Reduction of nitroaromatic compounds on supported gold nanoparticles by visible and ultraviolet light

Shedding light: Nitroaromatic compounds on gold nanoparticles (3 wt %) supported on ZrO2 can be reduced directly to the corresponding azo compounds when illuminated with visible light or ultraviolet light at 40 °C (see picture). The process occurs with high selectivity and at ambient temperature and pressure, and enables the selection of intermediates that are unstable in thermal reactions.

Room temperature synthesis of Mn2+ doped ZnS d-dots and observation of tunable dual emission: Effects of doping concentration, temperature, and ultraviolet light illumination

Mn2+ doped (0-50.0 molar %) ZnS d-dots have been synthesized in water medium by using an environment friendly low cost chemical technique. Tunable dual emission in UV and yellow-orange regions is achieved by tailoring the Mn2+ doping concentration in the host ZnS nanocrystal. The optimum doping concentration for achieving efficient photoluminescence (PL) emission is determined to be similar to 1.10 (at. %) corresponding to 40.0 (molar %) of Mn2+ doping concentration used during synthesis. The mechanism of charge transfer from the host to the dopant leading to the intensity modulated tunable (594-610 nm) yellow-orange PL emission is straightforwardly understood as no capping agent is used. The temperature dependent PL emission measurements are carried out, viz., in 1.10 at. % Mn2+ doped sample and the experimental results are explained by using a theoretical PL emission model. It is found that the ratio of non-radiative to radiative recombination rates is temperature dependent and this phenomenon has not been reported, so far, in Mn2+ doped ZnS system. The colour tuning of the emitted light from the samples are evident from the calculated chromaticity coordinates. UV light irradiation for 150 min in 40.0 (molar %) Mn2+ doped sample shows an enhancement of 33% in PL emission intensity. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4795779]

Multiwavelength visible and white light generation by upconversion emission in Ho/Tm/Yb triply doped fluorogermanate glass-ceramic

Energy transfer excited multiwavelength visible upconversion emission and white light generation is described in a single sample of PbGeO(3)-PbF(2)-CdF(2) glass-ceramic triply doped With Ho/Tm/Yb under single infrared laser excitation. Blue (475 nm), green (540 mn), and red (650 nm), upconversion luminescence signals are generated, and the emissions are assigned, respectively, to thulium ((1)G(4)-(3)H(6)), and holmium ((5)S(2);(5)F(4)) -> (5)I(8), (5)F(5) -> (5)I(8)) ions transitions, both excited via successive energy transfers from ytterbium ions. It is experimentally shown that with a proper combination of the rare earth ions contents, white light may be produced, with the simultaneous generation of fluorescence with controllable intensities at the wavelengths of the three primary colours in a single sample and using a single near-infrared excitation source.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation

Studies of the optical properties and catalytic capabilities of noble metal nanoparticles (NPs), such as gold (Au) and silver (Ag), have formed the basis for the very recent fast expansion of the field of green photocatalysis: photocatalysis utilizing visible and ultraviolet light, a major part of the solar spectrum. The reason for this growth is the recognition that the localised surface plasmon resonance (LSPR) effect of Au NPs and Ag NPs can couple the light flux to the conduction electrons of metal NPs, and the excited electrons and enhanced electric fields in close proximity to the NPs can contribute to converting the solar energy to chemical energy by photon-driven photocatalytic reactions. Previously the LSPR effect of noble metal NPs was utilized almost exclusively to improve the performance of semiconductor photocatalysts (for example, TiO2 and Ag halides), but recently, a conceptual breakthrough was made: studies on light driven reactions catalysed by NPs of Au or Ag on photocatalytically inactive supports (insulating solids with a very wide band gap) have demonstrated that these materials are a class of efficient photocatalysts working by mechanisms distinct from those of semiconducting photocatalysts. There are several reasons for the significant photocatalytic activity of Au and Ag NPs. (1) The conduction electrons of the particles gain the irradiation energy, resulting in high energy electrons at the NP surface which is desirable for activating molecules on the particles for chemical reactions. (2) In such a photocatalysis system, both light harvesting and the catalysing reaction take place on the nanoparticle, and so charge transfer between the NPs and support is not a prerequisite. (3) The density of the conduction electrons at the NP surface is much higher than that at the surface of any semiconductor, and these electrons can drive the reactions on the catalysts. (4) The metal NPs have much better affinity than semiconductors to many reactants, especially organic molecules. Recent progress in photocatalysis using Au and Ag NPs on insulator supports is reviewed. We focus on the mechanism differences between insulator and semiconductor-supported Au and Ag NPs when applied in photocatalytic processes, and the influence of important factors, light intensity and wavelength, in particular estimations of light irradiation contribution, by calculating the apparent activation energies of photo reactions and thermal reactions.

