Improving Alkaline Hydrogen Oxidation through Dynamic Lattice Hydrogen Migration in Pd@Pt Core-Shell Electrocatalysts

Tracking the trajectory of hydrogen intermediates during hydrogen electro-catalysis is beneficial for designing synergetic multi-component catalysts with division of chemical labor. Herein, we demonstrate a novel dynamic lattice hydrogen (LH) migration mechanism that leads to two orders of magnitude increase in the alkaline hydrogen oxidation reaction (HOR) activity on Pd@Pt over pure Pd, even ≈31.8 times mass activity enhancement than commercial Pt. Specifically, the polarization-driven electrochemical hydrogenation process from Pd@Pt to PdH_x@Pt by incorporating LH allows more surface vacancy Pt sites to increase the surface H coverage. The inverse dehydrogenation process makes PdH_x as an H reservoir, providing LH migrates to the surface of Pt and participates in the HOR. Meanwhile, the formation of PdH_x induces electronic effect, lowering the energy barrier of rate-determining Volmer step, thus resulting in the HOR kinetics on Pd@Pt being proportional to the LH concentration in the in situ formed PdH_x@Pt. Moreover, this dynamic catalysis mechanism would open up the catalysts scope for hydrogen electro-catalysis.     

Potential Energy Function for State X1∑+ of LaH

The present work has derived the potential energy function for the ground state X1∑+of LaH in Murrell-Sorbie function form. In the first place, the electronic state and it′ s rea sonable dissodation limits are correctly determined based on Atomic and Molecular Reaction Statics (AMRS), and then, using the relativistic compact effective potential (RCEP) for La, the equilibrium geometry and dissociation energy for LaH have been calculated by the QCISD method. The calculated results for Re'De' Be' αe' ωe and ωexe are 2.125A, 2.623eV,3.7333cm-1, 0.0723 cm-1, 1461.73cm-1 and 21.383cm-1 respectively, which are in good agreement with experimental or calculated values in references.     

Extraction of Surface Roughness from the Central δ-peak of Light Scattering Using a Multi-wavelength Ar~ Laser

1　Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｓｏｍｅｕｓｅｃｏｎｔａｃｔｔｅｃｈｎｉｑｕｅｓ(ｓｕｃｈａｓｐｒｏｆｉｌｏｍｅｔｒｙ,ｓｃａｎｎｉｎｇｐｒｏｂｅｍｉｃｒｏｓｃｏｐｙ)ａｎｄｔｈｅｏｔｈｅｒｓｕｓｅｎｏｎｃｏｎｔａｃｔｔｅｃｈｎｉｑｕｅｓ,ｍｏｓｔｏｆｗｈｉｃｈａｒｅａｃｔｕａｌｌｙｏｐｔｉｃａｌｍｅｔｈｏｄｓ,ａｎｄｌｉｇｈｔｓｃａｔｔｅｒｉｎｇ[1,2],ｅｌｌｉｐｓｅｏｍｅｔｒｙ[3]ａｎｄｓｕｒｆａｃｅｐｌａｓｍｏｎｓｐｅｃｔｒｏｓｃｏｐｙ[4]ａｒｅｔｈｅｅｘａｍｐｌｅｓ.Ｕｐｔｏｎｏｗ,ｔｈｅｄｅｔｅｒ…     

弱散射屏的像面散斑自相关函数特性的实验研究

在对随机弱散射屏进行表面参数的原子力显微镜测量和建立了门积分取样平均的随机光强自相关函数测量系统的基础上,对弱散射屏在严格像面和离焦像面上产生的散斑自相关函数进行了测量。发现在严格像面上,散斑平均颗粒的大小随表面粗糙度增加而减小,且光强自相关函数次极大的相关间隔宽度随粗糙度增加而减小;而次极大的超伏随粗糙度的增大而增大;在离焦像面上,离焦量的增加使光强的自相关函数下降变得平滑,并使极小值点和次极大点变得不明显或者消失。     

金属镍吸附氢同位素的量子力学计算

根据原子分子反应静力学与群论，确定了ＮｉＨ、ＮｉＤ和ＮｉＴ的基电子状态为２Σ＋。应用基函数６－３１１Ｇ和组态相关ＣＩ或ＱＣＩＳＤ方法，计算了氢同位素分子及其镍化物的能量Ｅ、定容热容Ｃｖ和熵Ｓ。设用总能量中的电子和振动能量近似代表ＮｉＨ、ＮｉＤ和ＮｉＴ分子处于固态时的能量，用总熵中的电子和振动熵近似代表这些分子处于固态时的熵，进而计算了镍吸附Ｈ２、Ｄ２和Ｔ２分子过程的ΔＨ°、ΔＳ°、ΔＧ°和平衡压力，并导出它们与温度的函数关系。计算指出了同位素分子效应，结果合理。所以，本文所建议的用量子力学方法计算多相化学反应，有应用参考价值。     

A large deviation principle for bootstrapped sample means

A large deviation principle for bootstrapped sample means is established. It relies on the Bolthausen large deviation principle for sums of i.i.d. Banach space valued random variables. The rate function of the large deviation principle for bootstrapped sample means is the same as the classical one.

     

Kinetics and Mechanism of the oxygenation of triphenylphosphine by bis(ethyl-L-cysteinato)dioxomolybdenum(VI)

Summary The kinetics of oxygen-transfer from [MoO₂(Et-L-cys)₂] to PPh₃ and the reaction between [Mo₂O₃(Et-L-cys)₄] and O₂ in benzene solution have been investigated using spectrophotometric techniques between 25 and 40°. The rate laws-d[Mo⁶⁺]/dt = k₁[Mo⁶⁺][PPh₃] with k₁ (at 35°) = 2.95×10^–4dm³mol^–1s^–1 and -d[Mo⁵⁺]/dt = 2k₃[Mo⁵⁺][O₂] with k₃ (at 35°) = 6.3×10^–2 dm³mol^–1s^–1 account for the kinetic data obtained with activation parameters (at 35°) of H = 46 kJ mol^–1, S = –153 JK^–1mol^–1, and H = 50.8 kJ mol^–1, S = –95 JK^–1 mol^–1 respectively.     

两种高Tg非线性光学聚合物母体及掺杂,极化的研究

利用具有非线性光学活性的对硝基苯胺掺杂高玻璃化转变温度的聚芳醚砜(PES-C)和聚芳醚酮(PEK-C),得到了两种掺杂含量较高的掺杂型非线性光学聚合物体系。电晕极化表明较高的取向和较慢的松驰。     

二阶非线性光学极化聚合物

本文综述了二阶非线性光学极化聚合物材料研究概况，包括器件对材料的要求、材料的研究进展及目前存在的问题。     

(E/Z)‐Isomerization of 3′‐Epilutein

3′‐Epilutein (=(all‐E,3R,3′S,6′R)‐4′,5′‐didehydro‐5′,6′‐dihydro‐β,β‐carotene‐3,3′‐diol; 1 ), isolated from the flowers of Caltha palustris, was submitted to both thermal isomerization and I₂‐catalyzed photoisomerization. The structures of the main products (9Z)‐ 1 , (9′Z)‐ 1 , (13Z)‐ 1 , (13′Z)‐ 1 , (15Z)‐ 1 , and (9Z,9′Z)‐ 1 were determined based on UV/VIS, CD, ¹H‐NMR, and MS data.