Surface charging behaviors of electrocatalytic interfaces with partially charged chemisorbates

The surface charge is a key concept in electrochemistry. Mathematically, the surface charge is obtained from a spatial integration of the volume charge along a particular direction. Ambiguities thus arise in choosing the starting and ending points of the integration. As for electrocatalytic interfaces, the presence of chemisorbates further complicates the situation. In this minireview, I adopt a definition of the surface charge within a continuum picture of the electric double layer. I will introduce surface charging behaviors of firstly ordinary electrochemical interfaces and then electrocatalytic interfaces featuring partially charged chemisorbates. Particularly, the origin of nonmonotonic surface charging behaviors of electrocatalytic interfaces is explained using a primitive model. Finally, a brief account of previous studies on the nonmonotonic surface charging behavior is presented, as a subline of the spectacular history of electric double layer.     

Amorphous High-Entropy Hydroxides of Tunable Wide Solar Absorption for Solar Water Evaporation

The high-entropy materials have raised much attention in recent years due to their extraordinary performances in mechanical, catalysis, energy storage fields. Herein, a new type of high-entropy hydroxides (e.g., NiFeCoMnAl(OH)_x) that are amorphous and capable of broad solar absorption is reported. A facile one-pot co-precipitation method is employed to synthesize these amorphous high-entropy hydroxides (a-HEHOs) under ambient conditions. The a-HEHOs thus obtained display widely tunable bandgap (e.g., from 2.6 to 1.1 eV) due to their high-entropy and amorphous characteristics, enabling efficient light absorbance and photothermal conversion in the solar regime. Further solar water evaporation measurements show that the a-HEHOs delivered a considerable energy conversion efficiency of 55%, comparable to black titanium oxides that are synthesized using more complex and expensive methods.     

阳离子交换皂石黏土在基质辅助激光解吸电离飞行时间质谱分析中的应用

将一种人工合成的无机聚合物——蒙脱石皂石黏土（smectite，Sm）应用于基质辅助激光解吸电离飞行时间质谱分析（matrix-assisted laser desorption/ionization time of flight mass spectrometry, MALDI-TOF-MS），以检测糖类化合物。 将传统的有机基质2，4，6-三羟基苯乙酮（trihydroxyacetophenone, THAP）与阳离子交换后的皂石黏土混合制备成新型复合基质，应用于糖类化合物的检测。通过比较不同的制样方法，测定不同分子直径的糖类化合物，发现由于受复合基质晶面间距的限制，只有小分子糖类化合物能进入晶面间隙充分接触有机基质并被离子化，从而实现对小分子糖类化合物的选择性检测。     

Two timescales asymptotes of the weakly compressible Stokes system

We establish a two timescale asymptotics of the weakly compressible Stokes system which has dissipation of order $\epsilon >0$. For any $L^2$ initial data, over time scale of order 1, the solutions of the weakly compressible Stokes system converge strongly to those of the acoustic system as $\epsilon \to 0$. Over time scale of order $1/\epsilon$, the limit system is the incompressible Stokes system with the initial data projected on the incompressible mode. For the periodic domain, the convergence is weak due to the fast oscillation generated by acoustic waves. For the Navier-slip boundary condition with the reciprocal of slip length being square of the Knudsen number, the acoustic waves are damped by the viscous boundary layer, and consequently the strong convergence is justified.     

XANES/EPR Evidence of the Oxidation of Nickel(II) Quinolinylpropioamide and Its Application in Csp3−H Functionalization

An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved.     

A simple method for extracting both active oily and water soluble extract (WSE) from Nigella sativa (L.) seeds using a single solvent system

The current study provides a way of extraction for both active NSO and WSE from Nigella sativa seeds using 98% methanol. About 1?kg of ground seeds was macerated by 1:2.5 w/v (g/mL) for 72?hours. After rotary evaporation and 7 days of continuous drying and chilling at 50 and 4?°C, NSO and WSE were obtained at the same instant. Solubility tests of 24 solvents and 11 thin layer chromatographic analyses while 2, 2-diphenyl-1-picrylhydrazyl free radical scavenging assay of NSO (73.66) , WSE (33.32) and NSO?+?WSE (78.22) against ascorbic acid (IC50?=?4.28?mg/mL) was performed. WSE was found to be highly soluble in water and 5% NaOH exhibiting the same Rf value of 0.95 for EtOH:DMSO (9:1) against the honey. WSE has revealed more than twofold higher anti-oxidant activity than others. Formulation of WSE with Tualang honey may provide better targeted hydrophilic drug delivery systems.     

