Search Results
Beyond graphene oxide: Laser engineering functionalized graphene for flexible electronics
Carbon nanomaterials, especially graphene, are promising due to their abundance and the possibility to exploit them in lightweight, flexible, and wearable electronics enabling paradigms such as the Internet of Things. However, conventional methods to synthesize and integrate graphene into functional materials and flexible devices are either hazardous, time demanding, or excessively energy-consuming. To overcome these issues, here we propose a new concept based on the laser processing of single-layer diazonium-functionalized graphene. This is a safe, inexpensive, and environmentally-friendly method making it a competitive alternative for graphene-device fabrication. Flexible chemiresistors exhibit sensitivity for breath (water vapor and CO2) and ethanol detection up to 1500% higher than laser-reduced graphene oxide devices. We attribute this enhanced sensitivity to an optimal balance between structural defects and electrical conductivity. Flexible electronic circuits demonstrate a superb resilience against scratching and high current stability up to 98% with durability against 180° bending cycles for continuous operation of several weeks. This work can impact biomedical technology and electronics where tunable electrical conductivity, sensitivity, and mechanical stability are of uttermost importance. © 2020 The Royal Society of Chemistry.
Magnetically responsive composites: electron beam assisted magnetic nanoparticle arrest in gelatin hydrogels for bioactuation
As emerging responsive materials, ferrogels have become highly attractive for biomedical and technical applications in terms of soft actuation, tissue engineering or controlled drug release. In the present study, bioderived ferrogels were fabricated and successfully deformed within moderate, heterogeneous magnetic fields. Synthesis was realized by arresting iron oxide nanoparticles in porcine gelatin by introduction of covalent crosslinks via treatment with energetic electrons for mesh refinement. This approach also allows for tuning thermal and mechanical stability of the gelatin matrix. Operating the bioferrogel in compression, magnetic forces on the nanoparticles are counterbalanced by the stiffness of the hydrogel matrix that is governed by a shift in thermodynamic equilibrium of swelling, as derived in the framework of osmosis. As gelatin and iron oxide nanoparticles are established as biocompatible constituents, these findings promise potential for in vivo use as contactless mechanical transducers.
Judging the feasibility of TiO2 as photocatalyst for chemical energy conversion by quantitative reactivity determinants
In this study we assess the general applicability of the widely used P25-TiO2 in gas-phase photocatalytic CO2 reduction based on experimentally determined reactivity descriptors from classical heterogeneous catalysis (productivity) and photochemistry (apparent quantum yield/AQY). A comparison of the results with reports on the use of P25 for thermodynamically more feasible reactions and our own previous studies on P25-TiO2 as photocatalyst imply that the catalytic functionality of this material, rather than its properties as photoabsorber, limits its applicability in the heterogeneous photocatalytic CO2 reduction in the gas phase. The AQY of IrOx/TiO2 in overall water splitting in a similar high-purity gas-solid process was four times as high, but still far from commercial viability.
Endohedral metal-nitride cluster ordering in metallofullerene-NiII(OEP) complexes and crystals : A theoretical study
The ordering of endohedral clusterfullerenes Sc3N@C80 and YSc2N@C80 co-crystallized with Ni(OEP) and isolated complexes with Ni(OEP) have been investigated theoretically. Having used multiple orientations of M3N clusters inside the cages with Fibonacci sampling, we describe the effect of intermolecular interactions on the orientation of the endohedral cluster. © the Owner Societies.
Optical microresonator arrays of fluorescence-switchable diarylethenes with unreplicable spectral fingerprints
High-security identification requires authentication that is hard to counterfeit and replicate. For anti-counterfeiting data storage and rewritable memory devices, chromic materials are adoptable, where the dichromatic colours can be switched by external stimuli. If further individual information is embedded in each pixel, a much higher-level security system beyond the zero/one data array will be realized. For this purpose, a fine whispering gallery mode (WGM) fingerprint pattern from a microresonator is applicable. Here we propose that photoswitchable optical microresonators made of a fluorescent photochromic organic material function as anti-counterfeiting, rewritable optical memories. The WGM photoluminescence of the resultant microspheres can be switched on and off repeatedly by irradiation with ultraviolet and visible light. The shape of the microresonator varies from a sphere to an oblate ellipsoid and hemisphere, depending on the self-assembly process, and the WGM spectral pattern depends sensitively on the morphology of the resonators. Furthermore, surface self-assembly on a hydrophobic/hydrophilic micropatterned substrate affords a highly integrated array of microresonators as dense as millions of pixels per square centimetre. The spectral fingerprints of all pixels are different from one another; therefore, the photoswitchable microarrays are applicable as an ultimate anti-counterfeiting system which is hard to replicate. This journal is © 2020 The Royal Society of Chemistry.
