Simultaneous measurement of SO_2 and NO_2 concentration using an optical fiber-based LP-DOAS system

SO2 and NO2 are the most important pollution in atmosphere.An optimized long path(LP)differential optical absorption spectroscopy(DOAS)system of high light intensity at an ultraviolet(UV)wavelength is proposed and used to measure the concentration of SO2 and NO2 simultaneously.In contrast to the traditional DOAS,the system adopted a Y-type optical fiber structure instead of a combination of mirrors in the telescope.The UV light intensity test shows that the light intensity of UV can arrive to above 80% of the max measuring range when the light path reaches 135 m,and the integral time of the spectrograph is only 15 ms.The system is proved to be efficacious through laboratory calibration.The maximum error of SO2 calibration is 4.19%,and is 5.22% for NO2.The error of the SO2 and NO2 mixture calibration is within 10%.Field measurement is implemented in a wastewater treatment plant in winter.The measurement light path is 738 m.The concentration of SO2 varies from 6μg/m^3(2.26 ppb)to 20μg/m^3(7.52 ppb),and the concentration of NO2varies from 100μg/m^3(53.2 ppb)to 200μg/m^3(106.4 ppb)approximately.The results are in accordance with the data from a monitoring station nearby in magnitude order and variation tendency mostly.     

高压烧结制备Tb掺杂n型(Bi1–xTbx)2(Te0.9Se0.1)3合金及其微结构和热电性能

采用高压烧结技术制备了稀土元素Tb掺杂的n型Bi2Te2.7Se0.3基纳米晶块体热电材料.将高压烧结成型的样品于633 K真空退火36 h.研究了Tb掺杂量对样品的晶体结构和热电性能的影响.结果表明,高压烧结制备的样品为纳米结构, Tb掺杂使样品的晶胞体积变大,功率因子增大,热导率降低,从而使ZT值提高.Tb掺杂量为x=0.004是最优的掺杂量,该掺杂量的高压烧结样品经退火处理后,于373 K时ZT值达到最大为0.99,并且在323-473 K范围内, ZT值均大于0.8,这对用于温差发电领域具有重要意义.     

光学共振增强的表面铯激活银纳米结构光阴极

金属光阴极因其超短脉冲发射和运行寿命长的特性从而具有重要应用价值,但是较高的功函数和较强的电子散射使其需要采用高能量紫外光子激发且光电发射量子效率极低.本文利用Mie散射共振效应增强银纳米颗粒中的局域光学态密度,提升光吸收率和电子的输运效率,并利用激活层降低银的功函数,从而增强光阴极在可见光区的量子效率.采用时域有限差分方法分析银纳米球阵列的光学共振特性,采用磁控溅射和退火工艺在银/氧化锡铟复合衬底上制备银纳米球,紧接着在其表面沉积制备铯激活层,最后在高真空腔体中测试光电发射量子效率.实验结果表明平均粒径150 nm的银纳米球光阴极在425 nm波长的量子效率超过0.35%,为相同激活条件下银薄膜光阴极的12倍,峰值波长与理论计算的Mie共振波长相符合.     

脱氧核糖核酸与对二甲氨基偶氮苯邻羧酸作用机理的荧光光谱研究

通过实验,采用荧光光谱法研究了对二甲氨基偶氮苯邻羧酸(JJR)与脱氧核糖核酸(DNA)结合反应的特征.由Stern-Volmer方程和双倒数曲线Lineweaver-Burk方程获得了反应的猝灭常数Ksv=1×106～2×106 L/mol、结合常数KA≈0.5×106 mol/L以及对猝灭的类型做出了推断.通过热力学参数、离子强度实验讨论并得到它们以氢键、嵌插入、范德华力等几种方式作用.该反应的最佳实验条件为pH值控制在6.1左右;加入顺序为JJR+DNA+(B-R)适宜反应体系;线性范围在0～100 mg/L之间.     

Separation of inorganic anions by reversed-phase ion-pair chromatography with direct UV detection

In this paper, a separation method of the inorganic anions including I^–, NO ₂ ^– , NO ₃ ^– , IO ₃ ^– and SCN^– on the reversed-phase ion-pair chromatography with direct UV detection has been developed, and the limits of detection of these inorganic anions were determined. The effects of the organic modifier volume fraction and concentration of the ion-pair reagent on the retention of inorganic anions were discussed.     

