Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm(-2), in contrast to MnO2, which produced a maximum power density of 9.2 mW cm(-2). The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.
The thermoluminescence (TL) glow curves and kinetics parameters of Thulium (Tm) doped silica cylindrical fibers (CF) are presented. A linear accelerator (LINAC) was used to deliver high-energy radiation of 21MeV electrons and 10MV photons. The CFs were irradiated in the dose range of 0.2-10Gy. The experimental glow curve data was reconstructed by using WinREMS. The WinGCF software was used for the kinetic parameters evaluation. The TL sensitivity of Tm-doped silica CF is about 2 times higher as compared to pure silica CF. Tm-doped silica CF seems to be more sensitive to 21MeV electrons than to 10MV photons. Surprisingly, no supralinearity was displayed and a sub-linear response of Tm-doped silica CF was observed within the analyzed dose range for both 21MeV electrons and 10MV photons. The Tm-doped silica CF glow curve consists of 5 individual glow peaks. The Ea of peak 4 and peak 5 was highly dependent on dose when irradiated with photons. We also noticed that the electron radiation (21MeV) caused a shift of glow peak by 7-13°C to the higher temperature region compared with photons radiation (10MV). Our Tm-doped fibers seem to give high TL response after 21MeV electrons, which gives around 2 times higher peak integral as compared with 10MV photon radiation. We concluded that peak 4 is the first-order kinetic peak and can be used as the main dosimetric peak of Tm-doped silica CF.
A facile one-pot impregnation-thermal reduction strategy was employed to fabricate sandwich-like graphene-g-C3N4 (GCN) nanocomposites using urea and graphene oxide as precursors. The GCN sample exhibited a slight red shift of the absorption band edge attributed to the formation of a C-O-C bond as a covalent cross linker between graphene and g-C3N4. The GCN sample demonstrated high visible-light photoactivity towards CO2 reduction under ambient conditions, exhibiting a 2.3-fold enhancement over pure g-C3N4. This was ascribed to the inhibition of electron-hole pair recombination by graphene, which increased the charge transfer.
Graphene is an attention-grabbing material in electronics, physics, chemistry, and even biology because of its unique properties such as high surface-area-to-volume ratio. Also, the ability of graphene-based materials to continuously tune charge carriers from holes to electrons makes them promising for biological applications, especially in lipid bilayer-based sensors. Furthermore, changes in charged lipid membrane properties can be electrically detected by a graphene-based electrolyte-gated graphene field effect transistor (GFET). In this paper, a monolayer graphene-based GFET with a focus on the conductance variation caused by membrane electric charges and thickness is studied. Monolayer graphene conductance as an electrical detection platform is suggested for neutral, negative, and positive electric-charged membrane. The electric charge and thickness of the lipid bilayer (Q LP and L LP) as a function of carrier density are proposed, and the control parameters are defined. Finally, the proposed analytical model is compared with experimental data which indicates good overall agreement.
This paper reports a rapid and in-situ electrochemical polymerization method for the fabrication of polypyrrole nanoparticles incorporated reduced graphene oxide (rGO@PPy) nanocomposites on a ITO conducting glass and its application as a counter electrode for platinum-free dye-sensitized solar cell (DSSC). The scanning electron microscopic images show the uniform distribution of PPy nanoparticles with diameter ranges between 20 and 30 nm on the rGO sheets. The electrochemical studies reveal that the rGO@PPy has smaller charge transfer resistance and similar electrocatalytic activity as that of the standard Pt counter electrode for the I₃(-)/I(-) redox reaction. The overall solar to electrical energy conversion efficiency of the DSSC with the rGO@PPy counter electrode is 2.21%, which is merely equal to the efficiency of DSSC with sputtered Pt counter electrode (2.19%). The excellent photovoltaic performance, rapid and simple fabrication method and low-cost of the rGO@PPy can be potentially exploited as a alternative counter electrode to the expensive Pt in DSSCs.
