求助 HOMO和LUMO在使用低共熔溶剂(DES)浸出锂电池中的应用

gwh1206

各位老师您好！想咨询一下HOMO和LUMO在DES浸出锂电池过程中的应用。看了最近几篇新发表的文献，也看了卢老师关于“正确地认识分子的能隙(gap)、HOMO和LUMO”的文章。心里有点迷惑，感觉在这些文章中的应用大抵是不太正确的，所以想咨询一下这些或者如何正确应用。
（1）文章1：通过HOMO筛选DES的氢键受体（HBA）组分（主要是评估氢键受体的配位强度）

翻译过来就是：使用HBA的HOMO评估配位强度。HOMO能量越高，越接近过渡金属离子的LUMO能量，有利于更强的配位。例如图a所示，氯化胆碱（[Ch][Cl]）表现出最高的HOMO能量，表明Cl−与其他阴离子和 EG 相比，与过渡金属离子的配位更强。
非常疑惑是否可以这么使用，或者依据是什么。
（2）文献2：通过HOMO和LUMO解释化学反应活性。

原文解释：
Frontier orbital theory explains chemical reactivity via interactions between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). The value of energy gap (ΔEg) is a measure of reactivity, with smaller gaps indicating higher activity due to lower excitation energy. Frontier orbital analysis shows the reactivity of the DES and its binding mechanism with metal ions. A greater HOMO energy implies a more pronounced electron-donating potential, as the DES donates electrons from its HOMO to empty metal orbitals during complexation. [size=1em]Fig. 8(c) reveals the HOMO localization on the chloride ions in ChCl and the LUMO distribution on the CA hydroxyl/carboxyl groups in the DES, reflecting the hydrogen bonding interactions. After coordination, the HOMO shifts remain chloride-centered, confirming preferential metal-chloride binding. These calculations are consistent with the UV spectroscopy findings, providing molecular-level evidence for the formation of chlorine complexes. The observed orbital distributions suggest that the DES acts as an electron-rich donor, facilitating electron transfer to electrophilic metal ions and stabilizing complexes. Furthermore, ΔEg notably decreases compared to its initial value, as presented in [size=1em]Fig. 8(c). This decline can be ascribed to the molecular orbitals of individual components undergoing hybridization during complex formation. This hybridization generates fresh bonding and antibonding orbitals with diminished energy disparities. The reduced ΔEg promotes the activity between the DES and metal ions, which is beneficial for the recovery of spent LIBs. The DES exhibits an affinity for the precious metals in the sequence of Li > Mn > Co > Ni. This shows that the DES has the strongest reactivity and interaction tendency with Ni, followed by Co, Mn, and Li.
我疑惑的点在于利用DES与过渡金属结合后得到的HOMO-LUMO，为什么可以说明DES与Ni的反应性更强，因为我理解的是这个只能说明结合Ni后的DES这种物质（Ni-DES）本身可能反应活性更强，而不是说DES与Ni的反应性更强。
（3）文献3：通过HOMO和LUMO解释结合稳定性

原文解释：
[size=1em]Fig. 6 illustrates that the HOMO orbital of the DES molecule is located near the chloride ion, suggesting a favorable binding interaction between transition metal ions and chloride ions in the leaching process. The calculation results align with the UV spectrum analysis, providing additional evidence supporting the association between chloride ions and transition metal ions in leaching process. The bandgap represents the energy distinction between HOMO and LUMO, in which a smaller bandgap indicates a more stable binding between the DES and the metal ion. As shown in [size=1em]Fig. 6, the bandgaps of DES after binding with the three metal ions are indeed smaller than the initial bandgap of DES, indicating a stabilization of the structure upon metal ion adsorption. This result also confirms the adsorption capability of DES toward the three metal ions. The order of bandgaps for DES binding with the three metal ions is Mn > Co > Ni, which is consistent with the binding energy analysis.
这里说利用HOMO-LUMO表明结构稳定性，这里是否可以认为对比的一批分子之间有足够相似性，所以可以通过HOMO-LUMO来说明Mn-DES结构更稳定，DES更容易和Mn离子结合。
以上是我的疑惑，十分感谢各位老师答疑和批评！

芝兰玉树

能否提供原文？