天然气稳态运行优化的混合整数模型及其算法

天然气稳态运行优化问题的难点在于网络结构复杂、规模大、目标函数及约束高度非线性.针对其混合整数非线性规划模型,基于网络约简和线性化技术,建立了线性近似模型,并提出一种新的求解算法.将新算法用于优化我国西部天然气管网系统,结果表明所提算法是有效的.     

凝胶渗透色谱-气相色谱-离子阱质谱法测定桔梗原药和当归提取物中101种农药残留

建立了凝胶渗透色谱（GPC）-气相色谱-离子阱质谱同时检测桔梗原药和当归提取物中101种农药残留的分析方法。方法采用乙腈超声辅助提取桔梗原药和当归提取物,浓缩提取液至近干后用乙酸乙酯-环己烷（1∶1, v/v）复溶,采用凝胶渗透色谱法（选取40 cm长、内径20 mm的凝胶渗透色谱柱）对样品进行净化,弃去前段含脂类、色素等杂质的流出液,收集17~30 min洗脱液并旋转蒸发浓缩至近干,甲苯1 mL定容上机。选用DB-5MS毛细管色谱柱分离待测物,通过离子阱质谱实现对101种农药残留的高效检测。方法通过优化前处理条件和离子阱二级质谱参数,有效降低了复杂中药基质对待测化合物的干扰,最大限度提高了样品中农药的定量准确性和回收率,101种农药3水平添加的平均回收率为58.3%~108.9%,每个添加水平10次独立重复测定的相对标准偏差为0.4%~16.5%,检出限（LOD）范围为0.2~40.0 μg/kg,可满足当前韩国、日本、欧洲规定的最大残留限量（maximum residue limits, MRLs）要求。方法具有操作简单快速、灵敏度高、重复性好等特点,凝胶渗透色谱技术的应用克服了固相萃取小柱净化容量不足的弊端,离子阱技术的应用可以进一步排除共流出基体杂质的干扰,提高定量和定性的准确性,检测效果优于常用的气相色谱-质谱法,是对中药中同时分析多种农药残留检测方法的有益补充。     

Exposing the Oxygen-Centered Radical Character of the Tetraoxido Ruthenium(VIII) Cation [RuO4]+

The tetraoxido ruthenium(VIII) radical cation, [RuO₄]⁺, should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO₄]⁺, produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO₄]⁺ is identified by the chemical shift at the ruthenium M₃ edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO₄]⁺ to the closed-shell [RuO₄H]⁺ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO₄]⁺ than for [OsO₄]⁺.     

Aggregation-induced Emission Materials for High-efficiency Perovskite Solar Cells

The perovskite solar cells (PSCs) with high efficiency and stability are in great demand for commercial applications. Although the remarkable photovoltaic feature of perovskite layer plays a great role in improving the PCE of PSCs, the inevitable defects and poor stability of perovskite, etc. are the bottleneck and restrict the commercialization of PSCs. Herein, a review provides a strategy of applying aggregation-induced emission (AIE) molecules, containing passivation functional groups and distinct AIE character, which serves as the alternative materials for fabricating high-efficiency and high-stability PSCs. The methods of introducing AIE molecules to PSCs are also summarized, including additive engineering, interfacial engineering, hole transport materials and so on. In addition, the functions of AIE molecule are discussed, such as defects passivation, morphology modulation, well-matched energy level, enhanced stability, hole transport ability, carrier recombination suppression. Finally, the detailed functions of AIE molecules are offered and further research trend for high performance PSCs based on AIE materials is proposed.     

Cu-Doped MoSi2N4 Monolayer as a Potential NH3 Sensor

Cu doped MoSi₂N₄ monolayer (Cu-MoSi₂N₄) was firstly proposed to analyze adsorption performances of common gas molecules including O₂, N₂, CO, NO, NO₂, CO₂, SO₂, H₂O, NH₃ and CH₄ via density functional theory (DFT) combining with non-equilibrium Green's function (NEGF). The electronic transport calculations indicate that Cu-MoSi₂N₄ monolayer has high sensitivity for CO, NO, NO₂ and NH₃ molecules. However, only NH₃ molecule adsorbs on the Cu-MoSi₂N₄ monolayer with moderate strength (−0.55 eV) and desorbs at room temperature (2.36×10⁻³ s). Thus, Cu-MoSi₂N₄ monolayer is demonstrated as a potential NH₃ sensor.     

