Oscillatory electrocatalytic oxidation of methanol on an Ni(OH)2 film electrode

A film of Ni(OH)₂ deposited cathodically on a roughened nickel substrate consists of even nanoparticles, which were characterized by atomic-force microscopy (AFM). The mechanism of potential oscillations in the electrocatalytic oxidation of methanol on this film electrode in alkaline medium was studied in situ by means of Raman spectroscopy in combination with electrochemical measurements. The redox change of the nickel hydroxide film, the concentration distribution of methanol in the diffusion layer, and the oxidation products of methanol were characterized in situ by time-resolved, spatial-resolved, and potential-dependent Raman spectroscopy, respectively. Electrochemical reactions, i.e. methanol oxidation and periodic oxygen evolution, coupling with alternately predominant diffusion and convection mass transfer of methanol, account for the potential oscillations that occur during oxidation of methanol above its limiting diffusion current. This mechanism is totally different from that of methanol oxidation on platinum electrodes, for which surface steps, i.e. formation and removal of CO_ad, are essential.This work is dedicated to Professor Gyorgy Horanyi on the occasion of his 70th birthday in recognition of his numerous contributions to field of electrochemical oscillations and electrocatalysis at Ni-hydroxide electrodes.     

Stable Potential Windows for Long‐Term Electrocatalysis by Manganese Oxides Under Acidic Conditions

Efficient, earth‐abundant, and acid‐stable catalysts for the oxygen evolution reaction (OER) are missing pieces for the production of hydrogen via water electrolysis. Here, we report how the limitations on the stability of 3d‐metal materials can be overcome by the spectroscopic identification of stable potential windows in which the OER can be catalyzed efficiently while simultaneously suppressing deactivation pathways. We demonstrate the benefits of this approach using gamma manganese oxide (γ‐MnO₂), which shows no signs of deactivation even after 8000 h of electrolysis at a pH of 2. This stability is vastly superior to existing acid‐stable 3d‐metal OER catalysts, but cannot be realized if there is a deviation as small as 50‐mV from the stable potential window. A stable voltage efficiency of over 70 % in a polymer–electrolyte membrane (PEM) electrolyzer further verifies the availability of this approach and showcases how materials previously perceived to be unstable may have potential application for water electrolysis in an acidic environment.     

Crystal Structure and Magnetic Property of a 2-D Hexa-Circular Ring Cu(II)/Na(I)-Substituted Sandwich-Type Arsenotungstate

A new compound H₈[NaCu₅Cl(H₂O)₃(B-α-AsW₉O₃₃)₂] 24H₂O (1) is synthetized by the reaction of the CuCl₂ 2H₂O and Na₂₇[NaAs₄W₄₀O₁₄₀] 60H₂O in aqueous solution, which is constructed from a {Cu₅Na} hexagon moiety sandwiched by two trilacunary [B-α-AsW₉O₃₃]^9? units. The structure is determined by single-crystal X-ray diffraction technique and further characterized by IR spectroscopy. Single-crystal X-ray diffraction analysis reveals that 1 is built by two trilacunary [B-α-AsW₉O₃₃]^9? units incorporating a {Cu₅Na} hexagon moiety and further linked to each other to form an infinitely extended 2-D network via Cu–O–W bridges. Notably, magnetic measurement demonstrates that the occurrence of intramolecular ferromagnetic Cu–Cu interactions within {Cu₅Na} hexagon moiety.     

The large quadrupole of water molecules

Many quantum mechanical calculations indicate water molecules in the gas and liquid phase have much larger quadrupole moments than any of the common site models of water for computer simulations. Here, comparisons of multipoles from quantum mechanical∕molecular mechanical (QM∕MM) calculations at the MP2∕aug-cc-pVQZ level on a B3LYP∕aug-cc-pVQZ level geometry of a waterlike cluster and from various site models show that the increased square planar quadrupole can be attributed to the p-orbital character perpendicular to the molecular plane of the highest occupied molecular orbital as well as a slight shift of negative charge toward the hydrogens. The common site models do not account for the p-orbital type electron density and fitting partial charges of TIP4P- or TIP5P-type models to the QM∕MM dipole and quadrupole give unreasonable higher moments. Furthermore, six partial charge sites are necessary to account reasonably for the large quadrupole, and polarizable site models will not remedy the problem unless they account for the p-orbital in the gas phase since the QM calculations show it is present there too. On the other hand, multipole models by definition can use the correct multipoles and the electrostatic potential from the QM∕MM multipoles is much closer than that from the site models to the potential from the QM∕MM electron density. Finally, Monte Carlo simulations show that increasing the quadrupole in the soft-sticky dipole-quadrupole-octupole multipole model gives radial distribution functions that are in good agreement with experiment.     

