The scarcity of water leads to research nowadays to focus on techniques for treating wastewater. Photocatalysis emerged as a technique of interest due to its nature of friendliness. It utilizes light and catalyst to degrade the pollutants. One of the popular catalysts to be used is zinc oxide (ZnO), but its usage is limited due to the high recombination rate of electron-hole pair. Herein, in this study, ZnO is modified with graphitic carbon nitride (GCN), and the GCN loading amount was varied to study the impact on photocatalytic degradation of mixed dye solution. To the best of our knowledge, this is the first work that reports on the degradation of mixed dye solution using modified ZnO with GCN. Structural analysis showed that GCN is present in the composites which proves the success of the modification. Photocatalytic activity revealed that the composite with 5 wt% loading of GCN showed the best activity at a catalyst dosage of 1 g/L with degradation rates of 0.0285, 0.0365, 0.0869, and 0.1758 min-1 for methyl red, methyl orange, rhodamine B, and methylene blue dyes, respectively. This observation is expected due to the formation of heterojunction between ZnO and GCN which creates a synergistic effect and thus led to an improvement in the photocatalytic activity. Based on these results, ZnO modified with GCN has a good potential to be used in the treatment of textile wastewater which consists of various dye mixtures.
Vanadia (V2O5)-incorporated fibrous silica-titania (V/FST) catalysts, which were successfully synthesized using a hydrothermal method followed by the impregnation of V2O5. The catalysts were then characterized using numerous techniques, including X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption analyses, ultraviolet-visible diffuse reflectance spectroscopy, Fourier-transform infrared, X-ray photoelectron spectroscopy, and photoluminescence (PL) analyses. The study found that varying the amount of V2O5 (1-10 wt%) had a significant impact on the physicochemical properties of the FST, which in turn improved the photodegradation efficiency of two organic compounds, ciprofloxacin (CIP) and congo red (CR). 5V/FST demonstrated the best performance in degrading 10 mg L-1 of CIP (83%) and CR (100%) at pH 3 using 0.375 g L-1 catalyst under visible light irradiation within 180 min. The highest photoactivity of 5V/FST is mainly due to higher crystallinity and the highest number of V2O5-FST interactions. Furthermore, as demonstrated by PL analysis, the 5V/FST catalyst has the most significant impact on interfacial charge transfer and reduces electron-hole recombination. The photodegradation of both contaminants follows the Langmuir-Hinshelwood pseudo-first-order model, according to the kinetic study. The scavenger investigation demonstrated that hydroxyl radicals and holes dominated species in the system, indicating that the catalyst effectively generated reactive species for pollutant degradation. A possible mechanism was also identified for FST and 5V/FST. Interestingly, V2O5 acts as an electron-hole recombination inhibitor on FST for selective hole oxidation of ciprofloxacin and congo red photodegradation. Finally, the degradation efficiency of the catalyst remained relatively stable even after five cyclic experiments, indicating its potential for long-term use in environmental remediation.
The current study was undertaken to investigate the radiological and dosimetric parameters of natural product-based composite (SPI/NaOH/IA-PAE/ Rhizophora spp .) phantoms. The radiological properties of the phantoms were measured at different gamma energies from Compton scatter of photons through angles of 0, 30, 45, 60, 75, and 90 degrees. Ionization chamber (IC) and Gafchromic EBT3 film dosimeters were employed to evaluate the dosimetric characteristics for photons (6-10 MV) and electrons (6-15 MeV). Radiological property results of the composite phantoms were consistent with good quality compared to those of solid water phantoms and theoretical values of water. Photon beam quality index of the SPI15 phantom with p-values of 0.071 and 0.073 exhibited insignificant changes. In addition, good agreement was found between PDD curves measured with IC and Gafchromic EBT3 film for both photons and electrons. The computed therapeutic and half-value depth ranges matched within the limits and are similar to those of water and solid water phantoms. Therefore, the radiological and dosimetric parameters of the studied composite phantom permit its use in the selection of convenient tissue- and water-equivalent phantom material for medical applications.
