Study of Zircon-Dolomite Reactions Monitored by Neutron Thermodiffractometry

The reaction mechanism that takes place in ZrSiO₄-Mg Ca(CO₃)₂ mixtures was studied in air up to 1300°C by collecting neutron diffraction patterns during the heating ramp. Neutron diffraction intensities were used to monitor and establish the mechanism of reaction that occurs in successive stages. (a) MgCa(CO₃)₂ decomposition yielding MgO and CaCO₃; (b) CaCO₃ decomposition; (c) reactions between CaO, MgO, and ZrSiO₄ involving the formation of phases such as: tetragonal-ZrO₂, α-Ca₂SiO₄, and Ca₃MgSi₂O₈, some of them acting as transitory phases; and (d) formation of CaZrO₃. The results obtained by this technique agree with data obtained by differential thermal analysis and thermogravimetry. The final product has a porous structure, due to the release of CO₂, with a very narrow pore size distribution (≈1 μm). This open-porosity can be controlled by tailoring the reaction sintering process.     

Ce(SO4)2‐Mediated Nitration of N,N‐Dialkylanilines with NaNO2 in Water

Ce(SO₄)₂‐mediated nitration of N,N‐dialkylanilines with NaNO₂ using water as the solvent has been achieved in good to excellent yields. The nitrating reaction proceeded smoothly at ambient temperature.     

The Efficient Synthesis of 3,4-Dihydropyrimidin-2-(1H)-Ones and Their Sulfur Derivatives with H2SO4 Immobilized on Activated Charcoal

Abstract

Various 3,4-dihydropyrimidin-2-(1H)-ones (DHPMs) and their sulfur derivatives were efficiently synthesized by a one-pot cyclocondensation reaction of aromatic and aliphatic aldehydes, β-dicarbonyl compounds and urea (or thiourea) in the presence of sulfuric acid immobilized on activated charcoal (133% w/w). The reactions were carried out in refluxing n-hexane-acetonitrile (2.5:0.5 mL) within 5–150 min to give 3,4-dihydropyrimidinones (or thiones) in high to excellent yields (81–97%).     

New Insight into CO2 Reduction to Formate by In Situ Hydrogen Produced from Hydrothermal Reactions with Iron

To reveal the nature of CO₂ reduction to formate with high efficiency by in situ hydrogen produced from hydrothermal reactions with iron, DFT calculations were used. A reaction pathway was proposed in which the formate was produced through the key intermediate species, namely iron hydride, produced in situ in the process of hydrogen gas production. In the in situ hydrogenation of CO₂, the charge of H in the iron hydride was −0.135, and the Fe–H bond distance was approximately 1.537 Å. A C-H bond was formed as a transition state during the attack of H^δ− on C^δ+. Finally, a HCOO species was formed. The distance of the C-H bond was 1.107 Å. The calculated free energy barrier was 16.43 kcal/mol. This study may provide new insight into CO₂ reduction to formate in hydrothermal reactions with metal.     

One-Pot Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones and Their Sulfur Derivatives with H2SO4 Supported on Silica Gel or Alumina

The one-pot condensation of aromatic aldehydes, β-dicarbonyl compounds, and urea or thiourea in the presence of H₂SO₄ supported on silica gel or alumina (80% m/m) in refluxing n-hexane produces 3,4-dihydropyrimidin-2(1H)-ones and their sulfur derivatives in high to excellent yields.     

氮和碳共掺杂TiO2纳米晶的制备及可见光催化性能

以钛酸四丁酯为钛源, 冰醋酸为抑制剂, 超细铵盐为固体载体, 采用新型溶胶-凝胶法制备了氮和碳共掺杂TiO2纳米晶(N-C-TiO2) 光催化剂. 透射电子显微镜(TEM)结果表明, N-C-TiO2样品颗粒均匀, 尺寸细小, 且分散性好; 热失重分析(TGA)、 X射线粉末衍射(XRD)和X射线光电子能谱(XPS)研究结果表明, 复合干凝胶经低温热处理, 使铵盐载体分解、 挥发去除, 样品为单一的锐钛矿相, N和C原子扩散进入晶格结点或间隙位置, 与TiO2化学键结合; 氮气等温吸附-脱附结果表明, 样品比表面积高达356 m2/g, 孔体积为0.27 mL/g. 以氙灯为可见光光源, 罗丹明B水溶液为模拟污染物, P25为参比催化剂, 在辐射强度为100 mW/cm2的可见光照射条件下, N-C-TiO2具有很高的光催化活性, 其可见光催化活性明显高于P25.     

