基于连续量子级联激光器的1103.4cm–1处NH3混叠吸收光谱特性研究

由于NH3在大气气溶胶化学中具有重要作用,所以快速和精确反演NH3浓度对环境问题非常重要.本文以9.05μm的室温连续量子级联激光器(quantum cascade laser,QCL)作为光源,采用波长扫描直接吸收可调谐二极管激光吸收光谱(tunable diode laser absorption spectroscopy,TDLAS)技术,研究了QCL在1103.4 cm–1的光谱特性,获得了激光器控制的温度电流与波长的关系.设计了QCL二级温控的低压实验平台,测量氨气在1103.4 cm–1处的6条混叠吸收线,在降低压强的情况下谱线展宽变小,使混叠光谱分离,由此计算各条吸收线的线强,进一步对测量不确定度进行分析.针对混叠严重的光谱提出了低压分离单光谱精确反演气体浓度的方法,并进行了实验验证.通过与HITRAN数据库进行结果对比,得出氨气在1103.4 cm–1的实验测量线强值与数据库偏差为2.71%-4.71%,实验测量线强值的不确定度在2.42%-8.92%,极低压条件下反演浓度与实际值的偏差在1%-3%.     

Photo-catalytic Staphylococcus aureus inactivation and biofilm destruction with novel bis-tridentate iridium(III) photocatalyst

Bacterial infection is currently a serious challenge globally, causing death of thousands of human beings. New antimicrobial agents with novel mechanism of action are urgently needed. Transition metal complexes have shown great potentials in photodynamic and photocatalytic therapy. Herein, we take full advantage of metal photocatalyst and successfully developed a novel cyclometalated iridium(III) complex (Ir1) with higher biofilm damage efficiency than the clinical antibiotics. Ir1 synergistically generates reactive oxygen species and coenzyme photocatalytic activity with high efficiency under white light irradiation. Combined with these properties, Ir1 exhibited excellent photoinactivation of S. aureus and effectively damaged the biofilm. This work provides a new approach for the development of antibacterial photodynamic therapy.     

长光程共振式二氧化碳气体光声传感器研究

二氧化碳(CO₂)是植物光合作用的原材料,也是一种温室气体,其过量地排放会影响动植物的生态环境。在碳达峰、碳中和的背景下,研制高灵敏度的CO₂检测装置具有重要意义。为了监测大气环境中CO₂含量的变化,设计了一种长光程共振式CO₂气体光声传感器,并以此搭建了光声检测装置。以中心波长为2 004 nm的分布式反馈激光器(DFB)作为激发光源,激光射入由漫反射材料制成的球型吸收腔,在腔内多次反射以增加气体的吸收路径。吸收腔外部被两个高热传导率的铝制半球包裹,降低由池体吸收光能后产生的热噪声。吸收腔上耦合一根声学管,当其工作在一阶纵向共振模态时,光声信号被放大,在管子末端达到极大值。为了进一步增大光声信号,通过饱和加湿样品的方式来加快CO₂气体的弛豫速率,加湿后的样品产生的光声信号是干燥样品的2.1倍左右。使用一系列浓度的湿润CO₂样品标定光声检测装置,结果表明,光声信号与浓度之间呈现良好的线性关系。在此基础上,通过对标准气体的检测实验,验证了装置的准确性与稳定性...     

Thermodynamic evaluation and optimization of the (NaF + AlF3 + CaF2 + BeF2 + Al2O3 + BeO) system

A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases and relevant gaseous species of the (NaF + AlF₃ + CaF₂ + BeF₂ + Al₂O₃ + BeO) system, and optimized model parameters have been found. The (NaF + AlF₃ + CaF₂ + Al₂O₃) subsystem, which is the base electrolyte used for the electro-reduction of alumina in Hall–Héroult cells, has been critically evaluated in a previous article. The Modified Quasichemical Model in the Quadruplet Approximation for short-range ordering was used for the molten salt phase. The thermodynamic database developed is a first step towards a quantitative study of the beryllium mass balance in an electrolysis cell. In particular, the predominant Be-containing species in the gas phase evolved at the anode were identified; and, for a given beryllium content of the alumina, the beryllium content of the electrolytic bath at steady state was assessed under several approximations.     

