硝酸铵对SO2在大气颗粒物表面气-粒转化影响的模拟研究

利用流动态的原位傅里叶变换红外漫反射光谱(DRIFTS)对含硝酸铵气溶胶(以α-Fe₂O₃为主模拟气溶胶)与SO₂的非均相反应进行了研究, 比较了硝酸铵与其它金属氧化物(CaO, MgO, α-Al₂O₃和SiO₂)与SO₂反应的情况.实验结果表明, 硝酸铵和α-Fe₂O₃混合颗粒物比硝酸铵和其它金属氧化物混合颗粒与SO₂反应的吸附系数高, 表明α-Fe₂O₃比其它金属氧化物催化能力变强.利用BET面积作为反应活性表面积, 发现含有6％(质量分数)NH₄NO₃的α-Fe₂O₃混合颗粒物与SO₂反应具有最高的比表面积吸附系数(γ_BET=2.42×10^-9), 比纯氧化铁的反应高了近1.8倍.而纯NH₄NO₃颗粒与SO₂不发生反应, 表明少量硝酸铵的存在在一定程度上提高了SO₂在气溶胶颗粒物表面转化成硫酸盐的能力. 本文还讨论了含硝酸铵气溶胶与SO₂的反应机制及其对大气环境的影响.     

NH3与Cl2在y-Al2O3颗粒物表面的非均相反应

使用离子色谱分析了常温、常压、湿润和氧气存在条件下,NH₃和Cl₂在γ-Al₂O₃颗粒物表面非均相反应的产物及其受NH₃浓度、反应时间等的影响;并定量分析了NH₃、Cl₂、SO₂和NO₂单独及共存条件下,γ-Al₂O₃表面Cl^-、NO₃^-和SO₄^2-等二次无机颗粒物的生成总量.结果表明：NH₃和Cl₂在γ-Al₂O₃表面具有协同作用,2 h后Cl^-的生成总量可达589.65 μg,其生成量随时间延长而不断增加.表面氯化物的生成量在NH₃浓度为400 ppm时达到峰值,且随NH₃浓度的增加呈先增加而后减少的趋势.活性氯存在下,NH₃对颗粒物表面Cl^-、NO₃^-和SO₄^2-的生成有促进作用,且四种气体共存时复合正反馈效应最明显.同时,本研究对NH₃和Cl₂在颗粒物表面的非均相反应机理及活性氯和氨的排放对大气中二次无机颗粒物的贡献进行了探讨.     

甲醇在CeO2担载Pd催化剂上分解机理的研究

采用原位红外(in-situFTIR)技术对甲醇在CeO₂和Pd/CeO₂催化剂上的吸附和反应进行了研究,提出一个新的甲醇分解反应机理模型.甲醇在CeO₂上容易吸附并结合其晶格氧生成甲酸盐物种,而甲醇分解的产物氢被Pd活化后,溢流到CeO₂上促进了甲酸盐物种的分解.Cl^-的存在加强了Pd/CeO₂催化剂与氢的相互作用,Pd和CeO₂通过对氢和氧物种的作用对甲醇分解反应的过程表现出协同效应.     

Pt掺杂碳纳米管吸附气体小分子的DFT计算

利用B3LYP/LANL2DZ方法对Pt掺杂(5,5)单壁碳纳米管(SCNT)吸附SO₂, HCHO和CO₂三种气体小分子进行了详细的理论计算. 通过分析吸附气体分子前后Pt掺杂SCNT的几何结构、电子态密度变化、前线轨道成分HOMO-LUMO能隙和红外光谱特征, 给出了SCNT-Pt是否有潜力检测这三种气体分子的理论依据.     

五氧化二氮(N2O5)非均相摄取系数的定量和参数化

颗粒物污染是我国超大城市地区面临的主要污染问题,大气化学受到非均相反应的强烈影响。N₂O₅非均相反应过程的定量描述对厘清我国超大城市地区夜间大气氧化性、区域NO_x收支、臭氧生成等问题具有重要意义。本文从反应机理、摄取系数测量技术和不同气溶胶基体测量结果等方面系统总结了N₂O₅非均相反应动力学研究进展。N₂O₅非均相摄取是典型的反应性摄取过程,是气溶胶流动管测量系统的理想应用对象。实验室动力学研究从硫酸盐等模型颗粒物出发,结合外场观测获取的颗粒物信息,模拟使用的颗粒物越来越接近实际大气条件。N₂O₅在不同颗粒物表面摄取系数在0.001~0.2之间,其变化范围超过两个数量级,主要受到环境温度、湿度、颗粒物组分中NO₃^-、Cl^-、SO₄^2-、含水量、有机物、颗粒物混合状态和相态等因素影响;颗粒物中H₂O、Cl^-、SO₄^2-的浓度升高会提高非均相摄取速率,而NO₃^-、有机物则会对摄取过程产生抑制作用。欧美地区外场观测研究表明这些影响因素并不是线性叠加的,而是存在非常复杂的相互作用,基于实验室测量结果开发的参数化公式不能很好地拟合观测结果。由于N₂O₅和颗粒物的高值区共存于污染城市地区,下一步研究需要在包括我国超大城市地区在内的典型城市大气条件下开展更多的外场实测研究和建立更准确的参数化公式。     

