Exo⇔Endo Isomerism, MEP/DFT, XRD/HSA-Interactions of 2,5-Dimethoxybenzaldehyde: Thermal, 1BNA-Docking, Optical, and TD-DFT Studies.

The exo⇔endo isomerization of 2,5-dimethoxybenzaldehyde was theoretically studied by density functional theory (DFT) to examine its favored conformers via sp2-sp2 single rotation. Both isomers were docked against 1BNA DNA to elucidate their binding ability, and the DFT-computed structural parameters results were matched with the X-ray diffraction (XRD) crystallographic parameters. XRD analysis showed that the exo-isomer was structurally favored and was also considered as the kinetically preferred isomer, while several hydrogen-bonding interactions detected in the crystal lattice by XRD were in good agreement with the Hirshfeld surface analysis calculations. The molecular electrostatic potential, Mulliken and natural population analysis charges, frontier molecular orbitals (HOMO/LUMO), and global reactivity descriptors quantum parameters were also determined at the B3LYP/6-311G(d,p) level of theory. The computed electronic calculations, i.e., TD-SCF/DFT, B3LYP-IR, NMR-DB, and GIAO-NMR, were compared to the experimental UV-Vis., optical energy gap, FTIR, and 1H-NMR, respectively. The thermal behavior of 2,5-dimethoxybenzaldehyde was also evaluated in an open atmosphere by a thermogravimetric-derivative thermogravimetric analysis, indicating its stability up to 95 °C.

Synthesis of a Family of Pd(II) Complexes Using Pyridyl-Ketone Ligands: Crystal Structure, Thermal, Physicochemical, XRD/HSA, Docking, and Heck Reaction Application.

Four Pd(II) complexes, (dpk)PdCl2 (complex-1), and (dpk)Pd(OAc)2 (complex-2) have been prepared using di(2-pyridyl) ketone as the chelate ligand (dpk). The (dpk·EtOH)PdCl2 (complex-3) and (dpk·EtOH)Pd(OAc)2 (complex-4) were synthesized by selectively introducing complex-1 and complex-2 to an EtOH in situ nucleophilic addition reaction on the O=C of the dpk ligand, respectively. All complexes were characterized using CHN-EA, UV-vis, FT-IR, FAB-MS, EDX, TGA, and NMR physicochemical tools. The XRD-crystallography technique was employed to ascertain the structure of complex-3. The analysis revealed a monoclinic/P21/c crystal system characterized by a square planar structure oriented in the cis direction around the Pd center. Several C-H···Cl and O-H···O H-bonds constructing 2D-S12 and S7 synthons were confirmed via XRD/HSA interactions. The influence of EtOH addition to the O=C group of dpk in (dpk)PdCl2 was documented by using UV-vis/FT-IR spectra and TGA analysis. As catalysts, all complexes have demonstrated a notable catalytic function in the Heck reaction, resulting in a high yield under gentle conditions using iodobenzene and methyl acrylate as model reactions. Moreover, the complex-1 and complex-3 docking activity was evaluated against 1BNA-DNA.

Nickel vanadate nitrogen-doped carbon nanocomposites for high-performance supercapacitor electrode.

A nickel-vanadium-based bimetallic precursor was produced using the polymerization process by urea-formaldehyde copolymers. The precursor was then calcined at 800 °C in an argon ambiance to form a Ni3V2O8-NC magnetic nanocomposite. Powerful techniques were used to study the physical characteristics and chemical composition of the fabricated Ni3V2O8-NC electrode. PXRD, Raman, and FTIR analyses proved that the crystal structure of Ni3V2O8-NC included N-doped graphitic carbon. FESEM and TEM analyses imaging showed the distribution of the Ni3V2O8 nanoparticles on the layered graphitic carbon structure. TEM images showed the prepared sample has a particle size of around 10-15 nm with an enhanced active site area of 146 m2/g, as demonstrated by BET analysis. Ni3V2O8-NC nanocomposite exhibits magnetic behaviors and a magnetization saturation value of 35.99 emu/g. The electrochemical (EC) studies of the synthesized Ni3V2O8-NC electrode proceeded in an EC workstation of three-electrode. In a 5 M potassium hydroxide as an electrolyte, the cyclic voltmeter exhibited an enhanced capacitance (CS) of 915 F/g at 50 mV/s. Galvanic charge-discharge (GCD) study also exhibited a superior capacitive improvement of 1045 F/g at a current density (It) of 10 A/g. Moreover, the fabricated Ni3V2O8-NC nanocomposite displays a good power density (Pt) of 356.67 W/kg, improved ion accessibility, and substantial charge storage. At the high energy density (Et) of 67.34 W h/kg, the obtained Pt was 285.17 W/kg. The enhanced GCD rate, cycle stability, and Et of the Ni3V2O8-NC magnetic nanocomposite nominate the sample as an excellent supercapacitor electrode. This study paves the way for developing effective, efficient, affordable, and ecologically friendly electrode materials.

