电子顺磁共振技术在化工基础研究中的应用进展

doi:10.11949/0438-1157.20230672

摘要/Abstract

摘要：

电子顺磁共振（electron paramagnetic resonance， EPR）技术能够检测自由基、过渡金属离子及缺陷等顺磁性物质，谱图具有高特异性，背景信号少，既可以检测溶液样品，也可以检测固态样品，且检测限低。在化工基础研究中，尤其是自由基相关过程研究中，EPR技术的优势是其他谱学无可比拟的。但是化工领域的科学家们使用EPR技术并不广泛。综述了EPR在化工基础相关研究中应用的一些例子，包括催化材料的表征、活性中间体的表征、溶剂性质表征及材料性能表征四个方面，希望能让更多化工领域工作者了解EPR技术，并使用EPR技术解决化工问题。

关键词: 电子顺磁共振, 催化剂, 活性中间体, 溶剂, 材料性能

Abstract:

Electron paramagnetic resonance (EPR) technology can be used to detect paramagnetic species such as free radicals, transition metal ions and defects. The spectrogram has high specificity and few background signals. It can detect both solution samples and solid samples with low detection limit. In chemical engineering field, especially in free radical related process, EPR technology has incomparable advantages compared with other spectroscopies. However, the EPR technology is not widely used by scientists in the chemical industry. Some examples of the application of EPR in chemical engineering field are reviewed, including the characterization of catalysts, reactive intermediate, solvent properties, and material properties. It is not a very comprehensive review, but rather to demonstrate the necessity and practicality of EPR technology in fundamental chemical industry research. It is hoped that chemical engineers can learn more about EPR and use EPR technology to solve more chemical engineering problems.

Key words: electron paramagnetic resonance, catalyst, reactive intermediate, solvent, material properties

中图分类号:

O 657.61

王欣雨, 王永涛, 姚加, 李浩然. 电子顺磁共振技术在化工基础研究中的应用进展[J]. 化工学报, 2024, 75(1): 74-82.

Xinyu WANG, Yongtao WANG, Jia YAO, Haoran LI. Progress in the application of electron paramagnetic resonance in fundamental chemical engineering research[J]. CIESC Journal, 2024, 75(1): 74-82.

图/表 6

图1 WO3和Ru-WO3-x 的EPR谱图[13]

Fig.1 EPR spectrums of WO3 and Ru-WO3-x[13]

图2 随着3-己醇中CuCl2浓度的增加CuCl2的EPR信号变化[28]

Fig.2 EPR signal of CuCl2 changed with the concentration of CuCl2 in 3-hexanol increased[28]

图3 几种常见的原位EPR检测装置示意图

Fig.3 Experimental set-ups for in situ EPR measurements

图4 硼掺杂金刚石在不同介质中电化学氧化（EO-BDD）的自由基中间体EPR信号[(ⅰ) EO-BDD在硫酸盐溶液中反应，DMPO捕获SO4-·的EPR信号（■）；(ⅱ) EO-BDD在含有硫酸盐、氯化物和碳酸盐的基质中反应，DMPO捕获的多自由基混合的EPR信号；(ⅲ) EO-BDD在过硫酸盐溶液中反应，TEMP捕获1O2的EPR信号（▲）；(ⅳ) EO-BDD在碳酸盐溶液中反应，DMPO捕获OH·的EPR信号（●）][36]

Fig. 4 EPR signal of radical adducts of EO-BDD [(ⅰ) EO-BDD in sulfate medium, DMPO with SO4-·(■), (ⅱ) EO-BDD in a real matrix containing sulfate, chloride, and carbonate, (ⅲ) EO-BDD in persulfate medium, TEMP with 1O2(▲), (ⅳ) EO-BDD in carbonate medium, DMPO with OH·(●)]

图5 修正的反应场示意图[58]

Fig.5 Diagram of the modified reaction field[58]

图6 含Co的MOFs材料吸收氨气前后的EPR谱图[77]

Fig.6 EPR signal of before and after Co containing MOFs absorbing NH3[77]

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