School of Resources and Environmental Engineering, Shanghai Polytechnic University, Shanghai, 201209, China.
School of Resources and Environmental Engineering, Shanghai Polytechnic University, Shanghai, 201209, China.
Chemosphere. 2022 Mar;290:133381. doi: 10.1016/j.chemosphere.2021.133381. Epub 2021 Dec 21.
Zero-valent iron supported with expanded graphite (ZVI/EG) were successfully prepared from ferric chloride and the graphite of spent lithium-ion battery (LIB) using carbothermic reduction as a new approach for recycling spent LIB. ZVI/EG composites synthesized with different ZVI mass ratios were used as catalysts for the 4-chlorophenol (4-CP) removal from water by heterogeneous Fenton reactions. ZVI/EG composites showed a BET specific surface area of 11.295 m g. ZVI/EG synthesized from expandable graphite and ferric chloride with mass ratio of 2:1 (ZVI/EG-2) showed the highest removal percentage of 4-CP, being 97% in 1 h. The degradation rate fitted to a pseudo first-order model better, and reached 0.0527 min for ZVI/EG-2. Moreover, ZVI/EG-2 showed high reactivity for 4-CP removal even in the sixth reuse cycle, being 82%. Hydroquinone and 4-chlorocatechol were identified as the intermediate products of 4-CP degradation. Increasing the ZVI/EG-2 dosage can enhance the 4-CP removal percentage through offering more reactive sites and Fe ions. Acidic pH values favorited the 4-CP removal due to the high H concentrations, while Alkaline pH value inhabited the 4-CP removal. A higher temperature increased the rate of •OH formation and enhanced the 4-CP removal percentage. At a fixed dosage of the ZVI/EG-2, the ratio of available reactive sites was less at higher initial concentrations. These results prove the possibility of synthesizing high active and stable ZVI/EG catalysts using graphite from spent LIB and ferric chloride. These catalysts show promising prospective for the 4-CP removal in water, with comparable activities to others previously reported.
采用碳热还原法,从氯化铁和废锂离子电池(LIB)的石墨中成功制备了负载型零价铁/膨胀石墨(ZVI/EG)复合材料,为回收废 LIB 开辟了新途径。以不同 ZVI 质量比合成的 ZVI/EG 复合材料作为非均相 Fenton 反应去除水中 4-氯苯酚(4-CP)的催化剂。ZVI/EG 复合材料的 BET 比表面积为 11.295 m²/g。由膨胀石墨和氯化铁以质量比 2:1 合成的 ZVI/EG(ZVI/EG-2)对 4-CP 的去除率最高,在 1 h 内达到 97%。降解速率更符合准一级动力学模型,ZVI/EG-2 的降解速率常数为 0.0527 min-1。此外,ZVI/EG-2 即使在第六次重复使用循环中,对 4-CP 的去除率仍高达 82%,表现出较高的反应活性。间苯二酚和 4-氯邻苯二酚被鉴定为 4-CP 降解的中间产物。增加 ZVI/EG-2 的用量可以通过提供更多的反应活性位点和 Fe 离子来提高 4-CP 的去除率。酸性 pH 值有利于 4-CP 的去除,因为高 H+浓度有利于生成•OH。而碱性 pH 值不利于 4-CP 的去除。较高的温度会增加•OH 的生成速率,从而提高 4-CP 的去除率。在固定的 ZVI/EG-2 用量下,初始浓度较高时,可用反应活性位点的比例较低。这些结果证明了使用废 LIB 石墨和氯化铁合成高活性和稳定 ZVI/EG 催化剂的可能性。这些催化剂在水中去除 4-CP 方面表现出良好的应用前景,其活性与其他已报道的催化剂相当。