基于XPS对硫铁矿去除SeO2-3的机理研究

硒是动植物及人体生长必需的十五种微量元素之一，具有清除体内自由基、抗氧化、增强免疫力等功能，但其安全剂量的范围却很窄。利用扫描电子显微镜（SEM）和X射线衍射仪（XRD）对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体，粒径范围在17～200 nm之间，平均粒径138 nm。XRD衍射图谱中的特征峰与FeS₂衍射图谱中各峰位置基本一致，因此判定硫铁矿中主要化学组分为FeS₂，且图谱中基本没有杂峰，表明制备过程中并未混入杂质，样品纯度较高。实验结果表明，该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪（XPS）对硫铁矿去除水体中SeO2-₃的机理进行了研究。研究结果表明, （1）在较为广泛的实验pH范围（pH 2.2～11.5），硫铁矿均能有效去除水体中SeO2-₃，去除效率（除pH值7.8以外）均达到90%以上；（2）硫铁矿与SeO2-₃发生反应后，其主要组成元素的XPS特征峰结合能有所减小，表明硫铁矿表面发生了一定化学变化；（3）酸碱环境下硫铁矿去除SeO2-₃的机理不完全相同，酸性环境下，硫铁矿对SeO2-₃的去除是单纯的氧化还原过程，即硫铁矿中被酸活化的S2-₂将SeO2-₃还原为单质Se(0)，并且酸性越强，SeO2-₃去除效果越好；碱性环境下，SeO2-₃的去除过程中氧化还原与络合反应并存，硫铁矿表面有络合态Fe(OH)SeO₃和单质Se(0)两种存在形态，且碱性越强，络合态Fe(OH)SeO₃含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-₃为代表的可变价金属阴离子提供重要理论依据和应用基础。     

室温铁磁性Sr3YCo4O10.5+δ多晶有序化的烧结工艺及电磁性能

采用固相反应法制备了不同烧结温度(950~1 180 ℃)、烧结时间、烧结次数共7种工艺的Sr₃YCo₄O_10.5+δ多晶块材,通过热分析、XRD、SEM确定了有序化相变和最佳烧结工艺(1 180 ℃/24 h+1 180 ℃/24 h),并研究了多晶的电磁性能。结果表明,964 ℃完全晶化的四方相Sr₃YCo₄O_10.5在1 042 ℃吸氧(δ)完成有序化,生成Sr₃YCo₄O_10.5+δ,而1 100 ℃和1 180 ℃烧结的样品均出现(103)、(215)超结构峰,验证了其结构的有序性。块材均呈半导体电输运行为,二次烧结晶格完整性提高,晶粒长大,300 K时电阻率仅为0.06 Ω·cm,居里温度(T_c)~335 K,零场冷曲线(ZFC)上的Hopkinson峰源于低温时被冻结的磁矩随温度升高转向磁场方向,磁化强度在298 K达到最大,随后受热扰动的影响减小。室温铁磁性源于有序结构导致的中自旋或高自旋态Co³⁺的e_g轨道有序。     

Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Tunneled metal oxides such as α-Mn₈O₁₆ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K⁺ ions (which act as structure-stabilizing dopants) and H₂O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K⁺-doped α-Mn₈O₁₆ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H₂O displaces K⁺ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K²⁺ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li⁺/Na⁺ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K²⁺) in the tunnels of hollandite.     

A Novel Energetic Ionic Salt: Hydroxylammonium Potassium 3,3’-Dinitro-5,5’-bis-1,2,4-triazole-1,1’-diolate Dihydrate

