Unravelling the Relationship between Raman Enhancement and Photocatalytic Activity on Single Anisotropic Au Microplates

Anisotropic noble‐metal structures are attracting increasing attention because of interesting size‐ and shape‐dependent properties and have emerging applications in the fields of optics and catalysis. However, it remains a significant challenge to overcome chemical contributions and acquire molecular insight into the relationship between Raman enhancement and photocatalytic activity. This study gives visualized experimental evidence of the anisotropic spatial distribution of Raman signals and photocatalytic activity at the level of single nanometer‐thin Au microtriangles and microhexagons. Theoretical simulations indicate an anisotropic spatial distribution and sharpness‐dependent strength of the electric‐field enhancement. Analysis by using statistical surface‐enhanced Raman scattering (SERS) supports this view, that is, Raman enhancement is on the order of corner>edge>face for a single microplate, but SERS measurements at different depths of focus also imply a concentration‐dependent feature of SERS signals, especially at the corners and edges. Similarly, the SERS signals of product molecules in plasmonic photocatalysis also exhibit asymmetrical strengths at different corners of the same microplate. However, by examining the variations in the relative intensities of the SERS peaks, the difference in the photocatalytic activities at the corners, edges, and faces has been successfully calculated and is highly consistent with electric‐field simulations, thus indicating that an increased number of molecules adsorbed at specific sites does not necessarily lead to a higher conversion ratio in noble‐metal photocatalysis. Our strategy weakens the assumed impact of plasmonic local heating and, to a certain extent, excludes the influence of concentration effects and chemical contributions in noble‐metal photocatalysis, thus clearly profiling plasmon‐related characteristics. This study also promises a new research direction to understand the enhancement mechanism of SERS‐active structures.     

A Superhydrophobic Surface Fabricated by an Electrostatic Process

We describe the fabrication of a biomimically designed superhydrophobic poly(ε‐caprolactone) surface, which was obtained using a modified electrostatic process. The fabricated surface exhibits a micron‐sized pyramid structure consisting of accumulated droplets and nanofibres. By using this simple one‐step process, we can achieve a superhydrophobic surface having both a high water contact angle and low threshold sliding angle, similar to that of the superhydrophobic plant leaf.

     

Density functional theory study of p‐chloroaniline adsorption on Pd surfaces and clusters

The adsorption mode of aromatic molecules on transition metal surfaces plays a key role in their catalytic transformation. In this study, by means of density functional theory calculations, we systematically investigate the adsorption of p‐chloroaniline on a series of Pd surfaces, including stepped surfaces, flat surfaces, and clusters. The adsorption energies of p‐chloroaniline on these substrates [Pd(221), Pd(211), Pd(111), Pd(100), Pd₁₃‐icosahedral, Pd₁₃‐cubo‐octahedron, Pd₅₅] are ?1.90, ?2.13, ?1.70, ?2.11, ?2.53, ?2.65, ?2.23 eV, respectively. Benzene ring is adsorpted on catalyst rather than amine group in p‐chloroaniline molecular. A very good linear relationship is further found between the adsorption energies of p‐chloroaniline and the d‐band center of both Pd surfaces and clusters. The lower of d‐band center of Pd models, the stronger adsorption of p‐chloroaniline on catalysts. In addition, the frontier molecular orbital and density of states analysis explain the adsorption energy sequence: cluster Pd₁₃ > stepped Pd(221) surface > flat Pd(111) surface. © 2014 Wiley Periodicals, Inc.     

Covalently Attached Liquids: Instant Omniphobic Surfaces with Unprecedented Repellency

Recent strategies to prepare “omniphobic” surfaces have demonstrated that minimizing contact angle hysteresis (CAH) is the key criterion for effectiveness. CAH is affected by chemistry and topography defects at the molecular and higher levels, thus most surfaces exhibit significant CAH. Preparative methods for stable coatings on smooth substrates with negligible CAH (<2°) for a broad range of liquids have not been reported. In this work, we describe a simple and rapid procedure to prepare omniphobic surfaces that are stable under pressure and durable at elevated temperatures. Consistent with theory, they exhibit sliding angles that decrease with liquid surface tension. Slippery omniphobic covalently attached liquid (SOCAL) surfaces are obtained through acid‐catalyzed graft polycondensation of dimethyldimethoxysilane. The smooth, stable, and temperature‐resistant coatings show extremely low CAH (≤1°) and low sliding angles for liquids that span surface tensions from 78.2 to 18.4 mN m^?1.     

气相中CrO2+活化甲烷C—H键的理论研究

用密度泛函UB3LYP/6-311＋＋G**方法计算研究了气相中CrO₂⁺ (²A₁/⁴A")活化甲烷C—H键的微观机理, 找到了四条反应通道. 对其中涉及的两态反应(TSR)进行了分析, 并对影响反应机理和反应速率的势能面交叉现象(potential energy surfaces crossing)进行了详细讨论, 进而运用Hammond假设和Yoshizawa等的内禀坐标单点垂直激发计算的方法找出了一系列势能面交叉点[crossing points (CPs)], 并作了相应的讨论. 进一步用碎片分子轨道理论[fragment molecular orbital (FMO)]对TS1中的轨道相互作用进行了分析, 解释了CrO₂⁺活化甲烷C—H键的机理.     

Wrinkle morphologies with two distinct wavelengths

Wrinkles with two distinct wavelengths formed sequentially on the same surface are investigated. A series of aligned wrinkles are formed through local strain application on a partially crosslinked elastomer. After the formation of these primary wrinkles, the elastomer is fully crosslinked, and a mechanical compressive strain is applied to the sample orthogonal to the primary wrinkles. This mechanical strain results in smaller secondary wrinkles superimposed on the larger primary aligned wrinkles. Resulting biaxial morphologies suggest that the primary pattern directs the formation of the smaller wrinkles. The modulus mismatch of the substrate on primary and secondary wrinkle formation dictates the ratio between the two resulting wavelengths, as well as the specific biaxial morphologies, ranging from zigzag ridges to ellipsoidal bumps or corn‐on‐the‐cob structures to the classic herringbone. The sequential strain wrinkling process has the potential to be used on an industrial scale for the facile formation of surface topography with two discrete, tunable lateral dimensions over large surface areas. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

A Facile Method for Preparation of Superhydrophobic Surfaces with Poly(furfuryl Alcohol)/PTFE Composites

A stable superhydrophobic surface have been fabricated with poly(furfuryl alcohol) (PFA)/polytetrafluoroethylene (PTFE) composite coatings on steel substrates by using a facile method. The observation of field emission scanning electron microscopy revealed that the hierarchical microstructures formed on the surfaces are controlled by varying the curing temperature. This method can be easily operated on substrates of steel, therefore is readily developed to other engineering metal substrates such as aluminum, copper, etc.     

Direct breath figure formation on PMMA and superhydrophobic surface using in situ perfluoro-modified silica nanoparticles

Breath figure formation was carried out directly on the surface of poly(methylmethacrylate) using a mixture of a good solvent, tetrahydrofuran, and a nonsolvent, water. Direct breath figure formation was coined for this method and a mechanism was proposed to describe the figure formation by the method based on hypothesizes available for the normal breath figure formation. The proposed mechanism is such that the sonication effect, immersion time, and water content on characteristics of the obtained figures can be explained. The figured surface was then made superhydrophobic with a water contact angle of 175° using in situ growing of perfluoro modified silica nanoparticles inside the figure cell by one-pot method. The spherical modified silica nanoparticles were detected being trapped by figure features providing a mechanical entrapment of the low-surface energy nanoparticles. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013