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新型仿生铁封装生物炭高效活化过二硫酸盐:电子传递途径和活性氧演化的关键作用。

Efficient activation of peroxodisulfate by novel bionic iron-encapsulated biochar: The key roles of electron transfer pathway and reactive oxygen species evolution.

机构信息

School of Resource and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, PR China; School of Construction and Environmental Engineering, Shenzhen Polytechnic, Shenzhen 518055, PR China.

State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, PR China.

出版信息

J Hazard Mater. 2023 Feb 5;443(Pt A):130204. doi: 10.1016/j.jhazmat.2022.130204. Epub 2022 Oct 19.

DOI:10.1016/j.jhazmat.2022.130204
PMID:36308934
Abstract

In this study, a novel iron-encapsulated biochar (Fe@BC) was prepared using the biomass cultivated with an iron-containing solution. The iron in Fe@BC showed the phase change from FeO to α-Fe, and to CFe, with the increase of pyrolysis temperature (500-900 °C), and a graphene shell formed on the surface of Fe@BC. In addition, the signals assigned to the π-π* shake up, pyridinic N, graphitic N, and defects of Fe@BC were found to be stronger as the pyrolysis temperature increased. The F4@B9 sample, which was prepared at 900 °C, exhibited an excellent performance (98.01 %) to activate peroxydisulfate (PDS) for the degradation of 2,4-dichlorophenol. Electron paramagnetic resonanceand chemical quenching experiments revealed that reactive oxygen radicals (ROS) including sulfate radical (•SO), hydroxyl radical (•OH), superoxide radical (•O), and singlet oxygen (O) existed in the F4@B9/PDS system. Furthermore, the micro-electrolysis process facilitated the generation of •O (12.35 %) and O (6.49 %) compared with the pure PDS system. Density functional theory revealed that, for the F4@B9-activated PDS process, the graphene shell of F4@B9 served as catalytic active sites as well. According to the correlation analysis, the iron specie of CFe was more favorable for the generation of ROS than α-Fe. Also, π-π* shake up, pyridinic N, graphitic N, and defects participated in the PDS activation. This study provides a new method for the preparation of high-performance catalysts from naturally grown biomass with high iron contents.

摘要

在这项研究中,使用含铁溶液培养的生物质制备了一种新型的铁封装生物炭(Fe@BC)。随着热解温度(500-900°C)的增加,Fe@BC 中的铁经历了从 FeO 到 α-Fe 再到 CFe 的相转变,并且在 Fe@BC 表面形成了石墨烯壳。此外,随着热解温度的升高,发现与 π-π* 激发、吡啶 N、石墨 N 和 Fe@BC 缺陷相关的信号变得更强。在 900°C 下制备的 F4@B9 样品在活化过二硫酸盐(PDS)降解 2,4-二氯苯酚方面表现出优异的性能(98.01%)。电子顺磁共振和化学猝灭实验表明,在 F4@B9/PDS 体系中存在活性氧自由基(ROS),包括硫酸根自由基(•SO)、羟基自由基(•OH)、超氧自由基(•O)和单线态氧(O)。此外,与纯 PDS 体系相比,微电解过程有利于生成•O(12.35%)和 O(6.49%)。密度泛函理论表明,对于 F4@B9 活化 PDS 过程,F4@B9 的石墨烯壳既作为催化活性位点,又作为催化活性位点。根据相关分析,CFe 的铁物种比α-Fe 更有利于生成 ROS。此外,π-π* 激发、吡啶 N、石墨 N 和缺陷参与了 PDS 的活化。这项研究为从富含铁的天然生长生物质中制备高性能催化剂提供了一种新方法。

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