Zhang Dong, Zhong Zhishun, Liu Zilong, He Shichong, Lin Jun, Lv Yiyan, Lü Ting, Pan Ying, Shi Huading, Zhao Hongting
Department of Environmental Science, College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou, 310018, China.
Guangdong Jiandi Agriculture Technology Co. Ltd., Foshan, Guangdong, 528200, China.
Chemosphere. 2024 Mar;352:141399. doi: 10.1016/j.chemosphere.2024.141399. Epub 2024 Feb 7.
Layered double hydroxides (LDHs) have been recognized to have great potential for the treatment of heavy metals in wastewater and soil through various mechanisms. Isomorphic substitution is an important mechanism for the sorption of heavy metal cations with LDH reconstruction and highly stable product formation. However, sorption performance, structure-related relationships, and, more importantly, stability are still poorly understood. In this study, a series of LDHs with different structures were synthesized to evaluate their cadmium (Cd) sorption performance and stability concerning the isomorphic substitution mechanism. Divalent cation types in the LDH lattice determined the Cd sorption capacity as well as the isomorphic substitution possibility, following the order of hydroxide solubility of divalent cations (M): Ca>Mg>(Cd) > Ni>Zn. In addition, CaAl-LDH exhibited a super-high Cd sorption capacity of 625.0 mg g. Cd sorption by LDHs with different interlayer anion types and divalent/trivalent cation molar ratios varied due to crystallite size-related M release through cation-exchange/isomorphic substitution. Coexisting cations (e.g., Zn, Ni, Mg) influence the sorption performance of M-LDH mainly through isomorphic substitution mechanism, largely depending on the solubility of M(OH) with a trend of stable product formation. Furthermore, MgCdAlCl-LDH was fabricated, and limited Cd dissolution without destruction of the LDH structure was observed under various conditions. For example, only 7.69%, 2.16% and 0.96% of Cd was released from as-prepared MgCdAlCl-LDH in NaCl solution (0.02 mol L, pH 5), soil extract, and soil matrix, respectively. The very low leaching of Cd from Cd-containing LDHs indicated the high stability of LDH-sorbed Cd via isomorphic substitution and feasible practical application in Cd sequestration in wastewater treatment and soil remediation.
层状双氢氧化物(LDHs)已被认为通过各种机制在处理废水和土壤中的重金属方面具有巨大潜力。同晶替代是LDH重构吸附重金属阳离子并形成高度稳定产物的重要机制。然而,吸附性能、结构相关关系,更重要的是稳定性,仍然了解甚少。在本研究中,合成了一系列具有不同结构的LDHs,以评估它们在同晶替代机制方面对镉(Cd)的吸附性能和稳定性。LDH晶格中的二价阳离子类型决定了Cd吸附容量以及同晶替代可能性,遵循二价阳离子(M)的氢氧化物溶解度顺序:Ca>Mg>(Cd) > Ni>Zn。此外,CaAl-LDH表现出625.0 mg g的超高Cd吸附容量。具有不同层间阴离子类型和二价/三价阳离子摩尔比的LDHs对Cd的吸附因通过阳离子交换/同晶替代与微晶尺寸相关的M释放而有所不同。共存阳离子(如Zn、Ni、Mg)主要通过同晶替代机制影响M-LDH的吸附性能,很大程度上取决于M(OH)的溶解度以及稳定产物形成的趋势。此外,制备了MgCdAlCl-LDH,并且在各种条件下观察到在不破坏LDH结构的情况下Cd的有限溶解。例如,在NaCl溶液(0.02 mol L,pH 5)、土壤提取物和土壤基质中,分别只有7.69%、2.16%和0.96%的Cd从制备好的MgCdAlCl-LDH中释放出来。含Cd的LDHs中Cd的极低浸出表明通过同晶替代吸附的Cd具有高稳定性,并且在废水处理和土壤修复中对Cd的螯合具有可行的实际应用。