可见光作用下LaTaON2催化剂光催化分解水制氢

 采用高温氮化技术,以氯化铵为矿化剂合成了层状钙钛矿型LaTaON2光催化剂. 与前驱体氧化物LaTaO4相比, LaTaON2的吸收边红移,在可见区呈现较强的吸收. 在可见光作用下,乙醇为牺牲剂时,同时负载Pt和Ru的LaTaON2能催化分解水放出H2, 且其光催化产氢效率大大高于单独负载Pt或Ru的LaTaON2催化剂.     

Cyclotron resonance in (GaAs)n/(AlAs)n superlattices under ultra-high magnetic fields

We present a review on recent study of the type I to type II transition in short-period superlattices (SLs) of GaAs/AlAs by means of cyclotron resonance (CR) in pulsed high magnetic fields. The behavior of CR varies depending on the thickness of the GaAs and AlAs layers. In CR of (GaAs)_n/(AlAs)_n, the resonance peak at the X minima was observed in the type II regime for n smaller than 14, whereas the resonance at the Γ point was observed for n>15. We estimated electron masses on X and Γ point in the SLs by using the empirical sp³ tight-binding method including second-nearest-neighbor interaction. These calculations have shown good agreement with the experimental results. Moreover, it was found that the angular dependence of the CR peak position does not obey the simple cosine dependence due to the subband mixing in high magnetic fields. From the angular dependence in the SLs, the longitudinal and transverses electron masses of AlAs at the X point were deduced to be m_t=0.21m₀ and m_l=1.04m₀, respectively.     

Efficient 1H NMR chiral discrimination of sulfoxides caused by the dynamic nature of (R,R)-3′,3″-biBINOL

A chiral BINOL dimer, (R,R)-3′,3″-BiBINOL, which possesses both rigid (atropos) and dynamic (tropos) axial chiralities, was found to work as an effective NMR chiral solvating reagent for the determination of the enantiomeric purities of various chiral sulfoxides. The unique chiral discrimination mechanism was also revealed by using DFT calculations and X-ray crystallographic analysis.     

Homopolymerization and copolymerization of a dilactone, 13,26‐dihexyl‐1,14‐dioxa‐cyclohexacosane‐2,15‐dione: Synthesis of bio‐based polyesters and copolyesters consisting of 12‐hydroxystearate sequences

A dilactone, 13,26‐dihexyl‐1,14‐dioxacyclohexacosane‐2,15‐dione (12‐HSAD), was synthesized by lipase‐catalyzed reaction of 12‐hydroxystearic acid (12‐HSA) in high yield. It was subjected to the ring‐opening polymerization with various catalysts to obtain poly(12‐hydroxystearate) (PHS). The polymerization system of 12‐HSAD showed an interesting polymerization behavior because of its large ring system. The polymers produced by this polymerization were directly reacted with L ‐lactide to obtain a diblock copolymer of poly(L ‐lactide)‐block‐poly‐(12‐hydroxystearate) (PLLA‐b‐PHS). Characterization of the resultant copolymers was also performed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

For overall water-splitting systems, it is essential to establish O₂-insensitive cathodes that allow cogeneration of H₂ and O₂. An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H₂ evolution in the presence of O₂. In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O₂ gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoO_x/Pt/SrTiO₃ with inhibited water formation from H₂ and O₂, which is the prevailing back reaction on the bare Pt/SrTiO₃ photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.     

Model calculation for ion mobility in air using the MOBCAL program

We determined new potential parameters for a calculation of ion mobility in air using the MOBCAL program. In our model, we regard air as a virtual uni-atomic molecular gas. And the Lennard-Jones parameters for various kinds of atoms in molecular ions were determined with simple and systematic methods. Using these parameters, we have calculated the mobilities of product ions from chemical warfare agents, normal saturated hydrocarbons, and illicit drugs. Most of the calculation results showed good agreement with the experimental values. Therefore this calculation method will be useful for understanding of the ion mobility spectrometry in air.     

Formation and High Reactivity of the anti‐Dioxo Form of High‐Spin μ‐Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C−H Bonds

Recently, it was shown that μ‐oxo‐μ‐peroxodiiron(III) is converted to high‐spin μ‐oxodioxodiiron(IV) through O?O bond scission. Herein, the formation and high reactivity of the anti‐dioxo form of high‐spin μ‐oxodioxodiiron(IV) as the active oxidant are demonstrated on the basis of resonance Raman and electronic‐absorption spectral changes, detailed kinetic studies, DFT calculations, activation parameters, kinetic isotope effects (KIE), and catalytic oxidation of alkanes. Decay of μ‐oxodioxodiiron(IV) was greatly accelerated on addition of substrate. The reactivity order of substrates is toluene<ethylbenzene≈cumene<trans‐β‐methylstyrene. The rate constants increased proportionally to the substrate concentration at low substrate concentration. At high substrate concentration, however, the rate constants converge to the same value regardless of the kind of substrate. This is explained by a two‐step mechanism in which anti‐μ‐oxodioxodiiron(IV) is formed by syn‐to‐anti transformation of the syn‐dioxo form and reacts with substrates as the oxidant. The anti‐dioxo form is 620 times more reactive in the C?H bond cleavage of ethylbenzene than the most reactive diiron system reported so far. The KIE for the reaction with toluene/[D₈]toluene is 95 at ?30 °C, which the largest in diiron systems reported so far. The present diiron complex efficiently catalyzes the oxidation of various alkanes with H₂O₂.