Spectral Signatures of Oxidation States in a Manganese-Oxo Cubane Water Oxidation Catalyst

We report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese-based water oxidation catalyst [(Mn₄O₄)(V₄O₁₃)(OAc)₃]³⁻. Simulated IR spectra show that V=O stretching vibrations in the 900–1000 cm⁻¹ region shift consistently by about 20 cm⁻¹ per oxidation equivalent. Multiple bands in the 1450–1550 cm⁻¹ region also change systematically upon oxidation/reduction. The computed UV/Vis spectra predict that the spectral range above 350 nm is characteristic of the managanese-oxo cubane oxidation state, whereas transitions at higher energy are due to the vanadate ligand. The presence of absorption signals above 680 nm is indicative of the presence of Mn^III atoms. Spectroelectrochemical measurements of the oxidation from [Mn Mn ] to [Mn ] showed that the change in oxidation state can indeed be tracked by both IR and UV/Vis spectroscopy.     

Cobalt oxide and carbon modified hematite nanorod arrays for improved photoelectrochemical water splitting

Given the proper band gap, low cost and good stability, hematite(α-Fe_2O_3) has been considered as a promising candidate for photoelectrochemical(PEC) water splitting, however suffers from the sluggish surface water oxidation reaction kinetics. In this study, a simple dip-coating process was used to modify the surface of α-Fe_2O_3 nanorod arrays with cobalt oxide(CoO_x) and carbon(C) for the improved PEC performance, with a photocurrent density at 1.6 V(vs. reversible hydrogen electrode, RHE) increased from 0.10 mA/cm~2 for the pristine α-Fe_2O_3 to 0.37 mA/cm~2 for the CoO_x/C modified α-Fe_2O_3 nanorods. As revealed by electrochemical analysis, thanks to the synergistic effect of CoO_x and C, the PEC enhancement could be attributed to the enhanced charge transfer ability, decreased surface charge recombination, and accelerated water oxidation reaction kinetics. This study serves as a good example for improving PEC water splitting performance via a simple method.     

Property correlations for composites based on ethylene propylene diene rubber reinforced with flax fibers

EPDM composites filled with short flax fibers were prepared by melt blending procedure. The effects of fiber loading on the mechanical, thermal and water uptake characteristics were studied. The physico-mechanical, morphological thermal properties and water absorption behavior were discussed using tensile testing, differential scanning calorimetry, thermogravimetrical analysis and scanning electron microscopy. Scanning electron microscopy revealed that the flax fibers were well dispersed in the polymer matrix. The tensile strength and hardness of the composites were found to be improved at higher fiber loading. The water absorption pattern of EPDM/fiber composites at room temperature follows a Fickian behavior for composites with 10, 15 and 20 phr flax fiber.     

Mesoporous hollow silica spheres as micro-water-tanks in proton exchange membranes

In order to decrease the swelling of Nafion^® and reduce the dependency of proton conductivity on high relative humidity (RH), mesoporous hollow silica spheres were synthesized and dispersed in Nafion matrix as micro-water-tanks in the proton exchange membranes (PEM). The morphologies of MHSi and Nafion/MHSi composite membranes are characterized by SEM and TEM. The effects of MHSi on water uptake, swelling, dehydration rate and proton conductivity of the composite membranes were investigated. The results show that, with a suitable portion of MHSi in the membrane, composite PEMs with enhanced water uptake, reduced swelling and improved proton conductivity are obtained.     

三氟化硼引发四氢呋喃聚合的研究——Ⅱ. 水的影响

<正> 分子量在3000以下的四氢呋喃聚合产物-聚丁二醇(PTMG)是重要的工业原料。前报中我们已证明用BF_3-环氧氯丙烷(ECH)引发四氢呋喃(THF)聚合时引发效率较高,在这一基础上有希望通过在聚合体系中加水以达到控制产物分子量的目的。 文献上对水在BF_3-ECH引发THF聚合反应中作用的研究不多,Kyzaeb等人     

Ferroelectric Polarization Modulated Facet-selective Charge Separation in Bi4NbO8Cl Single Crystal for Boosting Visible-light Driven Bifunctional Water Splitting