Noble metal photocatalysts under visible light and UV light irradiation

One of the greatest challenges for the study of photocatalysts is to devise new catalysts that possess high activity under visible light illumination. This would allow the use of an abundant and green energy source, sunlight, to drive chemical reactions. Gold nanoparticles strongly absorb both visible light and UV light. It is therefore possible to drive chemical reactions utilising a significant fraction of full sunlight spectrum. Here we prepared gold nanoparticles supported on various oxide powders, and reported a new finding that gold nanoparticles on oxide supports exhibit significant activity for the oxidation of formaldehyde and methanol in the air at ambient temperature, when illuminated with visible light. We suggested that visible light can greatly enhance local electromagnetic fields and heat gold nanoparticles due to surface plasmon resonance effect which provides activation energy for the oxidation of organic molecules. Moreover, the nature of the oxide support has an important influence on the activity of the gold nanoparticles. The finding reveals the possibility to drive chemical reactions with sunlight on gold nanoparticles at ambient temperature, highlighting a new direction for research on visible light photocatalysts. Gold nanoparticles supported on oxides also exhibit significant dye oxidation activity under visible light irradiation in aqueous solution at ambient temperature. Turnover frequencies of the supported gold nanoparticles for the dye degradation are much higher than titania based photocatalysts under both visible and UV light. These gold photocatalysts can also catalyse phenol degradation as well as selective oxidation of benzyl alcohol under UV light. The reaction mechanism for these photocatalytic oxidations was studied. Gold nanoparticles exhibit photocatalytic activity due to visible light heating gold electrons in 6sp band, while the UV absorption results in electron holes in gold 5d band to oxidise organic molecules. Silver nanoparticles also exhibit considerable visible light and UV light absorption due to surface plasmon resonance effect and the interband transition of 4d electrons to the 5sp band, respectively. Therefore, silver nanoparticles are potentially photocatalysts that utilise the solar spectrum effectively. Here we reported that silver nanoparticles at room temperature can be used to drive chemical reactions when illuminated with light throughout the solar spectrum. The significant activities for dye degradation by silver nanoparticles on oxide supports are even better than those by semiconductor photocatalysts. Moreover, silver photocatalysts also can degrade phenol and drive the oxidation of benzyl alcohol to benzaldehyde under UV light. We suggested that surface plasmon resonance effect and interband transition of silver nanoparticles can activate organic molecule oxidations under light illumination.

Minimal levels of ultraviolet light enhance the toxicity of TiO2 nanoparticles to two representative organisms of aquatic systems

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Metal nanoparticle photocatalysts: Emerging processes for green organic synthesis

Metal nanoparticle photocatalysts have attracted recent interest due to their strong absorption of visible and ultraviolet light. The energy absorbed by the metal conduction electrons and the intense electric fields in close proximity, created by the localized surface plasmon resonance effect, makes the crucial contribution of activating the molecules on the metal nanoparticles which facilitates chemical transformation. There are now many examples of successful reactions catalyzed by supported nanoparticles of pure metals and of metal alloys driven by light at ambient or moderate temperatures. These examples demonstrate these materials are a novel group of efficient photocatalysts for converting solar energy to chemical energy and that the mechanisms are distinct from those of semiconductor photocatalysts. We present here an overview of recent research on direct photocatalysis of supported metal nanoparticles for organic synthesis under light irradiation and discuss the significant reaction mechanisms that occur through light irradiation.

Toxicity assessment of TiO2 nanoparticles in zebrafish embryos under different exposure conditions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fotocatálise heterogênea de enterococcus faecalis e pseudomonas aeruginosa desencadeada pela ação da luz UV e branca em espátulas com revestimento de nanopartículas TiO2 e Ag

Nanotechnology, the science of minuscule, has developed products which are able t o manipulate atoms and molecules that could be applied in the sterilization process of dental instruments. Objetives: The objective of the present study was to evaluate the self-cleaning action of TiO2 and Ag nanoparticles coating on dental instruments by the photocataliys process under UV and visible light irradiation. Material and method: Microbiologic tests were done using dental cement spatulas coated with TiO2 and Ag nanoparticles (one or three layers), and contaminated with 10 mcrl of Pseudomonas aeruginosa and Enterococcus faecalis, respectively. After contamination, they were exposed to ultraviolet light and visible light for 120 minutes. Next, they were transferred to and stored in test tubes with BHI (Brain Heart Infusion) and incubated in 35 to 37 °C. Checking times for bacterial growth and for control and retrieval tests were done at: 24, 48, 72 and 96 hours. Result: The Pseudomonas aeruginosa was inactive after 120 minutes of ultraviolet light irradiation, thus confirming the heterogeneous photocatalytic activity of TiO2 and Ag. The Pseudomonas aeruginosa was not inactivated under visible light irradiation and the Enterococcus faecalis was not inactivated under UV and visible light irradiation of the dental cement spatulas coated with TiO2 and Ag nanoparticles in the readings to 96 hours, showing bacterial growth. Conclusion: There were no influence of one or three layers of TiO2 and Ag nanoparticles coating of the spatulas in the results. The heterogeneous photocatalysis activity of TiO2 and Ag under UV light irradiation was confirmed for Pseudomonas aeruginosa but not under visible light. Enterococcus faecalis did not confirmed the photocatalytics activity of TiO2 and Ag under UV light irradiation and visible lights irradiation.

