Structural and Electronic Insights into 1-Ethyl-3-Methylimidazolium Bis(fluorosulfonyl)imide Ion Pair Conformers: Ab Initio DFT Study.

An understanding of the nature of molecular interactions among the ion pairs of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide [EMI[FSI]] can offer a starting point and significant insight into the more dynamic and multiple interactions within the bulk liquid state. In this context, close inspection of ion pair conformers can offer insight into the effects in bulk [EMI][FSI] liquid. The current work, therefore, gives a detailed analysis of the [EMI][FSI] ion pair conformers through analysis of the interaction energies, stabilization energies, and natural orbital of the ion pair conformers. The structures of the cations, anions, and cation-anion ion pairs of the conformers are optimized systematically by the ωB97X-D method with the DGDZVP basis sets, considering both the empirical dispersion corrections and the presence of a polar solvent, and the most stable geometries are obtained. The [FSI]- anions, unlike [TFSI]- anions, exist at the top position with respect to imidazolium rings. The presence of out-of-plane interactions between the [EMI]+ and [FSI]- ions is in good agreement with the stronger interactions of the [FSI]- anions with alkyl group hydrogens. The presence of out-of-plane conformers could also be related to the interaction of the anion with the π clouds of the [EMI]+ ring. In the [EMI]+ cation, the aromatic ring is π-acidic due to the presence of a positive charge in the N1-C1-N2 ring, which leads to the presence of [FSI]- anion donor [EMI]+ π-acceptor type interactions. The [EMI]+ cation and [FSI]- anions tend to form multiple σ* and π* interactions but reduce the strength of the individual contributions from a potential (linear) maximum. For the ion pair [EMI][FSI], the absolute value of the interaction energies is lower than the normal hydrogen bond energy (50 kJ/mol), which indicates that there is a very weak electrostatic interaction between the [EMI]+ cations and [FSI]- anions. The weaker attraction between the [EMI]+ and [FSI]- ions is suggested to contribute to the larger diffusion coefficients of the ions.

3-Thiophenemalonic Acid Additive Enhanced Performance in Perovskite Solar Cells.

The development of ambient-air-processable organic-inorganic halide perovskite solar cells (OIHPSCs) is a challenge necessary for the transfer of laboratory-scale technology to large-scale and low-cost manufacturing of such devices. Different approaches like additives, antisolvents, composition engineering, and different deposition techniques have been employed to improve the morphology of the perovskite films. Additives that can form Lewis acid-base adducts are known to minimize extrinsic impacts that trigger defects in ambient air. In this work, we used the 3-thiophenemalonic acid (3-TMA) additive, which possesses thiol and carboxyl functional groups, to convert PbI2, PbCl2, and CH3NH3I to CH3NH3PbI3 completely. This strategy is effective in regulating the kinetics of crystallization and improving the crystallinity of the light-absorbing layer under high relative humidity (RH) conditions (30-50%). As a result, the 3-TMA additive increases the yield of the power conversion efficiency (PCE) from 14.9 to 16.5% and its stability under the maximum power point. Finally, we found that the results of this work are highly relevant and provide additional inputs to the ongoing research progress related to additive engineering as one of the efficient strategies to reduce parasitic recombination and enhance the stability of inverted OIHPSCs in ambient environment processing.

Green Synthesis of TiO2 Using Impatiens rothii Hook.f. Leaf Extract for Efficient Removal of Methylene Blue Dye.

In this work, TiO2 nanoparticles (NPs) were effectively synthesized by a green method using the Impatiens rothii Hook.f. leaf (IL) extract as a capping and reducing agent. The as-synthesized TiO2 NPs were characterized by different characterization methods such as the Brunauer-Emmett-Teller (BET) analysis, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), diffused reflectance spectroscopy (DRS), and X-ray diffraction (XRD) and Raman spectroscopy. The specific surface area from BET analysis was found to be 65 m2/g. The average crystallite size from XRD analysis and average particle size from SEM analysis were found to be ∼11 and ∼25 nm, respectively. The Raman spectroscopy and XRD results showed that the biosynthesized (IL-TiO2) nanoparticles were purely anatase phase. XPS analysis illustrated the formation of Titania with an oxidation state of +4. The DRS study showcased that a blue-shifted intense absorption peak of IL-TiO2 (3.39 eV) compared to the bulk material reported in the literature (3.2 eV). HRTEM micrograph showed the presence of grain boundary with d spacings of 0.352, 0.245, and 0.190, which correspond to the lattice planes of (101), (004), and (200), respectively. From the EDX analysis, the weight percents of titanium and oxygen were found to be 54.33 and 45.67%, respectively. The photoinduced degradation of methylene blue (MB) dye was investigated in the presence of biosynthesized IL-TiO2 NPs photocatalyst. The effect of parameters like catalyst dosage (30 mg/L), initial concentration of MB (15 ppm), pH (10.5), and contact time (100 min) on the removal efficiency was optimized. The maximum photodegradation efficiency under the optimized conditions was found to be 98%.

Improved biodiesel production from waste cooking oil with mixed methanol-ethanol using enhanced eggshell-derived CaO nano-catalyst.

In this report, the utilization of mixed methanol-ethanol system for the production of biodiesel from waste cooking oil (WCO) using enhanced eggshell-derived calcium oxide (CaO) nano-catalyst was investigated. CaO nano-catalyst was produced by calcination of eggshell powder at 900 °C and followed by hydration-dehydration treatment to improve its catalytic activity. The particle size, morphology, and elemental composition of a catalyst were characterized by using XRD, SEM, and EDX techniques, respectively. After hydration-dehydration the shape of a catalyst was changed from a rod-like to honeycomb-like porous microstructure. Likewise, average particle size was reduced from 21.30 to 13.53 nm, as a result, its surface area increases. The main factors affecting the biodiesel yield were investigated, accordingly, an optimal biodiesel yield of 94% was obtained at 1:12 oil to methanol molar ratio, 2.5 wt% catalyst loading, 60 °C, and 120-min reaction time. A biodiesel yield of 88% was obtained using 6:6 equimolar ratio of methanol to ethanol, the yield even increased to 91% by increasing the catalyst loading to 3.5 wt%. Moreover, by slightly increasing the share of methanol in the mixture, at 8:4 ratio, the maximum biodiesel yield could reach 92%. Therefore, we suggest the utilization of methanol-ethanol mixture as a reactant and eggshell-derived CaO as a catalyst for enhanced conversion of WCO into biodiesel. It is a very promising approach for the development of low-cost and environmentally friendly technology. Properties of the biodiesel were also found in good agreement with the American (ASTM D6571) fuel standards.