Products and mechanism of the reaction between NO3 and dimethylsulphide in air

The reaction between NO₃ and dimethylsulphide (DMS) in air has been studied in a 480 ℓ reaction chamber. Intermediates and end products were identified by FT-IR and ion chromatography.HNO₃, CH₂O, SO₂ and methanesulphonic acid were found to be the main products of the reaction, with methanesulphonic acid as the most abundant sulphur compound. Organic peroxynitrates and CH₃SNO₂ have been identified as intermediates from their characteristics spectral features. Based on the results obtained a mechanism for the reaction DMS+NO₃ is proposed, which has hydrogen abstraction as the first step. The formation of HNO₃ followed by removal of HNO₃ by deposition may represent an efficient night-time sink of NO_x in the marine troposphere.     

Fabricating Fe3O4-schwertmannite as a Z-scheme photocatalyst with excellent photocatalysis-Fenton reaction and recyclability

Here we reported an effective method to solve the rate-limiting steps, such as the reduction of Fe³⁺ to Fe²⁺ and an invalid decomposition of H₂O₂ in a conventional Fenton-like reaction. A magnetic heterogeneous photocatalyst, Fe₃O₄-schwertmannite (Fe₃O₄-sch) was successfully developed by adding Fe₃O₄ in the formation process of schwertmannite. Fe₃O₄-sch shows excellent electrons transfer ability and high utilization efficiency of H₂O₂ (98.5%). The catalytic activity of Fe₃O₄-sch was studied through the degradation of phenol in the heterogeneous photo-Fenton process. Phenol degradation at a wide pH (3 - 9) was up to 98% within 6 min under visible light illumination with the Fe₃O₄-sch as heterogeneous Fenton catalyst, which was higher than that using pure schwertmannite or Fe₃O₄. The excellent photocatalytic performance of Fe₃O₄-sch is ascribed to the effective recycling between Fe³⁺ and Fe²⁺ by the photo-generated electron, and also profit from the formation of the “Z-Scheme” system. According to the relevant data, photocatalytic mechanism of Fe₃O₄-sch for degrading phenol was proposed. This study not only provides an efficient way of enhancing heterogeneous Fenton reaction, but also gives potential application for iron oxyhydroxysulfate mineral.     

Acid-catalyzed heterogeneous reaction of 3-methyl-2-buten-1-ol with hydrogen peroxide

Acid-catalyzed heterogeneous oxidation with hydrogen peroxide(H2O2) has been suggested to be a potential pathway for secondary organic aerosol(SOA) formation from isoprene and its oxidation products. However, knowledge of the chemical mechanism and kinetics for this process is still incomplete. 3-Methyl-2-buten-1-ol(MBO321), an aliphatic alcohol structurally similar to isoprene, is emitted by pine forests and widely used in the manufacturing industries. Herein the uptake of MBO321 into H2SO4–H2O2mixed solution was investigated using a flow-tube reactor coupled to a mass spectrometer. The reactive uptake coefficients(γ) were acquired for the first time and were found to increase rapidly with increasing acid concentration. Corresponding aqueous-phase reactions were performed to further study the mechanism of this acid-catalyzed reaction. MBO321 could convert to 2-methyl-3-buten-2-ol(MBO232) and yield isoprene in acidic media. Organic hydroperoxides(ROOHs) were found to be generated through the acid-catalyzed route,which could undergo a rearrangement reaction and result in the formation of acetone and acetaldehyde. Organosulfates, which have been proposed to be SOA tracer compounds in the atmosphere, were also produced during the oxidation process. These results suggest that the heterogeneous acid-catalyzed reaction of MBO321 with H2O2 may contribute to SOA mass under certain atmospheric conditions.     

Kinetic study of the gas-phase reaction of O3 with three unsaturated alcohols

Rate constants for the reactions of ozone with 1-octen-3-ol, 1-nonen-3-ol and 1-nonen-4-ol have been determined at 298 ± 1 K and atmospheric pressure for the first time. The experiments were performed in a 100-L FEP Teflon film bag using absolute rate method; the rate constants were(1.91 ± 0.19) × 10~(-17),(1.89 ± 0.20) × 10~(-17), and(0.83 ± 0.08) × 10~(-17)cm~3/(molecule·sec) for 1-octen-3-ol, 1-nonen-3-ol, and 1-nonen-4-ol, respectively. The rate constants have been compared with those of unsaturated alcohols structural homologs, and used to estimate the reaction reactivity. The electronegativity of carbon–carbon double bond was calculated by atomic charges analysis. The calculated results show that the electronic effect of the lone pair electrons of hydroxyl oxygen is the main cause of the difference in rate coefficient. According to the obtained rate constants, the atmospheric lifetimes of studied unsaturated alcohols were also estimated, which indicates that the reaction with ozone is an important loss pathway in the atmosphere, especially in polluted areas.     