Synthesis, structure, and photoluminescence properties of a novel 3D 3d-4f heterometallic polymer: Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (H2Bpdc = 2,2′-bipyridyl-5,5-dicarboxylic acid)

A novel 3D 3d–4f heterometallic polymer Pr₄(H₂O)₉Cu_3.5Cl_0.5(Bpdc)_6.5(OH)₂ · 5H₂O (I) (H₂Bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid) has been hydrothermally synthesized by the reaction of CuCl₂ · 2H₂O, PrCl₃, H₂Bpdc, TAA (TAA = 1H-tetrazolyl-1-acetic acid) and glacial acetic acid and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting heterometallic 3D coordination framework constructed from 2D praseodymium-oxygen layers and [Cu(Bpdc)2]^3? and [CuCl(Bpdc)]^2? pillars. The photofluorescence properties of I have been investigated.     

Simultaneous determination of carbohydrates and organic acids in beer and wine by ion chromatography

The simultaneous determination of mono-organic acids and carbohydrates by ion chromatography with both conductometric and pulsed amperometric detection is described. The carbohydrates, such as mannitol, arabinose, glucose, fructose, lactose, sucrose, raffinose, and maltose, as well as monoorganic acids including acetate, glycolate, formate, pyruvate, and fluoride are separated as anions by ion-exchange chromatography with 0.080 mol/L sodium hydroxide eluent at 1 mL/min within 12 min. Carbohydrates are determined by pulsed amperometric detection and mono-organic acids are determined by suppressed conductivity detection. The species in beverages are determined.     

多相催化反应原位红外系统及其应用

设计和建立了一套能耐高温的用于多相催化反应研究的原位红外系统，反应温度从室温到１１５０Ｋ，系统真空为１．０＊１０＾５－１．０－１０＾－４Ｐａ，红外光谱检测范围为４８００－２００ｃｍ＾－１。此系统扩展了原仪器的功能，提高了仪器利用率和效率。     

Effect of environmental conditions on the sorption of radiocobalt from aqueous solution to treated eggshell as biosorbent

Carbonate hydroxylapatite (CHAP), prepared from eggshell waste, was used to remove ⁶⁰Co(II) from aqueous solutions. The sorption of ⁶⁰Co(II) on CHAP as a function of contact time, pH, ionic strength and foreign ions in the absence and presence of humic acid and fulvic acid under ambient conditions was studied. The sorption of ⁶⁰Co(II) on CHAP was strongly dependent on pH and ionic strength. The thermodynamic parameters (ΔH ⁰, ΔS ⁰, ΔG ⁰) of ⁶⁰Co(II) sorption on CHAP were calculated from the temperature-dependent sorption isotherms, and the results indicated that the sorption process of ⁶⁰Co(II) on CHAP was endothermic and spontaneous. At low pH, the sorption of ⁶⁰Co(II) was dominated by outer-sphere surface complexation and ion exchange with Na⁺/H⁺ on CHAP surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. Experimental results also indicated that CHAP was a suitable low-cost adsorbent for pre-concentration and solidification of ⁶⁰Co(II) from large volumes of aqueous solutions.     

Prediction of interaction between small molecule and enzyme using AdaBoost

The knowledge of whether one enzyme can interact with a small molecule is essential for understanding the molecular and cellular functions of organisms. In this paper, we introduce a classifier to predict the small molecule– enzyme interaction, i.e., whether they can interact with each other. Small molecules are represented by their chemical functional groups, and enzymes are represented by their biochemical and physicochemical properties, resulting in a total of 160 features. These features are input into the AdaBoost classifier, which is known to have good generalization ability to predict interaction. As a result, the overall prediction accuracy, tested by tenfold cross-validation and independent sets, is 81.76% and 83.35%, respectively, suggesting that this strategy is effective. In this research, we typically choose interactions between small molecules and enzymes involved in metabolism to ultimately improve further understanding of metabolic pathways. An online predictor developed by this research is available at . Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mechanical strength lowering in submicron Cu thin films by moderate DC current

This letter reports an experimental investigation into the direct current (DC) induced reduction in the yield strength of 60∼700-nm-thick Cu films. Results show that the larger the current density and the thinner the film, the greater the reduction when the film thickness is below about 340 nm. This reduction could be described on the basis of dislocation buckling, which, caused by the electron wind of the current flow, induces an increase in the dislocation length and a decrease in the critical stress for multiplying the dislocation.