XPS study of silicon spheres as a density standard

As density is one of the basic physical properties of materials, an accurate density standard is absolutely essential. To determine density with high accuracy and precision, two 1-kg single-crystal silicon spheres (NMIJ-S4 and NMIJ-S5) are used as the primary standard at the National Metrology Institute of Japan. For the accurate measurement of the mass and volume of the silicon spheres, the effects of the surface layer must be carefully considered. In this work, a surface layer model of NMIJ-S4 and NMIJ-S5 was proposed and the thicknesses of each surface layer were determined using X-ray photoelectron spectroscopy. A detailed uncertainty budget is presented to aid use of the density standard.     

浊度干扰下硝酸盐浓度紫外导数光谱检测方法研究

硝酸盐是水中“三氮”（硝酸盐氮、氨氮、总氮）之一，是反映水体受污染程度的一项重要指标。传统 “现场采样-离线分析” 的硝酸盐化学检测方法操作繁琐、耗时长，难以满足现代水环境实时在线检测需求。由于硝酸根在紫外区具有很强的紫外吸收特性，并且紫外吸收光谱法具有简便快速、可实现实时在线监测等特点，近年来被广泛用于硝酸盐浓度的测量。但使用紫外吸收光谱法检测水体硝酸盐含量时，容易受到水体浊度影响，造成谱线非线性抬升，导致测量误差。目前对浊度补偿算法的研究大都用于水中COD含量的检测，对硝酸盐检测中浊度干扰去除研究较少。为此提出一种基于一阶导数紫外吸收光谱的硝酸盐浓度测量方法，该方法可以减小浊度干扰，从而提高紫外光谱快速检测硝酸盐含量的准确度。通过测量福尔马肼与硝酸钠标准溶液和它们混合溶液在190~300 nm波段的紫外吸收光谱并做一阶导数光谱处理，处理后的光谱采用Savitzky-Golay滤波进行去噪平滑处理，比较浊度与硝酸盐紫外吸收一阶导数光谱特征，分波段研究浊度对硝酸盐紫外一阶导数光谱影响，结果表明硝酸盐导数光谱在220~230 nm波段受浊度影响小；选取220~230 nm波段作为光谱分析区间，以30种不同浓度混合的福尔马肼与硝酸钠溶液作为训练样本，利用偏最小二乘算法建立硝酸盐定量分析模型，使用该建模模型预测剩下的6种不同浓度福尔马肼与硝酸钠混合溶液中硝酸盐的浓度，结果表明福尔马肼干扰下硝酸盐测量结果的预测决定系数（correlation coefficient，R2）为0.994 3，预测均方根误差（root mean square error of prediction，RMSEP）为0.346 9 mg·L-1。为进一步验证该方法的准确性与稳定性，使用该建模模型预测高岭土与硝酸钾配制的混合水样中硝酸盐的浓度，结果表明该方法对高岭土干扰下硝酸盐测量结果的预测决定系数r2为0.991 5，预测均方根误差RMSEP为0.362 8 mg·L-1。综上所述，提出的硝酸盐浓度紫外导数光谱检测方法，采用220~230 nm波段的紫外导数光谱数据，结合PLS建模，可以快速准确测量在浊度干扰下水体硝酸盐的浓度，为发展实际水体硝酸盐在线监测技术与设备提供方法基础。     

X-ray absorption spectroscopy study of the electronic structure and local coordination of 1st row transition metal-promoted Chevrel-phase sulfides

Abstract

The electronic structures of S and Mo as well as the local coordination of Mo are investigated as a function of metal promotion Chevrel-phase (CP) sulfides. We observe the effect of metal promoter-induced electron donation into the stoichiometric range M_xMo₆S₈ (M?=?Fe, Ni, Cu; x?=?0–2) through analysis of X-ray absorption near-edge structure regions. We further observe the effect of this promotion on the bonding environment of Mo₆ metal centers through extended X-ray absorption fine structure analysis. We monitor expansion and contraction of Mo₆ octahedra with and without metal promotion, as has been predicted by Hückel molecular orbital theory. We further observe a marked tunability in the electronic structure of sulfur upon charge transfer between promoting species and Mo₆S₈ units. Average Mo₆ octahedron Mo–Mo bond contraction from 2.76 Å to as short as 2.69 Å was observed upon incorporation of metal promoters, while intercluster separation displays a pronounced increase for promoter-host lattices compared to un-promoted Mo₆S₈. To corroborate spectroscopically observed phenomena, we performed computational analyses of spin-polarized densities of state for the CP materials investigated herein, where a detectable increase in sulfur-based frontier orbital population is observed in accordance with experimentally validated orbital filling.