Simulation of Rarefied Gas Flows in Atmospheric Pressure Interfaces for Mass Spectrometry Systems

The understanding of the gas dynamics of the atmospheric pressure interface is very important for the development of mass spectrometry systems with high sensitivity. While the gas flows at high pressure (>1 Torr) and low pressure (<10^–3 Torr) stages are relatively well understood and could be modeled using continuum and molecular flows, respectively, the theoretical modeling or numeric simulation of gas flow through the transition pressure stage (1 to 10^–3 Torr) remains challenging. In this study, we used the direct simulation Monte Carlo (DMSC) method to develop the gas dynamic simulations for the continuous and discontinuous atmospheric pressure interfaces (API), with different focuses on the ion transfer by gas flows through a skimmer or directly from the atmospheric pressure to a vacuum stage, respectively. The impacts by the skimmer location in the continuous API and the temporal evolvement of the gas flow with a discontinuous API were characterized, which provide a solid base for the instrument design and performance improvement.

Detection of layer‐by‐layer self‐assembly multilayer films by low‐temperature plasma mass spectrometry

The detection of layer‐by‐layer self‐assembly multilayer films was carried out using low‐temperature plasma (LTP) mass spectrometry (MS) under ambient conditions. These multilayer films have been prepared on quartz plates through the alternate assembling of oppositely charged 4‐aminothiophenol (4‐ATP) capped Au particles and thioglycolic acid (TGA) capped Ag particles. An LTP probe was used for direct desorption and ionization of chemical components on the films. Without the complicated sample preparation, the structure information of 4‐ATP and TGA on films was studied by LTP‐MS. Characteristic ions of 4‐ATP (M) and TGA (F), including [M]^+?, [M‐NH₂]⁺, [M‐HCN‐H]⁺, and [F + H]⁺, [F‐H]⁺, [F‐OH]⁺, [F‐COOH]⁺ were recorded by LTP‐MS on the films. However, [M‐CS‐H]⁺ and [F‐SH]⁺ could not be observed on the film, which were detected in the neat sample. In addition, the semi‐quantitative analysis of chemical components on monolayer film was carried out, and the amounts of 4‐ATP and TGA on monolayer surface were 45 ng/mm² and 54 ng/mm², respectively. This resulted the ionization efficiencies of 72% for 4‐ATP and 54% for TGA. In order to evaluate the reliability of present LTP‐MS, the correlations between this approach and some traditional methods, such as UV–vis spectroscopy, atomic force microscope and X‐ray photoelectron spectroscopy were studied, which resulted the correlation coefficients of higher than 0.9776. The results indicated that this technique can be used for analyzing the films without any pretreatment, which possesses great potential in the studies of self‐assembly multilayer films. Copyright © 2013 John Wiley & Sons, Ltd.     

Pt/NbPWO双功能催化剂的制备及氢解碱木质素制备芳香单体

木质素是一种天然芳香族聚合物,约占木质纤维素的30%,是唯一通过裂解C―O醚键和C―C键生产芳香族化学品或液体燃料的可再生芳香族资源。迄今为止,对木质素氢解制备有价值化合物的研究主要集中在相对不稳定的C―O键的裂解上,这限制了木质素氢解的效率。采用水热法和湿浸渍法制备了多功能Pt/NbPWO催化剂。通过破坏碱木质素中的C―O键和C―C键,可以得到产率为18.02%的芳香族单体。该反应不仅可以断裂木质素聚合物中醚键,同时也可以断裂部分关键的C―C键。其氢解机理可能是丰富的Brønsted酸和Lewis酸位点参与了C―C的活化。此外,重点分析载体和Pt物种在Pt/NbPWO催化剂中的协同作用。     

Control of pore environment in highly porous carbon materials for C2H6/C2H4 separation with exceptional ethane uptake

