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Herein, the geometric, electronic, and nonlinear optical properties of excess electron zintl clusters Ge5AM3, Ge9AM5, and Ge10AM3 (AM = Li, Na, and K) are investigated. The clusters under consideration demonstrate considerable electronic stability as well as superalkali characteristics. The NBO charge is transferred from the alkali metal to the Ge-atoms. The FMO analysis shows fabulous conductive properties with a significant reduction in SOMO-LUMO gaps (0.79-4.04 eV) as compared with undoped systems. VBIT-12 The designed clusters are completely transparent in the deep UV-region and show absorption in the visible and near-IR region. Being excess electron compounds these clusters exhibit remarkable hyperpolarizability response up to 8.99 × 10-26 esu, where a static second hyperpolarizability (γ o) value of up to 2.15 × 10-30 esu was recorded for Ge9Na5 superatom clusters. The excitation energy is the main controlling factor for hyperpolarizability as revealed from the two-level model study. The electro-optical Pockel's effect and the second harmonic generation phenomenon (SHG) are used to investigate dynamic nonlinear optical features. At a lower applied frequency (=532 nm), the dynamic hyperpolarizability and second hyperpolarizability values are significantly higher for the studied clusters. Furthermore, for the Ge9K5 cluster, the hyper Rayleigh scattering (HRS) increases to 5.03 × 10-26 esu.This study aims to investigate the enhanced low temperature denitration activity and promotional mechanism of a cerium-based catalyst through copper modification. In this paper, copper and cerium oxides were supported on TiO2-ZrO2 by an impregnation method, their catalytic activity tests of selective catalytic reduction (SCR) of NO with NH3 were carried out and their physicochemical properties were characterized. The CuCe/TiO2-ZrO2 catalyst shows obviously enhanced NH3-SCR activity at low temperature ( less then 300 °C), which is associated with the well dispersed active ingredients and the synergistic effect between copper and cerium species (Cu2+ + Ce3+ ↔ Cu+ + Ce4+), and the increased ratios of surface chemisorbed oxygen and Cu+/Cu2+ lead to the enhanced low-temperature SCR activity. The denitration reaction mechanism over the CuCe/TiO2-ZrO2 catalyst was investigated by in situ DRIFTS and DFT studies. Results illustrate that the NH3 is inclined to adsorb on the Cu acidic sites (Lewis acid sites), and the NH2 and NH2NO species are the key intermediates in the low-temperature NH3-SCR process, which can explain the promotional effect of Cu modification on denitration activity of Ce/TiO2-ZrO2 at the molecular level. Finally, we have reasonably concluded a NH3-SCR catalytic cycle involving the Eley-Rideal mechanism and Langmuir-Hinshelwood mechanism, and the former mechanism dominates in the NH3-SCR reaction.Bimetallic Ni-Sn alloys have been recognised as promising catalysts for the transformation of furanic compounds and their derivatives into valuable chemicals. Herein, we report the utilisation of a supported bimetallic RANEY® nickel-tin alloy supported on aluminium hydroxide (RNi-Sn(x)/AlOH; x is Ni/Sn molar ratio) catalysts for the one-pot conversion of biomass-derived furfural and levulinic acid to 1,4-pentanediol (1,4-PeD). The as prepared RNi-Sn(1.4)/AlOH catalyst exhibited the highest yield of 1,4-PeD (78%). The reduction of RNi-Sn(x)/AlOH with H2 at 673-873 K for 1.5 h resulted in the formation of Ni-Sn alloy phases (e.g., Ni3Sn and Ni3Sn2) and caused the transformation of aluminium hydroxide (AlOH) to amorphous alumina (AA). The RNi-Sn(1.4)/AA 673 K/H2 catalyst contained a Ni3Sn2 alloy as the major phase, which exhibited the best yield of 1,4-PeD from furfural (87%) at 433 K, H2 3.0 MPa for 12 h and from levulinic acid (up to 90%) at 503 K, H2 4.0 MPa, for 12 h. Supported RANEY® Ni-Sn(1.5)/AC and three types of supported Ni-Sn(1.5) alloy (e.g., Ni-Sn(1.5)/AC, Ni-Sn(1.5)/c-AlOH, and Ni-Sn(1.5)/γ-Al2O3) catalysts afforded high yields of 1,4-PeD (65-87%) both from furfural and levulinic acid under the optimised reaction conditions.Single-atom alloys (SAAs) have been emerging as an important field of research in electrocatalysis owing to extremely high atom utilization, unique structure and high catalytic activity. In this work, the catalytic properties and thermal stability of PdCu SAAs with a crown-jewel (CJ) structure are studied by density functional theory (DFT) calculations and the molecular dynamics (MD) simulation method. The DFT results reveal that CJ-structured PdCu SAAs show excellent HER and ORR catalytic performance, and can be regarded as a promising alternative to Pt catalysts towards the ORR or HER. Additionally, we attempt to explain the high catalytic activity of PdCu SAAs by electronic structure analysis. In addition, MD simulation results confirm the thermal stability of CJ-structured PdCu. More importantly, we found that CJ-structured PdCu clusters undergo a structural transformation from cuboctahedral (Cubo) to icosahedral (Ico) structure by heating or after the adsorption of reaction intermediate, which indicates that Cubo is less stable than the Ico structure. Besides, Cubo-Ico transformation is size-dependent and only found in small clusters. Furthermore, the effects of size and morphology on melting properties are discussed. The melting point increases as cluster size increases, which agrees well with Pawlow's law.1,4-Dipolar cycloaddition has emerged as a powerful tool for the synthesis of various cyclic compounds. In the present work, 1H-pyrrole-2,3-diones are proposed as new dipolarophiles for 1,4-dipolar cycloaddition. Their [4 + 2] cycloaddition with dipoles generated from dimethyl acetylenedicarboxylate and pyridine was found to proceed regioselectively affording spiro[pyrido[2,1-b][1,3]oxazine-2,3'-pyrroles] as diastereomeric mixtures which exist in rapid equilibrium in solution. It was established that this phenomenon of rapid epimerization is a characteristic of other similar spiropyrido[2,1-b][1,3]oxazines and even related spiroquinolizines, which was