The Incorporation of Graphene Nanoplatelets in Tung Oil-Urea Formaldehyde Microcapsules: A Paradigm Shift in Physicochemical Enhancement.

Tung oil (TO) microcapsules (MCs) with a poly(urea-formaldehyde) (PUF) shell were synthesized via one-step in situ polymerization, with the addition of graphene nanoplatelets (GNPs) (1-5 wt. %). The synergistic effects of emulsifiers between gelatin (gel) and Tween 80 were observed, with gel chosen to formulate the MCs due to its enhanced droplet stability. SEM images then displayed an increased shell roughness of the TO-GNP MCs in comparison to the pure TO MCs due to the GNP species on the shell. At the same time, high-resolution transmission electron microscopy (TEM) images also confirmed the presence of GNPs on the outer layer of the MCs, with the stacked graphene layers composed of 5-7 layers with an interlayer distance of ~0.37 nm. Cross-sectional TEM imaging of the MCs also confirmed the successful encapsulation of the GNPs in the core of the MCs. Micromanipulation measurements displayed that the 5% GNPs increased the toughness by 71% compared to the pure TO MCs, due to the reduction in the fractional free volume of the core material. When the MCs were dispersed in an epoxy coating and applied on a metallic substrate, excellent healing capacities of up to 93% were observed for the 5% GNP samples, and 87% for the pure TO MC coatings. The coatings also exhibited excellent corrosion resistance for all samples up to 7 days, with the GNP samples offering a more strenuous path for the corrosive agents.

Strong Intermixing Effects of LFO1-x/STOx toward the Development of Efficient Photoanodes for Photoelectrocatalytic Applications.

Aiming to improve the photocatalytic properties of transition metal perovskites to be used as robust photoanodes, [LaFeO3]1-x/[SrTiO3]x nanocomposites (LFO1-x/STOx) are considered. This hybrid structure combines good semiconducting properties and an interesting intrinsic remanent polarization. All the studied samples were fabricated using a solid-state method followed by high-energy ball milling, and they were subsequently deposited by spray coating. The synthesized compounds were demonstrated to possess orthorhombic (Pnma) and cubic (Pm3¯m) structures for LFO and STO, respectively, with an average grain size of 55-70 nm. The LFO1-x/STOx nanocomposites appeared to exhibit high visible light absorption, corresponding to band gaps of 2.17-3.21 eV. Our findings show that LFO0.5/STO0.5 is the optimized heterostructure; it achieved a high photocurrent density of 11 µA/cm2 at 1.23 V bias vs. RHE and an applied bias photo-to-current efficiency of 4.1 × 10-3% at 0.76 V vs. RHE, as demonstrated by the photoelectrochemical measurements. These results underline the role of the two phases intermixing LFO and STO at the appropriate content to yield a high-performing photoanode ascribed to efficient charge separation and transfer. This suggests that LFO0.5/STO0.5 could be a potential candidate for the development of efficient photoanodes for hydrogen generation via photoelectrocatalytic water splitting.

Impact of probe sonication and sulfuric acid pretreatment on graphene exfoliation in water.

Graphene is a 2D material with promising commercial applications due to its physicochemical properties. Producing high-quality graphene economically and at large scales is currently of great interest and demand. Here, the potential of producing high-quality graphene at a large scale via water-phase exfoliation methods is investigated. By altering exfoliation parameters, the production yield of graphene and flake size are evaluated. Pretreatment of the precursor graphite powder using acidic solutions of H2SO4 at different concentrations is found to increase further the yield and structural quality of the exfoliated graphene flakes. These findings are confirmed through various spectroscopy and surface characterization techniques. Controlling flake size, thickness, and yield are demonstrated via optimization of the sonication process, centrifuge time, and H2SO4 pretreatment.

3D-Printed Microcubes for Catalase Drug Delivery.