Modern linear accelerators, the predominant teletherapy machine in major radiotherapy centres worldwide, provide multiple electron and photon beam energies. To obtain reasonable treatment times, intense electron beam currents are achievable. In association with this capability, there is considerable demand to validate patient dose using systems of dosimetry offering characteristics that include good spatial resolution, high precision and accuracy. Present interest is in the thermoluminescence response and dosimetric utility of commercially available doped optical fibres. The important parameter for obtaining the highest TL yield during this study is to know the dopant concentration of the SiO2 fibre because during the production of the optical fibres, the dopants tend to diffuse. To achieve this aim, proton-induced X-ray emission (PIXE), which has no depth resolution but can unambiguously identify elements and analyse for trace elements with detection limits approaching microg/g, was used. For Al-doped fibres, the dopant concentration in the range 0.98-2.93 mol% have been estimated, with equivalent range for Ge-doped fibres being 0.53-0.71 mol%. In making central-axis irradiation measurements a solid water phantom was used. For 6-MV photons and electron energies in the range 6, 9 and 12 MeV, a source to surface distance of 100 cm was used, with a dose rate of 400 cGy/min for photons and electrons. The TL measurements show a linear dose-response over the delivered range of absorbed dose from 1 to 4 Gy. Fading was found to be minimal, less than 10% over five days subsequent to irradiation. The minimum detectable dose for 6-MV photons was found to be 4, 30 and 900 microGy for TLD-100 chips, Ge- and Al-doped fibres, respectively. For 6-, 9- and 12-MeV electron energies, the minimum detectable dose were in the range 3-5, 30-50 and 800-1400 microGy for TLD-100 chip, Ge-doped and Al-doped fibres, respectively.
With interest in the potential of optical fibres as the basis of next-generation thermoluminescence dosimeters (TLDs), the development of suitable forms of material and their fabrication has become a fast-growing endeavour. Present study focuses on three types of Ge-doped optical fibres with different structural arrangements and/or shapes, namely conventional cylindrical fibre, capillary fibre, and flat fibre, all fabricated using the same optical fibre preform. For doses from 0.5 to 8 Gy, obtained at electron and photon energies, standard thermoluminescence (TL) characteristics of the optical fibres have been the subject of detailed investigation. The results show that in collapsing the capillary fibre into a flat shape, the TL yield is increased by a factor of 5.5, the yield being also some 3.2 times greater than that of the conventional cylindrical fibre fabricated from the same perform. This suggests a means of production of suitably sensitive TLD for in-vivo dosimeter applications. Addressing the associated defects generating luminescence from each of the optical fibres, the study encompasses analysis of the TL glow curves, with computerized glow curve deconvolution (CGCD) and 2(nd) order kinetics.
High-energy electron (2.0 MV) and gamma irradiation (60Co) has been used to modify polymeric silicone fluids of initial viscosities in the range, 90-700 cSt. Doses of electron and gamma radiation were delivered at rates of 0.246 kGy s(-1) and 15 kGy h(-1), respectively, exposure times being adjusted to ensure energy deposition in the range 30-360 kGy. Measurements were made using a differential viscometer based on a Bose Institute design. In line with expectation, samples of greater initial molecular weight (and hence greater viscosity), were observed to be more susceptible to radiation induced cross-linking than those of lower molecular weight. The role of dose rate and oxygen diffusion in determining the extent of change is discussed.
Previous scattering and depth-dose investigations involving use of the Malaysian hardwood Rhizophora spp have shown this medium to produce good agreement with measurements made in water. Present study extends the comparison, now including measurements of percentage depth-dose made for photons at 6MV and 5 and 12MeV electron beams. For the 6 MV photon and 5 MeV electron beams, discrepancies between percentage depth-dose for Rhizophora spp and water, at all depths, are found to be within 2.6 and 2.4% respectively. At 12 MeV electron energies, measured percentage depth-doses in Rhizophora spp beyond 3.5cm depth are found to be in significant discord with those for water. The absorbed dose in water measured in Rhizophora spp at d(max) for all three beams produces discrepancies of no more than 1.1% when compared with measurements made in water.
Material designs that use donor and acceptor units are often found in organic optoelectronic devices. Molecular level insight into the interactions between donors and acceptors are crucial for understanding how such interactions can modify the optical properties of the organic optoelectronic materials. In this paper, tris(4-(tert-butyl)phenyl)amine (pTPA) was synthesized as a donor in order to compare with unmodified triphenylamine (TPA) in a donor-acceptor system by having 2,4,6-triphenyl-1,3,5-triazine (TRZ) as an acceptor. Dimerization of donors and acceptors occurred in solvent when the concentration of solute is high. At 0 K, using a polarizable continuum model, the nitrogen atom of TPA is found to stack on top of the center of triazine of TRZ, whereas such alignment is offset in pTPA and TRZ. We attributed such alignment in TPA-TRZ as the result of attractive interactions between partial localization of 2pz electrons at the nitrogen atom of TPA and the π deficiency of triazine in TPA-TRZ. By taking into account random motions of the solvent effect at 300 K in quantum molecular dynamics and classical molecular dynamics simulations to interpret the marked difference in emission spectra between TPA-TRZ and pTPA-TRZ, it was revealed that the attractive interaction between pTPA and TRZ in toluene is weaker than TPA and TRZ. Because of the weaker attractive interaction between pTPA and TRZ in toluene, the dimers adopted numerous ground state conformations resulting in broad emission bands superimposed with multiple small Gaussian peaks. This is in contrast to TPA-TRZ which has only one dominant dimer conformation. This study demonstrates that the strength of intermolecular interactions between donors and acceptors should be taken into consideration in designing supramolecular structures.
