Restructuring and Activation of Cu(111) under Electrocatalytic Reduction Conditions

The dynamic restructuring of Cu surfaces in electroreduction conditions is of fundamental interest in electrocatalysis. We decode the structural dynamics of a Cu(111) electrode under reduction conditions by joint first-principles calculations and operando electrochemical scanning tunneling microscopy (ECSTM) experiments. Combining global optimization and grand canonical density functional theory, we unravel the potential- and pH-dependent restructuring of Cu(111) in acidic electrolyte. At reductive potential, Cu(111) is covered by a high density of H atoms and, below a threshold potential, Cu adatoms are formed on the surface in a (4×4) superstructure, a restructuring unfavorable in vacuum. The strong H adsorption is the driving force for the restructuring, itself induced by the electrode potential. On the restructured surface, barriers for hydrogen evolution reaction steps are low. Restructuring in electroreduction conditions creates highly active Cu adatom sites not present on Cu(111).     

Why Boron Nitride is such a Selective Catalyst for the Oxidative Dehydrogenation of Propane

Boron‐containing materials, and in particular boron nitride, have recently been identified as highly selective catalysts for the oxidative dehydrogenation of alkanes such as propane. To date, no mechanism exists that can explain both the unprecedented selectivity, the observed surface oxyfunctionalization, and the peculiar kinetic features of this reaction. We combine catalytic activity measurements with quantum chemical calculations to put forward a bold new hypothesis. We argue that the remarkable product distribution can be rationalized by a combination of surface‐mediated formation of radicals over metastable sites, and their sequential propagation in the gas phase. Based on known radical propagation steps, we quantitatively describe the oxygen pressure‐dependent relative formation of the main product propylene and by‐product ethylene. Free radical intermediates most likely differentiate this catalytic system from less selective vanadium‐based catalysts.     

丁二酸二油酯磺酸钠合成及纯化方法的改进

研究了丁二酸二油酯磺酸钠合成及纯化方法的改进，使其产率由30％提高到了80．9％。     

隐含风险中性分布在巨灾超额损失再保险定价中的应用

通过与标的风险相关的期权市场估计出隐含变换系数,然后以Esscher变换为工具,将巨灾损失统计分布风险中性化,从而对以该非交易风险为标的的巨灾超额损失再保险进行定价.同时,从期权定价的角度,结合Weibull极值分布和超额损失再保险的特点,给出了巨灾超额损失再保险定价的闭型表达式.     

Rh/SiO2催化剂上甲烷部分氧化制合成气的核磁共振研究

 利用1H MAS NMR技术,在甲烷部分氧化(POM)制合成气反应条件下研究了Rh/SiO2催化剂上氢与金属的相互作用及反应机理. 结果发现,氢气在Rh/SiO2上解离吸附后可能有四种存在形式: 化学位移为δ=-100～-120的可逆(αM)和不可逆(αI)吸附氢物种,δ=0～-100的“氢云”或“氢雾”形式的氢物种和δ=3.0的溢流氢物种. 溢流氢物种是由可逆吸附的氢物种和“氢云”或“氢雾”状态的氢物种溢流到SiO2上并弱吸附在桥式氧(Si-O-Si)附近而形成的. 溢流氢物种活化晶格氧,形成一种POM反应的活性氧物种OH-. 活性氧物种OH-反溢流到Rh上,并与CH4解离吸附在Rh上的CHx物种反应生成含氧中间物种CHxO. CHxO物种的化学位移为5～7. O2参与CHxO物种的进一步氧化,或补充溢流氢夺取桥式氧后形成的缺陷位上的晶格氧,在高温(973 K)反应条件下,O2可能优先补充缺陷位上的晶格氧,使CHx的氧化按表面反应机理进行.     

A Comparison-estimate of the second Rauch type for Ricci curvature

We establish a comparison-estimate of the second Rauch type for Ricci curvature. As an application, we get a result of local splitting for Riemannian manifolds. This work is partly supported by the National Natural Science Foundation (10371047) of China.     

Transition of Bery Phase and Pancharatnam Phase and Phase Change

Berry Phase and time-dependent Pancharatnam phase are investigated for nuclear spin polarization in a liquid by a rotation magnetic field, where two-state mixture effect is exactly included in the geometric phases. We find that when the system of nuclear spin polarization is in the unpolarized state, the transitive phenomena of both Berry phase and Pancharatnam phase are taken place. For the polarized system, in contrast, such a transition is not taken place. It is obvious that the transitions of geometric phase correspond to the phase change of physical system.     

医疗保险索赔数据的广义Pareto分布拟合

How to choose an optimal threshold is a key problemin the generalized Pareto distribution (GPD) model.This paper attains the exactthreshold by testing for GPD,and shows that GPD model allows the actuary to easily estimate high quantiles and the probable maximum loss from the medical insurance claims data.     

湖南省城镇居民消费的实证分析

本文利用递归的核回归模型 ,分析湖南省城镇居民消费性支出 ,以提高拟合度 ,减少预测误差     

A new model for sparse and low-rank matrix decomposition

The robust principal component analysis (RPCA) model is a popular method for solving problems with the nuclear norm and $\ell_1$ norm. However, it is time-consuming since in general one has to use the singular value decomposition in each iteration. In this paper, we introduce a novel model to reformulate the existed model by making use of low-rank matrix factorization to surrogate the nuclear norm for the sparse and low-rank decomposition problem. In such case we apply the Penalty Function Method (PFM) and Augmented Lagrangian Multipliers Method (ALMM) to solve this new non-convex optimization problem. Theoretically, corresponding to our methods, the convergence analysis is given respectively. Compared with classical RPCA, some practical numerical examples are simulated to show that our methods are much better than RPCA.