Oxidative stress, i.e., excessive production of reactive oxygen species (ROS), plays an important role in the pathogenesis of inflammatory diseases such as cardiovascular diseases, cancer, and neurodegenerative diseases. Catalase, an antioxidant enzyme, has great therapeutic potential; however, its efficacy is limited by its delivery to target cells or tissues. In order to achieve efficient delivery, consistent drug distribution, and drug activity, small and uniformly sized drug delivery vehicles are needed. Here, three-dimensional (3D) microcubes were printed by Nanoscribe Photonic Professional GT2, a high-resolution 3D printer, and the characteristics of 3D-printed microcubes as drug delivery vehicles for the delivery of catalase were investigated. The size of the 3D-printed microcubes was 800 nm in length of a square and 600 nm in height, which is suitable for targeting macrophages passively. Microcubes were also tunable in shape and size, and high-resolution 3D printing could provide microparticles with little variation in shape and size. Catalase was loaded on 3D-printed microcubes by nonspecific adsorption, and catalase on 3D-printed microcubes (CAT-MC) retained 83.1 ± 1.3% activity of intact catalase. CAT-MC also saved macrophages, RAW 264.7, from the cytotoxicity of H2O2 by 86.4 ± 4.1%. As drug delivery vehicles, 3D-printed microparticles are very promising due to their small and uniform size, which provides consistent drug distribution and drug activity. Therefore, we anticipate numerous applications of 3D-printed microparticles for delivering therapeutic proteins.

Effect of Sr and Ti substitutions on optical and photocatalytic properties of Bi1-x Sr x Fe1-x Ti x O3 nanomaterials.

The potential use of down-sized BFO-xSTO systems (x ≤ 25%) as highly efficient photoanodes for photocatalytic water splitting is investigated. BFO-xSTO is prepared by a solid-state method and subsequently deposited by spray coating. The compounds possess rhombohedral symmetry for x ≤ 15% and phase coexistence for x > 15%, as demonstrated by Raman spectroscopy and transmission electron microscopy. Our findings revealed a drastic grain size decrease with increasing STO content, namely 260 nm for BFO to 50 nm for BFO with 25% STO. Moreover, BFO-xSTO, x > 10% exhibited high optical absorption (> 80%) in the full spectrum and interestingly a very promising band alignment with water redox potentials. Moreover, the photochemical measurements revealed a photocurrent density of ∼0.17 µA cm-2 achieved for x = 15% at 0 bias. Using DFT calculations, the substitution effects on the electronic, optical, and photocatalytic performances of the BFO system were investigated and quantified. Surprisingly, a high hydrogen yield (∼191 µmol g-1) was achieved by BFO-12.5%STO compared to 1 µmol g-1 and 57 µmol g-1 for BFO and STO, respectively. This result highlights the beneficial effects of both the downsizing and substitution of BFO on the photocatalytic water splitting and hydrogen production performances of Bi1-x Sr x Fe1-x Ti x O3 systems.

Photoelectrochemical Enhancement of Graphene@WS2 Nanosheets for Water Splitting Reaction.

Tungsten disulfide nanosheets were successfully prepared by one-step chemical vapor deposition using tungsten oxide and thiourea in an inert gas environment. The size of the obtained nanosheets was subsequently reduced down to below 20 nm in width and 150 nm in length using high-energy ball milling, followed by 0.5 and 1 wt% graphene loading. The corresponding vibrational and structural characterizations are consistent with the fabrication of a pure WS2 structure for neat sampling and the presence of the graphene characteristic vibration modes in graphene@WS2 compounds. Additional morphological and crystal structures were examined and confirmed by high-resolution electron microscopy. Subsequently, the investigations of the optical properties evidenced the high optical absorption (98%) and lower band gap (1.75 eV) for the graphene@WS2 compared to the other samples, with good band-edge alignment to water-splitting reaction. In addition, the photoelectrochemical measurements revealed that the graphene@WS2 (1 wt%) exhibits an excellent photocurrent density (95 µA/cm2 at 1.23 V bias) compared with RHE and higher applied bias potential efficiency under standard simulated solar illumination AM1.5G. Precisely, graphene@WS2 (1 wt%) exhibits 3.3 times higher performance compared to pristine WS2 and higher charge transfer ability, as measured by electrical impedance spectroscopy, suggesting its potential use as an efficient photoanode for hydrogen evolution reaction.