A novel energetic ionic salt,hydroxylammonium potassium 3,3?-dinitro-5,5?-bis-1,2,4-triazole-1,1?-diolate dihydrate[(NH3OH)2K(DNOBT)1.5?2H2O],was synthesized and structurally characterized by elemental analysis,IR spectra,13C NMR and single-crystal X-ray diffraction.(NH3OH)2K(DNOBT)1.5?2H2O crystallizes in triclinic system,space group P with a=7.9212(6),b=9.1924(7),c=14.2549(15)?,a=103.917(2)°,β=99.736(2)°,g=104.8110(10)°,V=944.16(14)?^3,Z=2,Dc=1.855 g/cm^3,F(000)=538,μ=0.386 mm^-1,S=1.070,the final R=0.0525 and wR(I>2s(I))=0.1593.Thermal decomposition of(NH3OH)2K(DNOBT)1.5?2H2O and its intermediate potassium 1?-hydroxy-3,3?-dinitro-5,5?-bis-1,2,4-triazole-1-olate monohydrate[K(HDNOBT)?H2O]was studied by using DSC and TG-DTG.It was found that(NH3OH)2K(DNOBT)1.5?2H2O,which has primarily one exothermic decomposition process at 248.2℃,has better thermal stability than K(HDNOBT)?H2O which is decomposed at 210.9℃.     

细胞松弛素B阻断微核法鉴定男性个体辐射敏感性的方法初探

初步研究了男性个体辐射敏感性的鉴定方法及标准。采集50名男性志愿者的外周血，分别给予不同剂量X射线照射，采用细胞松弛素B阻断双核法测定微核率(MNF)，通过二阶多项拟合法，绘制微核剂量效应选项中心标准曲线，将个人微核剂量效应曲线与标准曲线比对后判断个体辐射敏感性。 $0.0\sim2.5 $ Gy剂量范围内，剂量效应二阶多项拟合的中心方程为(MNF=0.014 7+0.036 2D+0.023 1D 2， r=0.726)。50名志愿者中，辐射敏感的有13人，辐射抗性的有14人，基本符合正态分布。Spearman秩和相关分析结果显示，MNF在各个辐射剂量点与辐射敏感性均存在正相关,与辐射抗性呈负相关,MNF随剂量增加而增加。本研究初步建立了“以线代点”男性个体辐射敏感性鉴定方法,并发现男性外周血淋巴细胞的本底微核率与个体辐射敏感性呈正相关。     

Method validation,residue analysis and dietary risk assessment of trifloxystrobin and trifloxystrobin acid in milk,eggs and pork

Trifloxystrobin (TFS) is a widely used strobilurin fungicide and its residues accumulating in animal-derived food could result in potential harm to consumers. By optimization of extraction solvents and cleanup sorbents, a residue analysis method for TFS and its metabolite trifloxystrobin acid (TFSA) was established in milk, eggs and pork based on QuEChERS sample preparation and LC–MS/MS. The calibration curves exhibited good linearity with determination coefficients (R²) >0.9930 over the range of 0.5–250 ng/ml for both TFS and TFSA. The recoveries of the two analytes were 81–100% with RSD 3–10% and 76–96% with RSD 2–13%, respectively. The limit of quantification (LOQ) was 1 ng/g for both analytes. The milk, egg and pork samples, 30 each, were collected from the 30 main producing regions in China, and residues of TFS and TFSA were analyzed. The concentrations of both analytes were lower than the corresponding LOQs and maximum residue limits. Long-term dietary risk assessment showed that the hazard quotients were 0.001–0.003%, indicating an absence of unacceptable risks in milk, eggs and pork to the health of common consumers in China.     

Template synthesis of imine-based covalent organic framework core-shell structure and hollow sphere: a case of COF<Subscript>TTA-DHTA</Subscript>

Controllably synthesizing well-dispersed covalent organic frameworks (COFs) with uniform both morphology and size is still a challenge. Herein, we report the template-directed synthesis of COF_TTA-DHTA-based core-shell hybrids under solvothermal conditions by using amino-functionalized SiO₂ microspheres as templates coupled with stepwise addition of initial monomer molecules. The modified amino groups on the surfaces of SiO₂ templates play an important role in the formation of well-defined NH₂-f-SiO₂@COF_TTA-DHTA core-shell hybrids. COF_TTA-DHTA hollow spheres can be obtained by etching SiO₂ cores of NH₂-f-SiO₂@COF_TTA-DHTA. Both the NH₂-f-SiO₂@COF_TTA-DHTA and COF_TTA-DHTA hollow spheres possess the well-defined morphology, high crystallinity and porosity, excellent dispersion property and high chemical stability. The template synthesis method demonstrated in this work provides a general method for the shape-controlled synthesis of COF-based materials, which is important for the further applications in the fields such as energy storage, drug delivery and catalysis.