气相色谱法测定焦油中微量苯稠杂环化合物

利用蒸馏分离—气相色谱法技术,建立了同时测定煤焦油中苊、氧芴和芴的分析方法。通过对色谱条件的优化,以甲苯为溶剂,正十二烷为内标物,将煤焦油馏分采用DB-5毛细管柱,对煤焦油中苊、氧芴和芴定量分析。分析结果表明:3种主要成分线性关系良好,相关系数均大于0.9995,加标回收率为95.4%~102.4%,相对标准偏差为2.89%~7.14%。该方法分离效果好,检测结果准确、可靠。     

Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Deacetylated Cellulose Acetate/Polyurethane Composite Nanofiber Membranes with Highly Efficient Oil/Water Separation and Excellent Mechanical Properties

Nowadays, oil pollution has become more serious, which causes great threats both to the ecological environment and human life. In this study, a novel type of multifunctional deacetylated cellulose acetate/polyurethane (d-M_CA:M_TPU) composite nanofiber membranes for oil/water separation are successfully fabricated by electrospinning, which show super-amphiphilicity in air, super-hydrophilicity in oil, and oleophobicity in water. All the d-M_CA:M_TPU composite nanofiber membranes with different mass ratios can be used as water-removing, oil-removing, and emulsion separation substance only by gravity driving force. The highest separation flux for water and oil reaches up to 37 000 and 74 000 L m⁻² h⁻¹, respectively, and all the separation efficiencies are more than 99%. They have outstanding comprehensive mechanics performance, which can be controlled by simply adjusting the mass ratios. They show excellent antifouling and self-cleaning ability, endowing powerful cyclic stability and reusability. Those results show that d-M_CA:M_TPU composite nanofiber membranes have great application prospects in oil/water separation.     

Influence of the stoichiometry,microstructure, and metallization method on the dielectric properties of 0.94 Na0.5Bi0.5TiO3-0.06 BaTiO3

The morphotropic composition of the lead-free solid solution between Na_0.5Bi_0.5TiO₃ and BaTiO₃ (0.94 Na_0.5Bi_0.5TiO₃-0.06 BaTiO₃ or NBT-6BT) is of particular interest for the next generation of high-temperature capacitors but remains plagued by the diversity of dielectric properties reported in the literature. In order to explain the apparent inconsistencies among the reported dielectric properties of NBT-6BT, we examine the influence of stoichiometry, phase separation, and metallization method. We show that the nominal stoichiometry has a crucial effect, since increasing the nominal Na/Bi ratio increases conductivity and dielectric losses (tan δ). It also increases the real part of the permittivity (ε’) and the frequency dispersion of both ε’ and tan δ, thereby altering the shape of the evolution with temperature of the dielectric properties. Moreover it increases the depolarization temperature (T_d) and decreases the temperature of maximum permittivity (T_m). Phase separation also occurs during the synthesis of NBT-6BT as Na evaporation leads to the formation of secondary Ba-containing phases. We report that these phases can have a positive impact on the dielectric properties: a moderate volume fraction (2.5 to 3.0%) and average grain surface (0.9 to 3.0 µm²) of these secondary Ba-containing phases increase the relative permittivity, decrease the dielectric losses, and increase the insulation resistance. We also show that the metallization method impacts the dielectric properties and therefore may contribute to the differences between various reports. The dielectric properties of NBT-6BT samples are measured during successive heating/cooling cycles and reveal that the permittivity value is lower during the first heating when silver paste, even cured, is used. These three components contribute to explaining the diversity of the reported dielectric properties of NBT-6BT.     

Magnetically Guidable Proteinaceous Adhesive Microbots for Targeted Locoregional Therapeutics Delivery in the Highly Dynamic Environment of the Esophagus

The esophagus is a tubular-shaped muscular organ where swallowed fluids and muscular contractions constitute a highly dynamic environment. The turbulent, coordinated processes that occur through the oropharyngeal conduit can often compromise targeted administration of therapeutic drugs to a lesion, significantly reducing therapeutic efficacy. Here, magnetically guidable drug vehicles capable of strongly adhering to target sites using a bioengineered mussel adhesive protein (MAP) to achieve localized delivery of therapeutic drugs against the hydrodynamic physiological conditions are proposed. A suite of highly uniform microparticles embedded with iron oxide (IO) nanoparticles (MAP@IO MPs) is microfluidically fabricated using the genipin-mediated covalent cross-linking of bioengineered MAP. The MAP@IO MPs are successfully targeted to a specific region and prolongedly retained in the tubular-structured passageway. In particular, orally administered MAP@IO MPs are effectively captured in the esophagus in vivo in a magnetically guidable manner. Moreover, doxorubicin (DOX)-loaded MAP@IO MPs exhibit a sustainable DOX release profile, effective anticancer therapeutic activity, and excellent biocompatibility. Thus, the magnetically guidable locomotion and robust underwater adhesive properties of the proteinaceous soft microbots can provide an intelligent modular approach for targeted locoregional therapeutics delivery to a specific lesion site in dynamic fluid-associated tubular organs such as the esophagus.     

