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铁氧化物和氢氧化物催化的 HO 分解:氧产生和有机降解的见解。

Catalyzed HO decomposition over iron oxides and oxyhydroxides: Insights from oxygen production and organic degradation.

机构信息

School of Environmental Science and Engineering, Key Laboratory of Thin Film and Microfabrication Technology (Ministry of Education), Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.

School of Ecological and Environmental Science, Key Laboratory for Urban Ecological Processes and Eco-Restoration, East China Normal University, Shanghai, 200241, China.

出版信息

Chemosphere. 2022 Mar;291(Pt 1):133037. doi: 10.1016/j.chemosphere.2021.133037. Epub 2021 Nov 25.

Abstract

Iron minerals, such as iron oxides and iron oxyhydroxides, are the main influential soil components in catalyzed hydrogen peroxide propagation (CHP). Due to their dual effects on HO activation to produce reactive oxygen species (ROS) and invalid consumption to produce oxygen, the intrinsic reactivity of iron minerals toward HO decomposition requires comprehensive investigations. Herein, six iron minerals (hematite, magnetite, maghemite, goethite, feroxyhyte, and ferrihydrite) for HO decomposition were investigated by a combination of normalized kinetic rate constants of HO decomposition (Nk), O production (Nk), benzoic acid degradation (Nk), and hexachloroethane degradation (Nk) over the surface area of each mineral. The results indicate HO decomposition over iron minerals is a surface-related heterogeneous process. Hematite and goethite are the most promising minerals for environmental cleanup in terms of ROS production, because their HO utilization efficiency for benzoic acid (BA) degradation (0.138 and 0.024 mol BA/mol HO for hematite and goethite, respectively) are highest among the six iron minerals. Magnetite and maghemite are highly active for both HO decomposition and O production at neutral and basic pHs. The presence of organic compounds suppresses O production by more than 60%, which favors HO utilization. Ferrihydrite and feroxyhyte are considered as the problematic mineral for CHP due to that the two minerals acquire a high O production and negligible ROS generation at all pHs. The results of this study provide new insights to increase the understandings of HO-iron mineral systems and guide the application of iron minerals in chemical oxidation technologies.

摘要

铁矿物,如氧化铁和氢氧化铁,是在过氧化氢传播(CHP)中起主要作用的土壤成分。由于它们对 HO 激活产生活性氧物种(ROS)和无效消耗产生氧气的双重作用,铁矿物对 HO 分解的固有反应性需要综合研究。在此,通过归一化 HO 分解(Nk)、O 生产(Nk)、苯甲酸降解(Nk)和六氯乙烷降解(Nk)的表面面积上的动力学速率常数,对六种用于 HO 分解的铁矿物(赤铁矿、磁铁矿、磁赤铁矿、针铁矿、羟高铁矿和水铁矿)进行了研究。结果表明,铁矿物上的 HO 分解是一种表面相关的非均相过程。就 ROS 生成而言,赤铁矿和针铁矿是最有前途的环境清洁矿物,因为它们对苯甲酸(BA)降解的 HO 利用率(赤铁矿和针铁矿分别为 0.138 和 0.024 mol BA/mol HO)在六种铁矿物中最高。磁铁矿和磁赤铁矿在中性和碱性 pH 下对 HO 分解和 O 生产均具有高活性。有机化合物的存在抑制了超过 60%的 O 生成,有利于 HO 的利用。由于在所有 pH 值下,这两种矿物都具有高的 O 生成和可忽略不计的 ROS 生成,因此水铁矿和羟高铁矿被认为是 CHP 的问题矿物。本研究的结果提供了新的见解,以增加对 HO-铁矿物系统的理解,并指导铁矿物在化学氧化技术中的应用。

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