Spherical hollow mesoporous silica supported phosphotungstic acid as a promising catalyst for α-arylstyrenes synthesis via Friedel-Crafts alkenylation

This work presents a scalable approach for preparing spherical hollow mesoporous silica with high surface area/pore volume, serving as outstanding support for supported phosphotungstic acid catalyst with much superior catalytic performance to the one on previously reported spherical mesoporous silica toward diverse transformations, ascribed to the strengthened mass transfer and the enlarged exposure degree of acidic sites to reactants those resulting from unique hollow and mesoporous morphology.     

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.     

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.     

Smart Soft‐Templating Synthesis of Hollow Mesoporous Bioactive Glass Spheres

Hollow bioactive glass spheres with mesoporous shells were prepared by using dual soft templates, a diblock co‐polymer poly(styrene‐b‐acrylic acid) (PS‐b‐PAA) and a cationic surfactant cetyltrimethylammonium bromide (CTAB). Hollow mesoporous bioactive glass (HMBG) spheres comprise the large hollow interior with vertical mesochannels in shell, which realize large uptake of drugs and their sustained release. The formation of hydroxyapatite layer on the surface of HMBG particles shows the clear evidence for promising application in bone regeneration.     

TiO2/SnO2复合空心球在染料敏化太阳能电池中的应用

采用模板辅助法制备了SnO2/TiO2复合空心球,样品直径为1.5~4.0μm,比表面积达到了92.9 m^2·g^-1,复合空心球表现出优越的光散射性能.以这种复合空心球作为染料敏化太阳能电池的光阳极,电池的光电转换效率可达到7.72%,高于SnO2微米球(2.70%)和TiO2微米球(6.26%).此外,以锐钛矿型TiO2纳米晶作为底层,SnO2/TiO2复合空心球作为光散射层制备的双层结构光阳极,电池光电转换效率进一步提升至8.43%.     

On the use of edge cracked short bend beam specimen for PMMA fracture toughness testing under mixed-mode I/II

In this paper an inclined edge cracked short beam specimen subjected to symmetric three-point bend loading was designed and examined for conducting mixed-mode I/II fracture toughness experiments. The aspect ratio (i.e. length to width ratio) and the loading span distance are considered much lower than the other conventional cracked bend beam samples. Crack tip parameters such as stress intensity factors and T-stress were computed numerically for this specimen by several finite element analyses and it was demonstrated that the specimen is able to produce full combinations of mode I and II including pure mode II. The practical capability of the short bend beam specimen was studied experimentally by conducting a set of mixed-mode fracture tests on PolymethylMethacrylate (PMMA) as a well-known model brittle material. The critical stress intensity factors, the direction of fracture kinking and the path of fracture trajectory were investigated both experimentally and theoretically using two stress and strain-based fracture criteria. The fracture toughness of tested PMMA was decreased by moving towards mode II case due to the effect of T-stress on the fracture mechanism of the short bend beam specimen.     

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).     

基于中空多孔金纳米/石墨烯复合纳米材料的葡萄糖氧化酶直接电化学及其生物传感研究

采用溶液相牺牲模板法制备中空多孔金纳米粒子（HPAuNPs）,并将该材料与还原氧化石墨烯（rGO）复合,用于葡萄糖氧化酶（GOx）在玻碳电极（GCE）表面的有效固定,构建GOx/HPAuNPs/rGO/GCE传感界面。利用扫描和透射电镜、X射线光电子能谱、X射线衍射谱、红外光谱及电化学等方法对材料的形貌与结构,GOx的固定化过程,以及传感器的直接电化学和电催化性能进行表征。结果表明,HPAuNPs和rGO的协同作用能有效促进GOx与电极之间的直接电子转移（DET）。基于GOx/HPAuNPs/rGO/GCE对葡萄糖的良好电催化性能,该方法有效实现了对葡萄糖的高灵敏度检测,其电流响应的线性范围为0.05～7.0 mmol/L,检出限（S/N=3）为16μmol/L。该传感器具有良好的选择性、重现性及稳定性,对实际样品血清中血糖的测定结果令人满意,回收率为98.0%～103%,相对标准偏差不大于5.0%。     

纳米镍钴铁氧体空心微球的制备与性能

以乙二醇为溶剂,氯化铁、氯化钴、氯化镍和醋酸铵为反应试剂,采用溶剂热法制备纳米Ni_xCo_1-xFe₂O₄(x=0、0.3、0.5、0.7、1)铁氧体空心微球,研究镍含量对铁氧体空心球的磁性与吸波性能的影响。借助X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、振动样品磁强计(VSM)和网络分析仪对试样的物相组成、微观形貌和电磁特性进行表征。结果表明制备的镍钴铁氧体为尖晶石结构,且形貌为空心球,粒径在200nm左右。当x=0时,镍钴铁氧体空心球饱和磁化强度最大为81.7emu·g^-1,反射损耗在1658.8MHz有最小值为-16.9dB。     

多金核二氧化铈空心球用于硝基苯酚催化加氢

催化剂的微观结构在催化还原反应、有机物氧化反应及有机物转化反应中起着关键作用。本文利用无模板方法合成了多金核中空二氧化铈微球催化剂。将制备好的二氧化铈中空微球浸渍到一定浓度的氯金酸溶液中,然后多次洗涤除去表面吸附的氯金酸离子,最后通过硼氢化钠还原制成中空氧化铈微球包覆的多金核的核壳结构催化剂。将该核壳结构材料用于硝基苯酚加氢反应与金纳米粒子及氧化铈微球相比,多金核中空二氧化铈核壳结构表现出优越的活性和稳定性。通过这种浸渍洗涤再还原的简单方法合成的多金核二氧化铈催化剂有望应用于生物医药和能源环境等领域。