离子热处理合成氮缺陷石墨相氮化碳及其光解水制氢性能

以尿素和二氰二胺为原料热聚合得到石墨相氮化碳,分别采用直接二次煅烧和熔盐离子热后热处理在不同温度下对产物进行后热处理,得到氮缺陷氮化碳CN和CNS。利用X射线衍射(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)、透射电镜(TEM)等手段对所制备样品进行表征和分析,探讨了不同热处理温度和加热方法对催化剂微观聚合结构的影响;同时以光解水制氢为测试方法,考察了催化剂的可见光催化性能。结果表明,熔盐离子热更有利于氮化碳的层间聚合,得到高结晶度材料;在面内七嗪聚合单元中引入氮缺陷,产生末端氰基,优化电荷密度分布,增强电荷流动性;克服粒子尺寸效应,扩展催化剂的光吸收范围;当后热处理温度为500℃时,制备的CNS-500表现出优异的光解水制氢活性,是同温度下直接热处理得到的催化剂的3.84倍。     

Radiation-Induced Oxidation Reactions of 2-Selenouracil in Aqueous Solutions: Comparison with Sulfur Analog of Uracil

One-electron oxidation of 2-selenouracil (2-SeU) by hydroxyl (^●OH) and azide (^●N₃) radicals leads to various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by the density functional theory (DFT) method. The transient absorption spectra recorded in the reactions of ^●OH with 2-SeU are dominated by an absorption band with an λ_max = 440 nm, the intensity of which depends on the concentration of 2-SeU and pH. Based on the combination of conductometric and DFT studies, the transient absorption band observed both at low and high concentrations of 2-SeU was assigned to the dimeric 2c-3e Se-Se-bonded radical in neutral form (2^●). The dimeric radical (2^●) is formed in the reaction of a selenyl-type radical (6^●) with 2-SeU, and both radicals are in equilibrium with K_eq = 1.3 × 10⁴ M⁻¹ at pH 4 (below the pK_a of 2-SeU). Similar equilibrium with K_eq = 4.4 × 10³ M⁻¹ was determined for pH 10 (above the pK_a of 2-SeU), which admittedly involves the same radical (6^●) but with a dimeric 2c-3e Se-Se bonded radical in anionic form (2^●−). In turn, at the lowest concentration of 2-SeU (0.05 mM) and pH 10, the transient absorption spectrum is dominated by an absorption band with an λ_max = 390 nm, which was assigned to the ^●OH adduct to the double bond at C5 carbon atom (3^●) based on DFT calculations. Similar spectral and kinetic features were also observed during the ^●N₃-induced oxidation of 2-SeU. In principle, our results mostly revealed similarities in one-electron oxidation pathways of 2-SeU and 2-thiouracil (2-TU). The major difference concerns the stability of dimeric radicals with a 2c-3e chalcogen-chalcogen bond in favor of 2-SeU.     

丙炴醇聚合膜对铁在酸性溶液中的缓蚀作用

The formation of polymer film of propargyl alcohol(PA) and its protective ability against corrosion in Fe/H_2SO_4 and Fe/H_2SO_4+H_2S systems have been investigated using impedance measurement. The composition and morphology of the corrosion surface of iron, on which PA polymerized at different bines, were obtained with the aid of SEM and AFM as well as EDX. The results showed that PA polymerized into compact polymer film in Fe/H_2SO_4 and Fe/ H_2SO_4 + H_2S systems, which made iron surface smooth and have a morphologies of regular square structure in microscopic level. In Fe/H_2SO_4 system, macroscopic continuous polymer film of PA was not formed leading to local corrosion on electrode surface. In Fe/H_2SO_4 +H_2S system, the adsorption of H_2S and HS - on electrode surface slowed down the formation of polymer film of PA. However, the iron sulfide, produced after a longer time, increased the continuity of the polymer film of PA and therefore, the polymer film could perform its long-te...更多rm inhibition action.     

