Sumayli Abdulrahman, Alshahrani Saad M
Department of Mechanical Engineering, College of Engineering, Najran University, Najran, Saudi Arabia.
Department of Pharmaceutics, College of Pharmacy, Prince Sattam Bin Abdulaziz University, P.O.Box 173, Al-Kharj, 11942, Saudi Arabia.
Sci Rep. 2025 Aug 5;15(1):28637. doi: 10.1038/s41598-025-11683-7.
The adsorption behavior of the toxic molecules OCN and CN onto SiC fullerene-like cages was performed using density functional theory (DFT) calculations with the B3LYP and PBE functionals and a 6-311 + G** basis set, in both vacuum and aqueous phases (PCM model). Strong adsorption of OCN⁻ (nitrogen head) and CN⁻ (carbon head) to the cage surface results from covalent bonding and significant charge transfer from the fullerene-like cage to the anions in both phases. These adsorption processes, involving OCN via its nitrogen head and CN via its carbon head, were both spontaneous and exothermic, as indicated by the calculated adsorption energies and thermodynamic parameters. MD simulations show rapid OCN⁻ covalent bonding to the Si₁₂C₁₂ cage, followed by equilibration within 5 ps. The OCN⁻ exhibits higher mobility than the cage, as indicated by MSD analysis. This dynamic interaction, revealed by g(r) and MSD data, suggests a surface adsorption process. The impacts of OCN and CN interaction with the fullerene-like cage surface were assessed using infrared (IR) absorption spectroscopy. The photoelectron spectrum of OCN and CN adsorption suggests interactions between the fullerene-like cage and these molecules, emphasizing the involvement of strongly bonded electrons in facilitating these interactions. Significantly, during the adsorption process, there was a notable orbital hybridization between anions and fullerenes, as evidenced by the calculated total density of states (TDOS). DFT calculations show that SiC fullerene-like cage exhibits strong binding energies for OCN⁻ and CN⁻, suggesting its potential for highly efficient removal in environmental samples.
采用密度泛函理论（DFT）计算方法，使用B3LYP和PBE泛函以及6-311+G**基组，在真空和水相（PCM模型）中研究了有毒分子OCN和CN在类SiC富勒烯笼上的吸附行为。在两个相中，OCN⁻（氮端）和CN⁻（碳端）与笼表面的强吸附是由共价键以及从类富勒烯笼到阴离子的显著电荷转移导致的。如计算得到的吸附能和热力学参数所示，这些涉及OCN通过其氮端和CN通过其碳端的吸附过程都是自发且放热的。分子动力学（MD）模拟表明，OCN⁻与Si₁₂C₁₂笼快速形成共价键，随后在5皮秒内达到平衡。均方位移（MSD）分析表明，OCN⁻的迁移率高于笼。g(r)和MSD数据揭示的这种动态相互作用表明了一种表面吸附过程。利用红外（IR）吸收光谱评估了OCN和CN与类富勒烯笼表面相互作用的影响。OCN和CN吸附的光电子能谱表明类富勒烯笼与这些分子之间存在相互作用，强调了强键合电子在促进这些相互作用中的作用。值得注意的是，在吸附过程中，阴离子和富勒烯之间存在明显的轨道杂化，这由计算得到的态密度（TDOS）总和所证明。DFT计算表明，类SiC富勒烯笼对OCN⁻和CN⁻具有很强的结合能，表明其在环境样品中具有高效去除的潜力。