Adsorptive separation of C₂H₆ from C₂H₄ by adsorbents is an energy-efficient and promising method to boost the polymer grades C₂H₄ production. However, that C₂H₆ and C₂H₄ display very similar physical properties, making their separation extremely challenging. In this work, by regulating the pore environment in a family of chitosan-based carbon materials (C-CTS-1, C-CTS-2, C-CTS-4, and C-CTS-6)- we target ultrahigh C₂H₆ uptake and C₂H₆/C₂H₄ separation, which exceeds most benchmark carbon materials. Explicitly, the C₂H₆ uptake of C-CTS-2 (166 cm³/g at 100 kPa and 298 K) has the second-highest adsorption capacity among all the porous materials. In addition, C-CTS-2 gives C₂H₆/C₂H₄ selectivity of 1.75 toward a 1:15 mixture of C₂H₆/C₂H₄. Notably, the adsorption enthalpies for C₂H₆ in C-CTS-2 are low (21.3 kJ/mol), which will facilitate regeneration in mild conditions. Furthermore, C₂H₆/C₂H₄ separation performance was confirmed by binary breakthrough experiments. Under different ethane/ethylene ratios, C-CTS-X extracts a low ethane concentration from an ethane/ethylene mixture and produces high-purity C₂H₄ in one step. Spectroscopic measurement and diffraction analysis provide critical insight into the adsorption/separation mechanism. The nitrogen functional groups on the surface play a vital role in improving C₂H₆/C₂H₄ selectivity, and the adsorption capacities depend on the pore size and micropore volume. Moreover, these robust porous materials exhibit outstanding stability (up to 800 °C) and can be easily prepared on a large scale (kg) at a low cost (～$26 per kg), which is very significant for potential industrial applications.     

Photocatalytic removal of tetracycline by a Z-scheme heterojunction of bismuth oxyiodide/exfoliated g-C3N4: performance,mechanism, and degradation pathway

Antibiotics, once being released into the environment, become recalcitrant organic pollutants, which pose a potential risk to ecological balance and human health. In this study, a Z-scheme heterojunction of bismuth oxyiodide (BiOI)/exfoliated g-C₃N₄ (BiOI/ECN hereafter) was synthesized by the combination of thermal exfoliation of g-C₃N₄ and chemical precipitation of BiOI for efficient photocatalytic degradation of tetracycline in aqueous solutions under visible light irradiation. The optimized BiOI/ECN delivered an outstanding degradation rate at circa 0.0705 min^?1, which was 10 times higher than that of the bulk g-C₃N₄. The photocatalytic degradation efficiency of tetracycline remained almost unchanged in a pH range of 3–11, and the BiOI/ECN displayed an excellent photostability upon recycled usage. The photocatalytic mechanism of tetracycline was ascribed to the main reactive oxidation species of photogenerated holes and superoxide radicals. In addition, the possible degradation pathways of tetracycline were investigated by HPLC-MS to identify intermediates. The toxicity of photocatalytic-generated intermediates of tetracycline was found significantly alleviated according to the calculation of quantitative structure–activity relationship prediction. This work not only provides an attractive photocatalyst for the removal of tetracycline but also opens a new avenue for rational design of Z-scheme heterojunction composites for tetracycline degradation.     

Simultaneous photocatalytic oxidation and adsorption for efficient As(III) removal by magnetic BiOI/γ-Fe2O3 core–shell nanoparticles