The Microencapsulation of Tung Oil with a Natural Hydrocolloid Emulsifier for Extrinsic Self-Healing Applications.

In this work, tung oil was utilised as a catalyst-free self-healing agent, and an in-situ polymerization process was applied to encapsulate the tung oil core with a poly(urea-formaldehyde) (PUF) shell. The conventional poly(ethylene-alt-maleic-anhydride) (PEMA) polymer was compared to a more naturally abundant gelatin (GEL) emulsifier to compare the microcapsules' barrier, morphological, thermal, and chemical properties, and the crystalline nature of the shell material. GEL emulsifiers produced microcapsules with a higher payload (96.5%), yield (28.9%), and encapsulation efficiency (61.7%) compared to PEMA (90.8%, 28.6% and 52.6%, respectively). Optical and electron microscopy imaging indicated a more uniform morphology for the GEL samples. The thermal decomposition measurements indicated that GEL decomposed to a value 7% lower than that of PEMA, which was suggested to be attributed to the much thinner shell materials that the GEL samples produced. An innovative and novel focused ion beam (FIB) milling method was exerted on the GEL sample, confirming the storage and release of the active tung oil material upon rupturing. The samples with GEL conveyed a higher healing efficiency of 91%, compared to PEMA's 63%, and the GEL samples also conveyed higher levels of corrosion resistance.

A user-friendly FIB lift-out technique to prepare plan-view TEM sample of 2D thin film materials.

Plan-view transmission electron microscopy (TEM) or electron diffraction imaging of a bulk or 2D material can provide detailed information about the structural or atomic arrangement in the material. A systematic and easily implementable approach to preparing site-specific plan-view TEM samples for 2D thin film materials using FIB is discussed that could be routinely used. The methodology has been successfully applied to prepare samples from 2D materials such as, MoS2 thin film, vertically oriented graphene film (VG), as well as heterostructure material SnTiS3. It is worth mentioning that in contrast to planar conventional graphene, VG grows vertically from the substrate and takes nanosheet arrays. Samples prepared using this methodology provide a simple, faster, and precise course in obtaining valuable structural information. The top-view imaging offers various information about the growth nature of the materials suggesting the efficiency of the sample preparation process.

Photodetection Properties of MoS2, WS2 and MoxW1-xS2 Heterostructure: A Comparative Study.

Layered transition metals dichalcogenides such as MoS2 and WS2 have shown a tunable bandgap, making them highly desirable for optoelectronic applications. Here, we report on one-step chemical vapor deposited MoS2, WS2 and MoxW1-xS2 heterostructures incorporated into photoconductive devices to be examined and compared in view of their use as potential photodetectors. Vertically aligned MoS2 nanosheets and horizontally stacked WS2 layers, and their heterostructure form MoxW1-xS2, exhibit direct and indirect bandgap, respectively. To analyze these structures, various characterization methods were used to elucidate their properties including Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectrometry and high-resolution transmission electron microscopy. While all the investigated samples show a photoresponse in a broad wavelength range between 400 nm and 700 nm, the vertical MoS2 nanosheets sample exhibits the highest performances at a low bias voltage of 5 V. Our findings demonstrate a responsivity and a specific detectivity of 47.4 mA W-1 and 1.4 × 1011 Jones, respectively, achieved by MoxW1-xS2. This study offers insights into the use of a facile elaboration technique for tuning the performance of MoxW1-xS2 heterostructure-based photodetectors.

Short-wavelength infrared (SWIR) photodetector based on multi-layer 2D GaGeTe.

