High level of phosphotungstic acid (PWA) was self-immobilized on electrospun nylon nanofiberous sheet to fabricate highly selective methanol barrier layer for sandwich structured proton conducting membranes. Simple tuning for the assembly conditions of central layer and thickness of outer Nafion layers allowed obtaining different composite membranes with superior methanol barrier properties (namely, P=3.59×10(-8) cm2 s(-1)) coupled with proton conductivities reaching 58.6 mS cm(-1) at 30 °C. Comparable activation energy for proton transport and more than 20 times higher selectivity than Nafion 115 confirm the effectiveness of the central layer and resulting membranes for application in direct methanol fuel cells (DMFCs). When tested in DMFC single cell, the performance of hybrid membrane was far better than Nafion 115 especially at higher methanol concentrations.
Silicon dioxide (SiO2) is the most widely used dielectric for electronic applications. It is usually produced by thermal oxidation of silicon or by using a wide range of vacuum-based techniques. By default, the growth of SiO2 by thermal oxidation of silicon requires the use of Si substrates whereas the other deposition techniques either produce low quality or poor interface material and mostly require high deposition or annealing temperatures. Recent investigations therefore have focused on the development of alternative deposition paradigms based on solutions. Here, we report the deposition of SiO2 thin film dielectrics deposited by spray pyrolysis in air at moderate temperatures of ≈350 °C from pentane-2,4-dione solutions of SiCl4. SiO2 dielectrics were investigated by means of UV-vis absorption spectroscopy, spectroscopic ellipsometry, XPS, XRD, UFM/AFM, admittance spectroscopy, and field-effect measurements. Data analysis reveals smooth (RRMS < 1 nm) amorphous films with a dielectric constant of about 3.8, an optical band gap of ≈8.1 eV, leakage current densities in the order of ≈10(-7) A/cm(2) at 1 MV/cm, and high dielectric strength in excess of 5 MV/cm. XPS measurements confirm the SiO2 stoichiometry and FTIR spectra reveal features related to SiO2 only. Thin film transistors implementing spray-coated SiO2 gate dielectrics and C60 and pentacene semiconducting channels exhibit excellent transport characteristics, i.e., negligible hysteresis, low leakage currents, high on/off current modulation ratio on the order of 10(6), and high carrier mobility.
Catalytic CO2 hydrogenation is an effective approach to producing clean fuels, but this process is expensive, in addition to the low efficiency of catalysts. Thus, photothermal CO2 hydrogenation can effectively utilize solar energy for CH4 production. Metal-organic framework (MOF) derived materials with a controlled structure and morphology are promising to give a high number of active sites and photostability in thermal catalytic reactions. For the first time, a novel heterostructure catalyst was synthesized using a facile approach to in situ grow MOF-derived 0D Co3O4 over 1D TiO2 nanowires (NWs). The original 3D dodecahedral structure of the MOF is engineered into novel 0D Co3O4 nanospheres, which were uniformly embedded over Ni-dispersed 1D TiO2 NWs. In situ prepared 10Ni-7Co3O4@TiO2 NWs-I achieved an excellent photothermal CH4 evolution rate of 8.28 mmol/h at 250 °C under low-intensity visible light, whereas UV light treatment further increased activity by 1.2-fold. UV irradiations promoted high CH4 production while improving the susceptibility of the catalyst to visible light irradiation. The photothermal effect is prominent at lower temperatures, due to the harmonization of both solar and thermal energy. By paralleling with mechanically assembled 10Ni-7Co3O4/TiO2 NWs-M, the catalytic performance of the in situ approach is far superior, attributing to the morphological transformation of 0D Co3O4, which induced intimate interfacial interactions, formation of oxygen vacancies and boosted photo-to-thermal effects. The co-existence of metallic/metal oxide Ni-Co provided beneficial synergies, enhanced photo-to-thermal effects, and improved charge transfer kinetics of the composite. This work uncovers a facile approach to engineering the morphology of MOF derivatives for efficient photothermal CO2 methanation.
