Recent Advances in Spatial Self-Phase Modulation with 2D Materials and its Applications

In recent years, spatial self-phase modulation (SSPM) with two-dimensional (2D) materials has attracted the attention of many researchers as an emerging and ubiquitous nonlinear optical effect. In this review, the state of the art of 2D material-based SSPM is summarized. SSPM measures or tunes the nonlinearity of 2D materials, and it is also an effective approach to study the band structure of 2D materials. Several modified forms of SSPM, such as high-order, white-light-excited, vector field excited, and optically nonlinearly enhanced SSPM are also presented. Subsequently, the physical origin of the SSPM formation mechanism is compared and analyzed. Furthermore, the applications of SSPM with 2D materials, including passive photonic devices, generation of Bessel beams, and identifying the mode of the orbital angular momentum, are listed. Finally, several urgent problems of the SSPM with 2D materials, potential applications, and prospects for future development are presented.     

Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

Pd/PdO纳米复合微球的合成及催化性能

采用甲基丙烯酸锌加速还原氯化钯(PdCl₂) 溶液中的钯离子(Pd ²⁺)为钯(Pd) 纳米微球, 进而用得到的钯纳米微球直接制备钯/氧化钯(Pd/PdO) 纳米复合微球. 通过扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 粉末X射线衍射分析(XRD)及X射线光电子能谱分析(XPS) 等方法对 Pd/PdO 纳米复合微球进行表征, 结果表明, 制备的纳米复合微球为表面粗糙、 大小均一的纳米微球. 采用紫外-可见吸收光谱(UV-Vis) 等方法考察了 Pd/PdO 纳米复合微球在对硝基苯酚(4-NTP) 还原反应中的催化性能, 发现其具有良好的催化活性和循环稳定性.     

FTIR与XRD的均匀粒度分布Ce-Cu/TiO2空心微球制备机理研究

随着社会经济的发展，环境空气品质已经成为研究热点。TiO₂是一种化学稳定性高，耐腐蚀性强，对人体无毒无害的N型半导体材料。利用TiO₂的光催化性能提高室内环境空气品质已经成为研究焦点，但是由于TiO₂只能在紫外光源下才具有较高的光催化效率，而在可见光源下的光催化效率较低，从而极大的限制了TiO₂在室内环境领域的发展。因此，研发在可见光源下具有良好光催化性能的TiO₂复合材料势在必行。利用元素掺杂改性技术与提高比表面积方法可以改善光催化反应过程中量子效率和对光能的利用率，以加快电子和空穴向表面迁移的速率同时降低光生载流子的复合机率。以二氧化硅SiO₂为模板、聚乙烯吡咯烷酮为成膜剂、硝酸铈Ce(NO₃)₃·6H₂O和硝酸铜Cu(NO₃)₂·3H₂O为改性剂采用溶胶-凝胶法制备均匀粒度分布的Ce-Cu/TiO₂空心微球，并将制备过程分为四个阶段，即纳米SiO₂球模板的制备、Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备、Ce-Cu/TiO₂-SiO₂复合微球的制备和Ce-Cu/TiO₂空心微球的制备。利用傅里叶变换红外光谱仪（FTIR）与X射线衍射仪（XRD）对Ce-Cu/TiO₂空心微球的制备过程各阶段生成物进行测试与分析，即在纳米SiO₂球模板的制备阶段从微观角度研究纳米SiO₂球模板的搭建过程，在Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备阶段研究TiO₂附着于纳米SiO₂球模板的过程，在Ce-Cu/TiO₂-SiO₂复合微球的制备阶段研究煅烧工艺对Ce-Cu/TiO₂-SiO₂复合微球中晶相与结构的影响，在Ce-Cu/TiO₂空心微球的制备阶段研究氢氧化钠溶液对Ce-Cu/TiO₂-SiO₂复合微球中纳米SiO₂球模板洗涤效果的影响。利用紫外-可见分光光度计（UV-Vis）对Ce-Cu/TiO₂空心微球的光响应性能进行测试与分析，以研究Ce-Cu/TiO₂空心微球对可见光源的利用效率。利用激光粒度分析仪（LPSA）与扫描电子显微镜（SEM）对Ce-Cu/TiO₂空心微球的粒度分布与微观形貌进行测试与分析，以研究Ce-Cu/TiO₂空心微球的均匀粒度分布效果。结果表明：以Si-O-Si基团构建非晶体结构的无定形态纳米SiO₂球模板，有利于聚乙烯吡咯烷酮在纳米SiO₂球模板表面附着，从而控制Ce-Cu/TiO₂空心微球的空腔结构。Ce-Cu掺杂基本进入TiO₂晶体，极少进入纳米SiO₂球模板晶体，从而抑制了Ce-Cu/TiO₂-SiO₂复合微球中TiO₂由锐钛矿相向金红石相的转变。Ce-Cu掺杂TiO₂可以促使TiO₂内部形成新的能级，实现能量较小的光子捕获e-和h+，从而提高Ce-Cu/TiO₂空心微球对可见光源的利用效率。Ce-Cu/TiO₂空心微球的表面光滑且不存在明显的缺陷，其形貌呈现良好的球体且粒径分布均匀，即d₉₀为219.54 nm，d₅₀为151.60 nm、d₁₀为103.84 nm，以及d₉₀-d₁₀为115.70 nm。研究结果为进一步获得可见光源下具有良好光催化性能的均匀粒度分布Ce-Cu/TiO₂空心微球提供理论依据和研究基础。     

A Shell-by-Shell Approach for Synthesis of Mesoporous Multi-Shelled Hollow MOFs for Catalytic Applications

Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.     