Recent theoretical studies proposed that two-dimensional (2D) GaGeTe crystals have promising high detection sensitivity at infrared wavelengths and can offer ultra-fast operation. This can be attributed to their small optical bandgap and high carrier mobility. However, experimental studies on GaGeTe in the infrared region are lacking and this exciting property has not been explored yet. In this work, we demonstrate a short-wavelength infrared (SWIR) photodetector based on a multilayer (ML) GaGeTe field-effect transistor (FET). Fabricated devices show a p-type behavior at room temperature with a hole field-effect mobility of 8.6 - 20 cm2 V-1s-1. Notably, under 1310 nm illumination, the photo responsivities and noise equivalent power of the detectors with 65 nm flake thickness can reach up to 57 A/W and 0.1 nW/Hz1/2, respectively, at a drain-source bias (Vds) = 2 V. The frequency responses of the photodetectors were also measured with a 1310 nm intensity-modulated light. Devices exhibit a response up to 100 MHz with a 3dB cut-off frequency of 0.9 MHz. Furthermore, we also tested the dependence of the device frequency response on the applied bias and gate voltages. These early experimental findings stimulate the potential use of multilayer GaGeTe for highly sensitive and ultrafast photodetection applications.

Synthesis of holey graphene for advanced nanotechnological applications.

Holey or porous graphene, a structural derivative of graphene, has attracted immense attention due to its unique properties and potential applications in different branches of science and technology. In this review, the synthesis methods of holey or porous graphene/graphene oxide are systematically summarized and their potential applications in different areas are discussed. The process-structure-applications are explained, which helps relate the synthesis approaches to their corresponding key applications. The review paper is anticipated to benefit the readers in understanding the different synthesis methods of holey graphene, their key parameters to control the pore size distribution, advantages and limitations, and their potential applications in various fields.

Recent Advances in the Design of Plasmonic Au/TiO2 Nanostructures for Enhanced Photocatalytic Water Splitting.

Plasmonic nanostructures have played a key role in extending the activity of photocatalysts to the visible light spectrum, preventing the electron-hole combination and providing with hot electrons to the photocatalysts, a crucial step towards efficient broadband photocatalysis. One plasmonic photocatalyst, Au/TiO2, is of a particular interest because it combines chemical stability, suitable electronic structure, and photoactivity for a wide range of catalytic reactions such as water splitting. In this review, we describe key mechanisms involving plasmonics to enhance photocatalytic properties leading to efficient water splitting such as production and transport of hot electrons through advanced analytical techniques used to probe the photoactivity of plasmonics in engineered Au/TiO2 devices. This work also discusses the emerging strategies to better design plasmonic photocatalysts and understand the underlying mechanisms behind the enhanced photoactivity of plasmon-assisted catalysts.

Rapid discrimination of chemically distinctive surface terminations in 2D material based heterostructures by direct van der Waals identification.

We demonstrate that surfaces presenting heterogeneous and atomically flat domains can be directly and rapidly discriminated via robust intensive quantifiables by exploiting one-pass noninvasive methods in standard atomic force microscopy (AFM), single ∼2 min passes, or direct force reconstruction, i.e., ∼103 force profiles (∼10 min collection time), allowing data collection, interpretation, and presentation in under 20 min, including experimental AFM preparation and excluding only sample fabrication, in situ and without extra experimental or time load. We employ a misfit SnTiS3 compound as a model system. Such heterostructures can be exploited as multifunctional surface systems and provide multiple support sites with distinguishable chemical, mechanical, or opto-electronic distinct properties. In short, they provide an ideal model system to exemplify how current AFM methods can significantly support material discovery across fields.

Explaining doping in material research (Hf substitution in ZnO films) by directly quantifying the van der Waals force.

Non-monotonic behavior has been observed in the optoelectronic properties of ZnO thin films as doped with Hf (HZO). Here we propose that two competing mechanisms are responsible for such behaviour. Specifically, we propose that provided two crystal orientations dominate film growth, only one of them might be responsible for direct Hf substitution. Nonmonotonic behaviour is expected at once by considering that preferential growth of the crystal that allows for direct Hf substitution is inhibited by Hf concentration in the manufacturing process. This inhibition would also be a thermodynamic consequence of Hf substitution. Maxima in Hf substitution is thus reached at a point where enough crystals exhibit the preferential orientation, and where enough Hf is present on the surface for substitution. Outside this optimum scenario, Hf substitution can only decrease. We interpret the surface phenomena by discussing surface energy and the van der Waals forces as measured experimentally by means of atomic force microscopy.

