Enhancing hydrogen evolution of MoS2 basal planes by combining single-boron catalyst and compressive strain

MoS₂ is a promising candidate for hydrogen evolution reaction (HER), while its active sites are mainly distributed on the edge sites rather than the basal plane sites. Herein, a strategy to overcome the inertness of the MoS₂ basal surface and achieve high HER activity by combining single-boron catalyst and compressive strain was reported through density functional theory (DFT) computations. The ab initio molecular dynamics (AIMD) simulation on B@MoS₂ suggests high thermodynamic and kinetic stability. We found that the rather strong adsorption of hydrogen by B@MoS₂ can be alleviated by stress engineering. The optimal stress of −7% can achieve a nearly zero value of ΔG_H (~ −0.084 eV), which is close to that of the ideal Pt–SACs for HER. The novel HER activity is attributed to (i) the B– doping brings the active site to the basal plane of MoS₂ and reduces the band-gap, thereby increasing the conductivity; (ii) the compressive stress regulates the number of charge transfer between (H)–(B)–(MoS₂), weakening the adsorption energy of hydrogen on B@MoS₂. Moreover, we constructed a SiN/B@MoS₂ heterojunction, which introduces an 8.6% compressive stress for B@MoS₂ and yields an ideal ΔGH. This work provides an effective means to achieve high intrinsic HER activity for MoS₂.     

Faster Sickling Kinetics and Sickle Cell Shape Evolution during Repeated Deoxygenation and Oxygenation Cycles

Experimental Mechanics - Kinetics of cell sickling and morphological change have been recognized as important parameters that are correlated closely with altered blood rheology and vasoocclusion in...     

硬脂酸镉和山嵛酸镉混合LB膜的微结构

X-ray diffraction (XRD) was used to investigate the microstructure and phase separation of mixed multilayers of cadmium stearate (SA) and behenate (BA) deposited onto hydrophilic glass by the Langmuir-Blodgett technique. No unitary fatty acid diffraction peaks in the XRD spectra of the mixed LB films, which reveals that domains in these samples are small and uniform. The interplanar spacing of the mixed LB films changes with the ratio of BA to SA in a step-shaped curve, which suggests that with the changing of the ratio between BA and SA, only three kinds of ordered structure form in the mixed system, and each microstructure, in particular, the short chains against long chains meshed microstructure can be maintained in a certain ratio range . In addition, for the meshed microstructure, the alkyl chains of both SA and BA stand straight or may have exactly the same small tilted angle from the substrate normal, as is indicated by the symmetric and asymmetric stretching vibration of methylene (CH2) peaks which are at 2847.80 and 2914.37 cm-1respectively in the Fourier transform infrared (FT-IR) transmission spectra. The mixed system always goes through a longitudinal regularity decreasing process when BA/SA is out of the intermediate ratio range (BA/SA: 1/5-1/1), which is illustrated by the relative XRD intensity changing with the ratio of BA/ SA in a \W" shape. These results for the mixed LB films of BA/SA provide meaningful data for choosing the mixture ratio when fabricating composite films with special structure.     

Heat‐Free Biomimetic Metal Molding on Soft Substrates

Fabrication of bio‐templated metallic structures is limited by differences in properties, processing conditions, packing, and material state(s). Herein, by using undercooled metal particles, differences in modulus and processing temperatures can be overcome. Adoption of autonomous processes such as self‐filtration, capillary pressure, and evaporative concentration leads to enhanced packing, stabilization (jamming) and point sintering with phase change to create solid metal replicas of complex bio‐based features. Differentiation of subtle differences between cultivars of the rose flower with reproduction over large areas shows that this biomimetic metal patterning (BIOMAP) is a versatile method to replicate biological features either as positive or negative reliefs irrespective of the substrate. Using rose petal patterns, we illustrate the versatility of bio‐templated mapping with undercooled metal particles at ambient conditions, and with unprecedented efficiency for metal structures.     

