Rapid Microwave-Assisted Synthesis of CdS/Graphene/MoSx Tunable Heterojunctions and Their Application in Photocatalysis

Nanoscale two-dimensional nanostructures have shown great potential as functional components in photocatalysis. Here, investigations on the synthesis of heterostructured hybrids, comprised of 0D CdS nanoparticles as semiconductor and 2D/2D graphene/MoS_x as co-catalyst, are reported. The approach involves a rapid microwave-assisted reaction in autoclave conditions, by adopting either a one-step or a two-step protocol. The chemical speciation of the nanocomposites was found to depend strongly on the compounding conditions of the precursor substances. The photocatalytic activity was assessed by monitoring the photodegradation rate of 4-nitrophenol in solution using simulated solar light irradiation. The photocatalytic activity of the hybrids may be attributed to a combination of beneficial characteristics, strongly related to the chemical speciation of the composite components. Moreover, intimate contacts of the latter result in efficient heterojunctions. Overall, the present study provides valuable insight into the development of functional heterostructured photocatalysts comprised of two-dimensional nanomaterials.     

Signatures of Quantized Energy States in Solution‐Processed Ultrathin Layers of Metal‐Oxide Semiconductors and Their Devices

Physical phenomena such as energy quantization have to‐date been overlooked in solution‐processed inorganic semiconducting layers, owing to heterogeneity in layer thickness uniformity unlike some of their vacuum‐deposited counterparts. Recent reports of the growth of uniform, ultrathin (<5 nm) metal‐oxide semiconductors from solution, however, have potentially opened the door to such phenomena manifesting themselves. Here, a theoretical framework is developed for energy quantization in inorganic semiconductor layers with appreciable surface roughness, as compared to the mean layer thickness, and present experimental evidence of the existence of quantized energy states in spin‐cast layers of zinc oxide (ZnO). As‐grown ZnO layers are found to be remarkably continuous and uniform with controllable thicknesses in the range 2–24 nm and exhibit a characteristic widening of the energy bandgap with reducing thickness in agreement with theoretical predictions. Using sequentially spin‐cast layers of ZnO as the bulk semiconductor and quantum well materials, and gallium oxide or organic self‐assembled monolayers as the barrier materials, two terminal electronic devices are demonstrated, the current–voltage characteristics of which resemble closely those of double‐barrier resonant‐tunneling diodes. As‐fabricated all‐oxide/hybrid devices exhibit a characteristic negative‐differential conductance region with peak‐to‐valley ratios in the range 2–7.     

Highly Efficient Simulated Solar Light-Driven Photocatalytic Degradation of 4-Nitrophenol over CdS/Carbon/MoSx Hybrids

Among the various organic pollutants and industrial chemicals, 4-nitrophenol has been one of the most monitored substances in aqueous environments, due to its enhanced solubility in such systems. This research reports for the first time the microwave-assisted synthesis of CdS/carbon/MoS_x hybrids and the subsequent utilization of such systems as photocatalysts for 4-nitrophenol degradation. The hybrids demonstrated a variable photocatalytic activity, by using a variety of organic substances as precursors for the solvothermal carbonization step. By using ascorbic acid as precursor, the corresponding ternary composite exhibited excellent photocatalytic activity, with the 4-nitrophenol concentration been almost quantitatively decayed within 45 min of irradiation. This could be ascribed due to the generation of a high population of heterojunctions as well as the chemical speciation of Mo-based nanostructures. Such ternary hybrids may be utilized as potential photocatalytic systems in processes, where removal of toxic water-soluble substances is the key issue.     

Assessment of Novel Long‐Lasting Ceria‐Stabilized Zirconia‐Based Ceramics with Different Surface Topographies as Implant Materials

The development of long‐lasting zirconia‐based ceramics for implants, which are not prone to hydrothermal aging, is not satisfactorily solved. Therefore, this study is conceived as an overall evaluation screening of novel ceria‐stabilized zirconia–alumina–aluminate composite ceramics (ZA₈Sr₈‐Ce11) with different surface topographies for use in clinical applications. Ceria‐stabilized zirconia is chosen as the matrix for the composite material, due to its lower susceptibility to aging than yttria‐stabilized zirconia (3Y‐TZP). This assessment is carried out on three preclinical investigation levels, indicating an overall biocompatibility of ceria‐stabilized zirconia‐based ceramics, both in vitro and in vivo. Long‐term attachment and mineralized extracellular matrix (ECM) deposition of primary osteoblasts are the most distinct on porous ZA₈Sr₈‐Ce11_p surfaces, while ECM attachment on 3Y‐TZP and ZA₈Sr₈‐Ce11 with compact surface texture is poor. In this regard, the animal study confirms the porous ZA₈Sr₈‐Ce11_p to be the most favorable material, showing the highest bone‐to‐implant contact values and implant stability post implantation in comparison with control groups. Moreover, the microbiological evaluation reveals no favoritism of biofilm formation on the porous ZA₈Sr₈‐Ce11_p when compared to a smooth control surface. Hence, together with the in vitro in vivo assessment analogy, the promising clinical potential of this novel ZA₈Sr₈‐Ce11 as an implant material is demonstrated.     

Data envelopment analysis with nonlinear virtual inputs and outputs

An underlying assumption in DEA is that the weights coupled with the ratio scales of the inputs and outputs imply linear value functions. In this paper, we present a general modeling approach to deal with outputs and/or inputs that are characterized by nonlinear value functions. To this end, we represent the nonlinear virtual outputs and/or inputs in a piece-wise linear fashion. We give the CCR model that can assess the efficiency of the units in the presence of nonlinear virtual inputs and outputs. Further, we extend the models with the assurance region approach to deal with concave output and convex input value functions. Actually, our formulations indicate a transformation of the original data set to an augmented data set where standard DEA models can then be applied, remaining thus in the grounds of the standard DEA methodology. To underline the usefulness of such a new development, we revisit a previous work of one of the authors dealing with the assessment of the human development index on the light of DEA.