Thiolated Graphene – a New Platform for anchoring CdSe Quantum Dots for hybrid heterostructures

Effective organization of small CdSe quantum dots on graphene sheets has been achieved by a simple solution exchange with thiol terminated graphene prepared by diazonium salt chemistry. This generic methodology of CdSe nanoparticles attachment to any graphene surface has remarkable implications in designing hybrid heterostructure

What causes the forecasting failure of Markov-switching models ? A Monte Carlo study

This paper explores the forecasting abilities of Markov-Switching models. Although MS models generally display a superior in-sample fit relative to linear models, the gain in prediction remains small. We confirm this result using simulated data for a wide range of specifications. In order to explain this poor performance, we use a forecasting error decomposition. We identify four components and derive their analytical expressions in different MS specifications. The relative contribution of each source is assessed through Monte Carlo simulations. We find that the main source of error is due to the misclassification of future regimes.ou

Designing UiO-66-Based Superprotonic Conductor with the Highest Metal-Organic Framework Based Proton Conductivity

Metal−organic framework (MOF) based proton conductors have received immense importance recently. The present study endeavors to design two post synthetically modified UiO-66-based MOFs and examines the effects of their structural differences on their proton conductivity. UiO-66-NH2 is modified by reaction with sultones to prepare two homologous compounds, that is, PSM 1 and PSM 2, with SO3H functionalization in comparable extent (Zr:S = 2:1) in both. However, the pendant alkyl chain holding the −SO3H group is of different length. PSM 2 has longer alkyl chain attachment than PSM 1. This difference in the length of side arms results in a huge difference in proton conductivity of the two compounds. PSM 1 is observed to have the highest MOF-based proton conductivity (1.64 × 10−1 S cm−1 ) at 80 °C, which is comparable to commercially available Nafion, while PSM 2 shows significantly lower conductivity (4.6 × 10−3 S cm−1 ). Again, the activation energy for proton conduction is one of the lowest among all MOF-based proton conductors in the case of PSM 1, while PSM 2 requires larger activation energy (almost 3 times). This profound effect of variation of the chain length of the side arm by one carbon atom in the case of PSM 1 and PSM 2 was rather surprising and never documented before. This effect of the length of the side arm can be very useful to understand the proton conduction mechanism of MOF-based compounds and also to design better proton conductors. Besides, PSM 1 showed proton conductivity as high as 1.64 × 10−1 S cm−1 at 80 °C, which is the highest reported value to date among all MOF-based systems. The lability of the −SO3H proton of the post synthetically modified UiO-66 MOFs has theoretically been determined by molecular electrostatic potential analysis and theoretical pKa calculation of models of functional sites along with relevant NBO analyses

Photophysical and photoconductivity properties of thiol-functionalized graphene-CdSe QD composites

Graphene-semiconductor QD hybrid nanostructure materials have recently emerged as a new class of functional materials because of their potential applications in solar energy conversion, optoelectronic devices, sensing etc. Here, oleic acid-capped CdSe QDs are attached to -PhSH functionalized graphene by ligand exchange via bonding with the -SH group. The shifting of the G-band and D-band due to structural changes for the attachment of QD with graphene has been evaluated by using Raman spectroscopy. Steady state photoluminescence (PL) and time resolved fluorescence measurements have been employed to understand the electronic interactions between graphene and CdSe QDs. A time resolved fluorescence spectroscopic study has been used to understand the fluorescence dynamics of the photoexcitated CdSe QDs in the presence of graphene. It is evident that the electron transfer occurs from photoexcited QDs to graphene and the electron transfer rate is found to be 12.8 x 10(8) s(-1) for 3.8 nm CdSe QDs. Photoconductivity properties of the graphene-QD device under illumination have been examined and it is to be noted that 2-3 fold increase in the photocurrent is found in this composite device in presence of 1.5 AM solar simulated light. The enhancement of the photocurrent in this hybrid device is found to be suitable for potential applications in optoelectronic and solar cell systems