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掺铪稳定的 Ti/Sb-SnO 电极用于高效降解四环素。

Stabilized Hf-doped Ti/Sb-SnO electrode for efficient degradation of tetracycline.

机构信息

State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control On Chemical Processes, School of Resources and Environmental Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, P.R. China.

Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, P.R. China.

出版信息

Environ Sci Pollut Res Int. 2024 Jul;31(35):47960-47973. doi: 10.1007/s11356-024-34354-y. Epub 2024 Jul 17.

Abstract

The electrochemical advanced oxidation process (EAOP) has shown significant promise in the field of refractory organic wastewater treatment due to its high efficiency and environmentally friendly nature. In this study, Ti/Sb-SnO electrodes with varying proportions of Hf were prepared using the sol-gel method. The addition of Hf transformed the original collapsing and broken surface into a flat and regular surface. The results demonstrated that Ti/Sb-SnO-Hf electrode doped with 6% Hf exhibited a higher oxygen evolution potential (OEP) and excellent stability. The OEP increased from 2.315 V without Hf-doping to 2.482 V, and the corresponding actual life was 321.05% higher than that without Hf. The current density (5-40 mA·cm), electrolyte concentration (0.02-0.2 mol·L), pH (3-11), and initial pollutant concentration (5-80 mg·L) were evaluated to confirm the tetracycline (TC) degradation characterization of Ti/Sb-SnO-6%Hf electrodes. It was concluded that under the optimal degradation conditions, the removal rate of TC could reach 99.66% within 2 h. The degradation of TC follows first-order reaction kinetics. The oxidative degradation of TC was achieved through indirect oxidation, with ·OH playing a dominant role. TC's electrochemical oxidation degradation pathway has been proposed: Based on LC-MS results, three main pathways are speculated. During the electrocatalytic oxidation process, decarboxylation, deamidation, and ring-opening reactions occur under ·OH attack, producing intermediate compounds with m/z values of 427, 433, 350, 246, 461, 424, 330, 352, 309, 263, and 233. These intermediates are further oxidized to intermediate compounds with an m/z value of 218. This work introduces a new efficient anode electrochemical catalyst for the degradation of TC, providing a strategy for industrial applications.

摘要

电化学高级氧化工艺 (EAOP) 因其高效、环保的特性,在难处理有机废水处理领域显示出巨大的应用前景。本研究采用溶胶-凝胶法制备了不同比例 Hf 掺杂的 Ti/Sb-SnO 电极。Hf 的加入将原始的崩塌和破碎表面转变为平整和规则的表面。结果表明,掺杂 6%Hf 的 Ti/Sb-SnO-Hf 电极具有更高的析氧电位 (OEP) 和优异的稳定性。OEP 从无 Hf 掺杂时的 2.315 V 增加到 2.482 V,相应的实际寿命比无 Hf 时提高了 321.05%。评估了电流密度 (5-40 mA·cm)、电解质浓度 (0.02-0.2 mol·L)、pH (3-11) 和初始污染物浓度 (5-80 mg·L),以确认 Ti/Sb-SnO-6%Hf 电极对四环素 (TC) 的降解特性。结果表明,在最佳降解条件下,TC 的去除率在 2 h 内可达到 99.66%。TC 的降解遵循一级反应动力学。TC 通过间接氧化进行氧化降解,·OH 起主导作用。提出了 TC 的电化学氧化降解途径:根据 LC-MS 结果,推测出三条主要途径。在电催化氧化过程中,TC 经·OH 攻击发生脱羧、脱酰胺和开环反应,生成 m/z 值分别为 427、433、350、246、461、424、330、352、309、263 和 233 的中间产物。这些中间产物进一步氧化为 m/z 值为 218 的中间产物。本工作为 TC 的降解引入了一种新的高效阳极电化学催化剂,为工业应用提供了一种策略。

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