Tanujjal Bora

Enhanced visible light photocatalysis through fast crystallization of zinc oxide nanorods

Summary Hydrothermally grown ZnO nanorods have inherent crystalline defects primarily due to oxygen vacancies that enhance optical absorption in the visible spectrum, opening up possibilities for visible light photocatalysis. Comparison of photocatalytic activity of ZnO nanorods and nanoparticle films on a test contaminant methylene blue with visible light irradiation at 72 kilolux (klx) showed that ZnO nanorods are 12–24% more active than ZnO nanoparticulate films. This can be directly attributed to the increased effective surface area for adsorption of target contaminant molecules. Defects, in the form of interstitials and vacancies, were intentionally created by faster growth of the nanorods by microwave activation. Visible light photocatalytic activity was observed to improve by ≈8% attributed to the availability of more electron deficient sites on the nanorod surfaces. Engineered defect creation in nanostructured photocatalysts could be an attractive solution for visible light photocatalysis.

Photoselective excited state dynamics in ZnO-Au nanocomposites and their implications in photocatalysis and dye-sensitized solar cells.

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.

Highly efficient ZnO/Au Schottky barrier dye-sensitized solar cells: Role of gold nanoparticles on the charge-transfer process

Summary Zinc oxide (ZnO) nanorods decorated with gold (Au) nanoparticles have been synthesized and used to fabricate dye-sensitized solar cells (DSSC). The picosecond-resolved, time-correlated single-photon-count (TCSPC) spectroscopy technique was used to explore the charge-transfer mechanism in the ZnO/Au-nanocomposite DSSC. Due to the formation of the Schottky barrier at the ZnO/Au interface and the higher optical absorptions of the ZnO/Au photoelectrodes arising from the surface plasmon absorption of the Au nanoparticles, enhanced power-conversion efficiency (PCE) of 6.49% for small-area (0.1 cm2) ZnO/Au-nanocomposite DSSC was achieved compared to the 5.34% efficiency of the bare ZnO nanorod DSSC. The TCSPC studies revealed similar dynamics for the charge transfer from dye molecules to ZnO both in the presence and absence of Au nanoparticles. A slower fluorescence decay associated with the electron recombination process, observed in the presence of Au nanoparticles, confirmed the blocking of the electron transfer from ZnO back to the dye or electrolyte by the Schottky barrier formed at the ZnO/Au interface. For large area DSSC (1 cm2), ~130% enhancement in PCE (from 0.50% to 1.16%) was achieved after incorporation of the Au nanoparticles into the ZnO nanorods.

Hematoporphyrin-ZnO nanohybrids : Twin applications in efficient visible-light photocatalysis and dye-sensitized solar cells

Light-harvesting nanohybrids (LHNs) are systems composed of an inorganic nanostructure associated with an organic pigment that have been exploited to improve the light-harvesting performance over individual components. The present study is focused on developing a potential LHN, attained by the functionalization of dense arrays of ZnO nanorods (NRs) with a biologically important organic pigment hematoporphyrin (HP), which is an integral part of red blood cells (hemoglobin). Application of spectroscopic techniques, namely, Fourier transform infrared spectroscopy (FTIR) and Raman scattering, confirm successful monodentate binding of HP carboxylic groups to Zn(2+) located at the surface of ZnO NRs. Picosecond-resolved fluorescence studies on the resulting HP-ZnO nanohybrid show efficient electron migration from photoexcited HP to the host ZnO NRs. This essential photoinduced event activates the LHN under sunlight, which ultimately leads to the realization of visible-light photocatalysis (VLP) of a model contaminant Methylene Blue (MB) in aqueous solution. A control experiment in an inert gas atmosphere clearly reveals that the photocatalytic activity is influenced by the formation of reactive oxygen species (ROS) in the media. Furthermore, the stable LHNs prepared by optimized dye loading have also been used as an active layer in dye-sensitized solar cells (DSSCs). We believe these promising LHNs to find their dual applications in organic electronics and for the treatment of contaminant wastewater.

Importance of Plasmonic Heating on Visible Light Driven Photocatalysis of Gold Nanoparticle Decorated Zinc Oxide Nanorods

Herein we explore the role of localized plasmonic heat generated by resonantly excited gold (Au) NPs on visible light driven photocatalysis process. Au NPs are deposited on the surface of vertically aligned zinc oxide nanorods (ZnO NRs). The localized heat generated by Au NPs under 532 nm continuous laser excitation (SPR excitation) was experimentally probed using Raman spectroscopy by following the phonon modes of ZnO. Under the resonant excitation the temperature at the surface of the Au-ZnO NRs reaches up to about 300 °C, resulting in almost 6 times higher apparent quantum yield (AQY) for photocatalytic degradation of methylene blue (MB) compared to the bare ZnO NRs. Under solar light irradiation the Au-ZnO NRs demonstrated visible light photocatalytic activity twice that of what was achieved with bare ZnO NRs, while significantly reduced the activation energy required for the photocatalytic reactions allowing the reactions to occur at a faster rate.

