1,3,5-三甲苯的光电离的实验研究

利用超声分子束、真空紫外同步辐射和反射式飞行时间质谱仪开展1,3,5-三甲基苯(TMB,C9H12)的光电离和光解离研究.利用光电离质谱和光电离效率曲线,确定母体分子的电离能,主要碎片离子C9H+11和C8H+9的出现能分别为(8.32±0.03),(11.71±0.03)和(11.59±0.03)eV.根据经验公式,计算出形成C9H1+1和C8H+9的解离能(Ed)分别为(3.39±0.06)和(3.27±0.06)eV.再利用相关的热化学参数,推算出C9H1+2,C9H+11和C8H+9的标准生成焓为786.87,897.93和956.68kJ/mol.     

Eu~(3+)离子掺杂纳米TiO_2的制备及其光催化降解甲基兰溶液的研究

采用溶胶-凝胶法制备了系列不同原子摩尔比的Eu3+离子掺杂纳米TiO2光催化剂,通过XRD,SEM和UV-V is等测试手段对纳米TiO2晶型、颗粒度大小、形貌以及光学性能进行了表征;并以甲基兰溶液为目标物,对所制备样品的光催化活性进行了研究。结果表明,稀土Eu3+离子的掺杂能有效抑制纳米TiO2的晶型的转变进而减小晶粒尺寸、提高分散度;稀土Eu3+离子的掺杂使TiO2光催化剂紫外-可见吸收有一定的蓝移,并在可见区有一定的吸收峰;稀土Eu3+离子的掺杂有效提高了TiO2光催化剂的活性,并在本实验条件下,当掺杂原子摩尔比为1%、退火温度500℃时,对甲基兰溶液的光催化活性最强。     

Mesoporous Carbon Nanofibers Embedded with MoS2 Nanocrystals for Extraordinary Li‐Ion Storage

MoS₂ nanocrystals embedded in mesoporous carbon nanofibers are synthesized through an electrospinning process followed by calcination. The resultant nanofibers are 100–150 nm in diameter and constructed from MoS₂ nanocrystals with a lateral diameter of around 7 nm with specific surface areas of 135.9 m² g^?1. The MoS₂@C nanofibers are treated at 450 °C in H₂ and comparison samples annealed at 800 °C in N₂. The heat treatments are designed to achieve good crystallinity and desired mesoporous microstructure, resulting in enhanced electrochemical performance. The small amount of oxygen in the nanofibers annealed in H₂ contributes to obtaining a lower internal resistance, and thus, improving the conductivity. The results show that the nanofibers obtained at 450 °C in H₂ deliver an extraordinary capacity of 1022 mA h g^?1 and improved cyclic stability, with only 2.3 % capacity loss after 165 cycles at a current density of 100 mA g^?1, as well as an outstanding rate capability. The greatly improved kinetics and cycling stability of the mesoporous MoS₂@C nanofibers can be attributed to the crosslinked conductive carbon nanofibers, the large specific surface area, the good crystallinity of MoS₂, and the robust mesoporous microstructure. The resulting nanofiber electrodes, with short mass‐ and charge‐transport pathways, improved electrical conductivity, and large contact area exposed to electrolyte, permitting fast diffusional flux of Li ions, explains the improved kinetics of the interfacial charge‐transfer reaction and the diffusivity of the MoS₂@C mesoporous nanofibers. It is believed that the integration of MoS₂ nanocrystals and mesoporous carbon nanofibers may have a synergistic effect, giving a promising anode, and widening the applicability range into high performance and mass production in the Li‐ion battery market.     

Iridium‐ and Osmium‐decorated Reduced Graphenes as Promising Catalysts for Hydrogen Evolution

Renewable energy sources are highly sought after as a result of numerous worldwide problems concerning the environment and the shortage of energy. Currently, the focus in the field is on the development of catalysts that are able to provide water splitting catalysis and energy storage for the hydrogen evolution reaction (HER). While platinum is an excellent material for HER catalysis, it is costly and rare. In this work, we investigated the electrocatalytic abilities of various graphene–metal hybrids to replace platinum for the HER. The graphene materials were doped with 4f metals, namely, iridium, osmium, platinum and rhenium, as well as 3d metals, namely, cobalt, iron and manganese. We discovered that a few hybrids, in particular iridium‐ and osmium‐doped graphenes, have the potential to become competent electrocatalysts owing to their low costs and—more importantly—to their promising electrochemical performances towards the HER. One of the more noteworthy observations of this work is the superiority of these two hybrids over MoS₂, a well‐known electrocatalyst for the HER.     