Toward the use of CVD-grown MoS2 nanosheets as field-emission source.

Densely populated edge-terminated vertically aligned two-dimensional MoS2 nanosheets (NSs) with thicknesses ranging from 5 to 20 nm were directly synthesized on Mo films deposited on SiO2 by sulfurization. The quality of the obtained NSs was analyzed by scanning electron and transmission electron microscopy, and Raman and X-ray photoelectron spectroscopy. The as-grown NSs were then successfully transferred to the substrates using a wet chemical etching method. The transferred NSs sample showed excellent field-emission properties. A low turn-on field of 3.1 V/µm at a current density of 10 µA/cm2 was measured. The low turn-on field is attributed to the morphology of the NSs exhibiting vertically aligned sheets of MoS2 with sharp and exposed edges. Our findings show that the fabricated MoS2 NSs could have a great potential as robust high-performance electron-emitter material for various applications such as microelectronics and nanoelectronics, flat-panel displays and electron-microscopy emitter tips.

Investigation of plasmon resonance in metal/dielectric nanocavities for high-efficiency photocatalytic device.

Photocatalytic nanostructures loaded with metallic nanoparticles are being considered as a potential candidate for designing efficient water splitting devices. Here, we aim to unveil the plasmonic behavior of a device made of Au-TiO2 nanostructures through in-depth investigations combining electron energy loss spectroscopy (EELS) and cathodoluminescence (CL). The experiments confirm the existence of Au bulk plasmon excitation, intrinsic interband transitions, and plasmon losses over a wide range of energies (0.6-2.4 eV). Depending on the size and the shape of the obtained nanostructures, such as fishing hook (FH), asymmetric nanorod (AR), and a/symmetric nanoparticles, in our devices, the dephasing times and the quality factors of the modes vary. Finite difference time domain simulations were then carried out on FH and AR structures. These simulations indicate good agreement between the electric field enhancement and the obtained plasmon excitation as observed in EELS. Moreover, the plasmonic activity obtained by CL and EELS was correlated with the photocurrent measurements recorded with the device, which confirmed that the localized plasmons in Au generate hot electrons and enhance the photoresponse of the device. This study confirms the functionality of the metal dielectric photocatalyst device over a wide range of wavelengths ranging from UV to near IR.

Electron- and ion-beam-induced maneuvering of nanostructures: phenomenon and applications.

Electron-and ion-induced bending (EIB/IIB) phenomena have been studied in self-supported polycrystalline metallic and metal-amorphous bilayered nanocantilevers. The experiments reveal many interesting facts regarding electron/ion-matter interaction, which builds a proper foundation for the understanding of the phenomenon. The mechanism for bending of metallic cantilevers has been proposed to be primarily due to void-induced stress generation during ion beam irradiation. On the other hand, thermal effects have been found to play the dominant role in the case of bending of bilayer (amorphous-metal) nanocantilevers. The instantaneous, reversible, highly controllable and permanent nature of the process has been exploited to fabricate several complicated nanostructures in three dimensions. IIB of the fabricated cantilevers is shown to have a high precession mass sensing aptitude, capable of detecting a change in mass of the order of femtograms.

The out of beam sight effects in focused ion beam processing.

We report that during focused ion beam chemical vapor deposition (FIB-CVD) the effect of deposition is not limited to the area where the ion beam scanning takes place but occurs on regions which are out of sight of the incident beam and extends up to several micrometers away from the specified site. This phenomenon has deleterious effects, especially when the nanocontacts are fabricated for the electrical characterization of the nanodevices. The deposition occurs into the gap between the contact pads and acts as a resistance in parallel with the resistance of the nanostructure to be measured. The extended deposition has been explained on the basis of molecular cracking of the precursor gas molecules induced by forward scattered Ga ions, and appropriate measures to remove the effect have been suggested.