Multiple contaminants including heavy metals and phenolic compounds are normally co-exist in wastewater, which caused the treatment process is rather complicated. Herein, the synergistic photoredox of Cr(VI) and p-cresol (pC) by innovative fibrous silica zirconia (FSZr) photocatalyst was reported. The high surface area of FSZr comprised of microspheres with a bicontinuous concentric lamella structure morphology consisted of silica, while its core consisted of ZrO2 structure. The rearrangement of FSZr framework increased the crystallinity, formed Si-O-Zr bonds and narrowed the band gap of ZrO2 for enhanced of photoredox of Cr(VI) and pC. Compared to the reaction, the photoredox efficiency of FSZr for removing Cr(VI) and pC in simultaneous system was found to be 96 % and 59 %, respectively which are higher than that in its single system owing to the efficient electron-hole charge separation. Phenolic compound with high degree of electron donating group gave beneficial effect to photoreduction of Cr(VI). Consequently, a proposed mechanism involving multi-photoredox pathway were proposed based on photoredox reaction and scavengers studies. FSZr sustained the simultaneous photoredox activities after five runs demonstrating its possibility to be use in the wastewater treatment of various pollutants.
Mixed culture sludge has been widely used as a microbial consortium for biohydrogen production. Simple thermal treatment of sludge is usually required in order to eliminate any H2-consuming bacteria that would reduce H2 production. In this study, thermal treatment of sludge was carried out at various temperatures. Electron flow model was then applied in order to assess community structure in the sludge upon thermal treatment for biohydrogen production. Results show that the dominant electron sink was acetate (150-217 e- meq/mol glucose). The electron equivalent (e- eq) balances were within 0.8-18% for all experiments. Treatment at 100 °C attained the highest H2 yield of 3.44 mol H2/mol glucose from the stoichiometric reaction. As the treatment temperature increased from 80 to 100 °C, the computed acetyl-CoA and reduced form of ferredoxin (Fdred) concentrations increased from 13.01 to 17.34 e- eq (1.63-2.17 mol) and 1.34 to 4.18 e- eq (0.67-2.09 mol), respectively. The NADH2 balance error varied from 3 to 10% and the term e-(Fd↔NADH2) (m) in the NADH2 balance was NADH2 consumption (m = -1). The H2 production was mainly via the Fd:hydrogenase system and this is supported with a good NADH2 balance. Using the modified Gompertz model, the highest maximum H2 production potential was 1194 mL whereas the maximum rate of H2 production was 357 mL/h recorded at 100 °C of treatment.
This paper reports the synthesis of two-dimensional, hierarchical, porous, and (001)-faceted metal (Ag, Zn, and Al)-doped TiO2 nanostructures (TNSs) and the study of their photocatalytic activity. Two-dimensional metal-doped TNSs were synthesized using the hydrolysis of ammonium hexafluorotitanate in the presence of hexamethylenetetramine and metal precursors. Typical morphology of metal-doped TNSs is a hierarchical nanosheet that is composed of randomly stacked nanocubes (dimensions of up to 5 μm and 200 nm in edge length and thickness, respectively) and has dominant (001) facets exposed. Raman analysis and X-ray photoelectron spectroscopy results indicated that the Ag doping, compared to Zn and Al, much improves the crystallinity degree and at the same time dramatically lowers the valence state binding energy of the TNS and provides an additional dopant oxidation state into the system for an enhanced electron-transfer process and surface reaction. These are assumed to enhance the photocatalytic of the TNS. In a model of photocatalytic reaction, that is, rhodamine B degradation, the AgTNS demonstrates a high photocatalytic activity by converting approximately 91% of rhodamine B within only 120 min, equivalent to a rate constant of 0.018 m-1 and ToN and ToF of 94 and 1.57 min-1, respectively, or 91.1 mmol mg-1 W-1 degradation when normalized to used light source intensity, which is approximately 2 times higher than the pristine TNS and several order higher when compared to Zn- and Al-doped TNSs. Improvement of the crystallinity degree, decrease in the defect density and the photogenerated electron and hole recombination, and increase of the oxygen vacancy in the AgTNS are found to be the key factors for the enhancement of the photocatalytic properties. This work provides a straightforward strategy for the preparation of high-energy (001) faceted, two-dimensional, hierarchical, and porous Ag-doped TNSs for potential use in photocatalysis and photoelectrochemical application.