Herein, we report a detailed study on creating heterojunction between graphitic carbon nitride (g-C3N4) and bismuth phosphate (BiPO4), enhancing the unpaired free electron mobility. This leads to an accelerated photocatalysis of 2,4-dichlorophenols (2,4-DCPs) under sunlight irradiation. The heterojunction formation was efficaciously conducted via a modest thermal deposition technique. The function of g-C3N4 plays a significant role in generating free electrons under sunlight irradiation. Together, the generated electrons at the g-C3N4 conduction band (CB) are transferred and trapped by the BiPO4 to form active superoxide anion radicals (•O2-). These active radicals will be accountable for the photodegradation of 2,4-DCPs. The synthesized composite characteristics were methodically examined through several chemical and physical studies. Due to the inimitable features of both g-C3N4 and BiPO4, its heterojunction formation, 2.5wt% BiPO4/g-C3N4 achieved complete 2,4-DCP removal (100%) in 90 min under sunlight irradiation. This is due to the presence of g-C3N4 that enhanced electron mobility through the formation of heterojunctions that lengthens the electron-hole pairs' lifetime and maximizes the entire solar spectrum absorption to generate active electrons at the g-C3N4 conduction band. Thus, this formation significantly draws the attention for future environmental remediation, especially in enhancing the entire solar spectrum's harvesting.
Photocatalytic conversion of carbon dioxide (CO2) into gaseous hydrocarbon fuels is an auspicious way to produce renewable fuels in addition to greenhouse gas emission mitigation. In this work, non-metals (B, O, P, and S) doped graphitic carbon nitride (g-C3N4) was prepared via solid-state polycondensation of urea for photocatalytic CO2 reduction into highly needed methane (CH4) with water under UV light irradiation. The various physicochemical characterization results reveal the successful incorporation of B, O, P, and S elements in the g-C3N4 matrix. The maximum CH4 yield of 55.10 nmol/(mLH2O.gcat) over S-doped g-C3N4 has been obtained for CO2 reduction after 7 h of irradiation. This amount of CH4 production was 1.9, 1.4, 1.7, and 2.4-folds higher than B, O, P and bare g-C3N4 samples. The doping of S did not enlarge the surface area and photon absorption ability of the g-C3N4 sample, but this significant improvement was evidently due to effective charge separation and migration. The observed results imply that the doping of non-metal elements provides improved charge separation and is an effective way to boost photocatalyst performance. This work offers an auspicious approach to design non-metal doped g-C3N4 photocatalysts for renewable fuel production and would be promising for other energy application.
Constructing efficient structured materials for artificial photosynthesis of CO2 is a promising strategy to produce renewable fuels in addition of mitigating greenhouse effect. In this work, 2D porous g-C3N4 (PCN) coupled exfoliated 3D Ti3C2TA MXene (TiC) nanosheets with TiO2 NPs in-situ growth was constructed in a single step through HF treatment approach. The different exfoliated TiC structures were successfully synthesized for adjusting HF etching time (24 h, 48 h and 96 h). With growing etchant time from 24 to 96 h, the amount of TiO2 produced was increased, but it has adverse effects on CO and CH4 production rate. The maximum production rates for CO and CH4 of 317.4 and 78.55 µmol g-1 h-1 were attained when the 10TiC-48/PCN was employed than using TiC-24/PCN, TiC-96/PCN and PCN composite samples, respectively. The performance of 10TiC-48/PCN composite for CO and CH4 evolution were 9.9 and 6.7 folds higher than using pristine PCN sample, respectively. The possible mechanism is assigned to porous structure with intimate contact enabling efficient charge carrier separation with the role of TiO2 NPs to work as a bridge to transport electrons towards MXene surface. Among the reducing agents, water was favorable for CO evolution, whereas, methanol-water system promoted CH4 production. All these findings confirm that heterojunction formation facilitates charges separation and can be further used in solar energy relating application.
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.
