Self-dispersed crumpled graphene balls in oil for friction and wear reduction.

Ultrafine particles are often used as lubricant additives because they are capable of entering tribological contacts to reduce friction and protect surfaces from wear. They tend to be more stable than molecular additives under high thermal and mechanical stresses during rubbing. It is highly desirable for these particles to remain well dispersed in oil without relying on molecular ligands. Borrowing from the analogy that pieces of paper that are crumpled do not readily stick to each other (unlike flat sheets), we expect that ultrafine particles resembling miniaturized crumpled paper balls should self-disperse in oil and could act like nanoscale ball bearings to reduce friction and wear. Here we report the use of crumpled graphene balls as a high-performance additive that can significantly improve the lubrication properties of polyalphaolefin base oil. The tribological performance of crumpled graphene balls is only weakly dependent on their concentration in oil and readily exceeds that of other carbon additives such as graphite, reduced graphene oxide, and carbon black. Notably, polyalphaolefin base oil with only 0.01-0.1 wt % of crumpled graphene balls outperforms a fully formulated commercial lubricant in terms of friction and wear reduction.

Supramolecular Packing Controls H2 Photocatalysis in Chromophore Amphiphile Hydrogels.

Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within some of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap.

Graphene Oxide Sheets in Solvents: To Crumple or Not To Crumple?

Some earlier studies suggested that graphene oxide (GO) sheets adopt a crumpled configuration in water, similar to the shape of a paper ball, which turns into an even more compact, collapsed form upon addition of a poor solvent due to enhanced intrasheet affinity. Although those results have been debated in studies concerning membrane configurations, they are now often used to justify the existence of folds and wrinkles in solution-processed GO-based structures. This has led to a misconception that wrinkled and crumpled features may be intrinsic to solution processing and unavoidable. Here, we connect this problem to experimental observations of the liquid crystallinity of GO dispersions, which clearly show that the sheets are neither crumpled nor collapsed, with or without poor solvent. The sheets can simply fold flat or restack to hide their surfaces from poor solvent, without incurring the energetic cost of severe deformations to crumple.

Self-assembled two-dimensional nanofluidic proton channels with high thermal stability.

Exfoliated two-dimensional (2D) sheets can readily stack to form flexible, free-standing films with lamellar microstructure. The interlayer spaces in such lamellar films form a percolated network of molecularly sized, 2D nanochannels that could be used to regulate molecular transport. Here we report self-assembled clay-based 2D nanofluidic channels with surface charge-governed proton conductivity. Proton conductivity of these 2D channels exceeds that of acid solution for concentrations up to 0.1 M, and remains stable as the reservoir concentration is varied by orders of magnitude. Proton transport occurs through a Grotthuss mechanism, with activation energy and mobility of 0.19 eV and 1.2 × 10(-3) cm(2) V(-1) s(-1), respectively. Vermiculite nanochannels exhibit extraordinary thermal stability, maintaining their proton conduction functions even after annealing at 500 °C in air. The ease of constructing massive arrays of stable 2D nanochannels without lithography should prove useful to the study of confined ionic transport, and will enable new ionic device designs.

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production.

Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report here on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenon that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.