Indium gallium nitride nanocubes were syntheized via a low-temperature chemical route. Energy-dispersive X-ray spectroscopy and X-ray diffraction analyses confirmed the successful fabrication of (In,Ga)N with various indium mole fractions. The bandgap of the material was tunded as a function of the indium content. The fabricated nanocubes showed a deep level photoluminescence emission at 734 nm as well as in the visible region at 435-520 nm. The Hall effect measurements showed the hole concentration to constantly increase from 6.2 × 10(16) to 2.3 × 10(18) cm(-3), while the hole mobility to decrease from 0.92 to 0.1 cm(2) /(V s) as the doping ratio increases from 0.005 to 0.025 cm(-3). The solar cell device made of nanocubes film containing 0.4 indium on flexible substrates showed a short-circuit current density of 12.47 mA/cm(2) and an open-circuit voltage (Voc) of 0.48 V with 54% fill factor. The relationship between Voc and indium content in the fabricated films was also investigated.
Additive and antisolvent engineering strategies are outstandingly efficient in enhancing perovskite quality, photovoltaic performance, and stability of perovskite solar cells (PSCs). In this work, an effective approach is applied by coupling the antisolvent mixture and multi-functional additive procedures, which is recognized as antisolvent additive engineering (AAE). The graphene quantum dots functionalized with amide (AGQDs), which consists of carbonyl, amine, and long hydrophobic alkyl chain functional groups, are added to the antisolvent mixture of toluene (T) and hexane (H) as an efficient additive to form the CH3NH3PbI3 (MAPI):AGQDs graded heterojunction structure. A broad range of analytical techniques, including scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, space charge limited current, UV-visible spectroscopy, external quantum efficiency, and time-of-flight secondary ion mass spectrometry, are used to investigate the effect of AAE treatment with AGQDs on the quality of perovskite film and performance of the PSCs. Importantly, not only a uniform and dense perovskite film with hydrophobic property is obtained but also defects on the perovskite surface are significantly passivated by the interaction between AGQDs and uncoordinated Pb2+. As a result, an enhanced power conversion efficiency (PCE) of 19.10% is achieved for the champion PSCs treated with AGQD additive, compared to the PCE of 16.00% for untreated reference PSCs. In addition, the high-efficiency PSCs based on AGQDs show high stability and maintain 89% of their initial PCE after 960 h in ambient conditions.
MXene sheets, as new 2D nanomaterials, have been used in many advanced applications due to their superior thin-layered architecture, as well as their capability to be employed as novel nanocontainers for advanced applications. In this research, intercalated Ti3C2 MXene sheets were synthesized through an etching method, and then they were modified with 3-aminopropyltriethoxysilane (APTES). Cerium cations (Ce3+) as an eco-friendly corrosion inhibitor were encapsulated within Ti3C2 MXene sheets to fabricate novel self-healing epoxy nanocomposite coatings. The corrosion protection performance (CPP) of Ce3+-doped Ti3C2 MXene nanosheets (Ti3C2 MXene-Ce3+) in a 3.5 wt % sodium chloride (NaCl) solution was studied on bare mild steel substrates using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The self-healing CPP of epoxy coatings loaded with 1 wt % undoped and doped Ti3C2 MXene was evaluated using EIS, salt spray, and field emission scanning electron microscopy (FE-SEM) techniques. The introduction of Ti3C2 MXene-Ce3+ into the corrosive solution and artificially scribed epoxy coating enhanced the total impedance from 717 to 6596 Ω cm2 and 8876 to 32092 Ω cm2, respectively, after 24 h of immersion compared to the control samples.
