Photocatalytic performance of ZnO:Fe array films under sunlight irradiation

ZnO:Fe array thin films were prepared by the hydrothermal method using the sol-gel grown film as a seed layer. The samples were characterized by X-ray diffraction (XRD), ultraviolet/visible absorption spectra (UV-vis) and scanning electron microscopy (SEM). The photocatalytic activities of the prepared samples were investigated for the photodegradation of methylene blue (MB) under sunlight irradiation. The results show that the lattice constant a and the cell volume of ZnO:Fe film increase due to the substitution of Fe for Zn. The absorption edge of Fe-doped ZnO displays a red shift with a significant absorption between 600 and 700 nm. The ZnO:Fe array film is composed of disk particles with uniformity and compactness. Doping Fe ions enhances the photodegradation rate of ZnO array film for MB. 1.5% Fe doped ZnO sample exhibits the highest activity under irradiation time of 4 h. Its degradation rate increases about 1.6 times compared to the undoped ZnO.     

Upconversion in Highly Doped Er3+-Yb3+ Fiber Pumped by Ti:Sapphire Laser at 800 nm

The up-conversion processes were investigated in highly doped Er3+-Yb3+ silica fiber pumped by CW or mode-locked Ti:Sapphire laser at 800 nm band. The mechanism is different from that at 980 nm pumped band. The pumping wavelength and power dependences of green, blue and red fluorescence emission were obtained. The up-conversion efficiencies of different doped concentration were investigated. The strong infrared emissions, which limit the efficiency of up-conversion were observed.     

Facile Synthesis of Mg2+‐Doped Carbon Dots as Novel Biomaterial Inducing Cell Osteoblastic Differentiation

Carbon dots (CDs), as an emerging fluorescent nanomaterial with low toxicity, has been widely applied in various bio‐related fields. However, investigations on their capabilities in guiding osteogenic differentiation are rarely seen, which has great significance in osteoporosis therapy and bone regeneration. Herein, for the first time, a new kind of Mg²⁺‐doped CDs is facilely synthesized through a one‐step hydrothermal method from metal gluconate salts. The CDs can serve as nanocarrier of Mg²⁺ ions entering into cells, and the bioessential metal ions subsequently stimulate osteoblastic differentiation by improving alkaline phosphatase (ALP) activity and upregulation related mRNA expression. Noteworthy, the raw material has almost negligible performance on osteoblastic differentiation compared to Mg‐CDs, which is due to the ultrasmall sizes of CDs and the efficient uptake by cells. Moreover, benefitting from the fluorescence properties, Mg‐CDs can also be applied as cell labeling agents. This work proposes a new strategy to synthesize multifunctional metal ion‐doped CDs, which might had great potential in serving as promising nanodrugs for bone loss therapy.     

Kβ X-Ray Emission Spectroscopic Study of a Second-Row Transition Metal (Mo) and Its Application to Nitrogenase-Related Model Complexes

In recent years, X-ray emission spectroscopy (XES) in the Kβ (3p-1s) and valence-to-core (valence-1s) regions has been increasingly used to study metal active sites in (bio)inorganic chemistry and catalysis, providing information about the metal spin state, oxidation state and the identity of coordinated ligands. However, to date this technique has been limited almost exclusively to first-row transition metals. In this work, we present an extension of Kβ XES (in both the 4p-1s and valence-to-1s [or VtC] regions) to the second transition row by performing a detailed experimental and theoretical analysis of the molybdenum emission lines. It is demonstrated in this work that Kβ₂ lines are dominated by spin state effects, while VtC XES of a 4d transition metal provides access to metal oxidation state and ligand identity. An extension of Mo Kβ XES to nitrogenase-relevant model complexes shows that the method is sufficiently sensitive to act as a spectator probe for redox events that are localized at the Fe atoms. Mo VtC XES thus has promise for future applications to nitrogenase, as well as a range of other Mo-containing biological cofactors. Further, the clear assignment of the origins of Mo VtC XES features opens up the possibility of applying this method to a wide range of second-row transition metals, thus providing chemists with a site-specific tool for the elucidation of 4d transition metal electronic structure.     