Copper‐Catalyzed Aerobic Oxidative Reaction of Sulfonyl Hydrazides with Alcohols: An Easy Access to Sulfinates

A Cu‐catalyzed aerobic oxidative reaction between sulfonyl hydrazides and alcohols has been developed. In this reaction, sulfonyl hydrazides act as the sulfinic acid precursors to react with alcohols, resulting in sulfinic esters with up to 72 % yield. This catalytic system tolerates a wide range of sulfonyl hydrazide substrates, and represents a new strategy for the transformation of readily available sulfonyl hydrazides.     

The hydration properties of carboxybetaine zwitterion brushes

Combined quantum mechanical calculations and classical molecular dynamics simulations were conducted to investigate the hydration properties of carboxybetaine zwitterion brushes with varying separation distances between the quaternary ammonium cation and carboxylic anion. The brushes consist of zwitterion trimers and are investigated to mimic interacting zwitterion chains grafted on a substrate as well as polymers with interacting zwitterion side chains. Our results show that the values of both positive and negative charges, their separation distances as well as chain interactions appear to play a critical role in the hydration properties of the zwitterions. The overall hydration property of these zwitterions is dictated by the competition between the strong hydration of the charged groups and the dehydration of the hydrocarbon chains. The strongest hydration occurs when the ? CH₂? unit in the hydrocarbon chain reaches 6–8 for these trimers. Further increase in the hydrocarbon chain length to 10–14 leads to significant and sudden dehydration of the trimers. The water structure and the water residence time surrounding the zwitterions also demonstrate substantial alteration at this length scale. This hydrophilic‐to‐hydrophobic transition is induced by the hydrophobic interactions of the trimer chains. Our hydration results could explain the observed trend of the superiority of the methylated carbohydrates and poly(ethylene glycol) as antifouling materials compared to corresponding hydroxyl‐terminated compounds. © 2015 Wiley Periodicals, Inc.     

基于RBC模型的动态随机一般均衡的数值解

以一般均衡为框架,引入随机变量的动态随机一般均衡系统,由于模型的庞大和函数形式的复杂,往往不能给出明确的数值解.本文给出几种操作性强的、有效的寻求一般化模型数值解的方法,并通过介绍模型参数确定的办法,使得理论的模型有了现实的含义.     

La0.7Ca0.3Mn1-xCrxO3的激光超声研究

运用激光超声的方法测定了五种不同掺杂的巨磁锰氧化物La0.7Ca0.3Mn1-xCrxO3(0.01≤x≤0.60)室温(300 K)下的超声纵波声速.结合热导率的数据,对声速随掺杂浓度的变化原因进行了深入的分析.得到在顺磁绝缘态Cr3 离子的掺入造成了晶格局部涨落的变化,低掺杂使得晶格局部涨落增强,声子U散射弛豫时间减小.     

高分子网络凝胶法低温合成YAG∶Tb3+荧光粉

以金属硝酸盐为原料,丙烯酰胺为聚合单体以及N,N-亚甲基双丙烯桥酰胺为胶联剂,采用高分子网络凝胶法在低温下合成精细粒度Y3Al5O12∶Tb3 (YAG∶Tb3 )荧光粉.分别用热重-差热分析(TG-DTA)、X射线衍射(XRD)、扫描电子显微镜(SEM),以及激发和发射光谱测量对样品进行了表征,考察了烧结温度对样品结晶程度、颗粒大小的影响,以及样品发光性能与烧结温度和Tb3 浓度的关系.结果表明:YAG晶相形成温度为850℃;粉体颗粒大小均匀,随着烧结温度的升高,颗粒粒径增大,结晶程度提高;观察到Tb3 中4f-5d的吸收带以及5D4-7Fj(j=6,5,4,3)的特征发射带,最强吸收与最强发射分别发生在272,541.8 nm,与量子理论(E=1.24/λ)的计算结果相吻合,其发光强度随烧结温度的升高而增强;观察到了Tb3 在Y3Al5O12中的浓度猝灭现象.