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滴状晶型 CuCo-LDO/CN 催化剂高效类 Fenton 降解四环素:被忽视的溶解氧贡献。

Efficient Fenton-like degradation of tetracycline by stalactite-like CuCo-LDO/CN catalysts: The overlooked contribution of dissolved oxygen.

机构信息

College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China.

Changzhou Institute of Building Science, Changzhou, 213000, China.

出版信息

Chemosphere. 2023 Oct;338:139540. doi: 10.1016/j.chemosphere.2023.139540. Epub 2023 Jul 21.

DOI:10.1016/j.chemosphere.2023.139540
PMID:37480960
Abstract

In the Fenton-like processes, the resources that exist in the system itself (e.g., dissolved oxygen, electron-rich pollutants) are often overlooked. Herein, a novel CuCo-LDO/CN composite catalyst with a strong "metal-π" effect was fabricated by in situ calcination which could activate dissolved oxygen to generate active oxygen species and degrade the electron-rich pollutants directly. The CuCo-LDO/CN (1:10) with the largest specific surface aera, most C-O-M bonds and least oxygen vacancies exhibited the best catalytic performance for tetracycline (TC)degradation (TC removal efficiency 93.2% and mineralization efficiency 40%, respectively, after 40 min at neutral pH) compared to CuCo-LDO and other CuCo-LDO/CN composite catalysts. In the absence of HO, dissolved oxygen could be activated by the catalyst to generate O·and ·OH, which contributed to approximately 20.7% of TC degradation, providing a faster and cost-effective way for TC removal from wastewater. While in the presence of HO, it was activated by CuCo-LDO/CN to generate·OH as the dominant reactive oxygen species and meanwhile TC transferred electrons to HO through C-O-M bonds, accelerating the Cu/Cu and Co/Co redox cycles. The possible degradation pathways of TC were proposed, and the environmental hazard of TC is greatly mitigated according to toxicity prediction.

摘要

在类 Fenton 过程中,系统本身存在的资源(例如溶解氧、富电子污染物)经常被忽视。在此,通过原位煅烧制备了一种具有强“金属-π”效应的新型 CuCo-LDO/CN 复合催化剂,它可以激活溶解氧来产生活性氧物种并直接降解富电子污染物。比表面积最大、C-O-M 键最多、氧空位最少的 CuCo-LDO/CN(1:10)在中性 pH 下 40 min 后对四环素(TC)的降解(TC 去除率为 93.2%,矿化率为 40%)表现出最好的催化性能,优于 CuCo-LDO 和其他 CuCo-LDO/CN 复合催化剂。在没有 HO 的情况下,催化剂可以激活溶解氧生成 O·和·OH,这对 TC 降解的贡献约为 20.7%,为废水去除 TC 提供了一种更快、更具成本效益的方法。而在有 HO 的情况下,它被 CuCo-LDO/CN 激活生成·OH 作为主要的活性氧物种,同时 TC 通过 C-O-M 键将电子转移给 HO,加速了 Cu/Cu 和 Co/Co 的氧化还原循环。提出了 TC 的可能降解途径,并根据毒性预测大大减轻了 TC 的环境危害。

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