Theoretical Study of Ethanethiol Adsorption on HZSM-5 Zeolite

The density functional theory and the cluster model methods have been employed to investigate the interactions between ethanethiol and HZSM-5 zeolites. Molecular complexes formed by the adsorption of ethanethiol on silanol H3SiOH with two coordination forms, model Bronsted acid sites of zeolite cluster H3Si(OH)Al(OH)2SiH3 interaction with ethanethiol, aluminum species adsorbed ethanethiol have been comparatively studied. Full optimization and frequency analysis of all cluster models have been carried out using B3LYP hybrid method at 3-21G basis level for hydrogen atoms and 6-31G(d) basis set level for silicon, aluminum, oxygen, carbon, and sulfur atoms. The structures and energy changes of different coordination forms of H3Si(OH)Al(OH)2SiH3-ethanethiol, silanol-ethanethiol and Al(OH)3-ethanethiol have been studied. The calculated results showed the nature of interactions was van der Waals force as exhibited by not much change in geometric structures and properties. The preference order of ethanethiol adsorbed on HZSM-5 zeolite may be residual aluminum species, bridging hydroxyl groups and silanol OH groups from the adsorption heat. The adsorbed models of protonized ethanethiol on bridging hydroxyl OH groups and linear hydrogen bonded ethanethiol on bridging OH groups suggested in literature might not exist as revealed by this theoretical calculation. Possible adsorption models were obtained for the first time.     

Dynamic coating of a capillary with room-temperature ionic liquids for the separation of amino acids and acid drugs by capillary electrophoresis

A room-temperature ionic liquid (IL), 1-ethyl-3-methyl-imidazolium tetrafluoroborate (1E-3MI-TFB), used for the coating of a silica capillary enables one to reduce or invert the electroosmotic flow (EOF) in capillary zone electrophoresis. Excellent separations of amino acids and ary lalkanoic acids were obtained. Such separations could not be obtained in a naked capillary in the presence of the cationic surfactants cetyltrimethylammonium bromide (CTAB) or polycationic polymer hexadimethrine bromide (HDB). The results indicate that 1E-3MI-TFB not only modulates the EOF but also acts as a discriminator. Further experiments indicate that the interaction between hydrogen at C-2 carbon of IL and acid drugs plays an important role in the separation. The text was submitted by the authors in English.     

Thermal degradation kinetics of polyimide containing 2,6-benzobisoxazole units

A novel polyimide (PI) based on 2,6-bis(p-aminophenyl)-benzo[1,2-d;5,4-d′]bisoxazole has been synthesized via a conventional two-stage procedure with bis(ether anhydrides) (HQDPA). The intermediate poly(amic acid) had inherent viscosities of 1.70 dl/g and could be thermally converted into light yellow polyimide film. The resulted polyimide showed excellent thermal stability, and the glass transition temperatures (T_g) were above 283 °C, the 5% weight loss temperature of the polymer was at 572 °C in N₂. The thermal degradation of the polyimide was studied by thermogravimetric analysis (TGA) in order to determine the actual reaction mechanisms of the decomposition process. The activation energy of the solid-state process was determined using Flynn-Wall-Ozawa method, which does not require knowledge of the reaction mechanism, which resulted to be 361.36 kJ/mol. The activation energy of different mechanism models and pre-exponential factor (A) were determined by Coats-Redfern method. Compared with the value obtained from the Ozawa method, the actual reaction mechanism obeyed nucleation and growth model, Avrami-Erofeev function (A₃) with integral form g(X) = [−ln(1−X)]³.     

Anion and Additive Effects on the Structure of Mercury(II) Halides Complexes with Tripodal Ligand

The metal complexes [Hg₂(tbim)₂Br₄]·2DMF ( 1 ) and [Hg₂(tbim)I₄]·1.5DMF ( 2 ) were prepared by reactions of 1,3,5‐tris(benzimidazol‐1‐ylmethyl)‐2,4,6‐trimethylbenzene (tbim) with HgBr₂, HgI₂, respectively, and [Hg₂(tbim)I₄]·0.5(FeCp₂)·H₂O ( 3 ) was obtained by the same method with addition of ferrocene (FeCp₂) as additive. Their structures were determined by X‐ray crystallographic analyses. Complex 1 has a macrocyclic binuclear structure with one benzimidazole arm of the ligand free of coordination and the binuclear units are further connected by C‐H···N hydrogen bonds to give an infinite zigzag chain. Complexes 2 and 3 have a 2D network structure in which tbim serves as a tridentate ligand. The results showed that the halides of bromide and iodide have remarkable impact on the structure of the complexes. The FeCp₂ molecules are trapped in the voids of framework 3 .     

Competitive adsorption of Pb2+, Cu2+, and Cd2+ ions on microporous titanosilicate ETS-10

In the present study, the competitive adsorption characteristics of binary and ternary heavy metal ions Pb2+, Cu2+, and Cd2+ on microporous titanosilicate ETS-10 were investigated in batch systems. Pure microporous titanosilicate ETS-10 was synthesized with P25 as the Ti source and characterized by the techniques of X-ray diffraction (XRD), field emission-scanning electron microscope (FESEM), nitrogen adsorption, and zeta-potential. Equilibrium and kinetic adsorption data showed that ETS-10 displays a high selectivity toward one metal in a two-component or a three-component system with an affinity order of Pb2+ > Cd2+ > Cu2+. The equilibrium behaviors of heavy metals species with stronger affinity toward ETS-10 can be described by the Langmuir equation while the adsorption kinetics of the metals can be well fitted to a pseudo-second-order (PSO) model.     