Aqueous germanate solution,alternative sol–gel precursor for preparation of Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> diluted magnetic semiconductors

The solids content and gelation time of aqueous germanate solution were examined in this work. Samples of 5, 10 and 20 mol% Mn doped Ge were prepared by using the aqueous germanate solution as a liquid Ge precursor. No second phase such as Mn₅Ge₃ was detected in the 5 and 10 mol% Mn doped samples, implying that Mn ions were uniformly diluted into the Ge host matrix. The 5 and 10 mol% Mn-doped Ge samples exhibit room-temperature ferromagnetic behaviors that are likely originated from the RKKY (Ruderman–Kittel–Kasuya–Yosida)-like interaction between the localized Mn ions in the Ge matrix. Therefore, the aqueous germanate solution can be an alternative sol–gel precursor for preparation of the Mn _x Ge_1−x diluted magnetic semiconductors (DMSs).     

粉末紫外二阶非线性光学性能测试研究

为测定粉末材料的紫外波段二阶非线性光学特性,根据Kurtz-Perry粉末倍频效应理论,开展了紫外粉末二阶非线性光学性能测试的研究。测试光源为氙灯泵浦的Nd∶YAG-KTP电光调Q激光器,KTP为二倍频晶体,输出波长532 nm,单脉冲能量100 mJ,重复频率1～10 Hz,脉冲宽度为8 ns。为保证266 nm光的透过率,采用紫外融石英做窗口片,型号为JGS1;为保证测试的准确性,选择光栅光谱仪分光。经紫外常用的KDP、LBO、BBO等测试,证明本方法具有稳定可靠、判别精度高、操作简单等优点,可以有效地定性或半定量测试材料的紫外二阶非线性光学性能,为研究紫外二阶非线性光学材料提供了一种重要的测试手段。     

Structural,Spectroscopic and Thermal Analysis of Cocrystals of Carbamazepine and Piracetam with Hydroquinone

Abstract  

Cocrystals of two important active pharmaceutical ingredients, carbamazepine and piracetam, with hydroquinone are reported. Cocrystal formation between the selected APIs and hydroquinone is investigated with the aid of solid-state grinding methods. Both the crystal structures belong to the triclinic, P [`1]P bar{1} space group, with the cocrystal involving carbamazepine and hydroquinone having the unit cell parameters a = 6.9725 (14) ?, b = 8.8175 (18) ?, c = 15.083 (3) ?, α = 106.96 (3)°, β = 92.16 (3)°, γ = 103.23 (3)°, V = 858.0 (4) ?³ and Z = 2; and the cocrystal involving piracetam and hydroquinone has the unit cell parameters a = 6.4909 (13) ?, b = 6.5410 (13) ?, c = 11.612 (2) ?, α = 103.92 (3)°, β = 104.53 (3)°, γ = 91.06 (3)°, V = 461.59 (18) ?³ and Z = 2. Analysis of the cocrystals revealed that they are sustained by an alcohol–carboxamide heterosynthon. In addition, the cocrystal of carbamazepine and hydroquinone features an amide–alcohol heterosynthon and an alcohol–alcohol homosynthon. The cocrystal of piracetam and hydroquinone features an amide–amide dimer synthon. Cocrystal formation was evidenced from the shifts in the vibrational frequencies corresponding to the functional groups present on the cocrystal components.     

Ar+和trans-/cis-C2H2Cl2解离电荷转移反应的离子速度成像研究(英文)

本文利用离子速度成像方法研究了Ar⁺和trans-/cis-C₂H₂Cl₂的解离电荷转移反应,根据产物离子影像明确了三个反应通道的解离机制.其中,脱氯碎片离子C₂H₂Cl⁺是主要产物,大多数分布在靶分子附近,表明解离过程主要是在大碰撞参数下通过能量共振的电荷转移后发生;同时,有少量的C₂H₂Cl⁺分布在质心附近,这是由C₂H₂Cl₂和Ar⁺在小碰撞参数下发生的紧密碰撞导致的.次要产物C₂HCl⁺展现出与C₂H₂Cl⁺相似的速度分布.而截面最低的产物C₂HCl₂⁺经历了大碰撞参数下的能量共振电荷转移后快速脱氢,基...     