2D/1D MoS2 /TiO2 Heterostructure Photocatalyst with a Switchable CO2 Reduction Product.

Regulating the transfer pathway of charge carriers in heterostructure photocatalysts is of great importance for selective CO2 photoreduction. Herein, the charge transfer pathway and in turn the redox potential succeeded to regulate in 2D MoS2 /1D TiO2 heterostructure by varying the light wavelength range. Several in situ measurements and experiments confirm that charge transfer follows either an S-scheme mechanism under simulated solar irradiation or a heterojunction approach under visible light illumination, elucidating the switchable property of the MoS2 /TiO2 heterostructure. Replacing the simulated sunlight irradiation with the visible light illumination switches the photocatalytic CO2 reduction product from CO to CH4. 13 CO2 isotope labeling confirms that CO2 is the source of carbon for CH4 and CO products. The photoelectrochemical H2 generation further supports the switching property of MoS2 /TiO2 . Unlike previous studies, density functional theory calculations are used to investigate the band structure of Van der Waals MoS2 /TiO2 S scheme after contact, allowing to propose accurate charge transfer pathways, in which the theoretical results are well matched with the experimental results. This work opens the opportunity to develop photocatalysts with switchable charge transport and tunable redox potential for selective artificial photosynthesis.

Magnesium Bismuth Ferrite Nitrogen-Doped Carbon Nanomagnetic Perovskite: Synthesis and Characterization as a High-Performance Electrode in a Supercapacitor for Energy Storage.

Bismuth ferrite (BiFeO3) is regarded as an important ABO3 perovskite in the areas of energy storage and electronics. A high-performance novel MgBiFeO3-NC nanomagnetic composite (MBFO-NC) electrode was prepared using a perovskite ABO3-inspired method as a supercapacitor for energy storage. The electrochemical behavior of the perovskite BiFeO3 has been enhanced by magnesium ion doping in the basic aquatic electrolyte as the A-site. H2-TPR revealed that the doping of Mg2+ ions at the Bi3+ sites minimizes the oxygen vacancy content and improves the electrochemical characteristics of MgBiFeO3-NC. Various techniques were used to confirm the phase, structure, surface, and magnetic properties of the MBFO-NC electrode. The prepared sample showed an enhanced mantic performance and specific area with an average nanoparticle size of ∼15 nm. The electrochemical behavior of the three-electrode system was shown by cyclic voltammetry to have a significant specific capacity of 2079.44 F/g at 30 mV/s in 5 M KOH electrolyte. GCD analysis at a 5 A/g current density also showed an enhanced capacity improvement of 2159.88 F/g, which is 3.4× higher than that of pristine BiFeO3. At the power density of 5284.83 W/kg, the constructed MBFO-NC//MBFO-NC symmetric cell showed an exceptional energy density of 730.04 W h/kg. The MBFO-NC//MBFO-NC symmetric cell was employed as a direct practical application of the electrode material to entirely brighten the laboratory panel, which had 31 LEDs. This work proposes the utilization of duplicate cell electrodes made of MBFO-NC//MBFO-NC in portable devices for daily use.

One-Step Hydrothermal Synthesis of Anatase TiO2 Nanotubes for Efficient Photocatalytic CO2 Reduction.

The hydrothermal dissolution-recrystallization process is a key step in the crystal structure of titania-based nanotubes and their composition. This work systematically studies the hydrothermal conditions for directly synthesizing anatase TiO2 nanotubes (ATNTs), which have not been deeply discussed elsewhere. It has been well-known that ATNTs can be synthesized by the calcination of titanate nanotubes. Herein, we found the ATNTs can be directly synthesized by optimizing the reaction temperature and time rather than calcination of titanate nanotubes, where at each temperature, there is a range of reaction times in which ATNTs can be prepared. The effect of NaOH/TiO2 ratio and starting materials was explored, and it was found that ATNTs can be prepared only if the precursor is anatase TiO2, using rutile TiO2 leads to forming titanate nanotubes. As a result, ATNTs produced directly without calcination have excellent photocatalytic CO2 reduction than titanate nanotubes and ATNTs prepared by titanate calcination.