酞菁化合物LB单分子膜的SERRS

酞菁类化合物具有优良的光电特性,选择适当的取代侧链可得到稳定的LB成膜材料,可望在微电子器件等方面获得重要的应用.本工作观测了四-4-(2,4-二特戊基苯氧基)酞菁铜(CuPc(Dt-PP)_4)在银岛膜上的LB单分子层的表面增强共振拉曼散射(SERRS)光谱。比较其固体粉末的共振拉曼散射(RRS)光谱,讨论了酞菁铜分子大环在载片表面的取向及其可能的原因。1 实验CuPc(Dt-PP)_4样品由陈文启等合成,经元素分析、IR、NMR、色谱等研究确认其结构如图1所示.银岛膜用真空蒸镀法制备在玻璃载片上。用同时蒸镀在铜网上的银膜的透射电     

Controlling Metallophilic Interactions in Chiral Gold(I) Double Salts towards Excitation Wavelength‐Tunable Circularly Polarized Luminescence

Materials exhibiting excitation wavelength‐dependent photoluminescence (Ex‐De PL) in the visible region have potential applications in bioimaging, optoelectronics and anti‐counterfeiting. Two multifunctional, chiral [Au(NHC)₂][Au(CN)₂] (NHC=(4R,5R)/(4S,5S)‐1,3‐dimethyl‐4,5‐diphenyl‐4,5‐dihydro‐imidazolin‐2‐ylidene) complex double salts display Ex‐De circularly polarized luminescence (CPL) in doped polymer films and in ground powder. Emission maxima can be dynamically tuned from 440 to 530 nm by changing the excitation wavelength. The continuously tunable photoluminescence is proposed to originate from multiple emissive excited states as a result of the existence of varied Au^I???Au^I distances in ground state. The steric properties of the NHC ligand are crucial to the tuning of Au^I???Au^I distances. An anti‐counterfeiting application using these two salts is demonstrated.     

MIL-53(Al)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用

卤代苯胺是化学工业中重要的中间体,主要用于制造药物、聚合物、染料等含氮化学品,用多相金属催化剂催化卤代硝基芳烃加氢制备卤代苯胺是一种高效,绿色和可持续发展的生产工艺.该过程需要选择性加氢硝基基团,同时避免卤素基团的脱卤副反应发生.然而,化学选择性加氢存在巨大的挑战,难点在于催化剂的精准设计,一方面要求具备对硝基基团合适的加氢能力,另一方面要阻止对卤素基团的脱卤副反应发生.基于此,研制高效多相金属催化剂用于卤代硝基芳烃选择性加氢制备卤代苯胺反应引起了高度关注.近年来,单原子金属催化剂受到越来越多的关注,并在卤代硝基芳烃选择性加氢制备卤代苯胺反应中显现出极大的潜力.本文通过在金属有机骨架材料MIL-53(Al)自组装的过程中将金属Rh原位嫁接其骨架结构中,继而通过限域热解的方法制备了Rh@Al2O3@C单原子催化剂,其在间氯硝基苯(m-CNB)加氢制间氯苯胺(m-CAN)反应中显现了高效催化选择性.球差校正高角度环形暗场模式的透射电镜,CO作为探针分子的红外光谱和X射线光电子能谱等结果发现,Rh是以单原子的形式均匀的分布在Al2O3上并被无定型碳包覆,且Rh化学价态呈正价.而27Al固体核磁共振与密度泛函理论计算的结果则进一步确定Al2O3@C载体中存在的五配位的Al物种(AlV)是锚定Rh单原子的主要位点,AlV的不饱和的配位结构可以有效地稳定Rh单原子,对形成Rh位点的单原子分散至关重要.在间氯硝基苯选择性加氢制间氯苯胺反应中,与等体积浸渍法制备的Rh/C和Rh/γ-Al2O3纳米催化剂相比,Rh@Al2O3@C单原子催化剂表现出优异催化性能:其在313 K,氢气压力为20 bar的温和条件下转换频率(TOF)高达2317 molm-CNB·molRh-1·h-1,优于已报道的多相金属催化剂,是目前的最高值.此外,该催化剂展现出极佳的稳定性能,经过五次循环后,该催化剂对m-CAN的选择性仍旧保持在98％左右.Rh@Al2O3@C单原子催化剂的优异催化性能源自于金属单原子结构的形成对于金属位点电子结构的有效调节,进而调控催化剂加氢性能并实现对加氢脱卤副反应的抑制;与此同时,Rh@Al2O3@C催化剂增进了酸位点的可及性,从而促进了其串联步骤中包含的脱水反应的发生,进而有效提高催化剂的反应活性.     

原位拉曼光谱与X射线吸收光谱研究能源转换电催化反应

近年来,水分解、氧气/二氧化碳还原等电化学能源转换技术为解决全球能源短缺及环境问题提供了新的思路和方向.然而,对这些能源转换技术的反应机理及其催化剂的活性位点目前仍缺乏深刻的认识和理解,这限制了高效、稳定催化剂的开发,以致阻碍该类电化学技术的进一步发展.原位光谱技术的快速发展为解决上述问题提供了坚实的基础,其中拉曼光谱...     

Modification of porous lignin with metalloporphyrin as an efficient catalyst for the synthesis of cyclic carbonates

Transition Metal Chemistry - The conversion of carbon dioxide into useful chemical raw materials is a necessary development for advancing carbon dioxide capture and storage technology. In this...