Al3+ Modification of Graphene Oxide Membranes: Effect of Al Source.

Graphene oxide (GO) membranes are promising materials for water filtration applications due to abundant nanochannels in the membrane structure. Because GO membranes are unstable in water, metal cations such as Al3+ are often introduced to the membrane structure to promote cross-linking between individual GO sheets. Here, we describe a simple yet versatile method to incorporate Al3+ into GO membranes formed via a slow self-assembly process. Specifically, we directly added aluminum to acidic GO sheet solutions from a variety of sources: Al2O3, AlCl3 and Al foil. Each species reacts differently with water, which can affect the GO solution pH and thus the density of carboxylate groups on the sheet edges available for cross-linking to the Al3+ cations. We demonstrate through characterization of the GO sheet solutions as well as the as-formed membranes' morphologies, hydrophobicities, and structures that the extent to which the Al3+ cross-links to the GO sheet edges vs. the GO sheet basal planes is dependent on the Al source. Our results indicate that greatest enhancements in the membrane stability occur when electrostatic and coordination interactions between Al3+ and the carboxylate groups on the GO sheet edges are more extensive than Al3+-π interactions between basal planes.

Using Al3+ to Tailor Graphene Oxide Nanochannels: Impact on Membrane Stability and Permeability.

Graphene oxide (GO) membranes, which form from the lamination of GO sheets, attract much attention due to their unique nanochannels. There is much interest in controlling the nanochannel structures and improving the aqueous stability of GO membranes so they can be effectively used in separation and filtration applications. This study employed a simple yet effective method of introducing trivalent aluminum cations to a GO sheet solution through the oxidation of aluminum foil, which modifies the nanochannels in the self-assembled GO membrane by increasing the inter-sheet distance while decreasing intra-sheet spacing. The Al3+ modification resulted in an increase in membrane stability in water, methanol, ethanol, and propanol, yet decreased membrane permeability to water and propanol. These changes were attributed to strong interactions between Al3+ and the membrane oxygenated functional groups, which resulted in an increase in membrane hydrophobicity and a decrease in the intra-sheet spacing as supported by surface tension, contact angle, atomic force microscopy, and X-ray photoelectron spectroscopy measurements. Our approach for forming Al3+ modified GO membranes provides a method for improving the aqueous stability and tailoring the permeation selectivity of GO membranes, which have the potential to be implemented in vapor separation and fuel purification applications.

Phonon Polaritons in Monolayers of Hexagonal Boron Nitride.

Phonon polaritons in van der Waals materials reveal significant confinement accompanied with long propagation length: important virtues for tasks pertaining to the control of light and energy flow at the nanoscale. While previous studies of phonon polaritons have relied on relatively thick samples, here reported is the first observation of surface phonon polaritons in single atomic layers and bilayers of hexagonal boron nitride (hBN). Using antenna-based near-field microscopy, propagating surface phonon polaritons in mono- and bilayer hBN microcrystals are imaged. Phonon polaritons in monolayer hBN are confined in a volume about one million times smaller than the free-space photons. Both the polariton dispersion and their wavelength-thickness scaling law are altered compared to those of hBN bulk counterparts. These changes are attributed to phonon hardening in monolayer-thick crystals. The data reported here have bearing on applications of polaritons in metasurfaces and ultrathin optical elements.

Evolutionary selection growth of two-dimensional materials on polycrystalline substrates.

There is a demand for the manufacture of two-dimensional (2D) materials with high-quality single crystals of large size. Usually, epitaxial growth is considered the method of choice 1 in preparing single-crystalline thin films, but it requires single-crystal substrates for deposition. Here we present a different approach and report the synthesis of single-crystal-like monolayer graphene films on polycrystalline substrates. The technological realization of the proposed method resembles the Czochralski process and is based on the evolutionary selection 2 approach, which is now realized in 2D geometry. The method relies on 'self-selection' of the fastest-growing domain orientation, which eventually overwhelms the slower-growing domains and yields a single-crystal continuous 2D film. Here we have used it to synthesize foot-long graphene films at rates up to 2.5 cm h-1 that possess the quality of a single crystal. We anticipate that the proposed approach could be readily adopted for the synthesis of other 2D materials and heterostructures.

Anisotropic Etching of Hexagonal Boron Nitride and Graphene: Question of Edge Terminations.

Chemical vapor deposition (CVD) has been established as the most effective way to grow large area two-dimensional materials. Direct study of the etching process can reveal subtleties of this competing with the growth reaction and thus provide the necessary details of the overall growth mechanism. Here we investigate hydrogen-induced etching of hBN and graphene and compare the results with the classical kinetic Wulff construction model. Formation of the anisotropically etched holes in the center of hBN and graphene single crystals was observed along with the changes in the crystals' circumference. We show that the edges of triangular holes in hBN crystals formed at regular etching conditions are parallel to B-terminated zigzags, opposite to the N-terminated zigzag edges of hBN triangular crystals. The morphology of the etched hBN holes is affected by a disbalance of the B/N ratio upon etching and can be shifted toward the anticipated from the Wulff model N-terminated zigzag by etching in a nitrogen buffer gas instead of a typical argon. For graphene, etched hexagonal holes are terminated by zigzag, while the crystal circumference is gradually changing from a pure zigzag to a slanted angle resulting in dodecagons.

Effect of polymer residues on the electrical properties of large-area graphene-hexagonal boron nitride planar heterostructures.

Polymer residue plays an important role in the performance of 2D heterostructured materials. Herein, we study the effect of polymer residual impurities on the electrical properties of graphene-boron nitride planar heterostructures. Large-area graphene (Gr) and hexagonal boron nitride (h-BN) monolayers were synthesized using chemical vapor deposition techniques. Atomic van-der-Waals heterostructure layers based on varied configurations of Gr and h-BN layers were assembled. The average interlayer resistance of the heterojunctions over a 1 cm2 area for several planar heterostructure configurations was assessed by impedance spectroscopy and modeled by equivalent electrical circuits. Conductive AFM measurements showed that the presence of polymer residues on the surface of the Gr and h-BN monolayers resulted in significant resistance deviations over nanoscale regions.