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu30H18{E2P(OR)2}12] (E=S or Se; R=nPr,iPr or iBu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu₃₀H₁₈{S₂P(OnPr)₂}₁₂] ( 1_H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1_H reveals an unprecedented central Cu₁₂ hollow icosahedron. Six faces of this icosahedron are capped by Cu₃ triangles, the whole Cu₃₀ core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S₆ symmetry. The locations of the 18 hydrides in 1_H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ₃-H, interstitial μ₄-H (seesaw) and μ₅-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the ¹H NMR spectrum of 1_H are in line with their coordination environment in the solid state, retaining the S₆ symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu₃₀H₁₈{Se₂P(OR)₂}₁₂] ( 2_H : R=iPr 3_H : R=iBu) were synthesized from their sulfur relative 1_H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1_H – 3_H . In addition, the reaction of 1_H with [Pd(PPh₃)₂Cl₂] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu₁₄H₂{S₂P(OnPr)₂}₆(C≡CR)₆] ( 4 : R=Ph; 5 : R = C₆H₄F).     

Bare polyprolylene hollow fiber as extractive phase for in‐tube solid‐phase microextraction to determine estrogens in water samples

Polypropylene hollow fibers as the adsorbent were directly filled into a polyetheretherketone tube for in‐tube solid‐phase microextraction. The surface properties of hollow fibers were characterized by a scanning electron microscope. Combined with high performance liquid chromatography, the extraction tube showed good extraction performance for five environmental estrogen hormones. To achieve high analytical sensitivity, four important factors containing sampling volume, sampling rate, content of organic solvent in sample, and desorption time were investigated. Under the optimum conditions, an online analysis method was established with wide linear range (0.03–20 µg/L), good correlation coefficients (≥0.9998), low limits of detection (0.01–0.05 µg/L), low limits of quantitation (0.03–0.16 µg/L), and high enrichment factors (1087–2738). Relative standard deviations (n = 3) for intraday (≤3.6%) and interday (≤5.1%) tests proved the stable extraction performance of the material. Durability and chemical stability of the extraction tube were also investigated, relative standard deviations of all analytes were less than 5.8% (n = 3), demonstrating the satisfactory stability. Finally, the method was successfully applied to detect estrogens in real samples.     

Effect of rotation in magneto-thermoelastic transversely isotropic hollow cylinder with three-phase-lag model

This article deals with the various heat source responses in a transversely isotropic hollow cylinder under the purview of three-phase-lag (TPL) generalized thermoelasticity theory. In presence of magnetic field and due to the rotating behavior of the cylinder, the governing equations are redefined for generalized thermoelasticity with thermal time delay. In order to obtain the stress, displacement and temperature field, the field functions are expressed in terms of modified Bessel functions in Laplace transformed domain. When the outer radius of hollow cylinder tends to infinity, the corresponding results are discussed. Finally an appropriate Laplace transform inversion technique is adopted.     

Large‐scale production of nitrogen‐ and oxygen‐containing activated carbon microspheres for supercapacitors

A main issue in the production of robust supercapacitors is the creation of efficient and cost‐effective electrodes. We present here the realization of a kind of nitrogen‐ and oxygen‐containing activated carbon microspheres made from divinylbenzene, diallyl phthalate, and acrylonitrile monomers, which can be produced on a large scale for use in supercapacitors. The supercapacitor's performance is optimized by adjusting the carbonization temperature of the microspheres. Our preliminary result shows that the supercapacitor displays a maximum capacitance of 300 F/g at the current density of 1.0 A/g and retains ~82% of the capacitance after 10,000 charge–discharge cycles.     

A High Cell‐Bearing Capacity Multibore Hollow Fiber Device for Macroencapsulation of Islets of Langerhans

Macroencapsulation of islets of Langerhans is a promising strategy for transplantation of insulin‐producing cells in the absence of immunosuppression to treat type 1 diabetes. Hollow fiber membranes are of interest there because they offer a large surface‐to‐volume ratio and can potentially be retrieved or refilled. However, current available fibers have limitations in exchange of nutrients, oxygen, and delivery of insulin potentially impacting graft survival. Here, multibore hollow fibers for islets encapsulation are designed and tested. They consist of seven bores and are prepared using nondegradable polymers with high mechanical stability and low cell adhesion properties. Human islets encapsulated there have a glucose induced insulin response (GIIS) similar to nonencapsulated islets. During 7 d of cell culture in vitro, the GIIS increases with graded doses of islets demonstrating the suitability of the microenvironment for islet survival. Moreover, first implantation studies in mice demonstrate device material biocompatibility with minimal tissue responses. Besides, formation of new blood vessels close to the implanted device is observed, an important requirement for maintaining islet viability and fast exchange of glucose and insulin. The results indicate that the developed fibers have high islet bearing capacity and can potentially be applied for a clinically applicable bioartificial pancreas.