Addressing arsenite pollution in groundwater has drawn great attention. It is attractive to pre-oxidize highly mobile As(III) to relatively low-toxic As(V) with a subsequent adsorption separation process. Herein, BiOI anchoring on γ-Fe₂O₃ is performed to synthesize BiOI/γ-Fe₂O₃ core–shell nanoparticles for efficient removal of As(III) via a simultaneous photocatalytic oxidization–adsorption process. The physical and chemical structures of BiOI/γ-Fe₂O₃ are investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction measurements. The photoluminescence and electron spin resonance (ESR) characterization were employed to ascertain the possible reaction mechanism of visible-light-driven photocatalytic oxidation of As(III). Such BiOI/γ-Fe₂O₃ delivers a superior As(III) removal capability under visible light irradiation with an arsenic removal efficiency of 99.8% within 180 min, higher than those of BiOCl/γ-Fe₂O₃ (81.7%) and BiOBr/γ-Fe₂O₃ (98.9%). The optimal BiOI/γ-Fe₂O₃ (molar ratio of 2:1) is obtained by rationally adjusting the molar ratio of BiOI to γ-Fe₂O₃. The as-synthesized BiOI/γ-Fe₂O₃ performs well in a wide pH range of 2–8. Only coexisting PO₄^3? anions have a significant effect on the As(III) removal. The free radical trapping experiment and ESR results demonstrate that the ?O₂^? and h⁺ are the main active substances for the photocatalytic oxidation of As(III) on BiOI/γ-Fe₂O₃. This work not only gives a novel magnetic core–shell nanoparticle photocatalyst for efficient photocatalytic oxidation and adsorption of As(III) but also offers a new strategy to rationally design BiOX for its related practical applications.     

Quantitative Investigation on Structural Evolution of Co-continuous Phase under Shear Flow

Components of co-continuous phase can form an interpenetrating network structure, which has great potential to synergistically improve the mechanical properties of the blends, and to impart the functional blends superior electrical conductivity and permeability. In this work, the effects of shear rates (50–5000 s^?1) at different temperatures on the phase morphology, phase size and lamellar crystallites of biodegradable co-continuous polybutylene terephthalate (PBAT)/polybutylene succinate (PBS) blend are quantitatively investigated. The results show that the above features of the PBAT/PBS have a strong dependence on the shear flow and thermal field. The co-continuous phase of the blend is well maintained at 130 °C. Interestingly, this phase structure transforms into a “sea-island” structure at 160 °C, which gradually recovers to a co-continuous phase when the shear rate increases from 1000 s^?1 to 5000 s^?1. The phase size decreases with the increase of shear rate both at 130 °C and 160 °C due to the refinement and deformation of phase structures caused by strong shear stress. Unexpectedly, a unique phenomenon is observed that the shear-induced lamellar crystallites are oriented perpendicular to shear direction in the range of 500–5000 s^?1 at 130 °C, while the orientation of lamellar crystallites at 160 °C is along the shear direction within the whole range of shear rates. The degree of orientation for the PBAT/PBS blend crystals increases first and then decreases at both temperatures above. In addition, the range of shear rate has reached the level in the industrial processing. Therefore, this work has important guiding significance for the regulation of the co-continuous phase structure and the performance for the blend in the practical processing.

     

Efficient copper-catalyzed N-arylation of NH-containing heterocycles and sulfonamides with arenediazonium tetrafluoroborates

A practical copper-catalyzed N-arylation of NH-containing heterocycles with arenediazonium tetrafluoroborates has been developed using CuCl as catalyst and K₂CO₃ as additive under ligand-free conditions. This reaction system has wide substrate scope including imides, 1H-pyrazole, 1H-tetrazoles, 1,2-benzisothiazol-3(2H)-one, and related sulfonamides and gives moderate to excellent yields (up to 95%) of the desired products. This strategy is very general, simple, environmentally friendly, and tolerant of oxygen.     

Synthesis of Au nanoparticles with Bi adlayers using glucose as dispersant

Well-dispersed Au/Bi nanoparticles with average size below 10 nm were prepared by using NaBH₄ to reduce HAuCl₄ with glucose as dispersant. The obtained Au/Bi NPs were well characterized by UV-Vis spectra, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements. The electrochemical study found that Bi adlayers on the surface of Au nanoparticles owns two kinds of surface structures, including a low coverage (2 × 2)-Bi adlayer and a close-packed (p × √3)-2 Bi adlayer due to the strong interaction between the two Bi layers and the below Au atoms, which is same with that bulk on Au surface.