Magnetic field-responsive graphene oxide photonic liquids.

Modifying the environment around particles (e.g., introducing a secondary phase or external field) can affect the way they interact and assemble, thereby giving control over the physical properties of a dynamic system. Here, graphene oxide (GO) photonic liquids that respond to a magnetic field are demonstrated for the first time. Magnetic nanoparticles are used to provide a continuous magnetizable liquid environment around the GO liquid crystalline domains. In response to a magnetic field, the alignment of magnetic nanoparticles, coupled with the diamagnetic property of GO nanosheets, drives the reorientation and alignment of the nanosheets, enabling switchable photonic properties using a permanent magnet. This phenomenon is anticipated to be extendable to other relevant photonic systems of shape-anisotropic nanoparticles and may open up opportunities for developing GO-based optical materials and devices.

Self-assembly of cellulose nanocrystals confined to square capillaries.

Biological systems exploit restricted degrees of freedom to drive self-assembly of nano- and microarchitectures. Simplified systems, such as colloidal nanoparticles that behave as lyotropic liquid crystalline mesophases in confined geometric spaces, may be used to mimic biological structures. Cellulose nanocrystals (CNCs) are colloidally stable nanoparticles that self-assemble into chiral nematic (ChN) liquid crystalline mesophases. To date, the self-assembly of ChN mesophases of CNCs has been studied under confinement conditions within curved surfaces or under drying conditions that impose curvatures that can be exploited to control ChN ordering; however, their self-assembly has not been investigated in geometries with square cross-sections under static conditions. Here, we show that because of surface anchoring on perpendicular surfaces, the ChN CNC phase is unable to bend with the 90° angle of the square capillary under increasing confinement. Instead, the ChN phase forms radial layers in the shape of concentric squircle shells. With increasing layer distance from the capillary wall, the squircles transition into concentric cylinder shells. In larger capillaries, the radial shell layers appear as a continuous spiral pattern that engulfs fragmented ChN pseudolayers, a defect to accommodate the cylindrical confinement of the mesophase. These results are useful for understanding the fundamentals of self-assembling systems and development of new technologies.

Mechanically Responsive Circularly Polarized Luminescence from Cellulose-Nanocrystal-Based Shape-Memory Polymers.

Stimulus-responsive materials that display circularly polarized luminescence (CPL) have attracted great attention for application in chiral sensors and smart displays. However, due to difficulties in the regulation of chiral structures, fine control of CPL remains a challenge. Here, it is demonstrated that cellulose nanocrystal shape-memory polymers (CNC-SMPs) with luminescent components enable mechanically responsive CPL. The chiral nematic organization of CNCs in the material gives rise to a photonic bandgap. By manipulating the photonic bandgap or luminescence wavelengths of the luminescent CNC-SMPs, precise control of CPL emission with varied wavelengths and high dissymmetry factors (glum ) is achieved. Specifically, CPL emission can be switched reversibly by treating the luminescent CNC-SMPs with hot-pressing and recovery by heating. Pressure-responsive CPL with tunable glum values is ascribed to the pressure-responsive photonic bandgaps. Moreover, colorimetric and CPL-active patterns are created by imprinting desired forms into SMP samples. This study demonstrates a novel way to fabricate smart CPL systems using biomaterials.

Stable graphene oxide hydrophobic photonic liquids.

Graphene oxide (GO) is an important nanomaterial for producing photonic liquids due to its ability to display full-color reflections in water. However, the poor stability of GO photonic liquids and unsatisfactory dispersibility of GO nanosheets in hydrophobic liquid media have been significant drawbacks to developing photonic materials based on GO. Here, stable GO hydrophobic photonic liquids are demonstrated for the first time. GO nanosheets are directed into different hydrophobic liquid media, including reactive liquid precursors like tetraethoxysilane and ethyl acrylate, in the presence of phase transfer additives. These liquids exhibit tunable reflection wavelength up to ∼1300 nm with improved stability relative to aqueous GO photonic suspensions at elevated temperatures or under ambient conditions. Supported by an entropy-driven depletion mechanism, hydrophobic additives can effectively mediate the self-assembly of GO to produce tunable photonic liquids without the need to adjust GO concentrations. Furthermore, simultaneous infrared and visible light reflection can be achieved, enabling infrared photonic GO liquids to display visible colors. The improved stability and tunable photonic properties of hydrophobic GO liquids will open a way for developing GO-based optical materials and devices.

Tuning the photonic properties of graphene oxide suspensions with nanostructured additives.

