Facet-mediated degradation of 6PPD on hematite: From direct electron transfer to reactive oxygen species-driven accelerated oxidation

IF 7.2 2区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of Environmental Chemical Engineering Pub Date : 2025-09-10 DOI:10.1016/j.jece.2025.119231

Chenghe Yan, Zekun Li, Run Xie, Qian Gu, Zhiyu Zhou, Mengning Xi, Yixuan Liu, Chi Zhang, Kecheng Zhu, Hanzhong Jia

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引用次数: 0

Abstract

As a widely used tire antioxidant, N-(1,3-dimethylbutyl)-N’-phenyl-p-phenylenediamine (6PPD) is released into soil ecosystems through tire wear. However, knowledge gaps exist regarding the transformation mechanism and ecological implications resulting from the interaction between 6PPD and soil minerals. This study revealed that the degradation rates of 6PPD varied among different hematite facets, reaching 97 % for the hematite nano-rhombohedra (HNR) with {104} facets and 55 % for the hematite nanoplate (HNP) with {001} facets after a one-hour reaction. DFT calculations demonstrated that the higher reactivity of HNR was closely related to the stronger affinity between its surface Fe(III) and amino groups of 6PPD. This process led to more vigorous electron transfer, as verified by more environmentally persistent free radicals (EPFRs) formation. Moreover, more reactive oxygen species (ROS) induced by HNR were involved in 6PPD degradation, which significantly drove the oxidation of EPFRs and other intermediate products. The toxicity prediction suggested the reduced toxicity of the degradation products of 6PPD. Our results shed light on the catalytic potential of hematite in 6PPD degradation, offering new insights into alleviating the environmental pressures associated with 6PPD in soil.

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赤铁矿上6PPD的面介导降解：从直接电子转移到活性氧驱动的加速氧化

N-（1,3-二甲基丁基）-N′-苯基-对苯二胺（6PPD）是一种应用广泛的轮胎抗氧化剂，通过轮胎磨损释放到土壤生态系统中。然而，关于6PPD与土壤矿物质相互作用的转化机制和生态意义存在知识空白。研究表明，6PPD的降解率在不同的赤铁矿切面之间存在差异，反应1小时后，{104}切面的赤铁矿纳米菱形体（HNR）的降解率达到97 %，{001}切面的赤铁矿纳米板（HNP）的降解率达到55 %。DFT计算表明，HNR具有较高的反应活性与其表面Fe（III）与6PPD氨基之间的亲和力密切相关。这一过程导致了更有力的电子转移，正如更多的环境持久性自由基（EPFRs）形成所证实的那样。此外，HNR诱导的更多活性氧（ROS）参与了6PPD的降解，这显著推动了epfr和其他中间产物的氧化。毒性预测表明6PPD的降解产物毒性降低。我们的研究结果揭示了赤铁矿在6PPD降解中的催化潜力，为减轻土壤中与6PPD相关的环境压力提供了新的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Environmental Chemical Engineering Environmental Science-Pollution

CiteScore

11.40

自引率

6.50%

发文量

2017

审稿时长

27 days

期刊介绍： The Journal of Environmental Chemical Engineering (JECE) serves as a platform for the dissemination of original and innovative research focusing on the advancement of environmentally-friendly, sustainable technologies. JECE emphasizes the transition towards a carbon-neutral circular economy and a self-sufficient bio-based economy. Topics covered include soil, water, wastewater, and air decontamination; pollution monitoring, prevention, and control; advanced analytics, sensors, impact and risk assessment methodologies in environmental chemical engineering; resource recovery (water, nutrients, materials, energy); industrial ecology; valorization of waste streams; waste management (including e-waste); climate-water-energy-food nexus; novel materials for environmental, chemical, and energy applications; sustainability and environmental safety; water digitalization, water data science, and machine learning; process integration and intensification; recent developments in green chemistry for synthesis, catalysis, and energy; and original research on contaminants of emerging concern, persistent chemicals, and priority substances, including microplastics, nanoplastics, nanomaterials, micropollutants, antimicrobial resistance genes, and emerging pathogens (viruses, bacteria, parasites) of environmental significance.