The rush to develop graphene applications mandates mass production of graphene sheets. However, the currently available complex and expensive production technologies are limiting the graphene commercialization. The addition of a protective diluent to graphite during ball-milling is demonstrated to result in a game-changer yield (>90%) of defect-free graphene, whose size is controlled by the milling energy and the diluent type.

The rapid increase in graphene-based applications has been accompanied by novel top-down manufacturing methods for graphene and its derivatives (e.g., graphene nanoplatelets (GnPs)). The characterization of the bulk properties of these materials by imaging and surface techniques (e.g., electron microscopy and Raman spectroscopy) is only possible through laborious and time-consuming statistical analysis, which precludes simple and efficient quality control during GnP production. We report that thermogravimetry (TG) may be utilized, beyond its conventional applications (e.g., quantification of impurities or surfactants, or labile functional groups) to characterize bulk GnP properties. We characterize the structural parameters of GnP (i.e., defect density, mean lateral dimension, and polydispersity) by imaging and surface techniques, on one hand, and by a systematic TG, on the other. The combined data demonstrate that the combustion temperature of commercially available and laboratory-prepared GnPs is correlated with their mean lateral dimension and defect density, while the combustion temperature range is proportional to their polydispersity index. Mapping all these parameters allows one to evaluate the GnPs' structure following a simple thermogravimetric experiment (without necessitating further statistical analysis). Finally, TG is also used to detect and quantify different GnP constituents in powder and to conduct rapid quality-control tests during GnP production.

We report on an interesting mechanism of inducing chiroptical response at plasmonic silver nanoparticles (NPs) through the formation of plasmonic hot spots in small metal-NP–chiral-surfactant assemblies. Circular dichroism (CD) was measured at the surface plasmon resonance of cholate-coated silver nanostructures (AgCT) in the visible region of the spectrum. Low temperature cryogenic transmission electron microscopy (cryo-TEM) micrographs of the AgCT nanostructures in solution reveal small assemblies of silver NPs. Upon pH increase these assemblies are separated into individual NPs, and the induced plasmonic CD vanishes. This process was monitored via spectroscopy (CD and absorption), cryo-TEM, small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS) measurements. The synthesis of well-separated AgCT NPs, which was performed with a large excess of sodium cholate (NaCT), also did not show any chiroptical effects. We interpret and model the formation of strong CD signals in the visible range in terms of the molecule–plasmon interaction in plasmonic hot spots formed in nanoparticle aggregates. Importantly, this study of the chiral induction, transfer to the visible range, and local field enhancement offers very attractive possibilities for sensing and detection of chirality of small amounts of molecules using visible light.

Extensive work has been invested in the design of bio-inspired peptide emulsifiers. Yet, none of the formulated surfactants were based on the utilization of the robust conformation and self-assembly tendencies presented by the hydrophobins, which exhibited highest surface activity among all known proteins. Here we show that a minimalist design scheme could be employed to fabricate rigid helical peptides to mimic the rigid conformation and the helical amphipathic organization. These designer building blocks, containing natural non-coded α-aminoisobutyric acid (Aib), form superhelical assemblies as confirmed by crystallography and microscopy. The peptide sequence is amenable to structural modularity and provides the highest stable emulsions reported so far for peptide and protein emulsifiers. Moreover, we establish the ability of short peptides to perform the dual functions of emulsifiers and thickeners, a feature that typically requires synergistic effects of surfactants and polysaccharides. This work provides a different paradigm for the molecular engineering of bioemulsifiers.

Some oxygen defective metal oxides, such as cerium and bismuth oxides, have recently shown exceptional electrostrictive properties that are even superior to the best performing lead-based electrostrictors, e.g. lead-magnesium-niobates (PMN). Compared to piezoelectric ceramics, electromechanical mechanisms of such materials do not depend on crystalline symmetry, but on the concentration of oxygen vacancy (V O •• ) in the lattice. In this work, we investigate for the first time the role of oxygen defect configuration on the electro-chemomechanical properties. This is achieved by tuning the oxygen defects blocking barrier density in polycrystalline gadolinium doped ceria with known oxygen vacancy concentration, Ce0.9Gd0.1O2-δ, δ = 0.05. Nanometric starting powders of ca. 12 nm are sintered in different conditions, including field assisted spark plasma sintering (SPS), fast firing and conventional method at high temperatures. These approaches allow controlling grain size and Gd-dopant diffusion, i.e. via thermally driven solute drag mechanism. By correlating the electro-chemomechanical properties, we show that oxygen vacancy distribution in the materials play a key role in ceria electrostriction, overcoming the expected contributions from grain size and dopant concentration.

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Electromechanically active ceramic materials, piezoelectrics and electrostrictors, provide the backbone of a variety of consumer technologies. Gd- and Sm-doped ceria are ion conducting ceramics, finding application in fuel cells, oxygen sensors, and, potentially, as memristor materials. While optimal design of ceria-based devices requires a thorough understanding of their mechanical and electromechanical properties, reports of systematic study of the effect of dopant concentration on the electromechanical behavior of ceria-based ceramics are lacking. Here we report the longitudinal electrostriction strain coefficient ( M 33 ) of dense RE x Ce 1– x O 2– x /2 ( x ≤ 0.25) ceramic pellets, where RE = Gd or Sm, measured under ambient conditions as a function of dopant concentration within the frequency range f = 0.15–350 Hz and electric field amplitude E ≤ 0.5 MV/m. For >100 Hz, all ceramic pellets tested, independent of dopant concentration, exhibit longitudinal electrostriction strain coefficient with magnitude on the order of 10 –18 m 2 /V 2 . The quasi-static ( f < 1 Hz) electrostriction strain coefficient for undoped ceria is comparable in magnitude, while introducing 5 mol % Gd or 5 mol % Sm produces an increase in M 33 by up to 2 orders of magnitude. For x ≤ 0.1 (Gd)–0.15 (Sm), the Debye-type relaxation time constant (τ) is in the range 60–300 ms. The inverse relationship between dopant concentration and quasi-static electrostrictive strain parallels the anelasticity and ionic conductivity of Gd- and Sm-doped ceria ceramics, indicating that electrostriction is partially governed by ordering of vacancies and changes in local symmetry.