Self-discharge in positively charged polypyrrole–cellulose composite electrodes

Self-discharge is one of the most critical issues to address to allow for industrialization of conducting polymer (CP) based electric energy storage devices. The present work investigates the underlying cause of self-discharge in positively charged polypyrrole (PPy), which is one of the most frequently studied CPs for such devices. The analyzed material is a composite of PPy and cellulose from Cladophora sp. algae forming a free standing paper-like material. From the time dependence of the potential decay as well as from independent spectroelectrochemical investigations the decay was attributed to a kinetically limiting Faradaic reaction, intrinsic to the polymer, forming a reactive intermediate that irreversibly reacts with its surroundings in a kinetically non-limiting following reaction. As such, nucleophilic addition of electrolyte nucleophiles is not found to be rate-determining. These results provide insight into the self-discharge phenomenon in p-doped CPs, and information regarding the potential range in which CPs can operate with insignificant self-discharge.     

Faraday rotation spectrometer with sub-second response time for?detection of nitric oxide using a cw DFB quantum cascade laser at?5.33 μm

A Faraday modulation spectrometer for sensitive and fast detection of nitric oxide at 5.33 μm utilizing a room temperature continuous wave distributed feedback quantum cascade laser and a Peltier cooled MCT detector is presented. The magnetic field was modulated at 7.4 kHz whereas the laser wavelength was scanned at 20 Hz across the most favorable rotational-vibrational transition for FAMOS, Q _3/2(3/2), at 5.33 μm. Using a 15 cm optical path and lineshape fitting, the spectrometer provides a detection limit of 4.5 ppb for a response time of 1 s. An Allan variance analysis demonstrates that the system has an excellent stability, up to several hours of operation.     

Direct sunlight responsive Ag–ZnO heterostructure photocatalyst: Enhanced degradation of rhodamine B

The catalytic activity of Ag–ZnO heterostructure on the photocatalytic degradation of rhodamine B was investigated. It demonstrated that Ag–ZnO heterostructure exhibited an enhanced photocatalytic activity compared to pure ZnO nanoparticles under direct sunlight. The possible factors to the photocatalytic acitivity of the sample were explored, including Ag content, dispersity and calcination temperature. It was shown that the sample dispersed by PVP, with 5% mol ratio Ag content, calcined at 400 °C showed the highest photocatalytic acitivity and this catalyst was reusable.     

基于O2-O2吸收的非相干宽带腔增强吸收光谱浓度反演方法研究

针对传统非相干宽带腔增强吸收光谱浓度反演方法的定量结果易受镜片反射率标定误差的影响问题, 提出了一种基于测量大气O₂-O₂吸收的浓度反演方法. 该方法是将非相干宽带腔增强吸收光谱技术的光学增强腔等效成吸收光程不随波长变化的多次反射池, 首先根据测得的宽带腔增强大气吸收谱和参考谱计算出光学厚度, 并应用差分光学吸收光谱算法拟合修正后的气体吸收截面到光学厚度, 反演得到大气中O₂-O₂以及被测气体的柱浓度, 然后根据O₂-O₂在大气中的含量已知且相对稳定这一特性, 确定出等效多次反射池的吸收光程, 最后从被测气体的柱浓度中扣除吸收光程信息得到被测气体的浓度值. 以监测大气中NO₂实验为例, 应用该方法在454-487 nm波段反演得到了大气NO₂的浓度(1-30 ppbv范围内), 并将反演结果与传统浓度反演方法的结果进行了对比, 发现两者的不一致性在7%以内. 实验结果表明, 非相干宽带腔增强吸收光谱技术可以利用大气O₂-O₂的吸收来定量其他被测气体的浓度, 而且定量结果对镜片反射率的标定误差不敏感.     

取向比对椭球气溶胶粒子散射特性的影响

利用T矩阵和离散坐标法研究了取向比对椭球粒子散射特性的影响, 计算了小尺度范围内椭球粒子的散射特征参量, 包括消光效率因子、不对称因子、单次散射反照率、散射相矩阵及双向反射函数(BRDF). 结果表明, 椭球粒子的散射特性与取向比密切相关, 粒子取向比会影响散射参量的振荡频率和振幅, 与球形粒子散射参量的相对差异也呈周期振荡趋势. 研究还发现, 某些特殊粒子尺寸的散射参量与粒子取向比基本无关. 在多次散射条件下, 分析不同取向比粒子群的BRDF随反射角和光学厚度的变化特性. 结果显示: 不同取向比粒子群的BRDF随反射角的变化趋势基本一致, 球形粒子群比非球形粒子群的BRDF曲线波动振幅更大; 球形-非球形粒子的BRDF相对差异随光学厚度和取向比的增大而减小, 随入射角的增大而增大.