Sarina

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.

Capture of Radioactive Cesium and Iodide Ions from Water by Using Titanate Nanofibers and Nanotubes

Radioactive Cs and I ions are the products of uranium fission, and can be easily dissolved in water during an accident at a nuclear reactor, such as those that occurred at Chernobyl in 1986, at Three Mile Island in Pennsylvania in 1979, and in 2011 at Fukushima, Japan. In 2009, leaks of radioactive materials such as Cs and I isotopes also occurred during minor accidents at nuclear power stations in Britain, Germany, and the U.S. These leaks have raised concerns about exposure levels in the nearby communities because it is feared that these fission products could make their way into the food chain when present in waste water. Radioactive iodine is also used in the treatment of thyroid cancer, and, as a result, radioactive wastewater is discharged by a large number of medical research institutions. The wide use of radioisotopes requires effective methods to manage radioactive waste, and methods currently used are complex and extremely costly. Herein we demonstrate a potentially cost-effective method to remediate Cs and I ions from contaminated water by using the unique chemistry of titanate nanotubes and nanofibers, which can not only chemisorb these ions but efficiently trap them for safe disposal. Inorganic cation exchangers, such as crystalline silicotitanates, zeolites, clay minerals, layered Zr phosphates, and layered sulfide frameworks, have been studied for separation of Cs ions from nuclear wastewater and safe disposal of the exchanged cations because of the ability of these exchangers to withstand intense radiation and elevated temperatures, in addition to their high ion-exchange capacity. Because ion exchange in materials is usually a reversible process, except in micas, the radioactive ions in the exchanger may be released to water. Titanates are refractory mineral substances that are very stable with respect to radiation and chemical, thermal, and mechanical changes. Titanate nanofibers and nanotubes (with chemical formula Na2Ti3O7) can be easily synthesized at low cost under hydrothermal conditions. These materials possess a layered structure in which TiO6 octahedra are the basic structural units (Figure S1 in the Supporting Information). These layers carry negative charges and are approximately two oxygen atoms thick. Na ions are situated between the layers and can be exchanged with other cations. In the present study, we show how trititanate nanofibers (T3NF) and nanotubes (T3NT) can be used to efficiently remove radioactive Cs ions from aqueous solution by cation exchange. Figure 1a shows that the nanotubular T3NT can remove 80% of Cs ions from solutions with Cs concentrations up to 250 ppm. The ions can be completely removed when the Cs ion concentration is below 80 ppm. In contrast, the fibril T3NF has a comparatively lower absorption capacity than

Viable photocatalysts under solar-spectrum irradiation: nonplasmonic metal nanoparticles.

Supported nanoparticles (NPs) of nonplasmonic transition metals (Pd, Pt, Rh, and Ir) are widely used as thermally activated catalysts for the synthesis of important organic compounds, but little is known about their photocatalytic capabilities. We discovered that irradiation with light can significantly enhance the intrinsic catalytic performance of these metal NPs at ambient temperatures for several types of reactions. These metal NPs strongly absorb the light mainly through interband electronic transitions. The excited electrons interact with the reactant molecules on the particles to accelerate these reactions. The rate of the catalyzed reaction depends on the concentration and energy of the excited electrons, which can be increased by increasing the light intensity or by reducing the irradiation wavelength. The metal NPs can also effectively couple thermal and light energy sources to more efficiently drive chemical transformations.

Efficient photocatalytic Suzuki cross-coupling reactions on Au–Pd alloy nanoparticles under visible light irradiation

We report herein highly efficient photocatalysts comprising supported nanoparticles (NPs) of gold (Au) and palladium (Pd) alloys, which utilize visible light to catalyse the Suzuki cross-coupling reactions at ambient temperature. The alloy NPs strongly absorb visible light, energizing the conduction electrons of NPs which produce highly energetic electrons at the surface sites. The surface of the energized NPs activates the substrates and these particles exhibit good activity on a range of typical Suzuki reaction combinations. The photocatalytic efficiencies strongly depend on the Au : Pd ratio of the alloy NPs, irradiation light intensity and wavelength. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive Suzuki reactions. Results of the density functional theory (DFT) calculations indicate that transfer of the light-excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. The knowledge acquired in this study may inspire further studies of new efficient photocatalysts and a wide range of organic syntheses driven by sunlight.

Visible light enhanced oxidant free dehydrogenation of aromatic alcohols using Au–Pd alloy nanoparticle catalysts

We find that visible light irradiation of gold–palladium alloy nanoparticles supported on photocatalytically inert ZrO2 significantly enhances their catalytic activity for oxidant-free dehydrogenation of aromatic alcohols to the corresponding aldehydes at ambient temperatures. Dehydrogenation is also the dominant process in the selective oxidation of the alcohols to the corresponding aldehydes with molecular oxygen. The alloy nanoparticles strongly absorb light and exhibit superior catalytic and photocatalytic activity when compared to either pure palladium or gold nanoparticles. Analysis with a free electron gas model for the bulk alloy structure reveals that the alloying increases the surface charge heterogeneity on the alloy particle surface, which enhances the interaction between the alcohol molecules and the metal NPs. The increased surface charge heterogeneity of the alloy particles is confirmed with density function theory applied to small alloy clusters. Optimal catalytic activity was observed with a Au:Pd molar ratio of 1:186, which is in good agreement with the theoretical analysis. The rate-determining step of the dehydrogenation is hydrogen abstraction. The conduction electrons of the nanoparticles are photo-excited by the incident light giving them the necessary energy to be injected into the adsorbed alcohol molecules, promoting the hydrogen abstraction. The strong chemical adsorption of alcohol molecules facilitates this electron transfer. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive the dehydrogenation. These findings provide useful insight into the design of catalysts that utilize light for various organic syntheses at ambient temperatures.

