Photocatalysis and Bandgap Engineering Using ZnO Nanocomposites

Nanocomposites have a great potential to work as efficient, multifunctional materials for energy conversion and photoelectrochemical reactions. Nanocomposites may reveal more improved photocatalysis by implying the improvements of their electronic and structural properties than pure photocatalyst. This paper presents the recent work carried out on photoelectrochemical reactions using the composite materials of ZnO with CdS, ZnO with SnO2, ZnO with TiO2, ZnO with Ag2S, and ZnO with graphene and graphene oxide. The photocatalytic efficiency mainly depends upon the light harvesting span of a material, lifetime of photogenerated electron-hole pair, and reactive sites available in the photocatalyst. We reviewed the UV-Vis absorption spectrum of nanocomposite and photodegradation reported by the same material and how photodegradation depends upon the factors described above. Finally the improvement in the absorption band edge of nanocomposite material is discussed

Efficiency of irrigation borders as affected by inflow hydrograph shape.

The objective of this study was to determine how border irrigation performance is affected by inflow hydrograph shape. Sloping borders with open end boundary condition were selected for the study. A computer program called SRFR was used for simulations with the choice of zero inertia model as the mathematical model describing the movement of water along the border run. Five inflow hydrograph shapes were chosen from over fifteen shapes for evaluation. They are named as follows: constant (CON), cutback (CB), cablegation (CG), modified cutback (MCB), and modified cablegation (MCG). Different ranges of the input parameters were used to cover a wide spectrum of field conditions. Input parameters ranges and values are four infiltration families, 0.25, 0.5, 1.0, and 2.0; three slopes, 0.001, 0.0025, and 0.005; two field lengths, 650 ft and 1300 ft; three Manning's roughnesses, 0.04, 0.15, and 0.25; and three volumes, low, med., and high, which reflect 2, 4, and 6 inches of required depth. It has been found that the inflow hydrograph shape has a substantial influence on the maximum application efficiency, maximum Eₐ. Values of maximum Eₐ range from 61 percent to 80 percent. While CG gives the lowest average value of maximum Eₐ, 61 percent, CB and MCB give the highest average maximum Eₐ at 80 percent. CON gives an average value equal to 71 percent. MCG has an average value close to those given by CB and MCB and equal to 78 percent. The maximum Eₐ values range from low of zero to as high as 95 percent. Fortunately, more than 90 percent of the 216 values for each inflow hydrograph are above 70 percent for all shapes except CG. Most values fall between 70 to 80 percent for CON, 75 to 90 percent for CB, 80 to 95 for MCB, and 75 to 85 for MCG. CG has a much wider range with most maximum Eₐ values falling between 40 and 85 percent. CB and MCB are more sensitive to changes in the input parameters than CON and MCC, but far less than CG, which is the most sensitive

Drought Forecasting Using Stochastic Models in a Hyper-Arid Climate

Drought forecasting plays a crucial role in drought mitigation actions. Thus, this research deals with linear stochastic models (autoregressive integrated moving average (ARIMA)) as a suitable tool to forecast drought. Several ARIMA models are developed for drought forecasting using the Standardized Precipitation Evapotranspiration Index (SPEI) in a hyper-arid climate. The results reveal that all developed ARIMA models demonstrate the potential ability to forecast drought over different time scales. In these models, the p, d, q, P, D and Q values are quite similar for the same SPEI time scale. This is in correspondence with autoregressive (AR) and moving average (MA) parameter estimate values, which are also similar. Therefore, the ARIMA model (1, 1, 0) (2, 0, 1) could be considered as a general model for the Al Qassim region. Meanwhile, the ARIMA model (1, 0, 3) (0, 0, 0) at 3-SPEI and the ARIMA model (1, 1, 1) (2, 0, 1) at 24-SPEI could be generalized for the Hail region. The ARIMA models at the 24-SPEI time scale is the best forecasting models with high R2 (more than 0.9) and lower values of RMSE and MAE, while they are the least forecasting at the 3-SPEI time scale. Accordingly, this study recommends that ARIMA models can be very useful tools for drought forecasting that can help water resource managers and planners to take precautions considering the severity of drought in advance

Comparative Removal of Lead and Nickel Ions onto Nanofibrous Sheet of Activated Polyacrylonitrile in Batch Adsorption and Application of Conventional Kinetic and Isotherm Models