Polyethylene Terephthalate Deconstruction Catalyzed by a Carbon-Supported Single-Site Molybdenum-Dioxo Complex

Polyethylene terephthalate (PET) is selectively depolymerized by a carbon-supported single-site molybdenum-dioxo catalyst to terephthalic acid (PTA) and ethylene. The solventless reactions are most efficient under 1 atmosphere of H₂. The catalyst exhibits high stability and can be recycled multiple times without loss of activity. Waste beverage bottle PET or a PET + polypropylene (PP) mixture (simulating the bottle + cap) proceeds at 260 °C with complete PET deconstruction and quantitative PTA isolation. Mechanistic studies with a model diester, 1,2-ethanediol dibenzoate, suggest the reaction proceeds by initial retro-hydroalkoxylation/β-C−O scission and subsequent hydrogenolysis of the vinyl benzoate intermediate.     

Effects of composition on catalytic activities of molybdenum doped platinum nanoparticles

The physical and chemical properties of bimetallic nanoparticles can be optimized by tuning the particle composition. In this study, we identified CO adsorption and dissociation energetics on five Pt-Mo nanoparticles at different concentrations, the lowest energy Pt₇, Pt₆Mo, Pt₅Mo₂, Pt₄Mo₃, and Mo₇ clusters. We have shown that the CO adsorption and dissociation energies and preferred CO adsorption sites are largely dependent on the composition of the nanoparticles. As the Mo concentration increases, the strength of the C-O internal bond in the adsorption complex decreases, as indicated by a decrease in the C-O stretching frequency. Also, more Mo sites in the nanoparticle become available for CO adsorption, and the preferred CO adsorption site switches from Pt to Mo. For these reasons, dissociation of CO is energetically favorable on Pt₄Mo₃ and Mo₇. On both compositions, we have shown that the dissociation paths begin with CO adsorbed on a Mo site in a multifold configuration, in particular in a tilted configuration. These findings provide insight on the effects of the composition on the chemical and catalytical properties of Pt-Mo nanoparticles, thereby guiding future experiments on the synthesis of nanoparticles, especially those that may be suitable for various desired applications containing CO.     

Water stability of cobalt doped ZIF-8: a quantitative study using optical analyses

Zeolitic imidazolate frameworks (ZIFs), in particular ZIF-8 (made of Zn²⁺ and 2-methyilimidazolate) and cobalt-doped-ZIF-8, are found important for many energy and environmental applications. It was reported that ZIFs show excellent structural stability in water and thus ideal for aqueous applications. However, recent studies also found some evidence that ZIF-8 undergoes hydrolysis in water. Despite the importance of ZIF's stability in many aqueous applications, the extent of ZIFs' degradation in water is still not yet fully understood. In this study, we report a quantitative study of the water stability of 0–100 at% cobalt-doped ZIF-8, using a new combination of analytical tools. The study demonstrated the importance of analyzing both filtered powders and the filtrate liquid systematically, in particular by using UV–Vis spectroscopy and thermogravimetric analysis. The combination of analytical tools allowed the study on the effects of ZIF concentrations in water, cobalt doping levels, and amounts of ligands in water on the water stability of ZIF samples. The effect of cobalt-doping was investigated by using ZIF particles with identical sizes (200–400 nm), in order to eliminate the effects of particle size on hydrolysis. Unlike other synthesis methods, a mechanochemical ball milling method allowed the production of nano-scale ZIF-8 particles with similar sizes, independent of cobalt-doping levels. The proposed combination of analytical tools including UV–Vis spectroscopy can be applied to the study of the water stability of other MOF materials.     

Design of Broadband L-band Erbium Doped Fiber Amplifier

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后腔镜对掺Yb3+双包层光纤激光器性能影响的研究

采用自行研制的内包层为矩形的掺Yb^3 双包层石英光纤，以透射率不同的一组二向色镜为后腔镜构成了双包层光纤激光器。实验证明：后腔镜具有较高透射率为佳；后腔镜可以实现对激光波长的控制；激光斜率效率与后腔镜透射率之间的关系符合指数变化规律，在本实验的条件下，斜率效率的最大值约60％。     

掺铒光纤激光器中自脉冲的控制

在实验中观察到了掺铒光纤激光器中自脉冲，并通过加反馈的方法控制了自脉冲。在理论上利用带反馈的两激光器的耦合模型，成功地解释了自脉冲的产生及其控制的物理机制。结果表明，掺铒光纤激光器中两正交偏振态的反馈及其耦合对光脉冲的形成及控制的重要性。