Can simple 'molecular' corrections outperform projector augmented-wave density functional theory in the prediction of 35 Cl electric field gradient tensor parameters for chlorine-containing crystalline systems?

Many-body expansion (MBE) fragment approaches have been applied to accurately compute nuclear magnetic resonance (NMR) parameters in crystalline systems. Recent examples demonstrate that electric field gradient (EFG) tensor parameters can be accurately calculated for 14 N and 17 O. A key additional development is the simple molecular correction (SMC) approach, which uses two one-body fragment (i.e., isolated molecule) calculations to adjust NMR parameter values established using 'benchmark' projector augmented-wave (PAW) density functional theory (DFT) values. Here, we apply a SMC using the hybrid PBE0 exchange-correlation (XC) functional to see if this can improve the accuracy of calculated 35 Cl EFG tensor parameters. We selected eight organic and two inorganic crystal structures and considered 15 chlorine sites. We find that this SMC improves the accuracy of computed values for both the 35 Cl quadrupolar coupling constant (CQ ) and the asymmetry parameter ( η Q ) by approximately 30% compared with benchmark PAW DFT values. We also assessed a SMC that offers local improvements not only in terms of the quality of the XC functional but simultaneously in the quality of the description of relativistic effects via the inclusion of spin-orbit effects. As the inorganic systems considered contain heavy atoms bonded to the chlorine atoms, we find further improvements in the accuracy of calculated 35 Cl EFG tensor parameters when both a hybrid functional and spin-orbit effects are included in the SMC. On the contrary, for chlorine-containing organics, the inclusion of spin-orbit relativistic effects using a SMC does not improve the accuracy of computed 35 Cl EFG tensor parameters.

Modification of reinforced hollow fiber membranes with WO3 nanosheets for treatment of textile wastewater by membrane bioreactor.

In this study, performance of braid reinforced hollow fiber membrane containing polyvinylidene fluoride (PVDF) embedded with tungsten trioxide (WO3) nanosheets in a membrane bioreactor (MBR) was examined for textile wastewater treatment. The WO3 nanosheets was synthesized and blended at different concentrations (0.1-0.02 wt%) in casting solutions of the membranes. The WO3 nanosheets characterized using various tests such as XRD, FTIR, SEM, EDS, dot-mapping, and TEM. Furthermore, the effects of the increased WO3 nanosheets into the PVDF matrix on the membrane morphology, hydrophilicity, permeability, antifouling, and COD and color removal efficiency was investigated. The addition of 0.1 wt% of the nanosheets reduces the water contact angle from 69.3° to 62.5° while increasing overall porosity from 37.5 to 43.2%. COD and color removal for PVDF/0.10 wt% WO3 membrane was between 86-89% and 72-76%, respectively. While the TMP of modified WO3 membranes did not significantly increase due to antimicrobial properties of the WO3 nanosheets, the TMP of the pure PVDF membrane increase, indicating considerable cake layer fouling. The results of this study showed that modification of PVDF braid reinforced hollow fiber membrane using WO3 nanosheets is promising membrane for MBR systems.

Al-Ce co-doped BaTiO3 nanofibers as a high-performance bifunctional electrochemical supercapacitor and water-splitting electrocatalyst.

Supercapacitors and water splitting cells have recently played a key role in offering green energy through converting renewable sources into electricity. Perovskite-type electrocatalysts such as BaTiO3, have been well-known for their ability to efficiently split water and serve as supercapacitors due to their high electrocatalytic activity. In this study, BaTiO3, Al-doped BaTiO3, Ce-doped BaTiO3, and Al-Ce co-doped BaTiO3 nanofibers were fabricated via a two-step hydrothermal method, which were then characterized and compared for their electrocatalytic performance. Based on the obtained results, Al-Ce co-doped BaTiO3 electrode exhibited a high capacitance of 224.18 Fg-1 at a scan rate of 10 mVs-1, high durability during over the 1000 CV cycles and 2000 charge-discharge cycles, proving effective energy storage properties. Additionally, the onset potentials for OER and HER processes were 11 and - 174 mV vs. RHE, respectively, demonstrating the high activity of the Al-Ce co-doped BaTiO3 electrode. Moreover, in overall water splitting, the amount of the overpotential was 0.820 mV at 10 mAcm-2, which confirmed the excellent efficiency of the electrode. Hence, the remarkable electrocatalytic performance of the Al-Ce co-doped BaTiO3 electrode make it a promising candidate for renewable energy technologies owing to its high conductivity and fast charge transfer.

A BaTiO3/WS2 composite for piezo-photocatalytic persulfate activation and ofloxacin degradation.

Piezoelectric fields can decrease the recombination rate of photogenerated electrons and holes in semiconductors and therewith increase their photocatalytic activities. Here, a BaTiO3/WS2 composite is synthesized and characterized, which combines piezoelectric BaTiO3 nanofibers and WS2 nanosheets. The piezo-photocatalytic effect of the composite on the persulfate activation is studied by monitoring Ofloxacin (OFL) degradation efficiency. Under mechanical forces, LED lamp irradiation, and the addition of 10 mM persulfate, the OFL degradation efficiency reaches ~90% within 75 min, which is higher than efficiencies obtained for individual BaTiO3, WS2, or TiO3, widely used photocatalysts in the field of water treatment. The boosted degradation efficiency can be ascribed to the promotion of charge carrier separation, resulting from the synergetic effect of the heterostructure and the piezoelectric field induced by the vibration. Moreover, the prepared composite displays good stability over five successive cycles of the degradation process. GC-MS analysis is used to survey the degradation pathway of OFL during the degradation process. Our results offer insight into strategies for preparing highly effective piezo-photocatalysts in the field of water purification.

MIL-101(Cr), an Efficient Heterogeneous Catalyst for One Pot Synthesis of 2,4,5-tri Substituted Imidazoles under Solvent Free Conditions.

A chromium-containing metal-organic framework (MOF), MIL-101 (Chromium(III) benzene-1,4-dicarboxylate), was used to catalyze the one pot, three component synthesis of some 2,4,5-trisubstituted imidazoles under solvent-free conditions. The advantages of using this heterogeneous catalyst include short reaction time, high yields, easy and quick isolation of catalyst and products, low amount of catalyst needed, and that the addition of solvent, salt, and additives are not needed. This catalyst is highly efficient and can be recovered at least 5 times with a slight loss of efficiency. The structure of the metal-organic frameworks (MOF) was confirmed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (HNMR) were performed to confirm some of the synthesized products. Experimental data indicated that the optimum amount of catalyst was 5 mg for benzil (1 mmol), 4-chlorobenzaldehyde (1 mmol), and ammonium acetate (2.5 mmol), and the synthetic route to the various imidazoles is performed in 10 min by 95% yield, an acceptable result rivalling those of other catalysts.