Removal of radioactive iodine from water using Ag2O grafted titanate nanolamina as efficient adsorbent.

Emergency treatment of radioactive material leakage and safety disposal of nuclear waste is a constant concern all along with the development of radioactive materials applications. To provide a solution, titanate with large surface area (143 m(2)g(-1)) and a lamina morphology (the thickness of the lamina is in range of tens of nanometers) was prepared from inorganic titanium compounds by hydrothermal reactions at 433 K. Ag(2)O nanocrystals (5-30 nm) were deposited onto the titanate lamina. The surface of the titanate lamina has crystallographic similarity to that of Ag(2)O nanocrystals. Hence, the deposited Ag(2)O nanocrystals and titanate substrate join together at these surfaces, forming a well-matched phase coherent interface between them. Such coherence between the two phases reduces the overall energy by minimizing surface energy and anchors the Ag(2)O nanocrystals firmly on the external surface of the titanate structure. The composite thus obtained was applied as efficient adsorbent to remove radioactive iodine from water (one gram adsorbent can capture up to 3.4 mmol of I(-) anions). The composite adsorbent can be recovered easily for safe disposal. The structure changes of the titanate lamina and the composite adsorbent were monitored by various techniques. The isotherm and kinetics of iodine adsorption, competitive adsorption and column adsorption using the adsorbent were studied to assess its iodine removal abilities. The adsorbent exhibited a capacity as high as 3.4 mmol of iodine per gram of adsorbent in 1h. Therefore, Ag(2)O deposited titanate lamina is an effective adsorbent for removing radioactive iodine from water.

Tuning the Surface Structure of Nitrogen‐Doped TiO2 Nanofibres—An Effective Method to Enhance Photocatalytic Activities of Visible‐Light‐Driven Green Synthesis and Degradation

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400-700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.

Efficient removal of cationic and anionic radioactive pollutants from water using hydrotalcite-based getters

Hydrotalcite (HT)-based materials are usually applied to capture anionic pollutants in aqueous solutions. Generally considered anion exchangers, their ability to capture radioactive cations is rarely exploited. In the present work, we explored the ability of pristine and calcined HT getters to effectively capture radioactive cations (Sr(2+) and Ba(2+)) which can be securely stabilized at the getter surface. It is found that calcined HT outperforms its pristine counterpart in cation removal ability. Meanwhile, a novel anion removal mechanism targeting radioactive I(-) is demonstrated. This approach involves HT surface modification with silver species, namely, Ag2CO3 nanoparticles, which can attach firmly on HT surface by forming coherent interface. This HT-based anion getter can be further used to capture I(-) in aqueous solution. The observed I(-) uptake mechanism is distinctly different from the widely reported ion exchange mechanism of HT and much more efficient. As a result of the high local concentrations of precipitants on the getters, radioactive ions in water can be readily immobilized onto the getter surface by forming precipitates. The secured ionic pollutants can be subsequently removed from water by filtration or sedimentation for safe disposal. Overall, these stable, inexpensive getters are the materials of choice for removal of trace ionic pollutants from bulk radioactive liquids, especially during episodic environmental crisis.

Photon Energy Threshold in Direct Photocatalysis with Metal Nanoparticles: Key Evidence from the Action Spectrum of the Reaction

By investigating the action spectra (the relationship between the irradiation wavelength and apparent quantum efficiency of reactions under constant irradiance) of a number of reactions catalyzed by nanoparticles including plasmonic metals, nonplasmonic metals, and their alloys at near-ambient temperatures, we found that a photon energy threshold exists in each photocatalytic reaction; only photons with sufficient energy (e.g., higher than the energy level of the lowest unoccupied molecular orbitals) can initiate the reactions. This energy alignment (and the photon energy threshold) is determined by various factors, including the wavelength and intensity of irradiation, molecule structure, reaction temperature, and so forth. Hence, distinct action spectra were observed in the same type of reaction catalyzed by the same catalyst due to a different substituent group, a slightly changed reaction temperature. These results indicate that photon-electron excitations, instead of the photothermal effect, play a dominant role in direct photocatalysis of metal nanoparticles for many reactions.

Visible light-driven selective hydrogenation of unsaturated aromatics in an aqueous solution by direct photocatalysis of Au nanoparticles

Selective hydrogenation of various chemical bonds, such as CC, CC, CO, NO, and CN, is efficiently driven by visible light over a supported gold nanoparticle (AuNP) photocatalyst under mild reaction conditions. The reaction system exhibits high substituent tolerance and tunable selectivity by light wavelength. Density functional theory (DFT) calculations demonstrated a strong chemisorption between the reactant molecule and metal resulting in hybridized orbitals. It is proposed that direct photoexcitation between hybridized orbitals is the main driving force of the hydrogenation reaction. The hydrogenation pathway is investigated by the isotope tracking technique. We revealed the cooperation of water and formic acid (FA) as a hydrogen source and the hydrogenation route through Au–H species on the AuNP surface.