石墨烯
密度泛函理论
离解(化学)
键离解能
氟化物
环己烷
材料科学
粘结长度
石墨
碳纤维
计算化学
化学
结晶学
物理化学
晶体结构
有机化学
纳米技术
复合数
无机化学
复合材料
作者
Kelly Nieto,Brennan J. Walder,Todd M. Alam
标识
DOI:10.1021/acs.jpcc.3c00573
摘要
Fluorinated graphite materials are of interest for an assortment of applications and can be synthesized under a variety of synthetic conditions from many different types of carbon. Due to such variations, structural disorders in the form of defects and polymorphism are often present. Here, we investigate the impact of local structural variations on the C–F bond dissociation energies (BDEs) in carbon-based fluoride materials using density functional theory (DFT) computational methods. Employing fluorographene (FG) cluster models, we determine the impact of different C–F bonding configurations in the core of each platelet on the equilibrium BDEs for each C–F bond. The introduction of structural disorder decreases the first C–F BDE by approximately 1 eV compared to the canonical arrangement of axial C–F bonds ordered as in a network of cyclohexane “chairs”. Variability of calculated BDEs among the different polymorphs decreases upon subsequent F removal. Common structural tendencies of the adiabatic defluorination pathways for each polymorph are identified. Our analysis suggests that at F/C ratios near 1.0, disorder in the local structure can play a significant role in the energetics of the initial carbon fluoride defluorination and that the influence of this configurational disorder diminishes with decreasing F/C ratios.
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