A Theoretical Perspective to Decipher the Origin of High Hydrogen Storage Capacity in Mn(II) Metal-Organic Framework

Herein, we report a detailed periodic DFT investigation of Mn(II)-based [(Mn₄Cl)₃(BTT)₈]³⁻ (BTT³⁻=1,3,5-benzenetristetrazolate) metal-organic framework (MOF) to explore various hydrogen binding pockets, nature of MOF…H₂ interactions, magnetic coupling and, H₂ uptake capacity. Earlier experiments found an uptake capacity of 6.9 wt % of H_2, with the heat of adsorption estimated to be ∼10 kJ/mol, which is one among the highest for any MOFs reported. Our calculations unveil different binding sites with computed binding energy varying from −6 to −15 kJ/mol. The binding of H₂ at the Mn²⁺ site is found to be the strongest (site I), with H₂ found to bind Mn²⁺ ion in a η² fashion with a distance of 2.27 Å and binding energy of −15.4 kJ/mol. The bonding analysis performed using NBO and AIM reveal a strong donation of σ (H₂) to the d_z² orbital of the Mn²⁺ ion responsible for such large binding energy. The other binding pockets, such as −Cl (site II) and BTT ligands (site III and IV) were found to be weaker, with the binding energy decreasing in the order I>II>III>IV. The average binding energy computed for these four sites put together is 9.6 kJ/mol, which is in excellent agreement with the experimental value of ∼10 kJ/mol. We have expanded our calculations to compute binding energy for multiple sites simultaneously, and in this model, the binding energy per site was found to decrease as we increased the number of H₂ molecules suggesting electronic and steric factors controlling the overall uptake capacity. The calculated adsorption isotherm using the GCMC method reproduces the experimental observations. Further, the magnetic coupling computed for the unbound MOF reveals moderate ferromagnetic and strong antiferromagnetic coupling within the tetrameric {Mn₄} unit leading to a three-up-one-down spin configuration as the ground state. These were then coupled ferromagnetically to other tetrameric units in the MOF network. The magnetic coupling was found to alter only marginally upon gas binding, suggesting that both exchange interaction and the spin-states are unlikely to play a role in the H₂ uptake. This is contrary to the O₂ uptake studied lately, where strong dependence on exchange-coupling/spin state was witnessed, suggesting exchange-coupling/magnetic field dependent binding as a viable route for gas separation.     

Determination of carbonate content in barite ore by headspace gas chromatography

This paper reports a method for determining the carbonate content in barite ore using headspace gas chromatography. Based on the acidification reaction, the carbonate in the barite ore was converted to CO₂ in a closed headspace vial. When the carbonate content was significant, the pressure caused changes in the CO₂ and O₂ signals and affected the measurement accuracy. It was found that carbonate content is proportional to the intensity ratio of the CO₂ to O₂ signals. Thus, the carbonate content in barite ore can be measured indirectly using a theoretical model. The results showed that the carbonate in 3 g of barite ore sample with a particle size of 74 μm could react completely with a hydrochloric acid solution (2 mol/L) at 65°C for 5 min. The method described herein had good precision (relative standard deviation < 4.14%) and accuracy (relative differences < 6.12%). Further, the limit of quantification was 0.07 mol/L. Owing to its simplicity and speed, this method can be used for the batch determination of carbonate content in barite ore.     