The postsynthetic modification of metal-organic frameworks (MOFs) has opened up a promising area to widen their water treatment application. However, their polycrystalline powdery state still restricts their widespread industrial-scale applications. Herein, the magnetization of UiO-66-NH2 is reported as a promising approach to facilitate the separation of the used MOFs after water treatment. A two-step postmodification procedure employing 2,4,6-trichloro-1,3,5-triazine (TCT) and 5-phenyl-1H-tetrazole (PTZ) agents was introduced to level up the adsorption performance of the magnetic nanocomposite. Despite a decrement in porosity and specific surface area of the designed MOFs (m-UiO-66-TCT) compared to neat UiO-66-NH2, it outweighs in adsorption capacity. It was observed that m-UiO-66-TCT has an adsorption capacity of ≈298 mg/g for methyl orange (MO) with facile MOF separation using an external magnet. Pseudo-second-order kinetic model and Freundlich isotherm models suitably interpret the experimental data. Thermodynamic studies showed that MO removal using m-UiO-66-TCT is spontaneous and thermodynamically favorable at higher temperatures. The m-UiO-66-TCT composite exhibited easy separation, high adsorption capacity, and good recyclability, rendering it an attractive candidate for the adsorptive removal of MO dye from aqueous environments.
This paper presents a straightforward plasma treatment modification of graphene with an enhanced piezoresistive effect for the realization of a high-performance pressure sensor. The changes in the graphene in terms of its morphology, structure, chemical composition, and electrical properties after the NH3/Ar plasma treatment were investigated in detail. Through a sufficient plasma treatment condition, our studies demonstrated that plasma-treated graphene sheet exhibits a significant increase in sensitivity by one order of magnitude compared to that of the unmodified graphene sheet. The plasma-doping introduced nitrogen (N) atoms inside the graphene structure and was found to play a significant role in enhancing the pressure sensing performance due to the tunneling behavior from the localized defects. The high sensitivity and good robustness demonstrated by the plasma-treated graphene sensor suggest a promising route for simple, low-cost, and ultrahigh resolution flexible sensors.
Owing to its superior properties and versatility, graphene has been proliferating the energy research scene in the past decade. In this contribution, nitrogen (N-) and boron (B-) doped reduced graphene oxide (rGO) variants were investigated as a sole photocatalyst for the green production of H2 and their properties with respect to photocatalysis were elucidated for the first time. N- and B-rGOs were facilely prepared via the pyrolysis of graphene oxide with urea and boron anhydride as their respective dopant source. The pyrolysis temperature was varied (600-800 °C for N-rGO and 800-1000 °C for B-rGO) in order to modify dopant loading percentage (%) which was found to be influential to photocatalytic activity. N-rGO600 (8.26 N at%) and B-rGO1000 (3.59 B at%), which holds the highest at% from each of their party, exhibited the highest H2 activity. Additionally, the effects of the nature of N and B bonding configuration in H2 photoactivity were also examined. This study demonstrates the importance of dopant atoms in graphene, rendering doping as an effective strategy to bolster photocatalytic activity for standalone graphene derivative photocatalysts.
The photocatalytic conversion of CO2 to energy-rich CH4 solar fuel is an ideal strategy for future energy generation as it can resolve global warming and the imminent energy crisis concurrently. However, the efficiency of this technology is unavoidably hampered by the ineffective generation and utilization of photoinduced charge carriers. In this contribution, we report a facile in situ topotactic transformation approach where {001}-faceted BiOBr nanosheets (BOB-NS) were employed as the starting material for the formation of single-crystalline ultrathin Bi2WO6 nanosheets (BWO-NS). The as-obtained BWO-NS not only preserved the advantageous properties of the 2D nanostructure and predominantly exposed {001} facets but also possessed enlarged specific surface areas as a result of sample thickness reduction. As opposed to the commonly observed bandgap broadening when the particle sizes decrease to an ultrathin nanoscale owing to the quantum size effect, the developed BWO-NS exhibited a fascinating bandgap narrowing compared to those of pristine Bi2WO6 nanoplates (BWO-P) synthesized from a conventional one-step hydrothermal approach. Moreover, the electronic band positions of BWO-NS were modulated as a result of ion exchange for the reconstruction of the energy bands, where BWO-NS demonstrated significant upshifting of CB and VB levels; these are beneficial for photocatalytic reduction applications. This propitious design of BWO-NS through integrating the merits of BOB-NS caused BWO-NS to exhibit substantial 2.6 and 9.3-fold enhancements of CH4 production over BOB-NS and BWO-P, respectively.
