Investigating catalytic oxidative desulfurization of model fuel using hollow PW12/TiO2@MgCO3 and performance optimization via box-behnken design.

A facile and eco-friendly synthesis of PW12/TiO2@MgCO3 hollow tubes (PW12·âˆ¼· H3[PW12O40] = polyoxometalate) using a soluble and reusable MgCO3·3H2O micro-rods template was reported for the first time. The resultant hollow tubes were characterized by Fourier transform infrared spectroscopy (FT-IR), UV-visible spectroscopy, powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM), which indicated that the [PW12O40]3- structure remained intact within the hollow tubes. Furthermore, the specific surface area (88.982 m2/g) and average pore size (2.6 nm) of the PW12/TiO2@MgCO3 hollow tubes were calculated using the Brunauer-Emmett-Teller (BET) analysis. This study explored the catalytic performance of PW12/TiO2@MgCO3 hollow tubes using a three-level Box-Behnken design (BBD), through which optimization curves were designed. The desulfurization of model fuel using hollow tubes was optimally performed when the catalyst dose, time, temperature, and oxidant/sulfur (O/S) were 20-80 gm, 80-120 min, 25-80 °C and 3-8 molar ratio, respectively. These results were further processed, and the experiments were replicated twenty-nine times using a model based on two quadratic polynomials to create a response surface methodology (RSM). This permits a mathematical correlation linking the desulfurization and experimental parameters. The optimal performance of reaction mixture was evaluated to be 80 mg for catalyst concentration, 25 °C of temperature, reaction time of 100 min, and 5.5 for oxidant/sulfur molar ratio from 20 mL of octane simulation oil containing 350 ppm dibenzothiophene (DBT). The predicted desulfurization rate of the model fuel under these optimal conditions was 95.3%. The correspondence between the experimental results and predicted values was verified based on regression analysis, with an R2 value greater than 0.99. These hollow tubes could be used for their desulfurization properties ten times a row without significantly reducing catalytic activity.

Development of efficient bi-functional g-C3N4@MOF heterojunctions for water splitting.

Herein we report the development of highly efficient heterojunctions by combining n-type g-C3N4 and MOFs as bi-functional photoelectrocatalysts towards the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). g-C3N4@MIL-125(Ti) and g-C3N4@UiO-66 have been synthesized via in situ incorporation of pre-synthesized g-C3N4 nanoparticles into MIL-125(Ti) and UiO-66. Bare MIL-125(Ti) and UiO-66 are also prepared for comparison. All the synthesized samples have been characterized by Powder X-ray Diffraction analysis, Fourier Transform Infrared Spectroscopic analysis, Scanning Electron Microscopic analysis, Energy Dispersive X-ray Spectrometry and UV-Vis Spectroscopic analysis. Cyclic voltammetry and linear sweep voltammetry studies have been carried out for all samples which indicates that under visible light exposure the g-C3N4@MIL-125(Ti)/NF heterojunction achieved a current density of 10 mA cm-2 at just 86 and 173 mV overpotential for the HER and OER, respectively. Moreover, all the synthesized samples display significant stability and generate a constant current density up to 1000 cyles during water electrolysis performed at a constant applied potential 1.5 V.

Fabrication of Guided Tissue Regeneration Membrane Using Lignin-Mediated ZnO Nanoparticles in Biopolymer Matrix for Antimicrobial Activity.

Periodontal disease is a common complication, and conventional periodontal surgery can lead to severe bleeding. Different membranes have been used for periodontal treatment with limitations, such as improper biodegradation, poor mechanical property, and no effective hemostatic property. Guided tissue regeneration (GTR) membranes favoring periodontal regeneration were prepared to overcome these shortcomings. The mucilage of the chia seed was extracted and utilized to prepare the guided tissue regeneration (GTR) membrane. Lignin having antibacterial properties was used to synthesize lignin-mediated ZnO nanoparticles (∼Lignin@ZnO) followed by characterization with analytical techniques like Fourier-transform infrared spectroscopy (FTIR), UV-visible spectroscopy, and scanning electron microscope (SEM). To fabricate the GTR membrane, extracted mucilage, Lignin@ZnO, and polyvinyl alcohol (PVA) were mixed in different ratios to obtain a thin film. The fabricated GTR membrane was evaluated using a dynamic fatigue analyzer for mechanical properties. Appropriate degradation rates were approved by degradability analysis in water for different intervals of time. The fabricated GTR membrane showed excellent antibacterial properties against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacterial species.

