Microorganism-Templated Nanoarchitectonics of Hollow TiO2-SiO2 Microspheres with Enhanced Photocatalytic Activity for Degradation of Methyl Orange.

In this study, hollow SiO2 microspheres were synthesized by the hydrolysis of tetraethyl orthosilicate (TEOS) according to the Stober process, in which Pichia pastoris GS 115 cells were served as biological templates. The influence of the preprocessing method, the TEOS concentration, the ratio of water to ethanol, and the aging time on the morphology of microspheres was investigated and the optimal conditions were identified. Based on this, TiO2-SiO2 microspheres were prepared by the hydrothermal process. The structures and physicochemical properties of TiO2-SiO2 photocatalysts were systematically characterized and discussed. The photocatalytic activity for the degradation of methyl orange (MO) at room temperature under Xe arc lamp acting as simulated sunlight was explored. The result showed that the as-prepared TiO2-SiO2 microspheres exhibited a good photocatalytic performance.

Photoinduced Formation of Peroxide Ions on La2O3 and Nd2O3 under O2: Effects of Excitation Wavelength and Crystal Structure.

Photoinduced formation of peroxide ions on La2O3 and Nd2O3 under O2 was studied by in-situ microprobe Raman spectroscopy with attention focused on the effect of excitation wavelength and crystal structure on the O2(2-) formation. It was found that photoexcitations at 633, 532, 514, and 325 nm can induce O2(2-) formation over La2O3 at 450 °C. By contrast, photoexcitation at 785 nm does not cause formation of O2(2-) up to 500 °C. Photoexcitation at 325 nm can induce O2(2-) formation on cubic Nd2O3 at 25 °C, but cannot induce O2(2-) formation on hexagonal Nd2O3 up to 200 °C. The significant difference in the behavior of O2(2-) formation over the Nd2O3 samples of the two structures can be related to the difference in the capacity to adsorb O2. Since the number of oxygen vacancies in cubic Nd2O3 is larger than that in the hexagonal one, the former has a higher capacity than the latter to adsorb O2. As a result, cubic Nd2O3 is more favorable to the reaction of O2 with O(2-) to generate O2(2-). The structural similarity between cubic Nd2O3 and Nd2O2(O2) may be another factor in favor of peroxide formation.

Microorganism-mediated synthesis of chemically difficult-to-synthesize Au nanohorns with excellent optical properties in the presence of hexadecyltrimethylammonium chloride.

Closely packed, size-controllable and stable Au nanohorns (AuNHs) that are difficult to synthesize through pure chemical reduction are facilely synthesized using a microorganism-mediated method in the presence of hexadecyltrimethylammonium chloride (CTAC). The results showed that the size of the as-synthesized AuNHs could be tuned by adjusting the dosage of the Pichia pastoris cells (PPCs). The initial concentrations of CTAC, ascorbic acid (AA) and tetrachloroaurate trihydrate (HAuCl4·3H2O) significantly affected the formation of the AuNHs. Increasing the diameters of AuNHs led to a red shift of the absorbance bands around 700 nm in their UV-vis-NIR spectra. Interestingly, the AuNH/PPC composites exhibited excellent Raman enhancement such that rhodamine 6G with concentration as low as (10(-9) M) could be effectively detected. The formation process of the AuNHs involved the initial binding of the Au ions onto the PPCs with subsequent reduction by AA to form supported Au nanoparticles (AuNPs) based on preferential nucleation and initial anisotropic growth on the platform of the PPCs. The anisotropic growth of these AuNPs, which was influenced by CTAC and PPCs, resulted in the formation of growing AuNHs, while the secondary nucleation beyond the PPCs produced small AuNPs that were subsequently consumed through Ostwald ripening during the aging of the AuNHs. This work exemplifies the fabrication of novel gold nanostructures and stable bio-Au nanocomposites with excellent optical properties by combining microorganisms and a surfactant.

Plant-mediated synthesis of platinum nanoparticles and its bioreductive mechanism.

Pt nanoparticles (PtNPs) were biologically synthesized by reducing Na2PtCl4 with Cacumen Platycladi Extract (CPE). The effects of reaction temperature, initial Pt(II) concentration, and CPE percentage on Pt(II) conversion and the size distribution of the PtNPs were studied. The results showed that the Pt(II) conversion rate reached 95.9% and that PtNPs measuring 2.4±0.8nm were obtained under the following conditions: reaction temperature, 90°C; CPE percentage, 70%; initial Pt(II) concentration, 0.5mM; reaction time, 25h. In addition, the bioreduction of Pt(II) was attributed to reducing sugars and flavonoids rather than proteins. The elucidation of bioreductive mechanism of Pt(II) ions was achieved by investigating the changes that occurred in the reducing sugar, flavonoid and protein concentrations in the plant extract, leading to a good insight into the formation mechanism of such biosynthesized PtNPs.

Mechanistic aspects of photo-induced formation of peroxide ions on the surface of cubic Ln2O3 (Ln = Nd, Sm, Gd) under oxygen.

The photo-induced formation of peroxide ions on the surface of cubic Ln2O3 (Ln = Nd, Sm, Gd) was studied by in situ microprobe Raman spectroscopy using a 325 nm laser as excitation source. It was found that the Raman bands of peroxide ions at 833-843 cm(-1) began to grow at the expense of the Ln(3+)-O(2-) bands at 333-359 cm(-1) when the Ln2O3 samples under O2 were continuously irradiated with a focused 325 nm laser beam at temperatures between 25-150 °C. The intensity of the peroxide Raman band was found to increase with increasing O2 partial pressure, whereas no peroxide band was detected on the Ln2O3 under N2 as well as on the samples first irradiated with laser under Ar or N2 followed by exposure to O2 in the dark. The experiments using (18)O as a tracer further confirmed that the peroxide ions are generated by a photo-induced reaction between O2 and the lattice oxygen (O(2-)) species in Ln2O3. Under the excitation of 325 nm UV light, the transformation of O2 to peroxide ions on the surface of the above lanthanide sesquioxides can even take place at room temperature. Basicity of the lattice oxygen species on Ln2O3 also has an impact on the peroxide formation. Higher temperature or laser irradiation power is required to initiate the reaction between O2 and O(2-) species of weaker basicity.