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腐殖酸改变了天然氧化剂对二硫化钼纳米片环境转化的影响。

Humic acid changes effect of naturally occurring oxidants on the environmental transformation of molybdenum disulfide nanosheets.

机构信息

Department of Environmental Engineering, National Chung Hsing University, Taichung City 402, Taiwan.

出版信息

J Environ Manage. 2024 Sep;368:122190. doi: 10.1016/j.jenvman.2024.122190. Epub 2024 Aug 24.

DOI:10.1016/j.jenvman.2024.122190
PMID:39180818
Abstract

2H-phase molybdenum disulfide (2H-MoS) has been considered to be a chemically stable two-dimensional (2D) nanomaterial. Nonetheless, the persistence of 2H-MoS in the presence of environmental redox-active matrices, such as naturally occurring oxidants (e.g., manganese dioxide (MnO)) and natural organic matter (NOM), remains largely unknown. Herein, we examined the interplay between 2H-MoS, MnO (a common natural oxidant), and NOM species (i.e., Aldrich humic acid (ALHA) and Suwannee River natural organic matter (SRNOM)). The results show that MnO accelerates the oxidative dissolution of 2H-MoS, regardless of the presence of dissolved oxygen. The effect of NOM on the MnO-induced fate of 2H-MoS was found to depend on its affinity for 2H-MoS and the functionality of NOM. ALHA preferentially adsorbed on hydrophobic 2H-MoS nanosheets due to the enrichment of reductive polycyclic aromatics and polyphenolic constituents. The preferential ALHA adsorption counteracted the MnO-triggered oxidative transformation of 2H-MoS, as revealed by the cathodic response of 2H-MoS (i.e., decreased the open circuit potential by 0.0338 V) and the emergence of reductive Mo‒C bonds at 228.8 and 231.9 eV upon the addition of ALHA. This work evaluated the persistence of 2H-MoS, illustrating its susceptibility to decomposition by naturally occurring oxidants and the influence of NOM on it. These findings are crucial for revealing the fate and transport of MoS in aquatic environments and provide guidelines for related applications in natural or engineered systems for MoS and potentially other 2D materials.

摘要

二硫化钼(2H-MoS)被认为是一种化学稳定性的二维(2D)纳米材料。然而,2H-MoS 在环境氧化还原活性基质(如天然氧化剂(如二氧化锰(MnO))和天然有机物(NOM))存在下的持久性在很大程度上仍然未知。在此,我们研究了 2H-MoS、MnO(一种常见的天然氧化剂)和 NOM 物种(即 Aldrich 腐殖酸(ALHA)和苏万尼河天然有机物(SRNOM))之间的相互作用。结果表明,MnO 加速了 2H-MoS 的氧化溶解,无论是否存在溶解氧。发现 NOM 对 MnO 诱导的 2H-MoS 命运的影响取决于其对 2H-MoS 的亲和力和 NOM 的功能。由于富含有还原性多环芳烃和多酚成分,ALHA 优先吸附在疏水性 2H-MoS 纳米片上。ALHA 的优先吸附抵消了 MnO 引发的 2H-MoS 的氧化转化,这表现为 2H-MoS 的阴极响应(即开路电位降低了 0.0338 V)以及在添加 ALHA 后 228.8 和 231.9 eV 处出现还原 Mo‒C 键。这项工作评估了 2H-MoS 的持久性,说明了其易受天然氧化剂分解的影响以及 NOM 对其的影响。这些发现对于揭示 MoS 在水环境中的命运和迁移至关重要,并为 MoS 及潜在其他二维材料在自然或工程系统中的相关应用提供了指导。

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