In this work, advanced nanoscale surface characterization of CuO Nanoflowers synthesized by controlled hydrothermal approach for significant enhancement of catalytic properties has been investigated. The CuO nanoflower samples were characterized by field-emission scanning electron microscopy (FE-SEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, high-resolution transmission electron microscopy (HR-TEM), selected-area electron diffraction (SAED), high-angular annular dark field scanning transmission electron microscopy (HAADF-STEM) with elemental mapping, energy dispersive spectroscopy (STEM-EDS) and UV-Vis spectroscopy techniques. The nanoscale analysis of the surface study of monodispersed individual CuO nanoflower confirmed the fine crystalline shaped morphology composed of ultrathin leaves, monoclinic structure and purified phase. The result of HR-TEM shows that the length of one ultrathin leaf of copper oxide nanoflower is about ~650-700 nm, base is about ~300.77 ± 30 nm and the average thickness of the tip of individual ultrathin leaf of copper oxide nanoflower is about ~10 ± 2 nm. Enhanced absorption of visible light ~850 nm and larger value of band gap energy (1.68 eV) have further supported that the as-grown material (CuO nanoflowers) is an active and well-designed surface morphology at the nanoscale level. Furthermore, significant enhancement of catalytic properties of copper oxide nanoflowers in the presence of H2O2 for the degradation of methylene blue (MB) with efficiency ~96.7% after 170 min was obtained. The results showed that the superb catalytic performance of well-fabricated CuO nanoflowers can open a new way for substantial applications of dye removal from wastewater and environment fields.
This paper describes the synthesis of graphene-based activated carbon from carbonaceous rice straw fly ash in an electrical furnace and the subsequent potassium hydroxide extraction. The produced graphene has a proper morphological structure; flakes and a rough surface can be observed. The average size of the graphene was defined as up to 2000 nm and clarification was provided by high-resolution microscopes (FESEM and FETEM). Crystallinity was confirmed by surface area electron diffraction. The chemical bonding from the graphene was clearly observed, with -C=C- and O-H stretching at peaks of 1644 cm-1 and 3435 cm-1, respectively. Impurities in the graphene were found using X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy. The measured size, according to zeta-potential analysis, was 8722.2 ± 25 nm, and the average polydispersity index was 0.576. The stability of the mass reduction was analyzed by a thermogravimetric at 100 °C, with a final reduction of ~ 11%.
This report shows a simple solution cast methodology to prepare plasticized polyvinyl alcohol (PVA)/methylcellulose (MC)-ammonium iodide (NH4I) electrolyte at room temperature. The maximum conducting membrane has a conductivity of 3.21 × 10-3 S/cm. It is shown that the number density, mobility and diffusion coefficient of ions are enhanced by increasing the glycerol. A number of electric and electrochemical properties of the electrolyte-impedance, dielectric properties, transference numbers, potential window, energy density, specific capacitance (Cs) and power density-were determined. From the determined electric and electrochemical properties, it is shown that PVA: MC-NH4I proton conducting polymer electrolyte (PE) is adequate for utilization in energy storage device (ESD). The decrease of charge transfer resistance with increasing plasticizer was observed from Bode plot. The analysis of dielectric properties has indicated that the plasticizer is a novel approach to increase the number of charge carriers. The electron and ion transference numbers were found. From the linear sweep voltammetry (LSV) response, the breakdown voltage of the electrolyte is determined. From Galvanostatic charge-discharge (GCD) measurement, the calculated Cs values are found to drop with increasing the number of cycles. The increment of internal resistance is shown by equivalent series resistance (ESR) plot. The energy and power density were studied over 250 cycles that results to the value of 5.38-3.59 Wh/kg and 757.58-347.22 W/kg, respectively.
Improving the stability of cuprous oxide (Cu2 O) is imperative to its practical applications in artificial photosynthesis. In this work, Cu2 O nanowires are encapsulated by metal-organic frameworks (MOFs) of Cu3 (BTC)2 (BTC=1,3,5-benzene tricarboxylate) using a surfactant-free method. Such MOFs not only suppress the water vapor-induced corrosion of Cu2 O but also facilitate charge separation and CO2 uptake, thus resulting in a nanocomposite representing 1.9 times improved activity and stability for selective photocatalytic CO2 reduction into CH4 under mild reaction conditions. Furthermore, direct transfer of photogenerated electrons from the conduction band of Cu2 O to the LUMO level of non-excited Cu3 (BTC)2 has been evidenced by time-resolved photoluminescence. This work proposes an effective strategy for CO2 conversion by a synergy of charge separation and CO2 adsorption, leading to the enhanced photocatalytic reaction when MOFs are integrated with metal oxide photocatalyst.
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.
