In this work, we have successfully synthesized a bimetallic (Zinc and Cobalt) Zeolitic Imidazolate Framework (Zn50Co50-ZIF), a class in a wider microporous Metal-Organic Framework (MOF) family. The synthesized nanostructures maintain both water stability like ZIF-8 (solely Zn containing) and charge transfer electronic band in the visible optical spectrum as ZIF-67 (solely Co containing). Crystal structure from XRD, high resolution transmission electron microscopy (HRTEM) followed by elemental mapping (EDAX) confirm structural stability and omnipresence of the metal atoms (Zn and Co) across the nanomaterial with equal proportion. Existence of charge transfer state consistent with ZIF67 and intact ultrafast excited state dynamics of the imidazolate moiety in both ZIF-8 and ZIF-67, is evidenced from steady state and time resolved optical spectroscopy. The thermal and aqueous stabilities of Zn50Co50-ZIF are found to be better than ZIF-67 but comparable to ZIF-8 as evidenced by solubility, scanning electron microscopy (SEM) and XRD studies of the material in water. We have evaluated the photoinduced ROS generation by the mixed ZIF employing dichloro-dihydro-fluorescein diacetate (DCFH-DA) assay. We have also explored the potentiality of the synthesized material for the alternate remediation of methicillin resistant Staphylococcus aureus (MRSA) infection through the photoinduced reactive oxygen species (ROS) generation and methylene blue (MB) degradation kinetics.
Energy harvesting from solar light employing nanostructured materials offer an economic way to resolve energy and environmental issues. We have developed an efficient light harvesting heterostructure based on poly(diphenylbutadiyne) (PDPB) nanofibers and ZnO nanoparticles (NPs)viaa solution phase synthetic route. ZnO NPs (~20 nm) were homogeneously loaded onto the PDPB nanofibers as evident from several analytical and spectroscopic techniques. The photoinduced electron transfer from PDPB nanofibers to ZnO NPs has been confirmed by steady state and picosecond-resolved photoluminescence studies. The co-sensitization for multiple photon harvesting (with different energies) at the heterojunction has been achievedviaa systematic extension of conjugation from monomeric to polymeric diphenyl butadiyne moiety in the proximity of the ZnO NPs. On the other hand, energy transfer from the surface defects of ZnO NPs (~5 nm) to PDPB nanofibers through Förster Resonance Energy Transfer (FRET) confirms the close proximity with molecular resolution. The manifestation of efficient charge separation has been realized with ~5 fold increase in photocatalytic degradation of organic pollutants in comparison to polymer nanofibers counterpart under visible light irradiation. Our results provide a novel approach for the development of nanoheterojunctions for efficient light harvesting which will be helpful in designing future solar devices.
9 June 2011 in Physical Chemistry Chemical Physics
Improving the performance of photoactive solid-state devices begins with systematic studies of the metal–semiconductor nanocomposites (NCs) upon which such devices are based. Here, we report the photo-dependent excitonic mechanism and the charge migration kinetics in a colloidal ZnO–Au NC system. By using a picosecond-resolved Förster resonance energy transfer (FRET) technique, we have demonstrated that excited ZnO nanoparticles (NPs) resonantly transfer visible optical radiation to the Au NPs, and the quenching of defect-mediated visible emission depends solely on the excitation level of the semiconductor. The role of the gold layer in promoting photolytic charge transfer, the activity of which is dependent upon the degree of excitation, was probed using methylene blue (MB) reduction at the semiconductor interface. Incident photon-to-current efficiency measurements show improved charge injection from a sensitizing dye to a semiconductor electrode in the presence of gold in the visible region. Furthermore, the short-circuit current density and the energy conversion efficiency of the ZnO–Au NP based dye-sensitized solar cell (DSSC) are much higher than those of a DSSC comprised of only ZnO NP. Our results represent a new paradigm for understanding the mechanism of defect-state passivation and photolytic activity of the metal component in metal–semiconductor nanocomposite systems.