Establishing an effective metal-free photocatalyst for sustainable applications remains a huge challenge. Herein, we developed ultrathin oxygen-doped g-C3N4 nanosheets with carbon defects (OCvN) photocatalyst via a facile gas bubble template-assisted thermal copolymerization method. A series of OCvN with different dopant amounts ranging from 0 to 10% were synthesized and used as photocatalysts under illumination of low-power (2 × 18 W, 0.18 mW/cm2) and commercially available energy-saving light bulbs. Upon testing for photocatalytic Escherichia coli inactivation, the best-performing sample, OCvN-3, demonstrated an astonishing disinfection activity of over 7-log reduction after 3 h of illumination, boasting an 18-fold improvement in its antibacterial activity compared to that of pristine g-C3N4. The enhanced performance was attributed to the synergistic effects of increased surface area, extended visible light harvesting, improved electronic conductivity, and ultralow resistance to charge transfer. This study successfully introduced a green photocatalyst that demonstrates the most effective disinfection performance ever recorded among metal-free g-C3N4 materials. Its disinfection capabilities are comparable to those of metal-based photocatalysts when they are exposed to low-power light.
Ionotropic gelation has been an attractive method for the fabrication of biopolymeric oil-core microcapsules due to its safe and mild processing conditions. However, the mandatory use of a nozzle system to form the microcapsules restricts the process scalability and the production of small microcapsules (<100 μm). We report, for the first time, a nozzleless and surfactant-free approach to fabricate oil-core biopolymeric microcapsules through ionotropic gelation at the interface of an O/W Pickering emulsion. This approach involves the self-assembly of calcium carbonate (CaCO3) nanoparticles at the interface of O/W emulsion droplets followed by the addition of a polyanionic biopolymer into the aqueous phase. Subsequently, CaCO3 nanoparticles are dissolved by pH reduction, thus liberating Ca(2+) ions to cross-link the surrounding polyanionic biopolymer to form a shell that encapsulates the oil droplet. We demonstrate the versatility of this method by fabricating microcapsules from different types of polyanionic biopolymers (i.e., alginate, pectin, and gellan gum) and water-immiscible liquid cores (i.e., palm olein, cyclohexane, dichloromethane, and toluene). In addition, small microcapsules with a mean size smaller than 100 μm can be produced by selecting the appropriate conventional emulsification methods available to prepare the Pickering emulsion. The simplicity and versatility of this method allows biopolymeric microcapsules to be fabricated with ease by ionotropic gelation for numerous applications.
The ability of band offsets at multiferroic/metal and multiferroic/electrolyte interfaces in controlling charge transfer and thus altering the photoactivity performance has sparked significant attention in solar energy conversion applications. Here, we demonstrate that the band offsets of the two interfaces play the key role in determining charge transport direction in a downward self-polarized BFO film. Electrons tend to move to BFO/electrolyte interface for water reduction. Our experimental and first-principle calculations reveal that the presence of neodymium (Nd) dopants in BFO enhances the photoelectrochemical performance by reduction of the local electron-hole pair recombination sites and modulation of the band gap to improve the visible light absorption. This opens a promising route to the heterostructure design by modulating the band gap to promote efficient charge transfer.