We investigated the adsorption of lead (Pb2+) and nickel (Ni2+) ions by electrospun membranes of polyacrylonitrile (PAN) nanofiber activated with NaHCO3 (PANmod). Analysis by Fourier-transform infrared spectrometry (FTIR), field emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDX) validated the functionalization of PAN nanofibers with NaHCO3, and the successful agglomeration of Pb2+ and Ni2+ onto PANmod. After a rapid uptake of the heavy metal ions (15 min), the equilibrium contact time was attained (60 min) following a linear increase of both adsorption capacity and removal efficiency. PANmod showed a better affinity for Ni2+ than Pb2+. The adsorption on PANmod was best described by the pseudo-second-order kinetic model for both studied models, supporting chemisorption. By varying the solution pH from 2.0 to 9.0, we found that the adsorption capacity followed an increasing trend, reaching a maximum at the pH of 7.0. Despite increasing adsorption capacities, the removal efficiency of both heavy metal ions exhibited a decreasing trend with increase in initial concentrations. The amount of PANmod directly affects the removal efficiency, with 0.7 and 0.2 g being the optimum dose for maximum uptake of Pb2+ and Ni2+, respectively. The Langmuir model fitted well the Pb2+ adsorption data suggesting monolayer adsorption, and the Freundlich model perfectly fitted the Ni2+ adsorption data, indicating heterogeneous adsorption. The estimated values of the mean free energy of adsorption in the D–R isotherm indicated a physical adsorption of both heavy metal ions into the surface of the PANmod

Functionalized Bentonite Clay Composite with NiAl-Layered Double Hydroxide for the Effective Removal of Cd(II) from Contaminated Water

In this study, the efficiency of functionalized bentonite (F-bentonite) and NiAl-layered double hydroxide (LDH), as well as their nanocomposites, was explored regarding the adsorption of cadmium ions (Cd2+) in batch tests. Surface characterization using SEM, EDX, and FTIR analyses confirmed the successful loading of LDH (NiAl) onto the F-bentonite and the adsorption of Cd2+ onto the F-bentonite, LDH (NiAl), and LDH/F-bentonite composite adsorbent, suggesting ion exchange and surface precipitation as the main controlling mechanisms of the formation of adsorbent. An equilibrium contact period of 60 min was suggested, with the LDH/F-bentonite composite presenting the highest adsorption capacity and removal effectiveness as compared to the other adsorbents. The LDH/F-bentonite composite also presented the highest removal efficiency and maximum adsorption capacity at an optimum pH value of 7.0. A steady increase in the uptake capacity of Cd2+ was observed by increasing the dosage of the adsorbents, with the LDH/F-bentonite composite having the best adsorption capacity. The fitting of the pseudo second-order kinetic model to the adsorption data of Cd2+ suggested chemisorption on the adsorbents’ surfaces as the controlling mechanism. The Langmuir isotherm with a near-perfect fitting revealed a monolayer adsorption, while physical adsorption of Cd2+ onto all the adsorbents is proposed using the D–R isotherm. Finally, both homogeneous and heterogeneous adsorption systems are proposed for all the adsorbents due to the satisfactory fitting of the Sips and R–P isotherm models

Successful Application of Eucalyptus Camdulensis Biochar in the Batch Adsorption of Crystal Violet and Methylene Blue Dyes from Aqueous Solution

Eucalyptus camdulensis biochar (Ec-bio) was used to adsorb crystal violet (CV) and methylene blue (MB) dyes, which was optimized and further evaluated using different isotherm and kinetic models. Microscopy and spectroscopy techniques showed the interactions of the dyes with the surface functional groups of the Ec-bio, resulting in the removal of the dyes from aqueous solution. Both dyes were immediately uptaken, with equilibrium reached in 60 min, with a higher sorption efficiency of CV compared to MB. Thermodynamic parameters showed endothermic adsorption and the nonspontaneous adsorption of both dyes onto the Ec-bio. Both the adsorption capacity and percentage removal increased with the increasing solution pH from 2.0 to 4.0 and to 10 for CV and MB. An increase in adsorption capacity was observed upon increasing the initial concentrations, with a corresponding decrease in the percentage removal. The pseudo-second-order (PSO) and Elovich kinetic models (nonlinear approach) were a good fit to the data of both dyes, confirming a chemisorptive adsorption process. The Langmuir isotherm fitted well to the CV data, supporting its monolayer adsorption onto the Ec-bio, while the Freundlich isotherm was a good fit to the MB dye data, suggesting the surface heterogeneity of the Ec-bio. The Dubinin–Radushkevich isotherm was a good fit to the adsorption CV data compared with the MB dye, suggesting the physisorption of both dyes onto the Ec-bio due to its mean free energy of adsorption of <8 kJ mol−1

Preparation of ZnMgAl-Layered Double Hydroxide and Rice Husk Biochar Composites for Cu(II) and Pb(II) Ions Removal from Synthetic Wastewater