Synthesis,characterization, and visible-light photocatalytic activity of transition metals doped ZTO nanoparticles

Transition metals doping has been proved to be a feasible way for tuning the physical properties on the surface and bulk of nanomaterials and also for the good performance in decontamination of emerging pollutants. In this context, doped samples of zinc tin oxide or zinc stannate nanoparticles (ZTO NPs) by several transition metals were synthesized in order to enhance the optical absorbance with the aims of reducing the band gap and therefore ameliorated their photocatalytic activity. They were characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy, Raman spectroscopy and photoluminescence. The XRD patterns and the microscopic observations showed the formation of spherical nanoparticles with an average size of about 30 nm and highly pure ZTO phase with an inverse spinel structure. The Raman spectra were dominated by bands relatives to the F2g (2) and A1g symmetries modes of inverse spinel structure. The band gap Eg is estimated to be 3.75 eV for the undoped sample, and 3.67, 3.64, 3.78 and 3.21 eV, for 2% Fe, 2% Mg, 2% Gd, and 2% Mn doped ZTO samples, respectively.Furthermore, the undoped ZTO NPs have the intrinsic problem of recombination of photogenerated charge carriers. We have shown that the reduction of the band gap and oxygen vacancies resulting from the doping effect could be a useful tool for trapping and avoid the recombination of electrons coming from photosensitized rhodamine B (RhB) under visible light irradiation. Owing to the structural advantages and low band gap, 2% Mn doped ZTO NPs, with the kinetic rate constants k of 0.024 min⁻¹, show enhanced performance for the elimination of RhB in aqueous solution compared to undoped and other doped ZTO NPs.     

某微细粒嵌布磁铁矿选矿工艺研究

针对某微细粒磁铁矿进行了全磁选流程和磁选-反浮选流程对比试验研究。结果表明,在最终磨矿细度相当的情况下,2种工艺流程都获得了产率48%左右、TFe品位66%左右、回收率80%左右的铁精矿指标,而采用磁选-反浮选流程的第三段磨矿量比全磁选流程减少了2/3。磁选-反浮选流程具有显著的节能降耗优势。     

Constructing magnetically recoverable CdS/CaFe2O4 P–N heterojunctions for enhanced photoelectrochemical properties towards H2 evolution reaction

A novel CdS/CaFe₂O₄ (CS/CFO) heterogeneous p-n junction was created by thermal deposition of CaFe₂O₄ nanoparticles on CdS rods. The CS/CFO hetero-structured photocatalysts exhibited increasingly efficient visible light harvesting compared to the bare CdS. The CS/CFO composites also presented higher photocurrent and slower decay of photoluminescence, suggesting a better separation of the photo-generated electrons and holes. The photocatalytic H₂ evolution quantity on the optimized CS/CFO composite from water in the presence of ethanol was up to 2200 μmol after 3-h visible light illumination, which is more than twice that of the pristine CdS. The chemical interaction between CdS and CaFe₂O₄ was confirmed by the shifts in the XPS peaks, which made it possible for the charge carriers to transfer across the p-n junction interface. This research highlights the importance of forming an interfacial p-n heterojunction between two semiconductors for efficient charge separation and improved photocatalytic performance.     

Initial and residual trapping of hydrogen and nitrogen in Fontainebleau sandstone using nuclear magnetic resonance core flooding

Hydrogen is among a few promising energy carriers of the future mainly due to its zero-emission combustion nature. It also plays an important role in the transition from fossil fuel to renewable. Hydrogen technology is relatively immature and serious knowledge gaps do exist in its production, transport, storage, and utilization. Although the economical generation of hydrogen to the scale required for such transition is still the biggest technical and environmental challenge, unlocking the large-scale but safe storage is similarly important. It is difficult to store hydrogen in solid and liquid states and storing it in the gaseous phase requires a huge volume which is just available in subsurface porous media. Sandstone is the most abundant and favourable medium for such storage as carbonate rock might not be suitable due to potential geochemical reactions.It is well established in the literature that interaction of the host rock-fluid and injected gas plays a crucial role in fluid flow, residual trapping, withdrawal, and more generally storing capacity. Such data for the hydrogen system is extremely rare and are generally limited to contact angle measurements, while being not representative of the reality of rock-brine-hydrogen interaction(s). Therefore, we have conducted, for the first time, a series of core flooding experiments using Nuclear Magnetic Resonance (NMR) to monitor hydrogen (H₂) and Nitrogen (N₂) gas saturations during the drainage and imbibition stages under pressure and temperature that represent shallow reservoirs. To avoid any geochemical reaction during the test, we selected a clean sandstone core plug of 99.8% quartz (Fontainebleau with a gas porosity of 9.7% and a permeability of 190 mD).Results show significantly low initial and residual H₂ saturations in comparison with N₂, regardless of whether the injection flow rate or capillary number were the same or not. For instance, when the same injection flow rate was used, H₂ saturation during primary drainage was 4% and it was <2% after imbibition. On other hand, N₂ saturation during the primary drainage was 26% and it was 17% after imbibition. However, when the same capillary number of H₂ was utilised for the N₂ experiment, the N₂ saturation values were ～15% for initial gas saturation and 8% for residual gas saturation. Our results promisingly support the idea of hydrogen underground storage; however, we should emphasise that more sandstone rocks of different clay mineralogy should be investigated before reaching a conclusive outcome.     

离子型稀土矿山淋洗及尾水富集试验研究

对浸矿后离子型稀土原地浸矿场采用清水进行淋洗，在184天的清水淋洗过程中，尾水氨氮值从最开始的507mg/L，降低至140mg/L，淋洗尾水pH4.52~3.10。淋洗尾水采用两级反渗透膜分离，既回收有价资源稀土，又能使出水氨氮达标。结果表明，产水氨氮浓度稳定低于15mg/L，对稀土的截留率高于98.25%，浓水中稀土离子平均浓度313.4mg/L，可进一步回收稀土资源。