硫掺杂镍铁层状双氢氧化物的氧析出电催化性能

氧析出反应(OER)是裂解水、二氧化碳还原、以及可充电的锌空电池等许多技术中重要的半反应,但受限于其迟缓的反应动力学,开发高效的氧析出催化剂迫在眉睫.在OER出反应中,性能较好的非贵金属催化剂主要是第四周期过渡金属的一些化合物,如氧化物、氢氧化物、硫化物、硒化物、磷化物等等.在这些材料中,镍铁双金属化合物被认为是最优的氧析出材料,尤其是镍铁层状双氢氧化物(Ni Fe-LDHs)它拥有较大的电化学活性面积以暴露较多活性位点,同时镍铁两种过渡金属元素存在协同效应,使得其具有良好的催化性能.然而,这一类材料的OER性能仍然有优化的空间.研究表明,将硫化物氧化得到的氢氧化物会有少量的硫元素残留,这种硫残留的氢氧化物拥有十分优异的OER性能.为了进一步认识硫的引入对Ni Fe-LDHs的OER行为的影响,本文通过水热法合成了硫掺杂的Ni Fe-LDHs,考察了硫的掺杂量对催化剂性能的影响,验证了微量硫的存在对Ni Fe-LDHs的OER性能的贡献.扫描电镜图片显示,水热合成的催化剂是厚度为几十纳米的薄片,拥有较高的比表面积, X射线荧光光谱分析证明合成的硫掺杂Ni Fe-LDHs中镍铁的元素比例为4:1,而且硫的掺杂量并不影响催化剂的形貌和其中镍铁元素比.X射线光电子能谱分析表明,硫原子的引入使得铁原子结合能降低,即硫与铁的相互作用部分降低了铁的价态,这种硫和铁的相互作用能够优化OER反应中间体OH*与O*在铁活性位点上的吸附自由能,降低氧析出反应的过电势.电化学测试表明,拥有0.43%的硫掺杂Ni Fe-LDHs拥有最好的氧析出性能, 10 m A cm^-1下超电势仅有257 m V, Tafel斜率61.5 m V dec^-1.此后,随着硫掺杂量的提升,其性能先保持稳定,随后有所下降.在稳定测试中,硫掺杂的镍铁层状双氢氧化物在10 m Acm-1电流密度下循环30 h后过电位仅衰减14 m V.在对稳定性测试后的催化剂进行表征表明,催化剂发生了轻微了变形,但这对性能的影响不大.综上,本文提供了一种简便的通过非金属元素掺杂调控过渡金属氧化物的结构和电子态的方法,有望为设计高活性OER电催化剂提供新思路.     

Layered double hydroxide films on nanoporous anodic aluminum oxide/aluminum wire: a new fiber for rapid analysis of Origanum vulgare essential oils

Zn/Al layered double hydroxide (LDH) films were fabricated in situ with anodic aluminium oxide aluminium as both the substrate and the sole aluminium source by means of urea hydrolysis. Headspace solid phase microextraction using LDH fibre in combination with capillary GC–MS was utilised as a monitoring technique for the collection and detection of the volatile compounds of Origanum vulgare. Experimental parameters, including the sample weight, microwave power, extraction time and humidity effect, were examined and optimised.     

Solvent-free synthesis of three layered manganese sulfate-oxalates with different pore apertures

Three manganese sulfate-oxalates, namely, H₂pip·Mn₂(SO₄)₂(ox)(H₂O)₂·2H₂O (1), H₃ipa⋅Mn₂(SO₄)(ox)_2.5·H₂O (2), and H₃dpta⋅Mn₂(SO₄)₂(ox)_1.5(H₂O)₃ (3), were prepared under solvent-free conditions, where pip = piperazine, ox = oxalate, ipa = 3,3′-iminobis(N,N-dimethylpropylamine), and dpta = dipropylenetriamine. These compounds have different layered structures intercalated with organic cations. Their pore apertures range from small 8-membered ring (8 MR) to large 12 MR and extra-large 20 MR. The temperature dependence of the magnetic susceptibility of these compounds were also investigated.     

Stabilization of antioxidant gallate in layered double hydroxide by exfoliation and reassembling reaction

As for the stabilization of chemically sensitive bioactive molecule in this study, gallic acid (GA) with antioxidant property was intercalated into interlayer space of layered double hydroxide (LDH), which was realized by exfoliation and reassembling reaction. At first, the pristine nitrate-type Zn₂Al-LDH in solid state was synthesized via co-precipitation followed by the hydrothermal treatment at 80 °C for 6 h, and then exfoliated in formamide to form a colloidal solution of exfoliated LDH nanosheets, and finally reassembled in the presence of GA to prepare GA intercalated LDH (GA-LDH) desired, where the pH was adjusted to 8.0 in order to deprotonate GA to form gallate anion. According to the XRD analysis, GA-LDH showed well-developed (00l) diffraction peaks with a basal spacing of 1.15 nm, which was estimated to be larger than that of the pristine LDH (0.88 nm), indicating that gallate molecules were incorporated into LDH layers with perpendicular orientation. From the FT-IR spectra it was found that gallic acid was completely deprotonated into gallate, and stabilized in between LDH lattices via electrostatic interaction. The content of GA in GA-LDH was determined to be around 23 wt% by UV–vis spectroscopic study, which was also confirmed by HPLC analysis. According to the in-vitro release of GA out of GA-LDH in PBS solution (pH 7.4) at 4 °C, GA was sustainably released from GA-LDH nanohybrid up to 86% within 72 h. The antioxidant property of GA-LDH was almost the same with that of intact GA which was examined by DPPH. The photostability of GA-LDH under UV light irradiation was immensely enhanced compared to intact GA. It is, therefore, concluded that the present GA-LDH nanohybrid can be considered as an excellent antioxidant material with high chemical- and photo-stabilities, and controlled release property.     