Guided bone regeneration (GBR) scaffolds are futile in many clinical applications due to infection problems. In this work, we fabricated GBR with an anti-infective scaffold by ornamenting 2D single crystalline bismuth-doped nanohydroxyapatite (Bi-nHA) rods onto segmented polyurethane (SPU). Bi-nHA with high aspect ratio was prepared without any templates. Subsequently, it was introduced into an unprecedented synthesized SPU matrix based on dual soft segments (PCL-b-PDMS) of poly(ε-caprolactone) (PCL) and poly(dimethylsiloxane) (PDMS), by an in situ technique followed by electrospinning to fabricate scaffolds. For comparison, undoped pristine nHA rods were also ornamented into it. The enzymatic ring-opening polymerization technique was adapted to synthesize soft segments of PCL-b-PDMS copolymers of SPU. Structure elucidation of the synthesized polymers is done by nuclear magnetic resonance spectroscopy. Sparingly, Bi-nHA ornamented scaffolds exhibit tremendous improvement (155%) in the mechanical properties with excellent antimicrobial activity against various human pathogens. After confirmation of high osteoconductivity, improved biodegradation, and excellent biocompatibility against osteoblast cells (in vitro), the scaffolds were implanted in rabbits by subcutaneous and intraosseous (tibial) sites. Various histological sections reveal the signatures of early cartilage formation, endochondral ossification, and rapid bone healing at 4 weeks of the critical defects filled with ornamented scaffold compared to SPU scaffold. This implies osteogenic potential and ability to provide an adequate biomimetic microenvironment for mineralization for GBR of the scaffolds. Organ toxicity studies further confirm that no tissue architecture abnormalities were observed in hepatic, cardiac, and renal tissue sections. This finding manifests the feasibility of fabricating a mechanically adequate nanofibrous SPU scaffold by a biomimetic strategy and the advantages of Bi-nHA ornamentation in promoting osteoblast phenotype progression with microbial protection (on-demand) for GBR applications.
Near-infrared (NIR) small-molecule acceptors that absorb at wavelengths of up to 1000 nm are attractive for applications in organic photodetectors (OPDs) and biometrics. In this study, we incorporated IEICO-4F as the third component for PffBT4T-2OD:PC71BM-based OPDs to provide an efficient NIR response while greatly suppressing the leakage current at reverse bias. By varying the blend ratio and thickness (250-600 nm), we obtained an NIR OPD displaying an ultralow dark-current density (JD = 2.62 nA cm-2), ultrahigh detectivity [D* = 7.2 × 1012 Jones (850 nm)], high sensitivity, and photoresponsivity covering the region from the ultraviolet to the NIR. We used tapping-mode atomic force microscopy, optical microscopy, grazing-incidence wide-angle X-ray scattering, and contact angle measurements to investigate the effect of IEICO-4F on the performance of the ternary OPDs. The low compatibility of PffBT4T-2OD and IEICO-4F, originating from weak intermolecular interactions, allowed us to manipulate the degree of phase separation between the donor and acceptor in the ternary blends, leading to an optimized blend morphology featuring efficient charge separation, transport, and collection. To demonstrate its applicability, we integrated our OPD with two light-emitting diodes and used the system for precisely calculated transmissive pulse oximetry.
A systematic investigation was carried out by incorporating an ultrathin aluminum oxide (Al2O3) as an interlayer between yttrium oxide (Y2O3) passivation layer and GaN substrate. The sandwiched samples were then subjected to postdeposition annealing in oxygen ambient from 400 to 800 °C. The Al2O3 interlayer was discovered to play a significant role in slowing down inward diffusion of oxygen through the Y2O3 passivation layer as well as in impeding outward diffusion of Ga(3+) and N(3-) from the decomposed GaN surface. These beneficial effects have suppressed subsequent formation of interfacial layer. A mechanism in association with the function of Al2O3 as an interlayer was suggested and discussed. The mechanism was explicitly described on the basis of the obtained results from X-ray diffraction, X-ray photoelectron spectroscopy, energy-filtered transmission electron microscopy (TEM), high resolution TEM, and electron energy loss spectroscopy line scan. A correlation between the proposed mechanism and metal-oxide-semiconductor characteristics of Y2O3/Al2O3/GaN structure has been proposed.
An ultrathin RF-magnetron sputtered Al2O3 gate on GaN subjected to postdeposition annealing at 800 °C in O2 ambient was systematically investigated. A cross-sectional energy-filtered transmission electron microscopy revealed formation of crystalline Al2O3 gate, which was supported by X-ray diffraction analysis. Various current conduction mechanisms contributing to leakage current of the investigated sample were discussed and correlated with metal-oxide-semiconductor characteristics of this sample.