双功能型嵌入镍纳米颗粒的碳棱柱状微米棒电极用于电化学甲醇氧化助力的节能产氢

With the rapid development of human society, clean energy forms are imperative to sustain the normal operations of various mechanical and electrical facilities under a cozy environment. Hydrogen is considered among the most promising clean energy sources for the future. Recently, electrochemical water splitting has been considered as one of the most efficient approaches to harvest hydrogen energy, which generates only non-pollutant water on combustion. However, the sluggish anodic oxygen evolution reaction significantly restricts the efficiency of water splitting and requires a relatively high cell voltage to drive the electrolysis. Therefore, seeking a thermodynamically favorable anodic reaction to replace the sluggish oxygen evolution reaction by utilizing highly active bifunctional electrocatalysts for the anodic reaction and hydrogen evolution are crucial for achieving energy-efficient hydrogen production for industrial applications. Nevertheless, it is known that the oxygen evolution reaction can be replaced with other useful and thermodynamically favorable reactions to reduce the electrolysis voltage for realizing energy-efficient hydrogen production. Therefore, in this study, we present a bifunctional nickel nanoparticle-embedded carbon (Ni@C) prism-like microrod electrocatalyst synthesized via a two-step method involving the synthesis of a precursor metal-organic framework-74 and subsequent carbonization treatment for methanol oxidation and hydrogen evolution. The interfacial structure consisting of a nickel and carbon skeleton was realized via in situ carbonization. However, the dispersed nickel nanoparticles do not easily aggregate owing to the partition by the surrounding carbon as it would sufficiently expose the active Ni sites to the electrolytes, ensuring fast charge transfer between the catalyst and electrolytes by accelerating the electrochemical kinetics. In the anodic methanol oxidation, the products were detected as carbon dioxide and formate with faradaic efficiencies of 36.2% and 62.5%, respectively, at an applied potential of 1.55 V. Meanwhile, the Ni@C microrod catalyst demonstrated high activity and durability (2.7% current decay after 12 h of continuous operation) toward methanol oxidation, which demonstrates that methanol oxidation precedes oxidation under voltage forces. Notably, the bifunctional catalyst not only exhibits excellent performance toward methanol oxidation but also yields a low overpotential of 155 mV to drive 10 mA∙cm⁻² toward hydrogen evolution in 1.0 mol∙L⁻¹ KOH aqueous solution with 0.5 mol∙L⁻¹ methanol at room temperature, which guarantees the hydrogen production efficiency. More importantly, the constructed two-electrode electrolyzer produced a current density of 10 mA∙cm⁻² at a low cell voltage of 1.6 V, which decreased by 240 mV after replacing the oxygen evolution reaction with methanol oxidation.     

Highly efficient non-doped blue fluorescent OLEDs with low efficiency roll-off based on hybridized local and charge transfer excited state emitters

Designing a donor–acceptor (D–A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D–π–A fluorescent molecule (triphenylamine–anthracene–phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L''Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A⁻¹, power efficiency of 12.35 lm W⁻¹, luminescence of ≈29 900 cd cm⁻², and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m⁻² with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.

A new pure fluorescent blue HLCT-emitter was designed and synthesized. Highly efficient non-doped blue OLEDs with low efficiency roll-off were achieved.     

Dithienylmaleimide-based D-A Conjugated Polymer Film: Photo-Responsive Behavior and Application in Electrical Memory and Logic Gates

Solid-stated smart polymers responsive to external stimuli have attracted much attention for potential application in the field of photoelectron devices, logic gates, sensor, data storage and security. However, it is a bigger challenge for polymers than that for small molecules in solid state to acquire stimuli-responsive properties, because polymers with high molecular weight are not as easy to change the packing structure as small molecules under external stimulation. Here, a D-A type alternat...     

2-氨基-4-苯基-硒唑Ni(Ⅱ)、Cu(Ⅱ)配合物的合成与表征

合成了2-氨基-4-苯基-硒唑（L）配体与过渡金属镍（Ⅱ）、铜（Ⅱ）的配合物Ni（L）（NO3）2（1）和Cu（L）（Ac）2·H2O（2）．用元素分析、摩尔电导、红外光谱、紫外一可见光谱、核磁共振和热重分析进行了表征;确定了配合物的组成并推断了它们的结构。     

应用极化水分子模型研究单分子层受限水的介电性质

受限条件下水的介电性质因测量极具挑战,其在诸多电化学过程与反应输运过程中如何扮演关键角色从未被定量地澄清.本工作利用平衡态分子动力学模拟和受限体系介电性质计算方法,系统性地探索了0.65 nm限域尺寸、5×10⁸ Pa限域压强、不同温度条件下单分子受限冰和受限水的介电性质.详细比较了恒定偶极矩SPC/E水分子模型和可极化的SWM4-NDP水分子模型在描述受限冰、水结构与介电性质上的优劣势,包括统计分析SWM4-NDP模型模拟的单分子层受限水和受限冰的瞬时分子偶极矩概率密度分布,计算每个模拟体系的静态结构因子、静态偶极空间关联函数、静态介电常数、体系偶极时间关联函数和德拜弛豫时间.首次发现了极化水分子模型描述的低维度受限水和受限冰的奇异分子极性变化,并观察到两种模型描述静态结构性质的效果相当, SWM4-NDP模型对于静态介电常数描述的优势会因受限条件的增强而被大幅削减.但在受限水介电极化弛豫动力学性质描述上SWM4-NDP模型明显优于SPC/E模型.我们推断SWM4-NDP模型在探索受限水结构相变动力学以及受限体系离子输运和溶剂化动力学等过程的模拟研究中是比SPC...