Modulation of defect-mediated energy transfer from ZnO nanoparticles for the photocatalytic degradation of bilirubin

Summary In recent years, nanotechnology has gained significant interest for applications in the medical field. In this regard, a utilization of the ZnO nanoparticles for the efficient degradation of bilirubin (BR) through photocatalysis was explored. BR is a water insoluble byproduct of the heme catabolism that can cause jaundice when its excretion is impaired. The photocatalytic degradation of BR activated by ZnO nanoparticles through a non-radiative energy transfer pathway can be influenced by the surface defect-states (mainly the oxygen vacancies) of the catalyst nanoparticles. These were modulated by applying a simple annealing in an oxygen-rich atmosphere. The mechanism of the energy transfer process between the ZnO nanoparticles and the BR molecules adsorbed at the surface was studied by using steady-state and picosecond-resolved fluorescence spectroscopy. A correlation of photocatalytic degradation and time-correlated single photon counting studies revealed that the defect-engineered ZnO nanoparticles that were obtained through post-annealing treatments led to an efficient decomposition of BR molecules that was enabled by Förster resonance energy transfer.

Dynamics of light harvesting in ZnO nanoparticles

We have explored light harvesting of the complex of ZnO nanoparticles with the biological probe Oxazine 1 in the near-infrared region using picosecond-time-resolved fluorescence decay studies. We have used ZnO nanoparticles and Oxazine 1 as a model donor and acceptor, respectively, to explore the efficacy of the Förster resonance energy transfer (FRET) in the nanoparticle-dye system. It has been shown that FRET from the states localized near the surface and those in the bulk of the ZnO nanoparticles can be resolved by measuring the resonance efficiency for various wavelengths of the emission spectrum. It has been observed that the states located near the surface for the nanoparticles (contributing to visible emission at lambda approximately 550 nm) can contribute to very high efficiency (>90%) FRET. The efficiency of light harvesting dynamics of the ZnO nanorods has also been explored in this study and they were found to have much less efficiency (approximately 40%) for energy transfer compared to the nanoparticles. The possibility of an electron transfer reaction has been ruled out from the picosecond-resolved fluorescence decay of the acceptor dye at the ZnO surface.

Controlled Defects of Zinc Oxide Nanorods for Efficient Visible Light Photocatalytic Degradation of Phenol

Environmental pollution from human and industrial activities has received much attention as it adversely affects human health and bio-diversity. In this work we report efficient visible light photocatalytic degradation of phenol using supported zinc oxide (ZnO) nanorods and explore the role of surface defects in ZnO on the visible light photocatalytic activity. ZnO nanorods were synthesized on glass substrates using a microwave-assisted hydrothermal process, while the surface defect states were controlled by annealing the nanorods at various temperatures and were characterized by photoluminescence and X-ray photoelectron spectroscopy. High performance liquid chromatography (HPLC) was used for the evaluation of phenol photocatalytic degradation. ZnO nanorods with high surface defects exhibited maximum visible light photocatalytic activity, showing 50% degradation of 10 ppm phenol aqueous solution within 2.5 h, with a degradation rate almost four times higher than that of nanorods with lower surface defects. The mineralization process of phenol during degradation was also investigated, and it showed the evolution of different photocatalytic byproducts, such as benzoquinone, catechol, resorcinol and carboxylic acids, at different stages. The results from this study suggest that the presence of surface defects in ZnO nanorods is crucial for its efficient visible light photocatalytic activity, which is otherwise only active in the ultraviolet region.

Demonstration of side coupling to cladding modes through zinc oxide nanorods grown on multimode optical fiber

A novel concept is introduced that utilizes the scattering properties of zinc oxide nanorods to control light guidance and leakage inside optical fibers coated with nanorods. The effect of the hydrothermal growth conditions of the nanorods on light scattering and coupling to optical fiber are experimentally investigated. At optimum conditions, 5% of the incident light is side coupled to the cladding modes. This coupling scheme could be used in different applications such as distributed sensors and light combing. Implementation of the nanorods on fiber provides low cost and controllable nonlithography-based solutions for free space to fiber coupling. Higher coupling efficiencies can be achieved with further optimization.

One-Diode Model Equivalent Circuit Analysis for ZnO Nanorod-Based Dye-Sensitized Solar Cells: Effects of Annealing and Active Area

Electrical characteristics of 1-D zinc oxide (ZnO) nanorod-based dye-sensitized solar cells (DSSCs) were experimentally measured and followed by theoretical analysis using simple one-diode model. Defect sites (mostly oxygen vacancies) in ZnO are typically responsible for lower DSSC performance, which are removed by annealing the ZnO nanorods at high temperatures up to 450 °C. The DSSC performances with respect to the different annealing temperatures (250 °C, 350 °C, and 450°C) were determined by measuring their I-V characteristics at 1-sun irradiation (AM 1.5G). The variations in series and shunt resistances of DSSC were estimated by fitting the experimental I-V characteristics with the ideal I-V curve obtained from the one-diode equivalent model of the DSSC. By increasing annealing temperature, reduction in the series resistance Rs of the DSSCs with a subsequent increase in the shunt resistance Rsh was obtained. Annealing temperature of 350 °C was found to be optimum at which maximum DSSC performances with 1-cm2 cell active area showing minimum Rs (0.02 kΩ) with high Rsh (1.08 kΩ) values were observed. Reduction in the active area of the DSSCs from 1 to 0.25 cm2 and further to 0.1 cm2 demonstrated improved device performance with ~56% and ~24% enhancement in the fill factor and open-circuit voltage Voc, respectively, due to the reduced sheet resistance and lower recombination rate resulting low series resistance and high shunt resistance, respectively. At the optimum annealing temperature, maximum DSSC efficiency of 4.60% was obtained for the 0.1-cm2 cell active area.