I$_2$和CH$_3$I在过渡金属修饰的二维材料基底上吸附的第一性原理研究：电子结构与反应动力学的见解

中文摘要 AI 辅助

放射性碘物种，特别是I$_2$和CH$_3$I，由于其高挥发性、化学稳定性以及与传统基底和吸附材料的相对较弱相互作用，构成了显著的环境和技术危害。在这项工作中，我们提出了一系列过渡金属（TM）（Fe、Ni、Cu、Zn）修饰的硼掺杂石墨烯（BDG）和二维MoTe2基底，用于高效吸附捕获和缓解此类挥发性碘物种。通过系统的第一性原理密度泛函理论（DFT）计算，我们通过分析吸附时电子结构的变化，阐明了增强吸附的微观起源。更重要的是，我们使用爬坡弹性带（CI-NEB）计算方法分析了这些新设计基底上吸附的热力学和动力学可行性，并发现TM修饰作为有效的催化中心，从而使反应在热力学和动力学上变得可行。相反，在没有TM原子作为催化中心的原始基底上，反应在热力学和动力学上变得不利。这项工作加深了我们对增强吸附和反应动力学电子起源的理解，所做出的预测将对实验实现有用。

英文摘要

Radioactive iodine species, particularly I$_2$ and CH$_3$I, pose significant environmental and technological hazards owing to their high volatility, chemical stability, and relatively weak interaction with traditional substrate and sorption materials. In this work, we proposed a series of transition-metal (TM) (Fe, Ni, Cu, Zn) decorated boron-doped graphene (BDG) and 2D-MoTe2 substrates for efficient adsorptive capture and mitigation of such volatile Iodine species. Using systematic first-principles density functional theory (DFT) calculations, we elucidate the microscopic origin of the enhanced adsorption by analyzing the changes in the electronic structure upon adsorption. More importantly, we analyzed the thermodynamic and kinetic feasibility of adsorption on these newly designed substrates using Climbing-Image Nudged Elastic band (CI-NEB) calculations and found that TM decoration serves as an effective catalytic center, thereby making the reaction thermodynamically and kinetically feasible. Conversely, the reaction becomes thermodynamically and kinetically unfavorable on pristine substrates in the absence of a TM atom as a catalytic center. This work deepens our understanding of the electronic origin of the enhanced adsorption and reaction kinetics, and the predictions made will be useful for experimental realization.

发表机构

• Indira Gandhi Centre for Atomic Research（印度原子能研究中心）

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