Adsorption and molecular transformation mechanisms of mercury sulfide on mackinawite surfaces: A DFT-D3 study

IF 7.1 Q1 ENGINEERING, CHEMICAL Chemical Engineering Journal Advances Pub Date : 2025-03-02 DOI:10.1016/j.ceja.2025.100724

Fayang Guo , Yi Zhang , Yuxiang Mao , Yinchuan Li , Shunlin Tang , Mingshi Wang , Mingfei Xing , Fengcheng Jiang , Qiaoyun Huang , Xingmin Rong

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Abstract

Mackinawite (FeS), a common metallic sulfide mineral, plays a crucial role in regulating the bioavailability and mobility of mercury sulfide (HgS) in the environment. However, molecular-level insights into HgS interactions with FeS surfaces are currently limited. This study used density functional theory (DFT) to investigate HgS adsorption and transformation on FeS (001), FeS (011), and FeS (111) surfaces, including their defect surfaces. Bonding characteristics were analyzed using electron density difference, Bader charge, projected density of states (PDOS), and crystal orbital bonding index (COBI). HgS adsorption capacity on FeS surfaces is determined by surface reactivity in the order FeS (011) > FeS (111) > FeS (001). Additionally, S-defective FeS (001) and FeS (111) surfaces demonstrate enhanced HgS adsorption compared to Fe-defective surfaces. A potential risk of Hg release from HgS exists on FeS (001) and FeS (111) surfaces compared to FeS (011) surfaces. The dissociation of HgS molecules can be more stably adsorbed on the FeS (011) surface rather than releasing Hg. This study enriches the understanding of HgS adsorption and transformation on metal sulfides, shedding light on the microscopic cycling of HgS in soil systems.

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硫化汞在mackinawite表面的吸附和分子转化机制：DFT-D3研究

Mackinawite （FeS）是一种常见的金属硫化物矿物，在调节环境中硫化汞（HgS）的生物利用度和流动性方面起着至关重要的作用。然而，分子水平上对HgS与FeS表面相互作用的认识目前是有限的。本研究利用密度泛函理论（DFT）研究了HgS在FeS（001）、FeS（011）和FeS（111）表面及其缺陷表面的吸附和转化。利用电子密度差、Bader电荷、投影态密度（PDOS）和晶体轨道成键指数（COBI）分析了成键特性。HgS在FeS表面的吸附量由表面反应性决定，其顺序为FeS (011) >；FeS (111) >；菲斯(001)。此外，与铁缺陷表面相比，s缺陷FeS（001）和FeS（111）表面表现出更强的HgS吸附。与FeS（011）表面相比，FeS（001）和FeS（111）表面存在Hg释放的潜在风险。HgS分子的解离可以更稳定地吸附在FeS（011）表面，而不是释放Hg。本研究丰富了对HgS在金属硫化物上的吸附和转化的认识，揭示了HgS在土壤系统中的微观循环。

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