Developing bifunctional water-splitting photocatalysts is meaningful, but challenged by the harsh requirements of specific-facet single crystals with spatially separated reactive sites and anisotropic charge transfer paths contributed by well-built charge driving force. Herein, tunable ferroelectric polarization is introduced in Bi₄NbO₈Cl single crystal nanosheets to strengthen the orthogonal charge transfer channels. By manipulating the in-plane polarization from octahedral off-centering of Nb⁵⁺ and out-of-plane polarization from lone pair electron effect of anisotropic Bi³⁺, both the fast charge recombination in bulk catalyst and the process of charge trapping into surface states can be effectively modulated. Collaborating with modest polarization electric field and facet junction induced built-in electric field, cooperative charge tractive force is constructed, which reinforces the spatial separation and migration of photogenerated electrons and holes to {110} reductive site facet and {001} oxidation site facet, respectively. While excessive polarization charges impair the facet-selective charge separation characteristics and conversely promote charge recombination on the surface. As a result, polarity-optimized Bi₄NbO₈Cl shows an excellent H₂ and O₂ evolution rate of 54.21 and 36.08 μmol ⋅ h⁻¹ in the presence of sacrificial reagents under visible light irradiation. This work unveils the function of ferroelectric polarization in tuning the intrinsic facet-selective charge transfer process of photocatalysts.     

离聚体的化学物理功能研究——稀土系离聚体的吸水性能研究

稀土系离聚体由于其独特的结构特征,具有较一般离聚体大得多的吸水性能。本文系统地研究了离聚体中不同稀土金属离子、不同可离子化基团含量、不同中和度、不同反离子以及温度和时间的变化对离聚体吸水性能的影响规律,为离聚体的性能表征及使用提供了必要的应用参数。     

水包水乳液的合成及其相组成的研究

系统地研究了聚丙烯酰胺(PAM)-聚乙二醇(PEG)、聚丙烯酸钠(PSA)-PEG水包水乳液的合成条件,从相图上得到上述乳液能够稳定存在的区域,用极谱并结合核磁共振、激光拉曼光谱和相差显徽镜分析该高分子体系,结果表明,PEG溶液为连续相,PAM和PSA溶液分别为各自体系的分散相,两相之间无作用。     

Boosting Reactive Oxygen Species Generation Using Inter-Facet Edge Rich WO3 Arrays for Photoelectrochemical Conversion

Water oxidation reaction leaves room to be improved in the development of various solar fuel productions, because of the kinetically sluggish 4-electron transfer process of oxygen evolution reaction. In this work, we realize reactive oxygen species (ROS), H₂O₂ and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter-facet edge (IFE) rich WO₃ arrays in an electrolyte containing CO₃²⁻. Our results demonstrate that the IFE favors the adsorption of CO₃²⁻ while reducing the adsorption energy of OH⋅, as well as suppresses surface hole accumulation by direct 1-electron and indirect 2-electron transfer pathways. Finally, we present selective oxidation of benzyl alcohol by in situ using the formed OH⋅, which delivers a benzaldehyde production rate of ≈768 μmol h⁻¹ with near 100 % selectivity. This work offers a promising approach to tune or control the oxidation reaction in an aqueous solar fuel system towards high efficiency and value-added product.     

Characterization of plants and seaweeds based corrosion inhibitors against microbially influenced corrosion in a cooling tower water environment

This study compares the inhibitory activities of methanolic extraction of various plants including Artemisia pallens (MEAP), mangrove leaves like Rhizophora mangle (MERM), Avicennia marina (MEAM) and seaweeds such as Pandia povanica (MEPP), Sargassum tenerrimum (MEST) on the corrosion of mild steel (MS) coupons that were incubated on Pseudomonas stutzeri (P. stutzeri) SKR4 strain isolated from the cooling tower water (CTW). The activities of inhibitors are found using GCMS analysis and interactions between microbes and inhibitors were examined in the test for antibacterial activity, minimal inhibition concentration, biofilm formation assay. These all show an excellent inhibitory effect against P. stutzeri. The weight loss, impedance spectroscopy, and Tafel polarization tests used to validate the corrosion investigations show that the inhibitors MEAP-75, MERM-71, MEAM-69, MEPP-66 and MEST-63 % are effective at inhibiting corrosion at 25 ppm. According to Potentiodynamic polarization plots, these five inhibitors act as mixed-type inhibitors. The surface investigation of MS metals by FTIR, SEM, XRD to examine the biofilm surface and it revealed deep pitting corrosion in the bacterial system. In the conclusion, eco-friendly green inhibitors have controlled the biocorrosion in cooling tower water and are recommended for usage in industries as an alternative to environmentally hazardous inhibitors.