Co- or Ni-modified Sn-MnOx low-dimensional multi-oxides for high-efficient NH3-SCR De-NOx: Performance optimization and reaction mechanism

NH₃-SCR performances were explored to the relationship between structure morphology and physio-chemical properties over low-dimensional ternary Mn-based catalysts prepared by one-step synthesis method.Due to its strong oxidation performance,Sn-MnOx was prone to side reactions between NO,NH₃ and O₂,resulting in the generation of more NO₂ and N₂ O,here most of N₂ O was driven from the non-selective oxidation of NH₃,while ...     

胡敏酸与Fe3+络合反应稳定性及热力学特征研究

采用离子交换平衡法研究了在不同酸度、离子强度、温度条件下胡敏酸(HA)与Fe3 络合反应的稳定性和热力学特征.结果表明,在相同离子强度、反应温度条件下,随着pH的升高,HA与Fe3 络合表观稳定常数和配位数均增加,有利于络合反应的进行;相同pH和温度下,离子强度从0到0.10 mol·L-1,HA与Fe3 络合反应表观稳定常数和配位数增加,但离子强度从0.10 mol·L-1继续上升到0.15 mol·L-1,则上述2个特征常数呈现下降的趋势;胡敏酸络合Fe3 标准自由能变△Gθm、焓变△Hθm、熵变△S:在298.2、308.2 K温度下均为负值,反应是自发进行的放热反应,较低的温度有利于反应的进行.     

光Fenton反应的Ce-Fe/Al2O3催化剂制备及性能表征

采用等量浸渍法制备具有相同铁负载量的Fe/Al2O3和Ce-Fe/Al2O3催化剂,以解决光Fenton反应过程中催化剂溶出的问题并提高反应过程的pH值.通过X射线衍射(XRD)、扫描电镜(SEM)、氢程序升温还原(H2-TPR)及紫外-可见漫反射(UV-Vis DRS)等手段分别表征催化剂的物相结构、表面形貌、还原性能及光吸收特性,利用媒介黄的光Fenton脱色反应来考察催化剂的活性和稳定性.结果表明,铈掺杂使活性组分Fe2O3分散均匀,有效防止Fe2O3颗粒的长大,增加催化剂对光的吸收,增强催化剂的储氧能力,提高了催化剂的催化活性,降低铁的溶出.该催化剂在pH3.0～6.0条件下,60min内可将100mg/L媒介黄完全脱色,在pH6.0连续使用10次,其催化能力保持稳定.     

Catalytic performance and reaction mechanisms of NO removal with NH3 at low and medium temperatures on Mn-W-Sb modified siderite catalysts

Iron-based catalysts have been explored for selective catalytic reduction (SCR) of NO due to environmentally benign characters and good SCR activity. Mn-W-Sb modified siderite catalysts were prepared by impregnation method based on siderite ore, and SCR performance of the catalysts was investigated. The catalysts were analyzed by X-ray diffraction, H₂-temperature-programmed reduction, Brunauer-Emmett-Teller, Thermogravimetry-derivative thermogravimetry and in-situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS). The modified siderite catalysts calcined at 450°C mainly consist of Fe₂O₃, and added Mn, W and Sb species are amorphous. 3Mn-5W-1.5Sb-siderite catalyst has a wide temperature window of 180-360°C and good N₂ selectivity at low temperatures. In-situ DRIFTS results show NH₄⁺, coordinated NH₃, NH₂, NO₃⁻ species (bidentate), NO₂⁻ species (nitro, nitro-nitrito, monodentate), and adsorbed NO₂ can be discovered on the surface of Mn-W-Sb modified siderite catalysts, and doping of Mn will enhance adsorbed NO₂ formation by synergistic catalysis with Fe³⁺. In addition, the addition of Sb can inhibit sulfates formation on the surface of the catalyst in the presence of SO₂ and H₂O. Time-dependent in-situ DRIFTS studies also indicate that both of Lewis and Brønsted acid sites play a role in SCR of NO by ammonia at low temperatures. The mechanism of NO removal on the 3Mn-5W-1.5Sb-siderite catalyst can be discovered as a combination of Eley-Rideal and Langmuir-Hinshelwood mechanisms with three reaction pathways. The mechanism of NO, oxidized by synergistic catalysis of Fe³⁺ and Mn^4+/3+ to form NO₂ among three pathways, reveals the reason of high NO_x conversion of the catalyst at medium and low temperatures.

