Direct visualization of structural defects in 2D semiconductors

Direct visualization of the structural defects in two-dimensional (2D) semiconductors at a large scale plays a significant role in understanding their electrical/optical/magnetic properties, but is challenging. Although traditional atomic resolution imaging techniques, such as transmission electron microscopy and scanning tunneling microscopy, can directly image the structural defects, they provide only local-scale information and require complex setups. Here, we develop a simple, non-invasive wet etching method to directly visualize the structural defects in 2D semiconductors at a large scale, including both point defects and grain boundaries. Utilizing this method, we extract successfully the defects density in several different types of monolayer molybdenum disulfide samples, providing key insights into the device functions. Furthermore, the etching method we developed is anisotropic and tunable, opening up opportunities to obtain exotic edge states on demand.     

利用新颖高效气体发生装置以氯气氧化法制备高锰酸钾实验设计及效果*

基于一种新颖高效气体发生装置,设计了以氯气为氧化剂,理论产率接近100%的将锰酸钾高效转化为高锰酸钾的实验方案。实验结果表明:使用本设计制备高纯度高锰酸钾,既可保证高锰酸钾的理论转化率,减少歧化反应副产物对纯度的影响,同时得到的副产品次氯酸钠及氯水可用做无机教学实验的基础试剂,符合“循环经济”指导思想。     

Unusual Hypochlorous Acid (HClO) Recognition Mechanism Based on Chlorine–Oxygen Bond (Cl−O) Formation

One of the most important endogenous reactive oxygen species, hypochlorous acid (HClO), is involved in numerous pathological and physiological processes. Herein, a near-infrared fluorescence probe (CyHR) was designed and synthesized for ultrafast (within 0.2 s), sensitive (limit of detection=39.44 nm ), and selective response to HClO. The reaction mechanism was systematically analyzed by MS, ¹H NMR spectroscopy, HPLC-MS techniques, and theoretical calculations. The results indicated that HClO can be recognized by CyHR, which is based on chlorine–oxygen (Cl−O) bond formation. To the best of our knowledge, this study is the first to find Cl−O bonds among organic aromatic compounds, given that Cl−O bonds are common among inorganics. Through biological experiments, CyHR was successfully applied to image exogenous and endogenous HClO in macrophage cells (RAW 264.7). Thus, CyHR is a promising tool for HClO-related physiological and pathological studies and may provide a means for designing HClO-specific fluorescence probes.     

Kinetics studies of 5-methyl-2-hexanol, 2,2-dimethyl-3-hexanol,and 2,4,4-trimethyl-1-pentanol with chlorine atoms: Photooxidation mechanism of 2,4,4-trimethyl-1-pentanol

The rate constants for the reaction between chlorine atoms and either 5-methyl-2-hexanol, 2,2-dimethyl-3-hexanol, or 2,4,4-trimethyl-1-pentanol at 298 K were determined using the relative method with 2-butanol and 1-pentanol as reference compounds. The values obtained for 5-methyl-2-hexanol, 2,2-dimethyl-3-hexanol, and 2,4,4-trimethyl-1-pentanol (k × 10¹⁰ cm³ molec⁻¹ s⁻¹) were, respectively, (2.64 ± 0.5), (2.72 ± 0.5), and (2.50 ± 0.4), in agreement with the values of the rate constants reported in bibliography for similar alcohols and the values estimated by structure activity relationship methods. The photooxidation products of 2,4,4-trimethyl-1-pentanol initiated by chlorine atoms were identified (formaldehyde, 2-propanone, 2,2-dimethyl propanal, 4,4,-dimethyl-2-pentanone, and 3,3-dimethylbutanal), and the reaction mechanism was determined.     

Etched ZIF-8 as a Filler in Mixed-Matrix Membranes for Enhanced CO2/N2 Separation

Zeolite ZIF-8 has been etched with acid to form microporous ZIF-8-E crystals. These were then introduced into a polyethersulfone (PES) membrane matrix to enhance its CO₂/N₂ separation performance. Open through pores of size about 100 nm formed in the ZIF-8 crystals allow the ingrowth of polyethersulfone chains, ensuring a reduction in the number of nonselective voids, thereby achieving better interaction between ZIF-8-E and PES. As a result, the CO₂/N₂ separation performance of the ZIF-8-E/PES membrane increased significantly, showing a CO₂ permeability of 15.7 Barrer and a CO₂/N₂ ideal selectivity of 6.5.     

