Conventional photocatalytic micromotors are limited to the use of specific wavelengths of light due to their narrow light absorption spectrum, which limits their effectiveness for applications in biomedicine and environmental remediation. We present a multiwavelength light-responsive Janus micromotor consisting of a black TiO microsphere asymmetrically coated with a thin Au layer. The black TiO microspheres exhibit absorption ranges between 300 and 800 nm. The Janus micromotors are propelled by light, both in HO solutions and in pure HO over a broad range of wavelengths including UV, blue, cyan, green, and red light. An analysis of the particles' motion shows that the motor speed decreases with increasing wavelength, which has not been previously realized. A significant increase in motor speed is observed when exploiting the entire visible light spectrum (>400 nm), suggesting a potential use of solar energy, which contains a great portion of visible light. Finally, stop-go motion is also demonstrated by controlling the visible light illumination, a necessary feature for the steerability of micro- and nanomachines.
Vanadium pentoxide (V2O5) nanoparticles (30-60 nm) were made by a one-step and scalable flame spray pyrolysis (FSP) process. Optimization of the FSP processing conditions (precursor concentration and injection rate) enhanced the electrochemical performance of these nanoparticles. Increasing the cut-off potential for discharging from 1.5 to 2.5 V vs. Li/Li + improved the cycle life of these V2O5 nanoparticles. Particles with the lowest specific surface area ( 32 m 2 g −1 ) and highest phase purity (up to 98 wt%) showed excellent cyclability between 2.5 and 4.0 V vs. Li/Li + , retaining a specific charge of 110 mAh g −1 beyond 100 cycles at a specific current of 100 mA g −1 , and also superior specific charge of 100 mAh g −1 at specific current up to 20C rate (or 2000 mA g −1 ).
Superhydrophobic surfaces resisting water penetration into their texture under dynamic impact conditions and offering simultaneously additional functionalities can find use in a multitude of applications. We present a facile, environmentally benign, and economical fabrication of highly electrically conductive, polymer-based superhydrophobic coatings, with impressive ability to resist dynamic water impalement through droplet impact. To impart electrical conductivity, the coatings were prepared by drop casting suspensions with loadings of different kinds of carbon nanoparticles, namely, carbon black (CB), carbon nanotubes (CNT), graphene nanoplatelets (GNP) and their combinations, in a fluoropolymer dispersion. At 50 wt % either CB or CNT, the nanocomposite coatings resisted impalement by water drops impacting at 3.7 m/s, the highest attainable speed in our setup. However, when tested with 5 vol % isopropyl alcohol-water mixture, i.e., a lower surface tension liquid posing a stiffer challenge with respect to impalement, only the CB coatings retained their impalement resistance behavior. GNP-based surfaces featured very high conductivity ∼1000 S/m, but the lowest resistance to water impalement. The optimal performance was obtained by combining the carbon fillers. Coatings containing CB:GNP:polymer = 1:1:2 showed both excellent impalement resistance (up to 3.5 m/s with 5 vol % IPA-water mixture drops) and electrical conductivity (∼1000 S/m). All coatings exhibited superhydrophobic and oleophilic behavior. To exemplify the additional benefit coming from this property, the CB and the optimal, combined CB/GNP coatings were used to separate mineral oil and water through filtration of their mixture.
Understanding the redox properties of metal oxide based catalysts is a major task in catalysis research. In situ Electron Paramagnetic Resonance (EPR) spectroscopy is capable to monitor the change of metal ion valences and formation of active sites during redox reactions, allowing for the identification of ongoing redox pathways. Here in situ EPR spectroscopy combined with online gas analysis, supported by ex situ X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), temporal analysis of product (TAP), mass spectrometry (MS) studies was utilized to study the redox behavior of CuOCeO2 catalysts under PROX conditions (preferential oxidation of carbon monoxide in hydrogen). Two redox mechanisms are revealed: (i) a synergetic mechanism that involves the redox pair Ce 4+ /Ce 3+ during oxidation of Cu 0 /Cu + species to Cu 2+ , and (ii) a direct mechanism that bypasses the redox pair Ce 4+ /Ce 3+ . In addition, EPR experiments with isotopically enriched 17 O2 established the synergetic mechanism as the major redox reaction pathway. The results emphasize the importance of the interactions between Cu and Ce atoms for catalyst performance. Guided by these results an optimized CuO-CeO2 catalyst could be designed. A rather wide temperature operation window of 11 degrees (from 377 K to 388 K), with 99% conversion efficiency and 99% selectivity was achieved for the preferential oxidation of CO in a H2 feed.
A novel system for generation of engineered nanomaterials suitable for in situ toxicological characterization within biological matrices was developed. This Versatile Engineered Nanomaterial Generation System (VENGES) is based on industry-relevant, flame spray pyrolysis (FSP) aerosol reactors that can scaleably produce engineered nanomaterials (ENMs) with controlled primary and aggregate particle size, crystallinity and morphology. ENMs are produced continuously in the gas phase, allowing their continuous transfer to inhalation chambers, without altering their state of agglomeration. Freshly generated ENMs are also collected on Teflon filters for subsequent physico-chemical and morphological characterization and for in vitro toxicological studies. The ability of the VENGES system to generate families of ENMs of pure and selected mixtures of iron oxide, silica and nanosilver with controlled physico-chemical properties was demonstrated using a range of state-of-the-art-techniques. Specific surface area was measured by nitrogen adsorption using the Brunauer-Emmett-Teller (BET) method, and crystallinity was characterized by X-ray diffraction (XRD). Particle morphology and size were evaluated by scanning and transmission electron microscopy (STEM/TEM). The suitability of the VENGES system for toxicological studies was also shown in both in vivo and in vitro studies involving Sprague-Dawley rats and human alveolar-like monocyte derived macrophages, respectively. We demonstrated linkage between physico-chemical ENM properties and potential toxicity.
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