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可渗透反应墙技术中反应介质的研究进展

以PRBs技术中最为关键的填充反应介质为研究对象，介绍了常用的五种反应介质（零价铁、活性炭、无机矿物、黏土、和以固体废弃物为前体材料的反应介质）的研究现状，阐述了影响反应介质选择的主要因素，同时介绍了PRBs技术在实际工程应用中的典型案例，并对PRBs技术的现存问题和未来发展进行了总结和展望，以期为研发长期高效和环境友好型的PRBs反应介质提供有益的支持.     

An investigation of a Friedel-Crafts alkylation reaction in homogeneous supercritical CO2 and under subcritical and splitphase reaction conditions

This study investigates the Friedel-Crafts alkylation reaction of triphenylmethanol with methoxybenzene (anisole) in supercritical and subcritical carbon dioxide, and under two-phase (gas/liquid) reaction conditions at moderate pressures and temperatures. The reaction was initiated using trifluoroacetic acid to produce triphenylmethlycarbocation as the reaction intermediate. Isolated product yields of the Friedel-Crafts product, p-methoxytetraphenylmethane, are reported.     

制备及反应条件对Pt/Al2O3蜂窝状催化剂性能的影响

采用多次涂层 浸渍法制备了蜂窝状Pt Al2 O3 催化剂 .并对焙烧温度和焙烧时间等不同制备条件和反应温度、O2 浓度和空速等不同反应条件下NOx 的选择性催化还原性能进行了研究 .实验表明 ,蜂窝状Pt Al2 O3 催化剂上NOx 转化率在反应温度为 30 0℃左右时出现最高值 .而随反应温度的升高 ,达到最高转化率所需的O2 浓度不断减小 ,分别为 8% ,6 %和 4 % .这可能是由于在高温下O2 会与NO发生竞争吸附 ,从而阻碍了NO催化还原反应的进行 ;同时随着空速的依次增加 ,催化剂的活性逐渐下降 ,催化剂活性曲线的峰值依次向高温方向移动 .实验还说明 ,在过高的焙烧温度和较长的焙烧时间的制备条件下 ,蜂窝状Pt Al2 O3 的催化性能明显下降 .这是因为高的焙烧温度和较长的焙烧时间能够导致蜂窝状Pt Al2 O3 催化剂的表面发生烧结现象 ,使得催化剂的比表面减小 ,从而导致活性降低 .     

NaHSO3和KMnO4组合可渗透反应栅对苯胺的去除特性

采用亚硫酸氢钠（NaHSO₃）强化高锰酸钾（KMnO₄）去除苯胺（AN）.通过批次处理实验研究了AN去除率与反应条件的关系,分析了KMnO₄投加量、NaHSO₃投加量、初始pH值和反应时间之间的交互作用;以石蜡为胶结剂分别制备基于NaHSO₃和KMnO₄的可渗透反应栅（PRB）,对模拟AN污染地下水进行连续处理,研究不同PRB的释放规律和组合PRB对AN的去除特性.结果表明,NaHSO₃可显著强化KMnO₄对AN的降解速率,当AN初始浓度为5mg/L,NaHSO₃/KMnO₄/AN为5/5/1时,AN去除率达99.2%,高于单独KMnO₄处理的85.6%.AN去除率与KMnO₄投加量、NaHSO₃投加量和反应时间线性正相关,与溶液初始pH值线性负相关.采用二次多项式和逐步回归法拟合了AN去除率与反应条件间的关系,模拟值与验证实验结果相近,模型精度较好.PRB中NaHSO₃溶出速率显著大于KMnO₄.当NaHSO₃和KMnO₄混合的可渗透反应栅（SB/PM-PRB）质量为5g,进水流速和AN浓度分别为0.1mL/min和10mg/L时,168h内AN的去除率保持在99%以上,且克服了KMnO₄单独处理出水色度过高的问题.傅里叶变换红外光谱分析表明,反应前后PRB成分没有显著变化,PRB稳定性较好.紫外光谱扫描结果表明,AN和苯环特征峰强度均显著下降,表明SB/PM-PRB能使AN开环降解和破坏氨基结构.     

