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.     

Effect of additive length and chemistry on the morphology of blends of conjugated thiophenes and fullerene derivative acceptor molecules

Small molecule additives have been shown to increase the device efficiency of conjugated polymer (donor) and fullerene derivative (acceptor) based organic solar cells by modifying the morphology of the device active layer. In this paper we conduct a systematic study of how additives affect the donor‐acceptor morphology using molecular dynamics simulations of blends of thiophene‐based oligomers, mimicking poly(3‐dodecylthiophene) (P3DDT) or poly(2,2′:5′,2”‐3,3”‐didocyl‐terthiophene) (PTTT), and fullerene derivatives with additives of varying length and chemical functionalization, mimicking experimentally used additives like methyl ester additives, diiodooctane, and alkanedithiols. We find that functionalization of additives with end groups that are attracted to acceptor molecules are necessary to induce increased donor‐acceptor macrophase separation. In blends where acceptors intercalate between oligomer alkyl side chains, functionalized additives decrease acceptor intercalation. Functionalized additives with shorter alkyl segments increase acceptor macrophase separation more than additives with same chemical functionalization but longer alkyl segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1046–1057     

Investigation of closure approximations for fiber orientation distribution in contracting turbulent flow

We have investigated the orientation state of a dilute fiber suspension flow in a planar contraction at high Reynolds numbers in turbulent flow. High speed imaging is used to directly measure the orientation distribution function at different downstream positions along the contraction centerline. The results from the direct measurement of the orientation distribution are used to evaluate the existing closure models. The results show that the fitted orthotropic and natural closure approximations give almost identical results with the best agreement to the orientation distribution in the contraction flow considered here.     

Validation of the catalytic properties of Cu-Os/13X using single fixed bed reactor in selective catalytic reduction of NO

Catalytic decomposition of NO over Cu-Os/13X has been carried out in a tubular fixed bed reactor at atmospheric pressure and the results were compared with literature data performed by high-throughput screening (HTS). The activity and durability of Cu-Os/13X prepared by conventional ion-exchange method have been investigated in the presence of H₂O and SO₂. It was found that Cu-Os/13X prepared by ion-exchange shows a high activity in a wide temperature range in selective catalytic reduction (SCR) of NO with C₃H₆ compared to Cu/13X, proving the existence of more NO adsorption site on Cu-Os/13X. However, Cu-Os/13X exhibited low activity in the presence of water, and was quite different from the result reported in literature. SO₂ resistance is also low and does not recover its original activity when the SO₂ was blocked in the feed gas stream. This result suggested that catalytic activity between combinatorial screening and conventional testing should be compared to confirm the validity of high-throughput screening.     

Fully-developed pipe and planar flows of multimode viscoelastic fluids

Two solutions are presented for fully-developed pipe and planar flows of multimode viscoelastic models. The fluids have a Newtonian solvent contribution and the polymer modes are described by the Phan-Thien—Tanner (PTT), the FENE-P or the Giesekus equation. The first solution is exact and can handle any number of modes, but is only semi-analytical. The second solution, which is presented only for the PTT model with a linear stress coefficient and the FENE-P model, can also handle any number of modes. It is based on a truncated series expansion and is completely analytical, but provides only an approximated solution. The complexity of the multimode solutions is investigated first with the exact semi-analytical method and it is shown that at high Deborah number flows the high-order stresses can become as important as the stress of the first mode. It is also under these conditions that the approximated analytical solution deviates from the exact semi-analytical solution. A criterion for the accurate use of the approximated solution is presented. Fortran codes are provided to obtain these solutions at the internet address at the end.     

Fabricating tunable nanoparticle density gradients with the contact printing based approach

Recently, the generation of spatial gradient nanoparticle assemblies has attracted much attention. Such assemblies can be intriguing templates for building novel molecular architectures, and be employed as a combinatorial tool for quick determination of interaction selectivity for nanoparticles. In this communication, we report on convenient contact printing based techniques for generating lateral gradients containing nanoparticles with tunable geometry, scale and steepness. In the first method, octadecyltrichlorosilane (OTS) gradient surfaces were generated via the contact printing approach, and then spaces un-occupied by OTS molecules were back-filled with an amine-terminated silane, which allows the grafting of nanoparticles that were surface functionalized with carboxylic acid. By varying the size and geometry of the stamp, different geometrical gradients were generated. In addition, by changing the stamping procedures, either well-defined stepwise gradients or continuous gradients can be achieved. Furthermore, the contact printing based technique can be utilized in combination with diffusion of the aminosilane molecules to directly create its gradient, and consequently a nanoparticle density gradient.     

Preparation of dye-loaded SiO2 nanoparticles

A room temperature method for the encapsulation of pyrene in SiO₂ nanoparticles is described. The relation between alkoxysilane surfactant chain length, reactant molar ratios and the uptake of dye, sample morphology, photophysical properties, and the ability of the silicate matrix to protect the encapsulated dye was examined. The synthesis can easily be adapted for the encapsulation of other hydrophobic and thermolabile substances, and used in the development of nanostructured optically active coatings, films and monoliths.