连续流动化学发光法在线定量检测二氧化钛光催化产生的O2·-和H2O2及其生成动力学研究

doi:10.6023/A15010036

化学学报 ›› 2015, Vol. 73 ›› Issue (5): 388-394.DOI: 10.6023/A15010036 上一篇下一篇

研究论文

连续流动化学发光法在线定量检测二氧化钛光催化产生的O₂^·-和H₂O₂及其生成动力学研究

王大彬, 赵利霞, 郭良宏, 张辉, 万斌, 杨郁

中国科学院生态环境研究中心环境化学与生态毒理学国家重点实验室 100085

投稿日期:2015-01-14 发布日期:2015-03-20
通讯作者: 赵利霞 E-mail:zlx@rcees.ac.cn,lhguo@rcees.ac.cn
基金资助:
项目受国家重点基础研究计划(No. 2011CB936001)和国家自然科学基金(Nos. 21177138, 21207146, 21477146, 21377142)资助.

Online Quantification of O₂^·- and H₂O₂ and Their Formation Kinetics in Ultraviolet (UV)-Irradiated Nano-TiO₂ Suspensions by Continuous Flow Chemiluminescence

Wang Dabin, Zhao Lixia, Guo Lianghong, Zhang Hui, Wan Bin, Yang Yu

State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085

Received:2015-01-14 Published:2015-03-20
Supported by:
Project supported by the National Basic Research Program of China (No. 2011CB936001) and the National Natural Science Foundation of China (Nos. 21177138, 21207146, 21477146, 21377142).

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摘要/Abstract

O₂^·-和H₂O₂是TiO₂光催化反应过程中产生的重要活性氧物种. 本文使用鲁米诺作为化学发光探针, 针对两者寿命不同, 建立了连续流动化学发光在线定量检测方法. 对于O₂^·-, 由于寿命短, 标准品不易得到, 将光照后TiO₂样品10 s内与鲁米诺混合产生化学发光, 根据鲁米诺和O₂^·-化学计量关系, 将该发光强度对应的鲁米诺浓度转换成O₂^·-的浓度, 实现间接定量; 对于H₂O₂, 将光照后的TiO₂溶液于黑暗处30 min后进行定量. 该方法测得TiO₂光催化产生O₂^·-和H₂O₂的浓度范围分别为7.5～30 nmol/L和0.60～3.0 μmol/L, 检测限分别为1.95 nmol/L和18.0 nmol/L. O₂^·-和H₂O₂的生成动力学研究发现, 两者的生成均符合指数衰减函数增长, 通过拟合计算, 其生成速率常数(k_f)分别为0.0653 nmol·s^-1和15.0 nmol·s^-1, 表明在TiO₂光催化反应中H₂O₂的生成速率高于O₂^·-.

关键词: 连续流动化学发光, TiO₂光催化, O₂^·-, H₂O₂, 在线定量检测, 动力学研究

O₂^·- and H₂O₂, the two reactive oxygen species (ROS) produced in TiO₂ photocatalytic reactions, play important roles in the photodegradation of pollutants. In this work, according to the different lifetime of O₂^·- and H₂O₂, online quantification of O₂^·- and H₂O₂ was successfully achieved based on the two established continuous flow chemiluminescence (CFCL) methods using luminol as the chemiluminescence probe. For O₂^·-, the CL intensity was detected by mixing the irradiated TiO₂ suspension containing O₂^·- with luminol within 10 s due to its short lifetime and poor stability, and thus the concentration of O₂^·- was indirectly quantified according to the linear relationship between the CL intensity and the luminol concentration. For H₂O₂ detection with the luminol/K₃Fe(CN)₆ system, the CL intensity was detected after the irradiated TiO₂ suspension was placed in darkness for 30 min to ensure the complete disappearance of O₂^·-, and the concentration of H₂O₂ produced was directly quantified by the calibration curve between the CL intensity and H₂O₂ concentration. The concentration of O₂^·- and H₂O₂ was determined approximately in the range of 7.5～30 nmol/L and 0.60～3.0 μmol/L, and the detection limit was 1.95 nmol/L and 18.0 nmol/L respectively. Based on the proposed models of O₂^·- and H₂O₂ formation, the kinetic process of O₂^·- and H₂O₂ formation was studied, and both of them followed the increase of exponential decay function. By simulating the time-dependent concentration change of O₂^·- and H₂O₂ with their kinetic formulas, the formation rate constants (k_f) of O₂^·- and H₂O₂ were calculated to be 0.0653 nmol·s^-1, and 15.0 nmol·s^-1 respectively. The formation rate of H₂O₂ was higher than that of O₂^·- in the TiO₂ photocatalytic reactions. This work provides us more insight into the formation process of ROS, and may help to improve the photocatalytic efficiency of TiO₂ photocatalysis.

Key words: continuous flow chemiluminescence, TiO₂ photocatalysis, O₂^·-, H₂O₂, on-line quantification, kinetic study

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王大彬, 赵利霞, 郭良宏, 张辉, 万斌, 杨郁. 连续流动化学发光法在线定量检测二氧化钛光催化产生的O₂^·-和H₂O₂及其生成动力学研究[J]. 化学学报, 2015, 73(5): 388-394.

Wang Dabin, Zhao Lixia, Guo Lianghong, Zhang Hui, Wan Bin, Yang Yu. Online Quantification of O₂^·- and H₂O₂ and Their Formation Kinetics in Ultraviolet (UV)-Irradiated Nano-TiO₂ Suspensions by Continuous Flow Chemiluminescence[J]. Acta Chim. Sinica, 2015, 73(5): 388-394.

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连续流动化学发光法在线定量检测二氧化钛光催化产生的O₂^·-和H₂O₂及其生成动力学研究

Online Quantification of O₂^·- and H₂O₂ and Their Formation Kinetics in Ultraviolet (UV)-Irradiated Nano-TiO₂ Suspensions by Continuous Flow Chemiluminescence

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