SCR脱硝过程中SO2催化氧化的原位红外研究

采用工业用V₂O₅-WO₃/TiO₂催化剂,基于傅里叶原位红外光谱(FT-IR)技术考察SO₂的氧化过程及烟气组分对SO₂氧化行为的影响;结果表明,SO₂在催化剂表面氧化主要是首先吸附在催化剂表面V₂O₅活性位上,占据其O原子,以SO^2-₃形式存在,后与催化剂表面V⁵⁺-OH发生反应,生成金属硫酸盐(VOSO₄)中间产物,O₂重新氧化催化氧化过程中由于被SO₂夺取O原子而被还原的V₂O₅物种,使V⁴⁺转化为V⁵⁺,促进金属硫酸盐(VOSO₄)向SO₃转化;SO₂与NO、NH₃的竞争吸附阻碍SO₂在V₂O₅活性点位上的氧化;在SCR中,NO的脱除与SO₂的氧化是相互抑制的关系。     

CS2与大气颗粒物的多相催化反应研究

利用原位FTIR,XRD,XPS,BET,质谱和连续微量反应等手段研究了大气颗粒物及部分氧化物样品上CS₂多相催化反应,确认了反应产物,并对催化剂的晶化状况和比表面积等进行了考察.结果表明,CS₂在氧化物和大气颗粒物样品上发生氧化反应,生成COS及单质硫,部分样品上生成CO₂,活化状态下的[S]在大气颗粒物表面上能被进一步氧化为六价态硫.收集所得到的大气颗粒物样品成分主要是Ca(Al₂Si₂O₈)·4H₂O;CS₂在氧化物或大气颗粒物样品上催化生成COS是催化剂表面吸附氧的作用之故.     

无碱CO2加氢高效制甲酸Pd/g-C3N4催化剂的单原子和纳米簇的协同作用(英文)

气候变化威胁人类的生存.化石燃料的过度使用导致CO₂持续排放是引起全球变暖和气候变化的主要因素,须尽快减少CO₂排放.捕获CO₂并将其转化为高附加值的燃料和化学品从而循环利用是减少CO₂净排放的有效措施.其中, CO₂催化加氢制甲酸(HCOOH)是碳捕获与利用(CCU)的有效途径之一,其产物HCOOH可用于防腐剂、牲畜饲料抗菌剂和食品添加剂,也可作为氢载体和直接甲酸燃料电池的燃料.目前,工业上生产HCOOH的工艺包括两个步骤:甲醇和CO在强碱条件下反应生成甲酸甲酯(HCO₂CH₃),随后水解为HCOOH.该工艺利用来自化石燃料的两种原料,排放出大量CO₂,同时在水解步骤中使用了过量的酸性水,因此对生态环境产生一定的危害.近年来,以CO₂为可再生原料合成HCOOH被广泛研究,人们探索了电化学、光化学、生物和热化学反应等多种途径将CO₂还原为HCOOH,以期实现CO     

复杂烟气条件下太西活性焦脱除Hg0的实验研究

为了解复杂烟气条件下活性焦吸附剂的脱汞特性,利用汞渗透管和主要气体成分模拟复杂烟气,在实验室规模的固态吸附剂汞吸附效能测定系统上,进行了太西活性焦吸附单质汞的实验研究,并采用FT-IR对活性焦表面进行了光谱表征。结果表明,在活性焦表面存在各种含氧官能团;在CO₂/N₂/O₂/SO₂/Hg⁰烟气体系中,当SO₂加入量为400、855、1 520 mL/m³时,出口汞浓度分别为36、43、48 μg/m³,SO₂对系统吸附Hg⁰的能力有抑制作用;在CO₂/N₂/O₂/NO/Hg⁰烟气体系中,较低浓度的NO对Hg⁰脱除有抑制作用,而高浓度值的NO抑制作用减弱;在CO₂/N₂/O₂/NO/SO₂/Hg⁰烟气体系下,提高NO浓度对Hg⁰脱除有一定的促进作用,而提高SO₂浓度初期促进汞的脱除,后期则表现为抑制作用。     

HO2非均相摄取系数的测量与参数化

HO₂自由基与环境大气气溶胶的非均相反应是HO₂自由基的重要汇之一,对大气氧化能力有重要影响,对大气颗粒物的物化性质等进一步产生影响。HO₂的非均相反应过程的定量描述对不同地区大气氧化性与臭氧生成能力等问题的探求具有重要意义。目前不同研究小组测量的摄取系数可相差3到5个数量级,深入探究不同条件下不同种类气溶胶对HO₂自由基的非均相摄取机制,对摄取机制进行参数化表达,并准确测量摄取系数是量化其环境影响的关键。本文深入介绍了HO₂非均相摄取的原理与参数化表达,总结了已有的研究结果与进展,对不同的影响因素进行总结分析,并对此领域未来的发展方向提出建议与展望。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.