Assessment of the polluting effects of the Iponri-Alaka Canal,Lagos State,Nigeria

ABSTRACT

The polluting effects of Iponri-Alaka Canal in Surulere area of Lagos State on the environment have been studied using six sampling points. The study aimed at assessing the effects of exposure to pollutants on humans and other life forms. The quality of air, wastewater and sediments was assessed between March and August 2017. The concentrations of SO₂ and H₂S were measured using MSA Altair 5X. Temperature, pH and DO were measured in-situ using Thermometer, pH meter and Winkler method, respectively. TSS, TDS, TS, TA, TH, BOD, chloride Cl^?, PO₄^3-, SO₄^2- and NO₃^? were determined using appropriate standard methods in the laboratory. EC and some heavy metals (Cr, Pb, Mn, Cd and Ni) concentrations were determined using conductivity meter and Atomic Absorption Spectroscopy, respectively. The results showed that pH, TS, DO and TH were well within the WHO and FEPA maximum limits. EC, SO₄^2- and TDS were observed to be higher than guideline values only at one sampling point. The TSS, BOD, TA, NO₃^? and PO₄^3- were higher than WHO and FEPA guideline limits at all sampling points. Cr was seen to be within, while Pb and Mn were higher than WHO and FEPA guideline values. Cd was higher than guideline values only at two sampling points. Ni was below detection concentration at all the sampling points.

The concentration of SO₂ was seen to be higher than WHO and NESREA guideline values at two sampling points, while H₂S concentration was higher than WHO limit at all the six sampling points.     

Gas-Sensing Property of TM-MoTe2 Monolayer towards SO2, SOF2, and HF Gases

Detecting the characteristic decomposition products (SO₂, SOF₂, and HF) of SF₆ is an effective way to diagnose the electric discharge in SF₆-insulated equipment. Based on first-principles calculations, Au, Ag, and Cu were chosen as the surface modification transition metal to improve the adsorption and gas-sensing properties of MoTe₂ monolayer towards SO₂, SOF₂, and HF gases. The results show that Au, Ag, and Cu atoms tend to be trapped by T_H sites on the MoTe₂ monolayer, and the binding strength increases in the order of Ag < Au < Cu. In gas adsorption, the moderate adsorption energy provides the basis that the TM-MoTe₂ monolayer can be used as gas-sensing material for SO₂, SOF₂, and HF. The conductivity of the adsorption system changes significantly. The conductivity decreases upon gases adsorption on TM-MoTe₂ monolayer, except the conductivity of Ag-MoTe₂ monolayer increases after interacting with SOF₂ gas.     

CuSO<Subscript>4</Subscript> as a Mild,Green, and Efficient Catalyst for the One-pot Conversion of <Emphasis Type="Italic">THP</Emphasis> Ethers to Acetates

Summary. An efficient direct conversion of THP ethers into the corresponding acetates was achieved with acetic anhydride in the presence of CuSO₄ · 5H₂O as an available and green catalyst in high yields.     

NH3-SCR脱硝催化剂抗硫性能的研究进展

氮氧化物(NO_x)是一种重要的大气污染物, 它造成严重的环境问题, 同时威胁人类健康. 以钢铁烧结烟气为代表的固定源和以柴油机尾气为代表的移动源是氮氧化物的主要来源. 氨气选择性催化还原法(NH₃-SCR)是目前最有效且应用最广泛的NO_x脱除技术. 然而, 无论是固定源还是移动源上NH₃-SCR催化剂, 都不可避免地会被SO₂毒化, 造成催化剂失活, 限制了NH₃-SCR技术的进一步应用. 因此, 研究NH₃-SCR催化剂的SO₂中毒机制以及提高催化剂的抗硫性能至关重要. 我们对固定源脱硝的金属氧化物和移动源上脱硝的Cu基分子筛这两类不同催化剂体系的SO₂中毒机制的研究进展进行了介绍, 并对这两种催化剂上提高抗硫性能改性方法的研究进展进行了评述, 为未来的研究提供了参考.     

Current Status of the X + C2H6 [X ≡ H,F(2P), Cl(2P), O(3P), OH] Hydrogen Abstraction Reactions: A Theoretical Review

This paper is a detailed review of the chemistry of medium-size reactive systems using the following hydrogen abstraction reactions with ethane, X + C₂H₆ → HX + C₂H₅; X ≡ H, F(²P), Cl(²P), O(³P) and OH, and focusing attention mainly on the theoretical developments. These bimolecular reactions range from exothermic to endothermic systems and from barrierless to high classical barriers of activation. Thus, the topography of the reactive systems changes from reaction to reaction with the presence or not of stabilized intermediate complexes in the entrance and exit channels. The review begins with some reflections on the inherent problems in the theory/experiment comparison. When one compares kinetics or dynamics theoretical results with experimental measures, one is testing both the potential energy surface describing the nuclei motion and the kinetics or dynamics method used. Discrepancies in the comparison may be due to inaccuracies of the surface, limitations of the kinetics or dynamics methods, and experimental uncertainties that also cannot be ruled out. The paper continues with a detailed review of some bimolecular reactions with ethane, beginning with the reactions with hydrogen atoms. The reactions with halogens present a challenge owing to the presence of stabilized intermediate complexes in the entrance and exit channels and the influence of the spin-orbit states on reactivity. Reactions with O(³P) atoms lead to three surfaces, which is an additional difficulty in the theoretical study. Finally, the reactions with the hydroxyl radical correspond to a reactive system with ten atoms and twenty-four degrees of freedom. Throughout this review, different strategies in the development of analytical potential energy surfaces describing these bimolecular reactions have been critically analyzed, showing their advantages and limitations. These surfaces are fitted to a large number of ab initio calculations, and we found that a huge number of calculations leads to accurate surfaces, but this information does not guarantee that the kinetics and dynamics results match the experimental measurements.     

