This article presents a density functional theory (DFT) study that explores the chemical interactions and mechanisms in Li/Na-MXene systems with the aim of improving the performance of rechargeable batteries. Experimental studies indicate the presence of chemical and physical adsorption mechanisms in these systems. To understand the interaction mechanisms in the charging/discharging process, we investigated the ion intercalation/adsorption process and the induced chemical shielding. Different possible surface terminations have been investigated to determine which type of interaction is more likely to exist at the interlayer surfaces. The DFT results obtained in this study suggested the use of various methods, such as surface modification and expansion of the interlayer distance, to enhance the energy storage performance; nuclear magnetic resonance measurements can be used to check whether the ideal surface modifications have been experimentally achieved.
Both rhodium and copper show a catalytic activity for nitric oxide (NO) reduction; however, the reaction mechanisms can be different. Herein, we elucidate the difference in the NO reduction mechanisms between Rh and Cu clusters regarding the electronic structures using DFT computations and small cluster models involving four metal atoms. The computational results show that the dissociative adsorption proceeds on the Rh cluster with the reaction barrier of 33 kcal mol−1. The calculated heat of the reaction is almost zero. On the Cu cluster, the calculated reaction barrier reaches to 78 kcal mol−1 indicating that the dissociative adsorption hardly occurs. Instead of the dissociative adsorption, dimerization of NO initiates the catalytic NO reduction on Cu cluster. The calculated energy barrier for the dimerization is 8 kcal mol−1. The adsorbed NO dimer has a similar stability to co-adsorbed two NO molecules. In contrast, the dimerization hardly occurs on the Rh cluster; the reaction pathway is remarkably endothermic, and a stable adsorbed product is not found. The adsorption structures of NO can explain such differences. On Cu cluster, NO takes bent-nitrosyl conformation that acts as an electron acceptor. On Rh cluster, NO acts as an electron donor having linear-nitrosyl conformation.