Recent nanotechnological advances suggest that metal oxide nanoparticles (NPs) have been expected to be used in various fields, ranging from catalysis and opto-electronic materials to sensors, environmental remediation, and biomedicine. However, the growing use of NPs has led to their release into environment and the toxicity of metal oxide NPs on organisms has become a concern to both the public and scientists. Unfortunately, there are still widespread controversies and ambiguities with respect to the toxic effects and mechanisms of metal oxide NPs. Comprehensive understanding of their toxic effect is necessary to safely expand their use. In this review, we use CuO and ZnO NPs as examples to discuss how key factors such as size, surface characteristics, dissolution, and exposure routes mediate toxic effects, and we describe corresponding mechanisms, including oxidative stress, coordination effects and non-homeostasis effects.
Carbon nanofibers/silver nanoparticles (CNFs/AgNPs) composite nanofibers were fabricated by two steps consisting of the preparation of the CNFs by electrospinning and the hydrothermal growth of the AgNPs on the CNFs. The as-prepared nanofibers were characterized by scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, X-ray diffraction, resonant Raman spectra, thermal gravimetric and differential thermal analysis, and X-ray photoelectron spectroscopy, respectively. The results indicated that not only were AgNPs (25-50 nm) successfully grown on the CNFs but also the AgNPs were distributed without aggregation on the CNFs. Further more, by adjusting the parameters in hydrothermal processing, the content of silver supported on the CNFs could be easily controlled. The catalytic activities of the CNFs/AgNPs composite nanofibers to the reduction of 4-nitrophenol (4-NP) with NaBH(4) were tracked by UV-visible spectroscopy. It was suggested that the CNFs/AgNPs composite nanofibers exhibited high catalytic activity in the reduction of 4-NP, which might be attributed to the high surface areas of AgNPs and synergistic effect on delivery of electrons between CNFs and AgNPs. And, the catalytic efficiency was enhanced with the increasing of the content of silver on the CNFs/AgNPs composite nanofibers. Notably, the CNFs/AgNPs composite nanofibers could be easily recycled due to their one-dimensional nanostructural property.
One-dimensional electrospun nanofibers of p-type NiO/n-type ZnO heterojunctions with different molar ratios of Ni to Zn were successfully synthesized using a facile electrospinning technique. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance (DR) spectroscopy, resonant Raman spectroscopy, photoluminescence (PL) spectroscopy, and surface photovoltage spectroscopy (SPS) were used to characterize the as-synthesized nanofibers. The results indicated that the p-n heterojunctions formed between the cubic structure NiO and hexangular structure ZnO in the NiO/ZnO nanofibers. Furthermore, the photocatalytic activity of the as-electrospun NiO/ZnO nanofibers for the degradation of rhodamine B (RB) was much higher than that of electrospun NiO and ZnO nanofibers, which could be ascribed to the formation of p-n heterojunctions in the NiO/ZnO nanofibers. In particular, the p-type NiO/n-type ZnO heterojunction nanofibers with the original Ni/Zn molar ratio of 1 exhibited the best catalytic activity, which might be attributed to their high separation efficiency of photogenerated electrons and holes. Notably, the electrospun nanofibers of p-type NiO/n-type ZnO heterojunctions could be easily recycled without a decrease of the photocatalytic activity due to their one-dimensional nanostructural property.
Ultrabroad-spectrum absorption and highly efficient generation of available charge carriers are two essential requirements for promising semiconductor-based photocatalysts, towards achieving the ultimate goal of solar-to-fuel conversion. Here, a fascinating nonmetal plasmonic Z-scheme photocatalyst with the W O /g-C N heterostructure is reported, which can effectively harvest photon energies spanning from the UV to the nearinfrared region and simultaneously possesses improved charge-carrier dynamics to boost the generation of long-lived active electrons for the photocatalytic reduction of protons into H . By combining with theoretical simulations, a unique synergistic photocatalysis effect between the semiconductive Z-scheme charge-carrier separation and metal-like localized-surface-plasmon-resonance-induced "hot electrons" injection process is demonstrated within this binary heterostructure.
One-dimensional ZnO-carbon nanofibers (CNFs) heteroarchitectures with high photocatalytic activity have been successfully obtained by a simple combination of electrospinning technique and hydrothermal process. The as-obtained products were characterized by field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and IR spectrum. The results revealed that the secondary ZnO nanostructures were successfully grown on the primary CNFs substrates without aggregation. And, the coverage density of ZnO nanoparticles coating on the surface of the CNFs could be controlled by simply adjusting the mass ratio of zinc acetate to CNFs in the precursor during the hydrothermal process for the fabrication of ZnO-CNFs heterostructures. The obtained ZnO-CNFs heteroarchitectures showed high photocatalytic property to degrade rhodamine B (RB) because of the formation of heteroarchitectures, which might improve the separation of photogenerated electrons and holes. Moreover, the ZnO-CNFs heteroarchitectures could be easily recycled without the decrease in photocatalytic activity due to their one-dimensional nanostructural property.
The present paper studies the large-j asymptotics of the Lorentzian EPRL spinfoam amplitude on a 4d simplicial complex with an arbitrary number of simplices. The asymptotics of the spinfoam amplitude is determined by the critical configurations. Here we show that, given a critical configuration in general, there exists a partition of the simplicial complex into three type of regions R Nondeg , R Deg-A , R Deg-B , where the three regions are simplicial subcomplexes with boundaries. The critical configuration implies different types of geometries in different types of regions, i.e. (1) the critical configuration restricted into R Nondeg implies a nondegenerate discrete Lorentzian geometry, (2) the critical configuration restricted into R Deg-A is degenerate of type-A in our definition of degeneracy, but implies a nondegenerate discrete Euclidean geometry in R Deg-A , (3) the critical configuration restricted into R Deg-B is degenerate of type-B, and implies a vector geometry in R Deg-B .With the critical configuration, we further make a subdivision of the regions R Nondeg and R Deg-A into subcomplexes (with boundary) according to their Lorentzian/Euclidean oriented 4-volume V 4 (v) of the 4-simplices, such that sgn(V 4 (v)) is a constant sign on each sub-complex. Then in the each sub-complex, the spinfoam amplitude at the critical configuration gives the Regge action in Lorentzian or Euclidean signature respectively in R Nondeg or R Deg-A . The Regge action reproduced here contains a sign prefactor sgn(V 4 (v)) related to the oriented 4-volume of the 4-simplices. Therefore the Regge action reproduced here can be viewed a discretized Palatini action with on-shell connection.Finally the asymptotic formula of the spinfoam amplitude is given by a sum of the amplitudes evaluated at all possible critical configurations, which are the products of the amplitudes associated to different type of geometries.
Highly crystalline graphitic carbon nitride (g-C N ) with decreased structural imperfections benefits from the suppression of electron-hole recombination, which enhances its hydrogen generation activity. However, producing such g-C N materials by conventional heating in an electric furnace has proven challenging. Herein, we report on the synthesis of high-quality g-C N with reduced structural defects by judiciously combining the implementation of melamine-cyanuric acid (MCA) supramolecular aggregates and microwave-assisted thermolysis. The g-C N material produced after optimizing the microwave reaction time can effectively generate H under visible-light irradiation. The highest H evolution rate achieved was 40.5 μmol h , which is two times higher than that of a g-C N sample prepared by thermal polycondensation of the same supramolecular aggregates in an electric furnace. The microwave-assisted thermolysis strategy is simple, rapid, and robust, thereby providing a promising route for the synthesis of high-efficiency g-C N photocatalysts.
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