Photonic materials that can selectively reflect light across the visible spectrum are valuable for applications in optical devices, sensors, and decoration. Although two-dimensional (2D) colloids that stack into layers with spacing of hundreds of nanometers are able to selectively diffract light, controlling their separation in solution has proven challenging. In this work, we investigate the role of additives to control the photonic properties of hybrid colloidal suspensions of graphene oxide (GO). We discovered that low concentrations of colloidal additives like cellulose nanocrystals (CNCs) and clay nanoparticles (hectorite) added to GO suspensions lead to dramatic color changes. These hybrid colloidal suspensions demonstrate tunable structural colors and temperature-sensitive properties that likely originate from the entropically driven ejection of guests between the sheets, and from the interactions between colloidal electrical double layers and additional counterions. On the other hand, blending polymeric or molecular additives with GO suspensions either deteriorates or does not impact the photonic properties. These results are helpful to understand the interaction between GO suspensions and additives over different length scales, and open a path to advancing photonic materials based on hybrid colloidal suspensions.

Concentric chiral nematic polymeric fibers from cellulose nanocrystals.

Hierarchical biological materials, such as osteons and plant cell walls, are complex structures that are difficult to mimic. Here, we combine liquid crystal systems and polymerization techniques within confined systems to develop complex structures. A single-domain concentric chiral nematic polymeric fiber was obtained by confining cellulose nanocrystals (CNCs) and hydroxyethyl acrylate inside a capillary tube followed by UV-initiated polymerization. The concentric chiral nematic structure continues uniformly throughout the length of the fiber. The pitch of the chiral nematic structure could be controlled by changing the CNC concentration. We tracked the formation of the concentric structure over time and under different conditions with variation of the tube orientation, CNC concentration, CNC type, and capillary tube size. We show that the inner radius of the capillary tube is important and a single-domain structure was only obtained inside small-diameter tubes. At low CNC concentration, the concentric chiral nematic structure did not completely cover the cross-section of the fiber. The highly ordered structure was studied using imaging techniques and X-ray diffraction, and the mechanical properties and structure of the chiral nematic fiber were compared to a pseudo-nematic fiber. CNC polymeric fibers could become a platform for many applications from photonics to complex hierarchical materials.

In situ redox growth of mesoporous Pd-Cu2O nanoheterostructures for improved glucose oxidation electrocatalysis.

Interfaces of metal-oxide heterostructured electrocatalyst are critical to their catalytic activities due to the significant interfacial effects. However, there are still obscurities in the essence of interfacial effects caused by crystalline defects and mismatch of electronic structure at metal-oxide nanojunctions. To deeply understand the interfacial effects, we engineered crystalline-defect Pd-Cu2O interfaces through non-epitaxial growth by a facile redox route. The Pd-Cu2O nanoheterostructures exhibit much higher electrocatalytic activity toward glucose oxidation than their single counterparts and their physical mixture, which makes it have a promising potential for practical application of glucose biosensors. Experimental study and density functional theory (DFT) calculations demonstrated that the interfacial electron accumulation and the shifting up of d bands center of Cu-Pd toward the Fermi level were responsible for excellent electrocatalytic activity. Further study found that Pd(3 1 0) facets exert a strong metal-oxide interface interaction with Cu2O(1 1 1) facets due to their lattice mismatch. This leads to the sinking of O atoms and protruding of Cu atoms of Cu2O, and the Pd crystalline defects, further resulting in electron accumulation at the interface and the shifting up of d bands center of Cu-Pd, which is different from previously reported charge transfer between the interfaces. Our findings could contribute to design and development of advanced metal-oxide heterostructured electrocatalysts.

Aerogel materials with periodic structures imprinted with cellulose nanocrystals.

Novel aerogel materials with periodic structures derived from chiral nematic liquid crystalline cellulose nanocrystals (CNCs) are reported. The liquid crystalline structure of phase-separated CNCs is locked by a simple solvent exchange method or silica condensation. Both cellulose and silica/cellulose aerogel materials were obtained after critical point drying, and subsequent calcination of the silica/cellulose composite afforded a silica aerogel with periodic order. Gas adsorption and electron microscopy studies revealed that these materials have high surface areas and a unique chiral nematic structure imparted from the helicoidal CNC template. This is a new, scalable approach to aerogel materials with highly anisotropic structures. The high porosity and periodic, chiral features of these new materials may make them suitable for applications that require anisotropic properties or as hard templates for the construction of other ordered aerogels.