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如何测量天然羧酸铁(III)光解过程中羟基自由基的量子产率?

How to measure quantum yield of hydroxyl radical during photolysis of natural Fe(III) carboxylates?

作者信息

Tyutereva Yuliya E, Novikov Mikhail V, Snytnikova Olga A, Pozdnyakov Ivan P

机构信息

Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya str., 630090, Novosibirsk, Russian Federation; Novosibirsk State University, 2 Pirogova St., 630090, Novosibirsk, Russian Federation.

Novosibirsk State University, 2 Pirogova St., 630090, Novosibirsk, Russian Federation; International Tomography Center SB RAS, 3a Institutskaya str., 630090, Novosibirsk, Russian Federation.

出版信息

Chemosphere. 2022 Jul;298:134237. doi: 10.1016/j.chemosphere.2022.134237. Epub 2022 Mar 5.

Abstract

The efficiency of oxidative species generation is one of the crucial parameters for the application of any system based on advanced oxidation processes (AOPs). This paper presents an approach to the correct determination of quantum yields of the hydroxyl radical upon UV photolysis of natural Fe(III) carboxylates, which are widely used in the works devoted to Environmental Chemistry and Water Treatment. The approach is based on the use of [FeOH] hydroxocomplex as a reference system with the well-known quantum yield of hydroxyl radical and benzene as a selective trap for the OH radical. For the first time, the quantum yields of the OH radical have been determined for the most popular Fe(III) oxalate photosystem in the wide range of initial parameters (pH, excitation wavelength, concentration of oxalate and Fe(III) ions). Also the oxidation potential of Fe(III) oxalate photosystem was tested on a set of persistent organic herbicides, and quantum yields of the photodegradation of herbicides were compared with the quantum yield of the OH radical. The Fe(III) oxalate photosystem is recommended as a suitable system for the generation of OH radical at neutral pH under UV radiation.

摘要

氧化物种生成效率是任何基于高级氧化过程(AOPs)的系统应用的关键参数之一。本文提出了一种正确测定天然羧酸铁(III)在紫外光解时羟基自由基量子产率的方法,天然羧酸铁(III)在环境化学和水处理相关研究中广泛应用。该方法基于使用[FeOH]羟基配合物作为具有已知羟基自由基量子产率的参考体系,并使用苯作为羟基自由基的选择性捕获剂。首次在广泛的初始参数(pH值、激发波长、草酸盐和铁(III)离子浓度)范围内测定了最常用的草酸铁(III)光系统中羟基自由基的量子产率。此外,还对一组持久性有机除草剂测试了草酸铁(III)光系统的氧化电位,并将除草剂光降解的量子产率与羟基自由基的量子产率进行了比较。草酸铁(III)光系统被推荐为在紫外辐射下中性pH条件下生成羟基自由基的合适系统。

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