Electrospinning is a promising technique for the fabrication of bioscaffolds in tissue engineering applications. Pertaining issues of multiple polymer jets and bending instabilities result in random paths which lend poor controllability over scaffolds morphology for affecting the porosity and mechanical stability. The present study alleviates these challenges by demonstrating a novel self-directing single jet taking a specifically patterned path to deposit fibers into circular and uniform scaffolds without tuning any externally controlled parameters. High-speed camera observation revealed that the charge retention and dissipation on the collected fibers caused rapid autojet switching between the two jetting modes, namely, a microcantilever-like armed jet motion and a whipping motion, which sequentially expand the area and thickness of the scaffolds, respectively, in a layered-like fashion. The physical properties showed that the self-switching dual-jet modes generated multilayered microfibrous scaffolds (MFSs) with dual morphologies and varied fiber packing density, thereby establishing the gradient porosity and mechanical strength (through buckled fibers) in the scaffolds. In vitro studies showed that as-spun scaffolds are cell-permeable hierarchical 3D microporous structures enabling lateral cell seeding into multiple layers. The cell proliferation on days 6 and 9 increased 21% and 38% correspondingly on MFSs than on nanofibrous scaffolds (NFSs) done by conventional multijets electrospinning. Remarkably, this novel and single-step process is highly reproducible and tunable for developing fibrous scaffolds for tissue engineering applications.
Thin-film lithium-ion microbatteries with a high energy density and long lifespan are exceedingly desired for developing self-powered integrated micro-nano devices and systems. However, exploring high-performance thin-film anodes still remains a challenge. Herein, a double-layer-structure diamond-like carbon-ZnS (DLC-ZnS) thin-film anode fabricated by radio frequency magnetron sputtering exhibits high specific capacity and good cycling stability up to 1000 cycles, superior to the pure ZnS thin-film anode. To understand the mechanism, the bimodal amplitude modulated-frequency modulated atomic force microscopy was used to explore the mechanical properties of the thin films, and the DLC layer shows significantly higher Young's modulus than the ZnS thin film. The DLC interface with a high Young's modulus can effectively buffer the mechanical stress originating from the huge volume changes of the ZnS layer during lithiation/delithiation processes; therefore, the DLC interface maintains the higher mechanical integrity of the DLC-ZnS thin film and improves the utilization of ZnS. In addition, the electrochemical kinetics of the DLC-ZnS and ZnS thin films were also investigated by electrochemical methods. Electrochemical impedance spectroscopy tests indicate the obstacle of the DLC interface to Li+ ion diffusion in the initial charge/discharge processes; however, the DLC-ZnS thin film exhibits lower total resistance than the ZnS thin film afterward. In particular, galvanostatic intermittent titration technique tests were performed to find out the differences between the two thin films during the galvanostatical charge/discharge processes. The results demonstrate the obviously enhanced conversion reaction reversibility and decreased alloy reaction polarization of the DLC-ZnS thin film; therefore, it delivers higher reversible capacity.
We demonstrate efficient semipolar (11-22) 550 nm yellow/green InGaN light-emitting diodes (LEDs) with In0.03Ga0.97N barriers on low defect density (11-22) GaN/patterned sapphire templates. The In0.03Ga0.97N barriers were clearly identified, and no InGaN clusters were observed by atom probe tomography measurements. The semipolar (11-22) 550 nm InGaN LEDs (0.1 mm2 size) show an output power of 2.4 mW at 100 mA and a peak external quantum efficiency of 1.3% with a low efficiency drop. In addition, the LEDs exhibit a small blue-shift of only 11 nm as injection current increases from 5 to 100 mA. These results suggest the potential to produce high efficiency semipolar InGaN LEDs with long emission wavelength on large-area sapphire substrates with economical feasibility.