Aliphatic Organoimido Derivatives of Polyoxometalates Containing a Bioactive Ligand

A series of aliphatic organoimido derivatives of hexamolybdate based on amantadine, namely (nBu₄N)₂[Mo₆O₁₈(?NC₁₀H₁₅)] ( 1 ), (nBu₄N)₂ {cis‐[Mo₆O₁₇(?NC₁₀H₁₅)₂]} ( 2 ), (nBu₄N)₂{trans‐[Mo₆O₁₇(?NC₁₀H₁₅)₂]} ( 3 ), and (nBu₄N)₂[Mo₆O₁₆(?NC₁₀H₁₅)₃] ( 4 ), was synthesized in reasonable yield by dehydration with N,N′‐dicyclohexylcarbodiimide (DCC). They were characterized by IR and UV/Vis spectroscopy, elemental analysis, ESI mass spectrometry, and single‐crystal X‐ray structure analysis. The spectral and structural similarities and differences between monosubstituted, cis‐disubstituted, and trans‐disubstituted organoimido derivatives were elucidated and may provide guidance for related work on organoimido‐functionalized Lindqvist‐type polyoxometalates. In addition, trans‐disubstituted and polysubstituted derivatives containing aliphatic organoimido ligands have not yet been reported, and the crystal structure of the trans isomer may lead us to a deeper understanding of disubstituted derivatives. Furthermore, proliferation and morphology of MCF‐7 cells were studied with compound 1 . The present results show that the DCC‐dehydrating protocol could be an efficient approach to covalently graft bioactive ligands such as amantadine onto POMs and enhance their application in clinical cancer treatment.     

Neutral mononuclear, dinuclear, tetranuclear d7/d10 metal complexes containing bis-pyrazole/pyridine ligands supported by 2,6-bis(3-pyrazolyl)pyridine: synthesis, structure, spectra, and catalytic activity

A series of novel bis-pyrazole/pyridine complexes, [Zn(2)(HL(1))(2)(μ(2)-SO(4))](2)·EtOH·H(2)O (1), [Co(2)(HL(1))(2)(μ(2)-SO(4))](2)·2DMF·6H(2)O (2), [Zn(4)(HL(1))(4)(μ(4)-SO(4))][OH](2) (3), [Zn(2)(HL(2))(2)(μ(2)-SO(4))]·2H(2)O (4), [Zn(H(2)L(2))(H(2)O)(2)](SO(4))·0.87H(2)O (5) (H(2)L(1) = 2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine, H(2)L(2) = 2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine), were synthesized hydrothermally from the self-assembly of Zn(II) or Co(II) with different types of bipyrazolyl/pyridine derivative ligands. All the complexes were characterized by elemental analysis, IR and UV-vis spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Structural analyses revealed that metal atoms (Zn and Co) in complexes 1-5 are five-coordination modes, forming slightly distorted trigonal bipyramidal geometries. In complexes 1-3, H(2)L(1) ligand connected the two metal centers via the tetradentate fashion, and the same form of connection was found in complex 4 with H(2)L(2) ligand. While in complex 5, H(2)L(2) only connected with one metal center via the tridentate fashion, which was different from those in complexes 1-4. Additionally, there are abundant hydrogen bonding interactions in complexes 1-4. Interestingly, for hydrogen bonding connecting fashions being different, the molecules for the complexes 1 and 4 are held together by the hydrogen bond to form a 1D supramolecular structure, whereas complexes 2 and 3 are a hydrogen bonded dimer. In addition, quantum chemical calculations for 1, 3, and 4, thermal behaviors and photoluminescent properties for 1 and 3-5 were performed and discussed in detail. In the mean time, we found that these complexes had potential catalytic activity for the oxidation reaction of cyclohexane.