Fabricating Dual-Atom Iron Catalysts for Efficient Oxygen Evolution Reaction: A Heteroatom Modulator Approach

Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear Fe^III₂Fe^II complex (denoted as Fe₃) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of Fe^II by other metal(II) ions (e.g., Zn^II/Co^II) via synthesizing isostructural trinuclear-complex precursors (Fe₂Zn/Fe₂Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Studies on metabolism of total glucosides of paeony from Paeoniae Radix Alba in rats by UPLC‐Q‐TOF‐MS/MS

Total glucosides of paeony are the active constituents of Paeoniae Radix Alba. In this study, a novel strategy was proposed to find more metabolites and the differences between paeoniflorin, albiflorin and total glucosides of paeony (TGP). This strategy was characterized as follows: firstly, the animals were divided into three groups (paeoniflorin, albiflorin and TGP) to identify the source of TGP metabolites from paeoniflorin or albiflorin; secondly, a generic information‐dependent acquisition scan for the low‐level metabolites was triggered by the multiple mass defect filter and dynamic background subtraction; thirdly, the metabolites were identified with a combination of data‐processing methods including mass defect filtering, neutral loss filtering and product ion filtering; finally, a comparative study was used in the metabolism of paeoniflorin, albiflorin and TGP. Based on the strategy, 18 metabolites of TGP, 10 metabolites of paeoniflorin and 13 metabolites of albiflorin were identified respectively. The results indicated that the hydrolysis, conjugation reaction and oxidization were the major metabolic pathways, and the metabolic sites were the glycosidic linkage, the ester bond and the benzene ring. This study is first to explore the metabolism of TGP, and these findings enhance our understanding of the metabolism and the interactions of paeoniflrin and albiflorin in TGP. Copyright © 2015 John Wiley & Sons, Ltd.     

会"飞"的列车

2002年12月31日建成通车的上海磁悬浮列车是世界上第一条投入商业化磁浮示范运营线．从浦东的龙阳路到浦东机场，8分钟就滑过30km的距离，最高时速可达430km／h．     

Spectra Analysis of a Novel Ti-Doped LiAlO2 Single Crystal

LiAlO2 single crvstals doped with Ti at concentration 0.2at.% are grown by the Czochralskl technique with dimensions φ42×55mm. Ti ions in the crystal are quadrivalence proven by comparing the absorption and fluorescence spectra of pure LiAlO2 and Ti： LiAlO2. After air and Li-rich atmosphere annealing, the absorption peaks in the range of 600-800nm disappear. We conclude that 682 and 756nm absorption peaks are attributed to the VLi and Vo absorptions, respectively： The peaks at 716nm and 798nm may stem from the VLi^＋ and absorptions. The colour-centre model can be applied to explain the experimental phenomena. Ti^4＋-doping produces more lithium vacancies in the LiAlO2 crystal. The intensities of [LiO4] and the associated bonds remain unchanged, which improves the anti-hydrolyzation and thermal stability of LiAlO2 crystals.     

γ-LiAlO2晶体生长、改性和热学性质研究

采用快速提拉法生长出了透明、完整的γ-LiAlO2晶体,但是晶体的高熔点和易挥发性限制了γ-LiAlO2晶体质量.采用气相传输平衡法(vapor transport equilibration technique,VTE)工艺对晶体改性,半高宽(FWHM)值从116.9arcsec降至44.2arcsec,继续升高VTE处理温度至1300℃,FWHM值反而升高至55.2arcsec.快速提拉法生长出来晶体,[100]方向和[001]方向的热膨胀系数分别为17.2398×10-6/K,10.7664×10-6/K.经过三步VTE处理后[100]和[001]方向热膨胀系数降至16.6539×10-6/K和10.1784×10-6/K.     

Photoluminescence characteristics of ZnTiO3: Bi nanocrystals

The photoluminescence properties of the Bi³⁺ in sol-gel derived ZnTiO₃ nanocrystals have been investigated. An ultra-violet emission at 360 nm and a visible emission band at 506 nm have been observed, originating from two kinds of emission centers. The former is ascribed to the ³P₁-¹S₀ transition of Bi³⁺ and the latter to the recombination of the electrons with the photo-generated holes trapped in the zinc vacancies. In all cases the latter contribution is predominant.     

Hierarchical structures in a turbulent pipe flow

A hierarchical structure (HS) analysis (β-test and γ-test) is applied to a fully developed turbulent pipe flow. Velocity signals are measured at two cross sections in the pipe and at a series of radial locations from the pipe wall. Particular attention is paid to the variation of turbulent statistics at wall units 10<y⁺<3000. It is shown that at all locations the velocity fluctuations satisfy the She–Leveque hierarchical symmetry (Phys. Rev. Lett. 72 (1994) 336). The measured HS parameters, β and γ, are interpreted in terms of the variation of fluid structures. Intense anisotropic fluid structures generated near the wall appear to be more singular than the most intermittent structures in isotropic turbulence and appear to be more outstanding compared to the background fluctuations; this yields a more intermittent velocity signal with smaller γ and β. As turbulence migrates into the logarithmic region, small-scale motions are generated by an energy cascade and large-scale organized structures emerge which are also less singular than the most intermittent structures of isotropic turbulence. At the center, turbulence is nearly isotropic, and β and γ are close to the 1994 She–Leveque predictions. A transition is observed from the logarithmic region to the center in which γ drops and the large-scale organized structures break down. We speculate that it is due to the growing eddy viscosity effects of widely spread turbulent fluctuations in a similar way as in the breakdown of the Taylor vortices in a turbulent Couette–Taylor flow at high Reynolds numbers.