demonstrated by the investigation of related products of previously reported, and reproduced in this work, 1,4-dipolar cycloaddition reactions.Efficient directional moisture transport can remove excess sweat away from the human body and keep the body dry; fully utilizing this functionality to improve the wearing experience is urgently needed in the area of functional textiles. Herein, a facile strategy is used to design an eco-friendly and biodegradable PLA membrane with enhanced directional moisture transport and UV protection abilities. The PLA-based Janus membrane with asymmetric wettability is fabricated via sol-gel and electrospinning methods. Titanium dioxide nanoparticles (TiO2) were anchored onto the surface of the PLA fabric during the TiO2 sol-gel fabrication process using polydopamine, forming superhydrophilic TiO2@PDA-PLA. Then a thin PLA fibrous membrane layer showing hydrophobicity was electrospun onto this (PLA-E). The Janus PLA-E/TiO2@PDA-PLA membrane was successfully fabricated. Due to the asymmetric wettability and anchored TiO2, the PLA-E/TiO2@PDA-PLA Janus membrane exhibits efficient directional moisture transport and excellent UV protection abilities, and this work may provide a new pathway for fabricating multifunctional personal protective materials and have attractive potential applications in the future.The use of bacteria as catalysts for radical polymerisations of synthetic monomers has recently been established. However, the role of trans Plasma Membrane Electron Transport (tPMET) in modulating these processes is not well understood. We sort to study this by genetic engineering a part of the tPMET system NapC in E. coli. We show that this engineering altered the rate of extracellular electron transfer coincided with an effect on cell-mediated polymerisation using a model monomer. A plasmid with arabinose inducible PBAD promoters were shown to upregulate NapC protein upon induction at total arabinose concentrations of 0.0018% and 0.18%. These clones (E. coli (IP_0.0018%) and E. coli (IP_0.18%), respectively) were used in iron-mediated atom transfer radical polymerisation (Fe ATRP), affecting the nature of the polymerisation, than cultures containing suppressed or empty plasmids (E. coli (IP_S) and E. coli (E), respectively). These results lead to the hypothesis that EET (Extracellular Electron Transfer) in part modulates cell instructed polymerisations.In the coronavirus disease 2019 pandemic, protective clothing is required for medical staff at risk of infection. This study proposes functional smart fabrics with antimicrobial and water-repellent properties, using titanium dioxide (TiO2) and fluoropolymer-based precursors as coating materials. Experimental results indicated a uniform distribution of TiO2 particles with an average size below 200 nm throughout the fabric. A zone of inhibition test revealed that the fabric inhibited bacterial growth, specifically of Staphylococcus aureus and Klebsiella pneumoniae, before and after 10 wash cycles of the fabric. In wetting angle measurements, the contact angles of water droplets on the fabric ranged from 120° to 139°. A water repellency test confirmed that the coated fabrics retained their water-repellent property after 10 wash cycles.The activity of the hydrogen evolution reaction (HER) during photoelectrochemical (PEC) water-splitting is limited when using BiVO4 with an exposed [110] facet because the conduction band minimum is below the H+/H2O potential. Here, we enhance the photocatalytic hydrogen production activity through introducing an oxygen vacancy. Our first-principles calculations show that the oxygen vacancy can tune the band edge positions of the [110] facet, originating from an induced internal electric field related to geometry distortion and charge rearrangement. Furthermore, the induced electric field favors photogenerated electron-hole separation and the enhancement of atomic activity. More importantly, oxygen-vacancy-induced electronic states can increase the probability of photogenerated electron transitions, thus improving optical absorption. This study indicates that oxygen-defect engineering is an effective method for improving the photocatalytic activity when using PEC technology.Complexes [Pt(dfppy)(pbdtmi)]PF6 (1) and [Pt(ppy)(pbdtmi)]PF6 (2) have been constructed based on dithienylethene-based N^N ligand pbdtmi, showing supramolecular dimer structure in which two coordination cations connect each other through π⋯π stacking interaction. The crystalline state samples of both 1 and 2 reveal strong phosphorescence (emission peak around 579 nm for 1, and 551 nm for 2). Interestingly, a grinding treatment for either 1 or 2 leads to phosphorescence switching from on-state to off-state. The subsequent crystallization with toluene recovers the initial on-state. This work discusses the relationship between the supramolecular dimer structures and the related phosphorescence switching behaviors in 1 and 2, and also explores the photochromism of pbdtmi, 1 and 2.In this study, X80 pipeline steel was embedded in silty soil with different salinities and subjected to corrosion at a constant temperature for 24 h before electrochemical testing. The effect of soil medium, temperature, and salt content on the kinetics of corrosion behavior of X80 steel was analyzed. Furthermore, the compositions and structures of the corrosion products were analyzed by X-ray photoelectron spectroscopy and scanning electron microscopy. Based on the results, the anodic dissolution reaction mechanism of X80 steel in silty soil was determined, the differences in the corrosion process caused by different soil systems were comprehensively contrasted, and the impact of the migration process of heterogeneous silty soil on corrosion behavior under different conditions was systematically explored. Comparative analysis revealed that chloride ions possess strong adsorption ability at temperatures above freezing point and that more oxidized substances are present in the deposited layer on the surface of corroded steel, which facilitates the occurrence of corrosion under deposition.