Organic electrode materials (OEMs) are increasingly replacing conventional inorganic counterparts in metal ion batteries (MIBs) due to their cost-effectiveness and environmental compatibility. Porphyrin-based materials, particularly metalloporphyrins (M-Porph), have garnered significant attention for electrochemical energy storage systems (EESS) owing to their bipolar electrochemical reactivity, making them suitable as both cathodic and anodic materials. However, the correlation between their structure and performance needs further exploration. This computational study examines the redox properties, thermodynamics, and theoretical performance of Zinc(II)-Porphyrin (Zn-Porph) with furan and thiophene substituents. The redox potential (E°) of Zn-Porph changes by 0.17 V with thiophene substituents instead of furan. Thiophene stabilizes the LUMO by 0.105 eV, indicating enhanced electron affinity and faster electron-accepting processes, while the HOMO shows a 0.085 eV stabilization. Thermodynamic calculations reveal that the reduction process intermediates for Zinc(II)-thiophene-Porph are less stable (ΔΔG° = 0.12 eV) than those for furan, suggesting a more accelerated electrochemical process. Additionally, density of states (DOS) analysis of Zn-T18 shows a non-zero DOS at the Fermi energy, indicating available electronic states for occupancy and highlighting its conductive properties. Upon complexation with PF6¯, the Fermi level shifts, reflecting electronic state redistribution and stabilization. The oxidized form, Zn-T16, retains a non-zero DOS at the Fermi energy despite significant Fermi level shifts, ensuring continued electronic conductivity. These findings underscore the robustness and versatility of Zn-porphyrin cathodes in EESS, demonstrating their potential to meet the demands for efficient, cost-effective, and environmentally friendly energy storage solutions.

中文翻译：

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关于呋喃和噻吩官能化锌卟啉作为电化学储能系统高性能有机阴极的第一性原理计算见解


有机电极材料 （OEM） 因其成本效益和环境兼容性而越来越多地取代金属离子电池 （MIB） 中的传统无机材料。基于卟啉的材料，特别是金属卟啉 （M-Porph），由于其双极电化学反应性而受到电化学储能系统 （EESS） 的广泛关注，使其适合用作阴极和阳极材料。然而，它们的结构和性能之间的相关性需要进一步探索。这项计算研究考察了含有呋喃和噻吩取代基的锌 （II）-卟啉 （Zn-Porph） 的氧化还原性质、热力学和理论性能。Zn-Porph 的氧化还原电位 （E°） 变化 0.17 V，噻吩取代基而不是呋喃。硫酚使 LUMO 稳定 0.105 eV，表明电子亲和力增强和电子接受过程更快，而 HOMO 显示出 0.085 eV 的稳定性。热力学计算表明，锌 （II）-噻吩-Porph 的还原过程中间体比呋喃的还原过程中间体更不稳定 （ΔΔG° = 0.12 eV），表明电化学过程更加速。此外，Zn-T18 的状态密度 （DOS） 分析显示费米能量下的 DOS 不为零，表明可用的电子状态可供占用并突出其导电特性。与 PF6 ̄ 络合时，费米能级发生变化，反映出电子态的重新分布和稳定。尽管费米能级发生了显著的变化，但氧化形式的 Zn-T16 在费米能量处仍保持非零 DOS，从而确保了持续的电子导电性。 这些发现强调了 EESS 中 Zn-卟啉阴极的稳健性和多功能性，证明了它们满足对高效、经济和环保储能解决方案的需求的潜力。