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.     

金属蛋白研究中几个值得注意的动向

本文叙述了金属蛋白和金属酶研究中近年来几个值得注意的发展动向，即与金属离子相关的疾病（特别是神经退行性疾病）、金属离子在蛋白质的折叠、聚集和装配中的作用，金属伴侣分子、金属蛋白的设计和构建、金属蛋白与DNA相互作用。     

Optical bistability of planar metal/dielectric nonlinear nanostructures

We study theoretically a nonlinear response of the planar metal/dielectric nanostructures constituted from periodical array of ultra thin silver layers and the layers of Kerr-like nonlinear dielectric. We predict hysteresis-type dependences of the components of the tensor of effective dielectric permittivity on the field intensity allowing the change in material transmission properties from transparent to opaque and back at extremely low intensities of the light. It makes possible to control the light by light in all-optical nanoscale devices and circuits.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.     

Morphologies,microstructures, and mechanical properties of samples produced using laser metal deposition with 316 L stainless steel wire

Laser metal deposition (LMD) with a filler has been demonstrated to be an effective method for additive manufacturing because of its high material deposition efficiency, improved surface quality, reduced material wastage, and cleaner process environment without metal dust pollution. In this study, single beads and samples with ten layers were successfully deposited on a 316 L stainless steel surface under optimized conditions using a 4000 W continuous wave fibre laser and an arc welding machine. The results showed that satisfactory layered samples with a large deposition height and smooth side surface could be achieved under appropriate parameters. The uniform structures had fine cellular and network austenite grains with good metallurgical bonding between layers, showing an austenite solidification mode. Precipitated ferrite at the grain boundaries showed a subgrain structure with fine uniform grain size. A higher microhardness (205–226 HV) was detected in the middle of the deposition area, while the tensile strength of the 50 layer sample reached 669 MPa. In addition, ductile fracturing was proven by the emergence of obvious dimples at the fracture surface.     

石墨富集结合空间约束水体重金属LIBS检测方法研究

针对水体重金属污染检测的需求,研究了以高纯石墨片为水体富集基底,样品多次富集结合等离子体空间约束的水体重金属LIBS检测方法, 并对Pb,Cu,Cd,Ni等不同重金属元素的测量稳定性及检测限进行了分析。实验采用波长为1 064 nm的Nd∶YAG调Q激光器,分辨率为0.1 nm的光纤光谱仪分别对上述水体中重金属元素含量的特征光谱进行分光探测。结果表明,样品多次富集结合空间约束方法能够有效地提高水体重金属检测的灵敏度及稳定性并降低元素检测限,空间约束条件下特征光谱强度增强约2.5倍,光谱稳定性也得到提高,相对标准偏差由非约束情况下的11.34%降低至8.77%。对不同浓度的Pb,Cu,Cd,Ni四种重金属元素进行检测并建立定标曲线,Pb,Cu,Cd,Ni的检测限均低于国家工业废水排放标准的1/6,满足工业废水重金属的检测需求,为工业废水重金属的减排控制与超标排放预警监测提供了一种有效方法和技术支持。     

Fluorimetric metal ion sensing usingN-methyl-9-anthrylhydroxamic acid

We have synthesizedN-methyl-9-anthrylhydroxamic acid, which is a fluorescent analogue ofN-methylbenzohydroxamic acid. Complexation with various di- and trivalent metal ions occurs (logK from 4 to 5) in water with resulting fluorescence quenching. Because the Fe(III) and Al(III) complexes substituted rather slowly, the addition of EDTA provides a temporal method for obtaining some selectivity in the chemosensor.     

Ab initio study of sodium intercalation into metal oxides

Using the full-potential linearized augmented plane wave (FP-LAPW) method, we have studied the effect of chemistry on the average intercalation voltage (AIV) caused by the Na ions intercalating into transition metal oxides. The effect of transition metal was systematically studied by varying M=Co, Ni and Mn in NaMO₂ and fixing the α-NaFeO₂ layered structure. The effect of the guest atoms into the host material is discussed in terms of the structural and electronic properties. Comparatively to Li intercalation, a significant electron transfer towards transition metal was found. This observation suggests that the transition metal contribute to the AIV determination and confirms the common assumption that intercalated electron reduces M⁴⁺ to M³⁺.     

Metal deposition onto thiol-covered gold: Platinum on a 4-mercaptopyridine SAM

In this study we describe details of a new technique that allows to deposit metal on top of a self-assembled monolayer (SAM). Monoatomic high platinum islands were formed on a 4-mercaptopyridine SAM on Au(1 1 1) by first immersing the SAM-covered gold electrode in an aqueous solution of K₂PtCl₄ without potential control to allow Pt(II) ions to form a complex with the pyridine nitrogen. The complexed Pt(II) ions were then reduced electrochemically to Pt(0) after transferring the electrode to a Pt(II) ion-free solution. Upon reduction, monoatomic high Pt islands were observed in STM, the total coverage depending on the time for complexation. Ex situ angle-resolved XPS studies reveal that the Pt islands indeed reside on top of the SAM.     

TM掺杂Ⅱ-Ⅳ-Ⅴ2黄铜矿半导体的电磁性质

利用自旋局域密度泛函的第一性原理对3d过渡金属(TM=V，Cr，Mn，Fe，Co和Ni)掺杂的Ⅱ-Ⅳ-Ⅴ2(CdGeP2和ZnGeP2)黄铜矿半导体的电磁性质进行系统计算，结果发现：V和Cr掺杂的CdGeP2和ZnGeP2将出现铁磁状态(FM)，Mn，Fe以及Co掺杂的CdGeB和ZnGeP2将出现反铁磁状态(AFM)，而Ni掺杂时，稀磁半导体(DMS)的磁性比较不稳定，其中Cr掺杂的CdGeP2和ZnGeP2将可能是具有较高居里温度Tc的DMS，当TM-3d电子的t2g态部分被填充时，其掺杂的DMS将出现FM状态；而当TM-3d电子的t2g态全满或者全空时，其掺杂的DMS将出现AFM状态，在(Cd，Mn)GeP，和(Zn，Mn)(GeP2中分别掺入电子和空穴载流子，可以发现载流子是否具有TM-3d电子的巡游特性是。DMS是否出现FM状态的主要原因。