H2S在立方ZrO2(110)面的吸附与解离

采用量子化学的密度泛甬理论方法,探讨了H2S、HS和S在立方ZrO2(110)面上不同吸附位的吸附情况.构型优化的结果表明:在bridge位H2S以垂直底物平面H原子向上、垂直底物平面H原子向下、平行底物平面和hollow位H2S平行底物平面模式吸附在ZrO2(110)面发生解离吸附.SH和S的最佳吸附位分别为桥位和顶位.Mulliken布局和态密度分析显示S原子的p轨道与Zr原子的d轨道发生相互作用.通过计算解离反应的能垒,表明H2S分子在立方ZrO2(110)面发生两步解离.     

Reactions of pyridine-2-ethyl/methyl cyclopentadienes with metal carbonyls

Abstract

Thermal treatment of pyridine-2-ethyl cyclopentadiene (1) with Fe(CO)₅ and Ru₃(CO)₁₂ gave novel intramolecular C–H activated dinuclear products (3 and 5). In the case of Fe(CO)₅, the reaction also afforded the normal bis(cyclopentadienyl) diiron complex (4). However, similar reaction of pyridine-2-methyl cyclopentadiene (2) with Fe(CO)₅ and Ru₃(CO)₁₂ only afforded the normal bis(cyclopentadienyl) dinuclear metal complexes (7 and 8). For Ru₃(CO)₁₂, the reaction also yielded a pendant η¹-pyridyl-coordinated product (9). In addition, the reactions of 1 and 2 with Re₂(CO)₁₀ formed the corresponding pyridylethyl/pyridylmethyl cyclopentadienyl rhenium tricarbonyl complexes 10 and 11, which further underwent pyridine to rhenium cyclization via photoirradiation to provide the rhenium dicarbonyl complexes 12 and 13. The molecular structures of 3, 5, 6, 7, 8, 9, and 12 were determined by X-ray diffraction.     

Investigation on The Thermal Properties of Fe2O(SO4)2. Part II

Fe₂O(SO₄)₂ is a secondary product of the decomposition of FeSO₄⋅H₂O. Part I of this study presents results on the synthesis of Fe₂O(SO₄)₂ in gaseous environment containing either low or high concentration of oxygen. In this paper the existence of differences between the structures of Fe₂O(SO₄)₂ and Fe₂(SO₄)₃ is proved on the basis of a detailed thermal study of Fe₂O(SO₄)₂ upon dynamic heating (differential thermal analysis) and upon isothermal heating (thermal-analytic balance) in various gaseous environments as well as by presenting kinetic data on the processes of decomposition of both compounds. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ab initio and density functional theory study of the enthalpies of formation of F2SOx and FClSOx (x=1, 2)

Enthalpies of formation of F₂SO, F₂SO₂, FClSO and FClSO₂ molecules have been determined using ab initio molecular orbital theory and density functional theory (DFT) calculations. Different DFT approaches and levels of the Gaussian-3 and the complete basis set (CBS) ab initio model chemistries have been employed to calculate enthalpies of formation from both total atomization energies and isodesmic reaction schemes. The best values at 298 K for F₂SO, F₂SO₂, FClSO and FClSO₂ as derived from an average of G3, G3B3, CBS-Q and CBS-QB3 isodesmic energies are −140.6, −181.1, −92.6 and −132.3 kcal mol⁻¹, respectively. The results obtained suggest that the accumulated small component errors found in the DFT-based methods are significantly reduced at the ab initio levels employed. Structural properties, harmonic vibrational frequencies, mode assignations and infrared intensities derived from B3LYP and mPW1PW91 functional with the 6-311+G(3df) basis set are presented.