X射线荧光光谱法测定重整铂催化剂中氯

建立重整铂催化剂中氯的X射线荧光光谱测定方法。通过研磨机将铂催化剂研磨至粒径小于75 μm的颗粒,采用仪器压片制样,通过测量不同氯含量样品的计数率,建立铂催化剂中氯含量与计数率的线性关系。氯的质量分数在0.85%~1.04%范围内与计数率成良好的线性关系,相关系数为0.9995,检出限为0.0076%。样品加标回收率为96.2%~104.2%,测定结果的相对标准偏差小于2%(n=6)。该法测定结果与电位滴定法相吻合。该方法精密度高,分析速度快,满足重整装置生产调整的要求。     

N‐Alkyl Ammonium Resorcinarene Salts as High‐Affinity Tetravalent Chloride Receptors

N‐Alkyl ammonium resorcinarene salts (NARYs, Y=triflate, picrate, nitrate, trifluoroacetates and NARBr) as tetravalent receptors, are shown to have a strong affinity for chlorides. The high affinity for chlorides was confirmed from a multitude of exchange experiments in solution (NMR and UV/Vis), gas phase (mass spectrometry), and solid‐state (X‐ray crystallography). A new tetra‐iodide resorcinarene salt (NARI) was isolated and fully characterized from exchange experiments in the solid‐state. Competition experiments with a known monovalent bis‐urea receptor ( 5 ) with strong affinity for chloride, reveals these receptors to have a much higher affinity for the first two chlorides, a similar affinity as 5 for the third chloride, and lower affinity for the fourth chloride. The receptors affinity toward chloride follows the trend K₁?K₂?K₃≈ 5 >K₄, with K_a=5011 m ^?1 for 5 in 9:1 CDCl₃/[D₆]DMSO.     

Silver‐Assisted Chemical Etching on Silicon with Polyvinylpyrrolidone‐Mediated Formation of Silver Dendrites

Metal‐assisted chemical etching (MaCE) on silicon (Si)—mediated by polyvinylpyrrolidone (PVP)—is systematically investigated herein. It is found that the morphologies and crystallographic natures of the grown silver (Ag) dendrites can be significantly modulated, with the presence of PVP in the MaCE process leading to the formation of faceted Ag dendrites preferentially along the (111) crystallographic phase, rather than along the (200) phase. Further explorations of the PVP‐mediated effect on Si etching are also revealed. In contrast to the aligned Si nanowires formed by MaCE without PVP addition, only distributed nanopores with sizes of 200 to 400 nm appear on the Si surfaces in the presence of PVP. The origin of surface polishing on Si in the PVP‐mediated MaCE process can be attributed to the distinct transport pathway of holes supplied by the Ag⁺ ions, where the holes are injected directly into the primary Ag seeds, rather than through Ag dendrites, thus leading to the isotropic etching of the Si surface.     

Influence of Solution Volume on the Dissolution Rate of Silicon Dioxide in Hydrofluoric Acid

Experimental data and modeling of the dissolution of various Si/SiO₂ thermal coatings in different volumes of hydrofluoric acid (HF) are reported. The rates of SiO₂‐film dissolution, measured by means of various electrochemical techniques, and alteration in HF activity depend on the thickness of the film coating. Despite the small volumes (0.6–1.2 mL) of the HF solution, an effect of SiO₂‐coating thickness on the dissolution rate was detected. To explain alterations detected in HF activity after SiO₂ dissolution, spectroscopic analyses (NMR and FTIR) of the chemical composition of the solutions were conducted. This is associated with a modification in the chemical composition of the HF solution, which results in either the formation of an oxidized species in solution or the precipitation of dissolution products. HF₂^? accumulation in the HF solution, owing to SiO₂ dissolution was identified as the source of the chemical alteration.     

低功率超声增强碘帕醇氯氧化的效果和路径

研究了低功率超声(US, <38 W)对NaClO氧化非离子型碘代X射线造影剂—碘帕醇(IPM)的增强作用及机理, 考察了NaClO添加浓度和超声功率的影响, 分析并计算了体系中的主要活性物种及其贡献. 采用高效液相色谱/串联质谱(HPLC/MS/MS)对降解产物进行分析, 推测IPM的降解路径. 结果表明, 低功率US显著增强了NaClO对IPM的氧化效果, 在25 ℃, pH=5.8, NaClO浓度为0.12 mmol/L条件下, 10 mg/L IPM在60 min的降解率达到85.8%. 其中NaClO氧化、 HO·和活性氯自由基(RCSs)是US/NaClO增强IPM降解的主要原因, 自由基分析计算它们的贡献率分别为15.82%, 4.65%和79.53%. NaClO浓度在0~0.24 mmol/L范围内, IPM的降解率随NaClO浓度升高而增加, 60 min后降解率由4.75%增加到91.12%; 超声功率为28.5 W, 降解率达到最高. 在 15~45 ℃温度范围内, IPM的降解过程符合表观一级反应动力学, 反应活化能(E_a)为59.03 kJ/mol. HPLC/MS/MS共检测出5种中间产物, 结合密度泛函理论(DFT)计算结果, 初步推测了IPM在US/NaClO体系中的降解途径和机理.