边带差分吸收光谱分析方法及其应用

In industrial processes involving (electro) chemical reactions or physical changes in solution, the rapid analysis, measurement and monitoring of some key concentrated species is very important. The traditional "sampling - dilution - analysis" three-step method will not only cause dilution error, but also make long analysis cycle and high cost. There would no key real-time information of chemical concentration. Recently, our group has proposed a method that can directly detect high concentration samples - sideband differential absorption spectroscopy (SDAS) method. Although SDAS has provided the probability of on-line detection of high concentration species, there still exists many problems to be solved. First of all, this project intends to conduct a theoretical study of the physicochemical properties of SDAS in order to find out whether SDAS is a specific energy level transition or just a differential result. And then, the method of high concentration species analysis based on SDAS is studied, including its application range, selection criterion of high concentration reference and calibration method of spectrophotometer. Finally, several online sensing devices of typical high concentration samples based on the principle of SDAS are developed, including on-site chromate sensor for chrome plating solution, gold potassium sulfite sensor for gold plating solution, and typical red dye sensor in dyeing cylinder for printing and dyeing industry. These work will provide theoretical and technical support for the upgrading of relevant industries in our country.

在涉及溶液中（电）化学反应或物理变化的工业生产过程中，对一些关键高浓度物种的快速分析测量和监控非常重要。采用传统的 “取样-稀释-分析”三步法不仅会产生稀释误差，而且分析周期长、成本高，得不到关键化学量的实时浓度信息。最近我们组提出了可以直接检测高浓度的样品的边带差分吸收光谱（SDAS）方法。虽然SDAS的提出，为解决高浓度物种的在线检测提供了可能，但仍然有许多问题需要解决。本项目拟首先对SDAS的物理化学本质进行理论方面的研究，重点搞清SDAS是一种特定的能级跃迁还是仅仅是一种差分的结果；然后研究基于SDAS原理的高浓度物种分析方法，包括其适用范围、高浓度参比的选择规范及分光光度计的定标方法等；最后研制基于SDAS原理的几种典型的高浓度样品在线传感器件，包括镀铬液中铬酸根传感器、镀金液中的亚硫酸金钾传感器以及印染行业中典型红色染料传感器等，为我国相关产业升级改造提供理论及技术支持。

在涉及溶液中（电）化学反应或物理变化的工业生产过程中，对一些关键高浓度物种的快速分析测量和监控非常重要。采用传统的“取样-稀释-分析”三步法不仅会产生稀释误差，而且分析周期长、成本高，得不到关键化学量的实时浓度信息。为此，我们组提出了一种可用于直接检测高浓度样品的边带差分吸收光谱（SDAS）方法。本项目依托于上述重要的前期研究成果，深入阐释了SDAS方法的原理，发现SDAS法的峰值波长对应的是电子能级跃迁、振动和转动能级跃迁的吸收。同时，本项目科学界定了SDAS方法的应用条件，明确了边带差分吸收光谱分析方法的分析适用范围，并研制出了基于SDAS原理的高浓度在线传感器件，对镀铬液中的铬酸根、镀金液中的亚硫酸金钾以及印染行业中典型红色染料等实现了快速检测。.本项目还发展了以样品自身为参比的温度差分吸收光谱和电化学差分吸收光谱法，用以改善紫外吸收光谱法无法定性鉴别分子结构非常相似的有机物和检测复杂基底环境下没有特征吸收的某一组分的局限性。最后，本项目还将“信号差分校正”的研究思路进一步推广应用至电化学生物传感器领域，提出了两种基于界面温度调控的比率式免校正电化学适配体传感方法，对未稀释生物样本中的不同生物小分子均实现了便携式、快速的分析检测。