ZnO Nanoplatelets with Controlled Thickness: Atomic Insight into Facet-Specific Bimodal Ligand Binding Using DNP NMR

Colloidal nanoplatelets (NPLs) and nanosheets with controlled thickness have recently emerged as an exciting new class of quantum-sized nanomaterials with substantially distinct optical properties compared to 0D quantum dots. Zn-based NPLs are an attractive heavy-metal-free alternative to the so far most widespread cadmium chalcogenide colloidal 2D semiconductor nanostructures, but their synthesis remains challenging to achieve. The authors describe herein, to the best of their knowledge, the first synthesis of highly stable ZnO NPLs with the atomically precise thickness, which for the smallest NPLs is 3.2 nm (corresponding to 12 ZnO layers). Furthermore, by means of dynamic nuclear polarization-enhanced solid-state ¹⁵N NMR, the original role of the benzamidine ligands in stabilizing the surface of these nanomaterials is revealed, which can bind to both the polar and non-polar ZnO facets, acting either as X- or L-type ligands, respectively. This bimodal stabilization allows obtaining hexagonal NPLs for which the surface energy of the facets is modulated by the presence of the ligands. Thus, in-depth study of the interactions at the organic–inorganic interfaces provides a deeper understanding of the ligand–surface interface and should facilitate the future chemistry of stable-by-design nano-objects.     

基于超材料的无标记光学生物传感

超材料(metamaterials)因为能够在亚波长尺度范围内精细调控电磁波而受到人们广泛关注。超材料具有丰富的电磁模态,在表面支持高度局域场增强且对周围介电环境极其敏感,可应用于无标记光学生物传感领域。与传统光学生物传感器相比,超材料生物传感器具有小型化、集成化、高度灵敏、多功能可定制等突出优点。本文总结了近年来超材料生物传感器在可见光、近红外、中红外以及太赫兹波段的研究进展,包括折射率生物传感、表面增强拉曼散射、表面增强红外吸收和太赫兹生物传感等。     

One-step preparation of the superhydrophobic Al alloy surface with enhanced corrosion and wear resistance

Corrosion and wear failures are bottlenecks for restricting applications and developments of Al-based functional materials. As a new lubrication technology, superhydrophobic preparation provides an effective way to settle Al alloy corrosion. The preparation methods of superhydrophobic Al alloys are mainly multistep strategies. In this study, superhydrophobic Al alloy, has been prepared by an efficient one-step electrochemical etching process. Meanwhile, its micromorphology has been observed by a scanning electron microscope. The wettability has been measured by video optical contact angle meter. The corrosion behavior has been tested by electrochemical workstation, and wear performance has been characterized by friction tester. The results show that the micro-nanoterraced concave–convex structure has been fabricated and an as-prepared surface exhibits excellent superhydrophobic behavior. Further electrochemical and tribological tests show that corrosion resistance and wear resistance have also been significantly improved. This study provides a new method to prepare wear-resistant and corrosion-resistant Al alloy for widening applications of multifunctional Al-based engineering materials.     

Design,synthesis, characterization,and aging properties of a new end-capped three-dimensional high-refractive index hybrid organic–inorganic polysiloxane

The actual need for hybrid organic–inorganic polysiloxanes is very high due to their importance in optoelectronic applications, especially for the preparation of anti- and low-reflection layers, photopatterned overcoats, flexible hard coats, and glass and metal coatings. However, such three-dimensional hybrid polysiloxanes have very often a limited shelf life and aged very rapidly. Consequently, this type of polymer may require to be stored at cold temperatures and needs to be dilute in organic solvent to a very low solid content, which are unprofitable conditions for commercialization purposes. Therefore, there is an urgent demand to prepare three-dimensional polysiloxanes, which are more resistant toward aging processes. Herein, a new hybrid three-dimensional polysiloxane has been designed and synthesized from three different silane precursors using the sol–gel technology, and characterized using gel permeation chromatography, ¹H, ¹³C, and ²⁹Si nuclear magnetic resonance and MS spectroscopies. One-fourth of the silanol groups present in the polysiloxane have been protected with chlorotrimethylsilane. The refractive index of the silicon wafer coated with the new polysiloxane was found to be 1.53, which is higher compare to traditional values. Importantly, the new protected three-dimensional polysiloxane did not age after being stored at T = 40°C for 3 weeks.     