Electrically Tunable Selective Reflection of Light from Ultraviolet to Visible and Infrared by Heliconical Cholesterics

Acknowledgements This work was supported by NSF DMR-1410378 and DMR-1121288. We thank V. Borshch for helping with preparation of illustrations, to Y. K. Kim for the help in experiments, V. A. Belyakov and S. V. Shiyanovskii for useful discussions.

Assessment of daily light and ultraviolet exposure in young adults

Purpose: There are some limited reports, based on questionnaire data, which suggest that outdoor activity decreases the risk of myopia in children and may offset the myopia risk associated with prolonged near work. The aim of this study was to explore the relationship between near work, indoor illumination, daily sunlight and ultraviolet (UV) exposure in emmetropic and myopic University students, given that University students perform significant amounts of near work and as a group have a high prevalence of myopia. Methods: Participants were 35 students, aged 17 to 25 years who were classified as being emmetropic (n=13), or having stable (n=12) or progressing myopia (n=10). During waking hours on three separate days participants wore a light sensor data logger (HOBO) and a polysulphone UV dosimeter; these devices measured daily illuminance and accumulative UV exposure respectively; participants also completed a daily activity log. Results: No significant between group differences were observed for average daily illuminance (p=0.732), number of hours per day spent in sunlight (p=0.266), outdoor shade (p=0.726), bright indoor/dim outdoor light (p=0.574) or dim room illumination (p=0.484). Daily UV exposure was significantly different across the groups (p=0.003); with stable myopes experiencing the greatest UV exposure (versus emmetropes p=0.002; versus progressing myopes p=0.004). Conclusions: The current literature suggests there is a link between myopia protection and spending time outdoors in children. Our data provides some evidence of this relationship in young adults and highlights the need for larger studies to further investigate this relationship longitudinally.

Perception of ultraviolet light by crab spiders and its role in selection of hunting sites

The perception of ultraviolet (UV) light by spiders has so far been only demonstrated in salticids. Crab spiders (Thomisidae) hunt mostly on flowers and need to find appropriate hunting sites. Previous studies have shown that some crab spiders that reflect UV light use UV contrast to enhance prey capture. The high UV contrast can be obtained either by modulation of body colouration or active selection of appropriate backgrounds for foraging. We show that crab spiders (Thomisus sp.)hunting on Spathiphyllum plants use chromatic contrast, especially UV contrast, to make themselves attractive to hymenopteran prey. Apart from that, they are able to achieve high UV contrast by active selection of non-UV reflecting surfaces when given a choice of UV-reflecting and non-UV reflecting surfaces in the absence of odour cues. Honeybees (Apis cerana) approached Spathiphyllum plants bearing crab spiders on which the spiders were high UV-contrast targets with greater frequency than those plants on which the UV-contrast of the spiders was low. Thus, crab spiders can perceive UV and may use it to choose appropriate backgrounds to enhance prey capture, by exploiting the attraction of prey such as honeybees to UV.

Synthesis and characterization of carbon-covered alumina (CCA) supported TiO2 nanocatalysts with enhanced visible light photodegradation of Rhodamine B

The anatase phase of titania (TiO2) nano-photocatalysts was prepared using a modified sol gel process and thereafter embedded on carbon-covered alumina supports. The carbon-covered alumina (CCA) supports were prepared via the adsorption of toluene 2,4-diisocyanate (TDI) on the surface of the alumina. TDI was used as the carbon source for the first time for the carbon-covered alumina support system. The adsorption of TDI on alumina is irreversible; hence, the resulting organic moiety can undergo pyrolysis at high temperatures resulting in the formation of a carbon coating on the surface of the alumina. The TiO2 catalysts were impregnated on the CCA supports. X-ray diffraction analysis indicated that the carbon deposited on the alumina was not crystalline and also showed the successful impregnation of TiO2 on the CCA supports. In the Raman spectra, it could be deduced that the carbon was rather a conjugated olefinic or polycyclic hydrocarbons which can be considered as molecular units of a graphitic plane. The Raman analysis of the catalysed CCAs showed the presence of both the anatase titania and D and G band associated with the carbon of the CCAs. The scanning electron microscope micrographs indicated that the alumina was coated by a carbon layer and the energy dispersive X-ray spectra showed the presence of Al, O and C in the CCA samples, with the addition of Ti for the catalyst impregnated supports. The Brunauer Emmet and Teller surface area analysis showed that the incorporating of carbon on the alumina surface resulted in an increase in surface area, while the impregnation with TiO2 resulted in a further increase in surface area. However, a decrease in the pore volume and diameter was observed. The photocatalytic activity of the nanocatalysts was studied for the degradation of Rhodamine B dye. The CCA-TiO2 nanocatalysts were found to be more photocatalytically active under both visible and UV light irradiation compared to the free TIO2 nanocatalysts.