Heterogeneous reaction of SO2 on CaCO3 particles: Different impacts of NO2 and acetic acid on the sulfite and sulfate formation

Despite the heterogeneous reaction of sulfur dioxide (SO₂) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO₃) combined with NO₂ and acetic acid to investigate their effects on the heterogeneous reaction of SO₂ on CaCO₃ particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO₂ or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO₂ and SO₂ that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO₂ that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO₂ with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.     

短程硝化的生化机理及其动力学

短程硝化的生化反应机理和动力学是生物脱氮技术的理论基础,同时也是生物脱氮工艺设计、运行科学化和合理化的重要依据.基于短程硝化的生化机理、氨氧化菌的电子传递(能量产生)模式,从微生物学和化学计量学两个方面详细论述了短程硝化一系列复杂的生化反应过程.由此可知,短程硝化是一个涉及多种酶及多种中间产物,并伴随着电子(能量)传递的复杂生化反应过程,是基质(NH4 -N)利用(产能代谢)和微生物(氨氧化菌)增殖(合成代谢)两类反应的综合,因此,研究氨氮比利用速率和氨氧化菌比增殖速率动力学则是对短程硝化反应的深层次研讨.并建议采用积分法和微分法来确定动力学参数μnmax、KN、vnmax.     

L-半胱氨酸对酰胺类除草剂的离体脱氯反应与机制

研究了L-半胱氨酸与酰胺类除草剂的反应动力学、热力学及其机制.结果表明,L-半胱氨酸促进酰胺类除草剂的降解,该反应遵循二级动力学方程;除草剂降解速率同除草剂分子的亲电常数线性相关,降低顺序为甲草胺(kL-cysteine=7.65×10-3mol/(L×s))>乙草胺(kL-cysteine=7.23×10-3mol/(L×s))>丁草胺(kL-cysteine=6.01×10-3mol/(L×s))>S-异丙甲草胺(kL-cysteine=2.15×10-3mol/(L×s)),这与其土壤和高效菌降解速率顺序相一致;产物的质谱鉴定表明,L-半胱氨酸取代除草剂分子中氯原子.表明该反应为双分子亲核取代脱氯反应.热力学分析显示,该反应为焓控反应.除草剂间降解速率的差异性由熵变控制,且除草剂的降解速率与反应熵变(ΔS)具有良好的线性关系,ΔS数值越负,除草剂的降解速率越小.分子中N原子上的醚键取代基支链结构及链长度对反应速率影响较大,而芳环取代基结构没有明显影响.     

Investigation of the common intermediates over Fe-ZSM-5 in NH3-SCR reaction at low temperature by in situ DRIFTS

The surface species formed in the reaction of NO and NO₂ with pre-adsorbed NH₃ over a Fe-ZSM-5 catalyst (1.27 wt.% Fe, SiO₂/Al₂O₃ = 25) at low temperature (140°C) were studied by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Through using a background spectrum of NH₃-saturated Fe-ZSM-5, we clearly observed the formation of common intermediates resulting from the reaction of NO₂ or NO + O₂ with pre-adsorbed NH₃. This presents strong evidence that the oxidation of NO to form surface nitrates and nitrites is the key step for standard SCR at low temperature. In addition, the results suggest that in the SCR reaction at low temperature, the NH₄⁺ ions absorbed on Brønsted acid sites are less active than NH₃ adsorbed on Lewis acid sites related to Fe species.     

Laser studies of reaction dynamics

Laser and molecular beam techniques allow detailed study of many dynamical properties of single reactive collisions. The chemical scope of these methods is now very wide and includes internal state preparation of reactants, change of collision energies, state detection of products, and thus determination of state-to-state reaction rates. The great impact of laser spectroscopy on knowledge in the field of structure, molecular energy transfer and the mechanism of elementary chemical reactions is illustrated by a few selected examples, including studies in which laser-induced fluorescence (LIF) has been used to to determine the polarization of reaction products