Experimental particleboards are made from Rhizophora spp. wood trunk with three different percentages of lignin and soy flour (0%, 6% and 12%) as adhesives. The objective was to investigate the equivalence of Rhizophora spp. particleboard as phantom material with human soft tissue using Computed Tomography (CT) number. The linear and mass attenuation coefficient of Rhizophora spp. particleboard at low energy range was also explored using X-ray Fluorescence (XRF) configuration technique. Further characterization of the particleboard was performed to determine the effective atomic number, Zeff using Energy Dispersive X-Ray (EDX) method. Adhesive-bonded Rhizophora spp. particleboard showed close similarities with water, based on the average CT numbers, electron density calibration curve and the analysis of CT density profile, compared to the binderless particleboard. The effective atomic number obtained from the study indicated that the attenuation properties of all the particleboards at different percentages of adhesives were almost similar to water. The mass attenuation coefficient calculated from XRF configuration technique showed good agreement with water from XCOM database, suggesting its potential as phantom material for radiation study.
Mining of plant-derived antimicrobials is the major focus at current to counter antibiotic resistance. This study was conducted to characterize the antimicrobial activity and mode of action of linalyl anthranilate (LNA) against carbapenemase-producing Klebsiella pneumoniae (KPC-KP). LNA alone exhibited bactericidal activity at 2.5% (V/V), and in combination with meropenem (MPM) at 1.25% (V/V). Comparative proteomic analysis showed a significant reduction in the number of cytoplasmic and membrane proteins, indicating membrane damage in LNA-treated KPC-KP cells. Up-regulation of oxidative stress regulator proteins and down-regulation of oxidative stress-sensitive proteins indicated oxidative stress. Zeta potential measurement and outer membrane permeability assay revealed that LNA increases both bacterial surface charge and membrane permeability. Ethidium bromide influx/efflux assay showed increased uptake of ethidium bromide in LNA-treated cells, inferring membrane damage. Furthermore, intracellular leakage of nucleic acid and proteins was detected upon LNA treatment. Scanning and transmission electron microscopies again revealed the breakage of bacterial membrane and loss of intracellular materials. LNA was found to induce oxidative stress by generating reactive oxygen species (ROS) that initiate lipid peroxidation and damage the bacterial membrane. In conclusion, LNA generates ROS, initiates lipid peroxidation, and damages the bacterial membrane, resulting in intracellular leakage and eventually killing the KPC-KP cells.
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.
The crystal structure, electron charge density, band structure, density of states, and optical properties of pure and strontium (Sr)-doped β-Ga2O3 were studied using the first-principles calculation based on the density functional theory (DFT) within the generalized-gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE). The reason for choosing strontium as a dopant is due to its p-type doping behavior, which is expected to boost the material's electrical and optical properties and maximize the devices' efficiency. The structural parameter for pure β-Ga2O3 crystal structure is in the monoclinic space group (C2/m), which shows good agreement with the previous studies from experimental work. Bandgap energy from both pure and Sr-doped β-Ga2O3 is lower than the experimental bandgap value due to the limitation of DFT, which will ignore the calculation of exchange-correlation potential. To counterbalance the current incompatibilities, the better way to complete the theoretical calculations is to refine the theoretical predictions using the scissor operator's working principle, according to literature published in the past and present. Therefore, the scissor operator was used to overcome the limitation of DFT. The density of states (DOS) shows the hybridization state of Ga 3d, O 2p, and Sr 5s orbital. The bonding population analysis exhibits the bonding characteristics for both pure and Sr-doped β-Ga2O3. The calculated optical properties for the absorption coefficient in Sr doping causes red-shift of the absorption spectrum, thus, strengthening visible light absorption. The reflectivity, refractive index, dielectric function, and loss function were obtained to understand further this novel work on Sr-doped β-Ga2O3 from the first-principles calculation.