Determination of 3-chloro-1,2-propanediol in biological samples by quick-easy-cheap-effective-rugged-and-safe extraction coupled with gas chromatography-mass spectrometry and its biodistribution in rats

3-Chloro-1,2-propanediol is a common food contaminant, but reports on its determination in biological tissues are lacking. In the present study, a method was developed to detect 3-chloro-1,2-propanediol contents in rat tissues by quick-easy-cheap-effective-rugged-and-safe extraction and gas chromatography-mass spectrometry analysis. Biological samples were extracted with ethyl acetate and purified with adsorbents. The optimized adsorbent for each sample was selected from 4–5 combinations of N-propylethylenediamine, octadecylsilane, graphitized carbon black, strong anion exchange, and florisil. Extracted 3-chloro-1,2-propanediol was derivatized with heptafluorobutyric anhydride and subjected to gas chromatography-mass spectrometry. This method had good linearity (correlation coefficients >0.99) in the range of 2–2000 ng/g for blood, kidney, liver, testis, and brain samples. The limits of detection were under 0.8 ng/g; the limits of quantification were 2 ng/g; the recovery rates were 85%–102%; and the matrix effects were 1.98%–7.67%. This method also had good precision. The dynamic changes in 3-chloro-1,2-propanediol in rats gavaged with 20 mg/kg b.w. for 24 h were detected using this method. The 3-chloro-1,2-propanediol content in each tissue sharply increased to a peak, rapidly decreased within 2 h, and stabilized at 12 h. 3-Chloro-1,2-propanediol persisted in the kidney, testis, and liver 24 h after gavage.     

Production of high-purity carbon dioxide and sodium bicarbonate by lime cellar gas cleaning and chemical recycling: Process simulation and techno-economic analysis

The cement industry is responsible for 8% of total global CO₂ emissions, which mainly originate from limestone calcination and fuel combustion. In view of the application potential of using CO₂ to produce chemicals, this paper developed a novel process based on the Aspen Plus process simulation for the co-production of 99.99% CO₂ by means of Methyldiethanolamine (MDEA) absorption/desorption and NaHCO₃ by carbonization of CO₂, NH₃ and Na₂SO₄. The effects of absorption temperature, NH₃ and Na₂SO₄ feeding amount, crystallizer temperature and pressure on CO₂ capture rate and utilization rate were explored. The results showed that the best CO₂ capture rate was achieved when the cellar gas inlet temperature of the absorber tower was 37 °C; Saturated Na₂SO₄ solution was favorable for CO₂ absorption, and the CO₂ utilization rate increased with the increase of Na₂SO₄ dosage; NaHCO₃ yield decreased with the increase of crystallizing temperature, and the best NaHCO₃ yield was achieved when the crystallizer temperature was 35.5 °C; Crystallizing pressure had little impact on the reaction. Economic analysis showed that the project will start to be profitable in 6.48 years with a Net Return Rate (NRR) value of 13.51%. It indicates that the project has economic benefits and provides a new way to reduce CO₂ emissions from lime cellar gas.     

Density functional theory study on sensing properties of g-C3N4 sheet to atmospheric gasses: Role of zigzag and armchair edges

The ability of the polymer-based graphitic carbon nitride (g-C₃N₄) as a gas sensor toward NO, NO₂, CO, CO₂, SO₂, SO₃, and O₂ gasses is assessed using density functional theory (DFT) calculations in terms of energetic and electronic transport characteristics. In particular, this study is aimed to explore the role of zigzag and armchair edges of the g-C₃N₄ sheet on sensing performances. The electronic properties of adsorption systems, such as Bader charge analysis, band gaps, work function, and density of states (DOS), are used to understand the interaction between the adsorbed gas molecules and the g-C₃N₄ sheet. Our calculated results indicate that SOx (SO₃ and SO₂) gasses have higher adsorption energies on the g-C₃N₄ sheet than other gasses. Furthermore, the transport properties, such as current–voltage (I-V) and resistance-voltage (R-V) curves along the zigzag and armchair directions are calculated using the non-equilibrium Green's function (NEGF) method to understand the performance of the g-C₃N₄ sheet as a prominent conductive/resistive sensor. The I-V/R-V results indicate that the zigzag g-C₃N₄ sheet has excellent sensing ability toward SOx gasses at low applied voltages. However, the presence of H₂O degrades the sensing performance of the armchair g-C₃N₄ sheet. Theoretical recovery time has also been calculated to evaluate the reusability of g-C₃N₄ sheet-based gas sensors. Our results reveal that the zigzag g-C₃N₄ sheet-based sensing device has a remarkably high sensitivity (>300%) and selectivity toward SOx gasses and has the potential to work in a complex environment.