Polarization-dependent vibrational shifts on dielectric substrates
The interaction of light with matter at surfaces of dielectrics strongly depends on polarization. Here, we present the first infrared spectroscopic evidence for significant polarization effects in the spectroscopic detection of adsorbate vibrational frequencies. In addition to much larger peak intensities for p-polarized light relative to s-polarization, a small but distinct blue shift was identified for CO adsorbed at the surfaces of two prototype dielectric substrates, CeO2(111) and CaCO3(10.4). A simulation using a layer model yields very good agreement with experiment.
Proton dynamics in molecular solvent clusters as an indicator for hydrogen bond network strength in confined geometries
Hydrogen bonding leads to the formation of strong, extended intermolecular networks in molecular liquids such as water. However, it is less well-known how robust the network is to environments in which surface formation or confinement effects become prominent, such as in clusters or droplets. Such systems provide a useful way to probe the robustness of the network, since the degree of confinement can be tuned by altering the cluster size, changing both the surface-to-volume ratio and the radius of curvature. To explore the formation of hydrogen bond networks in confined geometries, here we present O 1s Auger spectra of small and large clusters of water, methanol, and dimethyl ether, as well as their deuterated equivalents. The Auger spectra of the clusters and the corresponding macroscopic liquids are compared and evaluated for an isotope effect, which is due to proton dynamics within the lifetime of the core hole (proton-transfer-mediated charge-separation, PTM-CS), and can be linked to the formation of a hydrogen bond network in the system. An isotope effect is observed in water and methanol but not for dimethyl ether, which cannot donate a hydrogen bond at its oxygen site. The isotope effect, and therefore the strength of the hydrogen bond network, is more pronounced in water than in methanol. Its value depends on the average size of the cluster, indicating that confinement effects change proton dynamics in the core ionised excited state.
Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids
Ionic liquids are an attractive material class due to their wide liquid range, intrinsic ionic conductivity, and high chemical as well as electrochemical stability. However, the widespread use of ionic liquids is hindered by significantly higher viscosities compared to conventional molecular solvents. In this work, we show how the transport properties of ionic liquids can be altered significantly, even for isostructural ions that have the same backbone. To this end, structure–property relationships have been determined for a set of 16 systematically varied representative ionic liquids. Variations in molecular structure include ammonium vs. phosphonium, ether vs. alkyl side chains, and rigid vs. flexible anions. Ab initio calculations are used to relate molecular structures to the thermal, structural and transport properties of the ionic liquids. We find that the differences in properties of ether and alkyl functionalised ionic liquids are primarily dependent on minimum energy geometries, with the conformational flexibility of ether side chains appearing to be of secondary importance. We also show unprecedented correlations between anion conformational flexibility and transport properties. Critically, increasing fluidity upon consecutive introduction of ether side chains and phosphonium centres into the cation is found to be dependent on whether the anion is flexible or rigid. We demonstrate that targeted design of functional groups based on structure–property relationships can yield ionic liquids of exceptionally high fluidity.
Parahydrogen-induced polarization with a metal-free P–P biradicaloid
Metal-free H2 activations are unusual but interesting for catalytic transformations, particularly in parahydrogen-based nuclear spin hyperpolarization techniques. We demonstrate that metal-free singlet phosphorus biradicaloid, [P(μ-NTer)]2, provides pronounced 1H and 31P hyperpolarization while activating the parahydrogen molecules. A brief analysis of the resulting NMR signals and the important kinetic parameters are presented.
The role of pH, metal ions and their hydroxides in charge reversal of protein-coated nanoparticles
In this study, we investigated charge inversion of protein-coated Au nanoparticles caused by the addition of metal ions. The addition of hydrolyzable metal ions (Lewis acids) can induce drastic pH changes and depending on this pH, the metal ions (e.g. M3+) are readily converted into the hydrolyzed species (MOH2+, M(OH)2+) or even into hydroxides (M(OH)3). Adsorbed metal hydroxides were identified to cause the charge inversion of the NPs by using a combination of cryo-TEM, EFTEM and ζ-potential measurements.