Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO₂ (rutile and P25) with increasing oxygen deficiency and Ti³⁺ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti³⁺ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti³⁺ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.     

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4]+

The tetraoxido ruthenium(VIII) radical cation, [RuO₄]⁺, should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO₄]⁺, produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO₄]⁺ is identified by the chemical shift at the ruthenium M₃ edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO₄]⁺ to the closed-shell [RuO₄H]⁺ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO₄]⁺ than for [OsO₄]⁺.     

Quantitative analysis of MWCNT agglomeration in polymeric‐based membranes using atomic force microscope

In this work, we performed an analysis on the surface properties of polyethersulfone (PES)‐based ultrafiltration membranes that were prepared by incorporating acid functionalized multiwalled carbon nanotube (f‐MWCNT) and polyvinylpyrrolidone into membrane matrix via simple blending method. The bonding‐chemistry of the nanocomposites implanted within the PES membrane was investigated by Fourier transform infrared spectrometer while atomic force microscope was employed to observe the distribution of f‐MWCNT in the membrane matrix and further measured its agglomeration quantitatively. The resultant 3D atomic force microscope images provided the most satisfactory way to examine the distribution of nanomaterials in the membranes, and with the help of ‘point profile data’ the maximum height and width of the agglomerated cluster could be quantitatively calculated. Moreover, the surface profile studies of the membrane surface provided the information about the length, volume, area, perimeter, radius and diameter of grains. It was observed that PES/nanocomposite blended membranes were held together via strong hydrogen bonding, but poor dispersion of MWCNT in the membrane matrix reduced the membrane performance in terms of protein (pepsin and bovine albumin serum) rejection and increased the surface roughness. Copyright © 2016 John Wiley & Sons, Ltd.     

Geodesic metrics on fractals and applications to heat kernel estimates

Science China Mathematics - It is well known that for a Brownian motion, if we change the medium to be inhomogeneous by a measure μ, then the new motion (the time-changed process) will diffuse...     

Velocity and turbulence measurements in combustion systems

A laser-Doppler velocimeter is used in the measurement of high-temperature gas flows. A two-stage fluidization particle generator provides magnesium oxide particles to serve as optical scattering centers. The one-dimensional dual-beam system is frequency shifted to permit measurements of velocities up to 300 meters per second and turbulence intensities greater than 100 percent.Exiting flows from can-type gas turbine combustors and burners with pre-mixed oxy-acetylene flames are described in terms of the velocity, turbulence intensity, and temperature profiles.The results indicate the influence of the combustion process on turbulence.List of Symbols A exit area of combustor or burner (m²) - A/F mass air-fuel ratio - D exit diameter of combustor or burner (m) - M mass flow rate of gases (kg/s) - N _D number of Doppler bursts used in each velocity measurement - Q volumetric flow rate at T _r (m³/s) - R exit radius of combustor or burner (m) - R _1/2 distance from centerline to radius where the velocity is one-half of the local centerline velocity (m) - Re exit Reynolds number based on cold flow, QD/A - r distance from centerline of flow (m) - T temperature (°C) - T _CL centerline temperature (°C) - T _r inlet (cold) air temperature of combustor or burner (°C) - T.I. turbulence intensity, - mean velocity (m/s) - U _i instantaneous velocity individually realized by LDV (m/s) - mean velocity at centerline of flow (m/s) - mean square velocity fluctuation (m²/s² - x distance along centerline downstream of exit (m) - absolute viscosity at T _r (kg/(ms)) - density at T _r (kg/m³)     

Generation and Reactivity of a One-Electron-Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand

The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [Mn^V(TAML)(N-Mes)]⁻ ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC₆H₄)₃N ]^+.[SbCl₆]⁻ and the resulting Mn^VI species readily undergoes H-atom transfer and nitrene transfer reactions.