Herein, we performed an encyclopedic analysis on the photoelectrocatalytic hydrogen production of BiVO4/g-C3N4 decorated with reduced graphene oxide (RGO) or graphene quantum dots (GQDs). The differences between RGO and GQDs as an electron mediator was revealed for the first time in the perspective of theoretical DFT analysis and experimental validation. It was found that the incorporation of GQDs as an electron mediator promotes better photoelectrocatalytic hydrogen performance in comparison to the RGO. The addition of GQD can significantly improve the activity by 25.2 and 75.7% in comparison to the BiVO4/RGO/g-C3N4 and binary composite samples, respectively. Correspondingly, the BiVO4/GQD/g-C3N4 attained the highest photocurrent density of 19.2 mA/cm2 with an ABPE of 0.57% without the presence of any sacrificial reagents. This enhancement is stemming from the low photocharge carrier transfer resistance which was further verified via DFT study. The DFT analysis revealed that the BiVO4/GQD/g-C3N4 sample shared their electronic cloud density through orbital hybridization while the BiVO4/RGO/g-C3N4 sample show less mutual sharing. Additionally, the charge redistribution of the GQDs-composite at the heterostructure interface articulates a more stable and stronger heterojunction than the RGO-composite. Notably, this study provides new insights on the effect of different carbonaceous materials (RGO and GQDs) which are often used as an electron mediator to enhance photocatalytic activity.
Non-small cell lung cancer (NSCLC) incited by epidermal growth factor receptor (EGFR) mutation makes up ∼85% of lung cancer diagnosed and death cases worldwide. The presented study introduced an alternative approach in detecting EGFR mutation using nano-silica integrated with polydimethylsiloxane (PDMS) polymer on interdigitated electrode (IDE) sensor. A 400 μm gap-sized aluminum IDE was modified with nano-polymer layer, which was made up of silica nanoparticles and PDMS polymer. IDE and PDMS-coated IDE (PDMS/IDE) were imaged using electron microscopes that reveals its smooth and ideal sensor morphology. The nano-silica-integrated PDMS/IDE surface was immobilized with EGFR probe and target to specify the lung cancer detection. The sensor specificity was justified through the insignificant current readouts with one-base mismatch and noncomplementary targets. The sensitivity of nano-silica-integrated PDMS/IDE was examined with mutant target spiked in human serum, where the resulting current affirms the detection of EGFR mutation. Based on the slope of the calibration curve, the sensitivity of nano-silica-integrated PDMS/IDE was 2.24E-9 A M-1 . The sensor recognizes EGFR mutation lowest at 1 aM complementary mutant target; however, the detection limit obtained based on 3σ calculation is 10 aM with regression value of 0.97.
Universal access to clean water has been a global ambition over the years. Photocatalytic water disinfection through advanced oxidation processes has been regarded as one of the promising methods for breaking down microbials. The forefront of this research focuses on the application of metal-free photocatalysts for disinfection to prevent secondary pollution. Graphitic carbon nitride (g-C3 N4 ) has achieved instant attention as a metal-free and visible-light-responsive photocatalyst for various energy and environmental applications. However, the photocatalytic efficiency of g-C3 N4 is still affected by its rapid charge recombination and sluggish electron-transfer kinetics. In this contribution, two-dimensionally protonated g-C3 N4 was employed as metal-free photocatalyst for water treatment and demonstrated 100 % of Escherichia coli within 4 h under irradiation with a 23 W light bulb. The introduction of protonation can modulate the surface charge of g-C3 N4 ; this enhances its conductivity and provides a "highway" for the delocalization of electrons. This work highlights the potential of conjugated polymers in antibacterial application.
The evolution of internal compressive stress from the intermetallic compound (IMC) Cu6Sn5 growth is commonly acknowledged as the key inducement initiating the nucleation and growth of tin (Sn) whisker. This study investigates the effect of Sn-0.7Cu-0.05Ni on the nucleation and growth of Sn whisker under continuous mechanical stress induced. The Sn-0.7Cu-0.05Ni solder joint has a noticeable effect of suppression by diminishing the susceptibility of nucleation and growth of Sn whisker. By using a synchrotron micro X-ray fluorescence (µ-XRF) spectroscopy, it was found that a small amount of Ni alters the microstructure of Cu6Sn5 to form a (Cu,Ni)6Sn5 intermetallic layer. The morphology structure of the (Cu,Ni)6Sn5 interfacial intermetallic layer and Sn whisker growth were investigated by scanning electron microscope (SEM) in secondary and backscattered electron imaging mode, which showed that there is a strong correlation between the formation of Sn whisker and the composition of solder alloy. The thickness of the (Cu,Ni)6Sn5 IMC interfacial layer was relatively thinner and more refined, with a continuous fine scallop-shaped IMC interfacial layer, and consequently enhanced a greater incubation period for the nucleation and growth of the Sn whisker. These verification outcomes proposes a scientifically foundation to mitigate Sn whisker growth in lead-free solder joint.