钙或钾催化锯齿形边缘炭化学吸附二氧化碳的波函数和分子反应性研究
Calcium or Potassium Catalyzed Study of the Wave Function and Molecular Reactivity of Carbon Dioxide Chemisorption by Zigzag Edge Carbon
DOI: 10.12677/japc.2024.132038, PDF,    国家自然科学基金支持
作者: 王 波, 詹世强, 张 杰*：上海理工大学能源与动力工程学院，上海
关键词: 二氧化碳；密度泛函理论；波函数理论；炭；钙；钾；CO2； Density Functional Reactivity Theory； Wave Function Theory； Char； Ca； K
摘要: 本研究采用波函数理论和密度泛函反应性理论，系统地研究掺杂了钙(Ca)或钾(K)的锯齿形边缘炭模型的分子反应性以及对化学吸附二氧化碳(CO2)性能的影响。通过比较不同金属负载炭模型的电负性、亲电性和亲核性，得出了CO2在其炭模型上的化学吸附是亲电反应的结论。并进一步分析了最低未占据分子轨道(LUMO)和最高已占据分子轨道(HOMO)，表明碱土金属Ca或碱金属K的掺杂改变了焦炭的电荷分布特性。通过研究电子局域化函数填色图和电子密度差，发现负载金属边缘充满更多的孤对电子，并且该边缘区域电子的局域化程度更高，因此更容易受到亲电攻击，易作为吸附位点考虑。借助双描述符、HOMO和LUMO的轨道成分的研究，预测了在掺杂了Ca或K的炭模型吸附CO2的位点。此外，计算了不同模型下化学吸附CO2释放的能量，最终吸附CO2的热力学结果与波函数理论和密度泛函反应性理论的预测结果一致。
Abstract: In this study, the molecular reactivity of char models with zigzag edges doped with calcium (Ca) or potassium (K) and the effect on the performance of chemisorption of carbon dioxide (CO2), were systematically investigated using wave function theory and density functional reactivity theory. By comparing the electronegativity, electrophilicity and nucleophilicity of different metal-doped char models, it was concluded that the chemisorption of CO2 on their char models is an electrophilic reaction. Further analysis of the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) indicated that the charge distribution characteristics of the char model were altered by the incorporation of Ca, an alkaline earth metal, or K, an alkali metal. By studying Coloring map of the electron localization function and the electron density difference, it was found that the loaded metal edge is filled with more lone pair electrons and that the edge region is more electronically localised, making it more susceptible to electrophilic attacks and easy to consider as an adsorption site. With the help of dual descriptors, the study of orbital compositions of HOMO and LUMO, the sites of adsorption of CO2 in carbon models doped with Ca or K were predicted. In addition, the energy released by CO2 chemisorption in various models was calculated, and the thermodynamic outcomes of CO2 adsorption were in agreement with the predictions of wave function theory and density functional reactivity theory.
文章引用：王波, 詹世强, 张杰. 钙或钾催化锯齿形边缘炭化学吸附二氧化碳的波函数和分子反应性研究[J]. 物理化学进展, 2024, 13(2): 326-337. https://doi.org/10.12677/japc.2024.132038

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