Newly discovered two-dimensional (2D) atomic crystals (nanosheet) of platinum diselenide (PtSe2) have progressively attracted attention due to their expected high performance in catalysis, sensing, electronics, and optoelectronics applications. Further extraordinary physicochemical properties are expected if these nanosheets of platinum diselenide can possess mesoporosity as this may enable a high range of molecular adsorption, enhancing their functionalities in catalysis, batteries, supercapacitors, and sensing. Here, we present for the first time a straightforward, aqueous-phase synthetic strategy for the preparation of scalable nanosheets of platinum diselenide with mesoporous structure via a surfactant-templated self-assembly followed by a thermal annealing phase-transformation process. We used hexamethylenetetramine as a hexagonal honeycomb (sp2-sp3 orbital) scaffold for assembling the Pt and Se organic complexes to form the nanosheet structure, which is stable, preserving the 2D structure and mesoporosity during a thermal annealing at 500 °C. Density functional theory analysis then indicated that the mesoporous nanosheets of platinum diselenide exhibit a high free-energy and large density of π electrons crossing the Fermi level, inferring a high-catalytic performance. This effortless strategy is currently being extended to the synthesis of other transition metal dichalcogenides, including the preparation of multi-metal atomic dichalcogenide nanosheets, for a wide variety of scientific and technological applications.
In this paper, a facile synthesis method for CaFe2O4 is introduced that produces a catalyst capable of significant photocatalytic degradation of POME under visible light irradiation. The co-precipitation method was used to produce two catalysts at calcination temperatures of 550 °C and 700 °C dubbed CP550 and CP700. CP550 demonstrated the maximum COD removal of 69.0% at 0.75 g/L catalyst loading after 8 h of visible light irradiation which dropped to 61.0% after three consecutive cycles. SEM images indicated that the higher calcination temperature of CP700 led to annealing which reduced the pore volume (0.025 cm3/g) and pore diameter (10.3 nm) while simultaneously creating a smoother and more spherical surface with lower SBET (9.73 m2/g). In comparison, CP550 had a rough hair-like surface with higher SBET (27.28 m2/g) and pore volume (0.077 cm3/g) as evidenced by BET analysis. XRD data indicated the presence of CaFe5O7 in the CP550 composition which was not present in CP700. The presence of Wustite-like FeO structures in CaFe5O7 are likely the cause for lower photoluminescence intensity profile and hence better charge separation of CP550 as these structures in CaFe2O4 have been known to increase resistivity and electron localization. The COD removal of CP550 dropped from 69.0% to just 7.0% upon adding a small quantity of isopropanol into the reaction mixture indicating hydroxyl radicals as the primary reactive oxidative species.
One of the difficulties with bobbin friction stir welding (BFSW) has been the visualisation of microstructure, particularly grain boundaries, and this is especially problematic for materials with fine grain structure, such as AA6082-T6 aluminium as here. Welds of this material were examined using optical microscopy (OM) and electron backscatter diffraction (EBSD). Results show that the grain structures that form depend on a complex set of factors. The motion of the pin and shoulder features transports material around the weld, which induces shear. The shear deformation around the pin is non-uniform with a thermal and strain gradient across the weld, and hence the dynamic recrystallisation (DRX) processes are also variable, giving a range of observed polycrystalline and grain boundary structures. Partial DRX was observed at both hourglass boundaries, and full DRX at mid-stirring zone. The grain boundary mapping showed the formation of low-angle grain boundaries (LAGBs) at regions of high shear as a consequence of thermomechanical nature of the process.