Effect of hydration temperature on the structure reconstruction of MgAlY layered materials

This contribution investigates the obtaining of layered double hydroxides (LDHs) modified with different concentrations of yttrium and the effect of the yttrium concentration and temperature during the rehydration of the mixed oxides derived from these solids. Mg₃Al_(1?x)Y_x-LDH (where x = 0.04–0.6) have been prepared using the standard coprecipitation method under low supersaturation conditions. After the calcination of these solids (460 °C, 18 h), the corresponding mixed oxides were obtained. The reconstruction of the layered structure was attempted by rehydration of the mixed oxides under two different conditions: (1) at 25 °C and (2) at 70 °C. All the aforementioned solids have been characterized by chemical analysis, X-ray diffraction, DRIFTS spectra, N₂ adsorption–desorption isotherms, and determination of base sites. Their catalytic activity was tested in cyanoethylation of ethanol with acrylonitrile. The results obtained after the characterization and the catalytic activity tests were compared with those obtained for a standard hydrotalcite Mg₃Al.     

(C2N2H10)2Mg(HP2O7)2·2H2O synthesis and crystal structure

(C₂N₂H₁₀)₂Mg(HP₂O₇)₂·2H₂O, is a new inorganic organic hybrid structure. It has been synthetized using wet chemistry. Its crystal structure consists of cis- and trans-edge sharing [MgO₄(H₂O)₂] octahedra resulting in chains, which are linked via [HP₂O₇] units to form [Mg(HP₂O₇)₂(H₂O)₂]⁴⁻ layers. The Mg²⁺ cations and the ethylendiammonium cations are located on centers of inversion. The ethylendiammonium cations are alternately located in the interlayer space. The cohesion of the crystal is well ensured by coulombic interactions between anions and cations and by several hydrogen bonds. The diphosphate anion shows an eclipsed conformation.     

Elastic thermal stresses in a hollow circular overlay/substrate system

This paper investigates the thermal elastic fields in the hollow circular overlay fully bonded to a rigid substrate, which is subjected to a temperature change. Following our previous work for a solid circular overlay/substrate system (Yuan and Yin, Mech. Res. Commun. 38, 283–287, 2011), this paper presents a closed form approximate solution to the axisymmetric boundary value problem using the plane assumption, whose accuracy is verified by the finite element models. When the inner radius is reduced to zero, the present solution recovers the previous solution. When the outer radius approaches infinite, the solution provides the elastic fields for a tiny hole in the overlay. The effects of thickness and width of the overlay are investigated and discussed. When a circular crack initiates in a solid circular overlay, the fracture energy release rate is investigated. This solution is useful for thermal stress analysis of hollow circular thin film/substrate systems and for fracture analysis of spiral cracking in the similar structures.     

FRP strengthened walls with delaminated regions – Geometrically nonlinear response

The paper studies the geometrically nonlinear behavior of walls that are strengthened with fiber reinforced polymer (FRP) composite materials but include pre-existing delaminated regions. The paper uses an analytical–numerical methodology. Three specially tailored finite elements that correspond to perfectly bonded regions, to delaminated regions where the debonded layers are in contact, and to delaminated regions where the debonded layers are not in contact are presented. All finite elements are based on a high order multi layered plate theory. The geometrical nonlinearity is introduced by means of the Von Karman nonlinear strains whereas the contact nonlinearity is handled iteratively. The validity and convergence of the finite element models is demonstrated for each type of element through comparison with closed form analytical solutions available for specific cases. The unified model that combines the three types of finite element is then used for studying the nonlinear behavior of a locally delaminated FRP strengthened wall under in-plane normal and in-plane shear loads. Finally, conclusions regarding the effect of the delamination on the response of the strengthening system, on the conditions that evolve in the bonded region that surrounds the delamination, and on the global response of the multi-layered structure are drawn. Additional conclusions regarding the application of the modeling approach to other delamination sensitive layered structural systems close the paper.     

Über die Isotopenzusammensetzung des Schwefels in Magmatiten

Eine Analyse der Isolopenzusammensetzung des Schwefels in Steinmeteoriten, ultrabasischen Gesteinen, basischen und sauren Plutoniten und in Vulkaniten auf der Basis der Vorstellungen über Isotopieeffekte bei der Bildung der Erdkruste und bei der Entstehung magmatischer Gesteine und auf der Basis globaler Isotopiebilanzen führt zu der Hypothese, daß bei der Bildung der Erdkruste vor 4 ? 10⁹ Jahren eine Anreicherung des ³¹S um mehr als 6‰ gegenüber dem Oberen Mantel eingetreten ist. Es wird vermutet, daß diese Anreicherung auf das Wirken von Isotopenaustauschgleichgewichten zwischen erstarrtem Gestein und Schmelze zurückgeht.     

Amorphous tracks induced by energetic ions in strongly anisotropic solids with layered structures

Common features of ion-induced tracks in layered structures are analysed in Y?Ba?Cu?O, Bi?Sr?Ca?Cu?O and in semiconducting GeS and MoS ₂. In all crystals, the conduction is poor along the normal layer. The anisotropic electron properties lead to the formation of an ion-induced broad and a narrow thermal spike in these solids. The contribution of the two spikes to the formation of tracks can be separated in GeS. When the gap energy is low or zero (Y?Ba?Cu?O, Bi?Sr?Ca?Cu?O, MoS ₂), only the narrow spike controls the track formation, and the localization of the energy deposition is the same as in insulators. However, the fraction of the deposited energy transferred to the narrow spike is only about one-third of that in insulators. The anisotropic features of tracks show the effect of the energy bands. Good quantitative agreement is found between the experimental data and the predictions of the author’s thermal spike model.