Magnetodielectric coupling in barium titanate–cobalt ferrite composites obtained via thermally-assisted high-energy ball milling

In this work, a magnetodielectric coupling observed in barium titanate–cobalt ferrite composites synthesized using high-energy ball milling assisted via a thermal treatment is discussed. Vibrating sample magnetometry and dielectric spectroscopy showed that multiferroic composites possess both ferromagnetic and dielectric behaviors inherited from the parent ferromagnetic cobalt ferrite and ferroelectric barium titanate phases. The magnetocapacitance (up to 35%) recorded for x = 0.3, (1-x)BaTiO₃–xCoFe₂O₄, can be attributed to the spin-dependent filtering mechanism. The composite with the aforementioned composition exhibited a homogeneous matrix–particle composite microstructure, which was achieved via high-energy ball milling during the mixing stage.     

Fabrication and characterization of hot-pressed B-rich boron carbide

Boron carbide has a wide solubility range owing to the substitution of B and C atoms in the crystal. In this study, boron carbides with different stoichiometric ratios were prepared using a hot-pressing sintering method, and the influences of the B/C atomic ratio on the microstructures and properties were explored in detail. X-ray diffraction analysis showed that excessive B atoms caused lattice expansion. Raman spectroscopy analysis showed disordered substitution of B atoms in the chains and icosahedra. Analysis of the densification process and microstructure evolution revealed that the addition of B promoted densification, and more stacking faults and twins occurred in B-rich boron carbide, and result in the densification mechanism gradually changes from atomic diffusion mechanism driven by thermal energy to plastic deformation mechanism dominated by the proliferation of dislocation and substructures. The introduction of chemical composition changes by dissolving excessive B into boron carbide further affected the microstructure and consequently the mechanical properties. The Vickers hardness, modulus, and sound velocity all decreased with the increase in B content. Moreover, the fracture toughness improved with increased B content. The flexural strength of the samples was optimised at the B/C stoichiometric ratio of 6.1.     

Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

重水浓度与吸光度关系曲线类型研究

重水作为反应堆的慢化材料，其浓度直接影响反应堆的安全和性能。为研究其重水浓度与吸光度间的关系曲线类型，基于朗伯-比尔定律，从理论上推导出液态重水中某种水分子的红外吸收峰分别与0~2种其他水分子的红外吸收峰发生重叠时重水浓度与吸光度间的关系式，分情况对二者之间的关系曲线类型进行讨论。采用傅里叶变换红外光谱仪，测得浓度为0.015%~99.98%（摩尔比）的重水标准样品吸收光谱，对重水浓度和吸光度间的关系曲线类型进行验证，理论推导与实际吻合。研究表明，一般情况下，宽浓度范围内，重水浓度与吸光度间的关系曲线类型为二次曲线；窄浓度范围内，关系曲线类型为线性。特殊情况下，吸光度为定值或关系曲线类型为线性。     

Enhancement of optical emission generated from femtosecond double-pulse laser-induced glass plasma at different sample temperatures in air

In double-pulse laser-induced breakdown spectroscopy(DP-LIBS), the collinear femtosecond double-pulse laser configuration is experimentally investigated with different initial sample temperatures using a Ti:sapphire laser. The glass sample is ablated to produce the plasma spectroscopy. During the experiment, the detected spectral lines include two Na(I) lines(589.0 nm and 589.6 nm) and one Ca(I) line at the wavelength of 585.7 nm. The emission lines are measured at room temperature(22 ℃) and three higher initial sample temperatures(T_s?=?100 ℃, 200 ℃, and 250 ℃). The inter-pulse delay time ranges from-250 ps to 250 ps.The inter-pulse delay time and the sample temperature strongly influence the spectral intensity,and the spectral intensity can be significantly enhanced by increasing the sample temperature and selecting the optimized inter-pulse time. For the same inter-pulse time of 0 ps(single-pulse LIBS), the enhancement ratio is approximately 2.5 at T_s?=?200 ℃ compared with that obtained at T_s?=?22 ℃. For the same inter-pulse time of 150 ps, the enhancement ratio can be up to 4 at T_s?=?200 ℃ compared with that obtained at T_s?=?22 ℃. The combined enhancement effects of the different initial sample temperatures and the double-pulse configuration in femtosecond LIBS are much stronger than that of the different initial sample temperatures or the double-pulse configuration only.     

Photoluminescence and thermal expansion of zirconium vanadate

The optical property and phase transition of ZrV₂O₇ were investigated by temperature-dependent X-ray diffraction, photoluminescence (PL), and Raman spectra. It was found that the material exhibited PL emission in the visible region. The temperature-dependent PL emission showed that the peak energy for emission (at red wavelength) presented a red shift from 10 to 80 K, and then a blue shift with the increase in temperature. The PL emission bands of ZrV₂O₇ shifted with change in temperature relating to its phase transition (80-100 K), which could be confirmed by temperature-dependent Raman spectra.