Iron and Manganese Codoped Cobalt Tungstates Co1-(x+y)Fe x Mn y WO4 as Efficient Photoelectrocatalysts for Oxygen Evolution Reaction.

Photoelectrocatalysts are robust materials for the production of energy through different ways such as water splitting. Narrow optical band gaps and high overpotentials are limiting the development of photoelectrocatalysts. In this study, a series of Co1-(x+y)Fe x Mn y WO4 solid solutions of cobalt tungstate codoped with iron and manganese have been synthesized hydrothermally. The synthesized solid solutions have been characterized by powder XRD, UV-visible spectra, cyclic voltammetry (CV), and linear sweep voltammetry (LSV). They all crystallize in a wolframite-type monoclinic crystal system with space group P2/c. Doping of iron and manganese leads to narrowing of the optical band gap of Co1-(x+y)Fe x Mn y WO4 from 2.60 to 2.04 eV. The electrocatalytic activity toward oxygen evolution reaction of all of the samples has been evaluated through LSV measurements. It is found that the sample named C5, which is codoped with manganese and iron, has the lowest onset potential and needs the lowest overpotential to attain the targeted 5 mA cm-2 and standard 10 mA cm-2 current densities as compared with all other synthesized samples. This study shows that the synthesized tungstates can be good candidates for the photoelectrocatalytic oxygen evolution reaction.

A series of lanthanide-quinoxaline-2,3(1H,4H)-dione complexes containing 1D chiral Ln2O3 (Ln = Eu, Tb, Sm, Dy) chains: luminescent properties and response to small molecules.

Five new isostructural lanthanide-organic complexes, [Ln2O2(OH)(HQXD)(H2QXD)2]·H2O (Ln = Eu 1, Tb 2, Sm 3 Dy 4 and Gd 5; H2QXD = quinoxaline-2,3(1H,4H)-dione), have been synthesized under hydrothermal conditions. These complexes are characterized by powder X-ray diffraction (PXRD), infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric-differential thermal analysis (TG-DTA) and photo-luminescent spectroscopy. Single crystal X-ray diffraction analysis of complex 1 revealed that the structure featured in 1D chiral "Eu2O3" chains surrounded by coordinating organic ligands. These chains are interconnected via hydrogen bonding and offset π⋯π stacking interactions of the ligands to form the 3D supramolecular frameworks. The photo-luminescence studies for complexes 1-5 disclosed that the ligand (H2QXD) showed an antenna effect to transfer energy toward the lanthanide cations. The energy transfer mechanism investigations show that the energy transition from the triplet energy level (3ππ*) of ligand H2QXD to the Tb3+ cation is more effective than to the Eu3+, Sm3+ and Dy3+ ions; therefore it has been selected as a representative to examine the potential for sensing small molecules. Complex 2', which was obtained by the heating treatment of 2 at 150 °C, displayed a high luminescence sensitivity towards small solvent molecules. Tertiary butanol (t-butanol) was found to be an excellent sensitizer, while tetrahydrofuran (THF) was a highly quenching species. Complex 2' could regain a higher photo-luminescence intensity after treating for 5 cycles with t-butanol, revealing a prospect for reusability.

Enhancement of Ferroelectricity for Orthorhombic (Tb0.861Mn0.121)MnO3-δ by Copper Doping.

Copper-doped (Tb0.861Mn0.121)MnO3-δ has been synthesized by the conventional solid state reaction method. X-ray, neutron, and electron diffraction data indicate that they crystallize in Pnma space group at room temperature. Two magnetic orderings are found for this series by neutron diffraction. One is the ICAM (incommensurate canted antiferromagnetic) ordering of Mn with a wave vector qMn = (∼0.283, 0, 0) with a ≈ 5.73 Å, b ≈ 5.31 Å, and c ≈ 7.41 Å, and the other is the CAM (canted antiferromagnetic) ordering of both Tb and Mn in the magnetic space group Pn'a21' with a ≈ 5.73 Å, b ≈ 5.31 Å, and c ≈ 7.41 Å. A dielectric peak around 40 K is found for the samples doped with Cu, which is higher than that for orthorhombic TbMnO3.