No abstract

Oxygen vacancies (V O s) in ZnO are well-known to enhance photocatalytic activity (PCA) despite various other intrinsic crystal defects. In this study, we aim to elucidate the effect of zinc interstitials (Zn i ) and V O s on PCA, which has applied as well as fundamental interest. To achieve this, the major hurdle of fabricating ZnO with controlled defect density requires to be overcome, where it is acknowledged that defect level control in ZnO is significantly difficult. In the present context, we fabricated nanostructures and thoroughly characterized their morphological (SEM, TEM), structural (XRD, TEM), chemical (XPS) and optical (photoluminescence, PL) properties. To fabricate the nanostructures, we adopted atomic layer deposition (ALD), which is a powerful bottom-up approach. However, to control defects, we chose polysulfone electrospun nanofibers as a substrate on which the non-uniform adsorption of ALD precursors is inevitable because of the differences in the hydrophilic nature of the functional groups. For the first 100 cycles, Zn i s were predominant in ZnO quantum dots (QDs), while the presence of V O s was negligible. As the ALD cycle number increased, V O s were introduced, whereas the density of Zn i remained unchanged. We employed PL spectra to identify and quantify the density of each defect for all the samples. PCA was performed on all the samples, and the percent change in the decay constant for each sample was juxtaposed with the relative densities of Zn i s and V O s. A logical comparison of the relative defect densities of Zn i s and V O s suggested that the former are less efficient than the latter because of the differences in the intrinsic nature and the physical accessibility of the defects. Other reasons for the efficiency differences were elaborated.

High molecular weight polymers and high polymer concentrations are desirable for the electrospinning of nanofibers since polymer chain entanglements and overlapping are important for uniform fiber formation. Hence, the electrospinning of nanofibers from non-polymeric systems such as cyclodextrins (CDs) is quite a challenge since CDs are cyclic oligosaccharides. Nevertheless, in this study, we have successfully achieved the electrospinning of nanofibers from chemically modified CDs without using a carrier polymer matrix. Polymer-free nanofibers were electrospun from three different CD derivatives, hydroxypropyl-β-cyclodextrin (HPβCD), hydroxypropyl-γ-cyclodextrin (HPγCD) and methyl-β-cyclodextrin (MβCD) in three different solvent systems, water, dimethylformamide (DMF) and dimethylacetamide (DMAc). We observed that the electrospinning of these CDs is quite similar to polymeric systems in which the solvent type, the solution concentration and the solution conductivity are some of the key factors for obtaining uniform nanofibers. Dynamic light scattering (DLS) measurements indicated that the presence of considerable CD aggregates and the very high solution viscosity were playing a key role for attaining nanofibers from CD derivatives without the use of any polymeric carrier. The electrospinning of CD solutions containing urea yielded no fibers but only beads or splashes since urea caused a notable destruction of the self-associated CD aggregates in their concentrated solutions. The structural, thermal and mechanical characteristics of the CD nanofibers were also investigated. Although the CD derivatives are amorphous small molecules, interestingly, we observed that these electrospun CD nanofibers/nanowebs have shown some mechanical integrity by which they can be easily handled and folded as a free standing material.

Heterojunctions are a well-studied material combination in photocatalysis studies, the majority of which aim to improve the efficacy of the catalysts. Developing novel catalysts begs the question of which photo-generated charge carrier is more efficient in the process of catalysis and the associated mechanism. To address this issue we have fabricated core-shell heterojunction (CSHJ) nanofibers from ZnO and TiO 2 in two combinations where only the 'shell' part of the heterojunction is exposed to the environment to participate in the photocatalysis. Core and shell structures were fabricated via electrospinning and atomic layer deposition, respectively which were then subjected to calcination. These CSHJs were characterized and studied for photocatalytic activity (PCA). These two combinations expose electrons or holes selectively to the environment. Under suitable illumination of the ZnO-TiO 2 CSHJ, e/h pairs are created mainly in TiO 2 and the electrons take part in catalysis (i.e. reduce the organic dye) at the conduction band or oxygen vacancy sites of the 'shell', while holes migrate to the core of the structure. Conversely, holes take part in catalysis and electrons diffuse to the core in the case of a TiO 2 -ZnO CSHJ. The results further revealed that the TiO 2 -ZnO CSHJ shows $1.6 times faster PCA when compared to the ZnO-TiO 2 CSHJ because of efficient hole capture by oxygen vacancies, and the lower mobility of holes.

We produced functional nanowebs, containing vanillin, having prolonged shelf-life and high temperature stability facilitated by cyclodextrin (CD) inclusion complexation. Polyvinyl alcohol (PVA) nanowebs incorporating vanillin/cyclodextrin inclusion complex (vanillin/CD-IC) were produced via electrospinning technique. The vanillin/CD-IC was prepared with three types of CDs; α-CD, β-CD and γ-CD to find out the most favourable CD type for the stabilization of vanillin. PVA/vanillin/CD-IC nanofibres, having fibre diameters around ∼200 nm, were successfully electrospun from aqueous mixture of PVA and vanillin/CD-IC. Our results indicated that vanillin with enhanced durability and high temperature stability was achieved for PVA/vanillin/CD-IC nanowebs due to complexation of vanillin with CD, whereas the PVA nanofibres without CD-IC could not effectively preserve the vanillin. Additionally, we observed that PVA/vanillin/γ-CD-IC nanoweb was more effective for the stabilization and slow release of vanillin suggesting that the strength of interaction between vanillin and the γ-CD cavity is stronger when compared to α-CD and β-CD. © 2012 Elsevier Ltd. All rights reserved