Elemental doping represents a prominent strategy to improve interfacial chemistry in battery materials. Manipulating the dopant spatial distribution and understanding the dynamic evolution of the dopants at the atomic scale can inform better design of the doping chemistry for batteries. In this work, we create a targeted hierarchical distribution of Ti4+, a popular doping element for oxide cathode materials, in LiNi0.8Mn0.1Co0.1O2 primary particles. We apply multiscale synchrotron/electron spectroscopy and imaging techniques as well as theoretical calculations to investigate the dynamic evolution of the doping chemical environment. The Ti4+ dopant is fully incorporated into the TMO6 octahedral coordination and is targeted to be enriched at the surface. Ti4+ in the TMO6 octahedral coordination increases the TM-O bond length and reduces the covalency between (Ni, Mn, Co) and O. The excellent reversibility of Ti4+ chemical environment gives rise to superior oxygen reversibility at the cathode-electrolyte interphase and in the bulk particles, leading to improved stability in capacity, energy, and voltage. Our work directly probes the chemical environment of doping elements and helps rationalize the doping strategy for high-voltage layered cathodes.
Cobalt incorporated sulfur-doped graphitic carbon nitride with bismuth oxychloride (Co/S-gC3N4/BiOCl) heterojunction is prepared by an ultrasonically assisted hydrothermal treatment. The heterojunction materials have employed in photoelectrochemical (PEC) water splitting. The PEC activity and stability of the materials are promoted by constructing an interface between the visible light active semiconductor photocatalyst and cocatalysts. The photocurrent density of Co-9% S-gC3N4/BiOCl has attained 393.0 μA cm-2 at 1.23 V vs. RHE, which is 7-fold larger than BiOCl and ~3-fold higher than 9% S-gC3N4/BiOCl. The enhanced PEC activity can be attributed to the improved electron-hole charge separation and the boosted charge transfer is confirmed by photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) analysis. The fabricated Co/S-gC3N4/BiOCl nanohybrid material has exhibited high stability of up to 10,800 s (3 h) at 1.23 V vs. RHE during PEC water splitting reaction and the obtained photo-conversion efficiency is 3.7-fold greater than S-gC3N4/BiOCl and 17-fold higher than BiOCl. The FESEM and HRTEM images have revealed the formation of heterojunction interface between S-gC3N4 and BiOCl and the elemental mapping has confirmed the presence of cobalt over S-gC3N4/BiOCl. The heterojunction interface has facilitated the photo-excited charge separation and transport across the electrode/electrolyte interface and also the flat-band potential, which is confirmed by Mott-Schottky analysis.
The interactions within microbial, chemical and electronic elements in microbial fuel cell (MFC) system can be crucial for its bio-electrochemical activities and overall performance. Therefore, this study explored polynomial models by response surface methodology (RSM) to better understand interactions among anode pH, cathode pH and inoculum size for optimising MFC system for generation of electricity and degradation of 2,4-dichlorophenol. A statistical central composite design by RSM was used to develop the quadratic model designs. The optimised parameters were determined and evaluated by statistical results and the best MFC systematic outcomes in terms of current generation and chlorophenol degradation. Statistical results revealed that the optimum current density of 106 mA/m2 could be achieved at anode pH 7.5, cathode pH 6.3-6.6 and 21-28% for inoculum size. Anode-cathode pHs interaction was found to positively influence the current generation through extracellular electron transfer mechanism. The phenolic degradation was found to have lower response using these three parameter interactions. Only inoculum size-cathode pH interaction appeared to be significant where the optimum predicted phenolic degradation could be attained at pH 7.6 for cathode pH and 29.6% for inoculum size.
This study assesses the optical properties and conductivity of PVA-H3PO4 (polyvinyl alcohol-phosphoric acid) polymer film blend irradiated by gamma (γ) rays. The PVA-H3PO4 polymer film blend was prepared by the solvent-casting method at H3PO4 concentrations of 75 v% and 85 v%, and then irradiated up to 25 kGy using γ-rays from the Cobalt-60 isotope source. The optical absorption spectrum was measured using an ultraviolet-visible spectrophotometer over a wavelength range of 200 to 700 nm. It was found that the absorption peaks are in three regions, namely two peaks in the ultraviolet region (310 and 350 nm) and one peak in the visible region (550 nm). The presence of an absorption peak after being exposed to hυ energy indicates a transition of electrons from HOMO to LUMO within the polymer chain. The study of optical absorption shows that the energy band gap (energy gap) depends on the radiation dose and the concentration of H3PO4 in the polymer film blend. The optical absorption, absorption edge, and energy gap decrease with increasing H3PO4 concentration and radiation dose. The interaction between PVA and H3PO4 blend led to an increase in the conductivity of the resulting polymer blend film.