The efficiency of a new composite material of the layered double hydroxide (LDH) of ZnMgAl and rice husk biochar (RHB) for the removal of Cu(II) and Pb(II) ions from synthetic wastewater was investigated in this study. The images of the scanning electron microscope showed extremely fine crystalline LDH particles decorated on the rough surface of the RHB, while the successful formation of the composite adsorbent (LDH/RHB) was confirmed by the corresponding energy dispersive X-ray and the Fourier-transform infrared spectroscopy. An equilibrium contact time of 30 and 15 min for Cu2+ and Pb2+, respectively, was proposed for the optimum performance of the batch adsorption process. The dose of the LDH/RHB adsorbent was optimized at 0.4 g L−1 yielding maximum adsorption capacities of 117 and 124 mg g−1 for Cu2+ and Pb2+, respectively, with corresponding maximum removal efficiencies of nearly 94% and 99%. A solution pH of 6.0 yielded optimum results with an increasing trend in adsorption capacities and percentage removal by changing the solution pH from 2.0 to 7.0. Based on the best fit of the pseudo-second-order kinetic model to the experimental data, chemisorption was suggested to be the controlling mechanism of adsorption. The fitting of the Langmuir model suggested a monolayer sorption of Cu2+ and Pb2+, and the application of the Dubinin–Radushkevich isotherm proposed physical adsorption

Adsorptive Removal of Reactive Black 5 from Wastewater Using Bentonite Clay: Isotherms, Kinetics and Thermodynamics

The studies of the kinetics and isotherms adsorption of the Reactive Black 5 (RB5) onto bentonite clay were explored in a batch study in a laboratory. The maximum RB5 adsorption conditions of bentonite clay were optimized such as shaking speed (100 rpm), temperature (323 K), pH (10), contact time (40 min), initial dye concentration (170 mg·L−1), and particle size (177 µm). The adsorbent surface was characterized using Fourier Transform Infrared Spectroscopy spectroscopy. The mechanisms and characteristic parameters of the adsorption process were analyzed using two parameter isotherm models which revealed the following order (based on the coefficient of determination): Harkin-Jura (0.9989) > Freundlich (0.9986) and Halsey (0.9986) > Langmuir (0.9915) > Temkin (0.9818) > Dubinin–Radushkevich (0.9678). This result suggests the heterogeneous nature of bentonite clay. Moreover, the adsorption process was chemisorption in nature because it follows the pseudo-second order reaction model with R2 value of 0.9998, 0.9933 and 0.9891 at 25, 75 and 100 mg·L−1 RB5 dye in the solution, respectively. Moreover, based on the values of standard enthalpy, Gibbs free energy change, and entropy, bentonite clay showed dual nature of exothermic and endothermic, spontaneous and non-spontaneous as well as increased and decreased randomness at solid–liquid interface at 303–313 K and 313–323 K temperature, respectively

Catalytic Nitrate Removal in Continuous Bimetallic Cu–Pd/Nanoscale Zerovalent Iron System

In this study, we investigated catalytic nitrate removal using nanoscale zerovalent iron (NZVI) supported Cu–Pd bimetallic catalyst (Cu–Pd/NZVI) in a continuous reactor system. Control experiments showed that Cu, Pd, and a proper supply of H₂ are essential for relatively sustainable nitrate (30 mg/L NO₃^–-N) reduction in continuous mode. When we optimized operational parameters to enhance removal efficiency and N₂ selectivity, we finally achieved complete nitrate removal with 48% N₂ selectivity at 9 h. During a longevity test (200 h reaction), excellent removal was observed (>91% in 24 h) with 42–60% N₂ selectivity. However, removal gradually decreased to 13% in 200 h with increasing nitrite production. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy analysis revealed that both the support (NZVI) and the Cu(0) oxidized after continuous denitrification. This indicated that loss of NZVI reductive capacity and the oxidation of Cu(0) to Cu­(I) and Cu­(II) deactivated nitrate removal during the continuous nitrate reduction by Cu–Pd/NZVI

A Component-Based Study of the Effect of Diameter on Bond and Anchorage Characteristics of Blind-Bolted Connections.

Structural hollow sections are gaining worldwide importance due to their structural and architectural advantages over open steel sections. The only obstacle to their use is their connection with other structural members. To overcome the obstacle of tightening the bolt from one side has given birth to the concept of blind bolts. Blind bolts, being the practical solution to the connection hindrance for the use of hollow and concrete filled hollow sections play a vital role. Flowdrill, the Huck High Strength Blind Bolt and the Lindapter Hollobolt are the well-known commercially available blind bolts. Although the development of blind bolts has largely resolved this issue, the use of structural hollow sections remains limited to shear resistance. Therefore, a new modified version of the blind bolt, known as the "Extended Hollo-Bolt" (EHB) due to its enhanced capacity for bonding with concrete, can overcome the issue of low moment resistance capacity associated with blind-bolted connections. The load transfer mechanism of this recently developed blind bolt remains unclear, however. This study uses a parametric approach to characterising the EHB, using diameter as the variable parameter. Stiffness and load-carrying capacity were evaluated at two different bolt sizes. To investigate the load transfer mechanism, a component-based study of the bond and anchorage characteristics was performed by breaking down the EHB into its components. The results of the study provide insight into the load transfer mechanism of the blind bolt in question. The proposed component-based model was validated by a spring model, through which the stiffness of the EHB was compared to that of its components combined. The combined stiffness of the components was found to be roughly equivalent to that of the EHB as a whole, validating the use of this component-based approach