion force of the graphene aerogels in contact with the water droplets and their surface tension are evaluated. For instance, the unique wettability and enhanced liquid absorption of the graphene aerogels can be exploited for reducing contamination from oil spills and chemical leakage accidents.
One-step in situ functionalization/electrochemical exfoliation in an innovative continuous-flow reactor enables the large-scale production of active materials for the fabrication of high performance thin-film supercapacitors.