Lithium Promotes Acetylide Formation on MgO During Methane Coupling Under Non-Oxidative Conditions.

A prototypical material for the oxidative coupling of methane (OCM) is Li/MgO, for which Li is known to be essential as a dopant to obtain high C2 selectivities. Herein, Li/MgO is demonstrated to be an effective catalyst for non-oxidative coupling of methane (NOCM). Moreover, the presence of Li is shown to favor the formation of magnesium acetylide (MgC2 ), while pure MgO promotes coke formation as evidenced by solid-state 13 C NMR, thus indicating that Li promotes C-C bond formation. Metadynamic simulations of the carbon mobility in MgC2 and Li2 C2 at the density functional theory (DFT) level show that carbon easily diffuses as a C2 unit at 1000 °C. These insights suggest that the enhanced C2 selectivity for Li-doped MgO is related to the formation of Li and Mg acetylides.

Sites for methane activation on lithium-doped magnesium oxide surfaces.

Density functional calculations yield energy barriers for H abstraction by oxygen radical sites in Li-doped MgO that are much smaller (12±6 kJ mol(-1)) than the barriers inferred from different experimental studies (80-160 kJ mol(-1)). This raises further doubts that the Li(+)O(˙-) site is the active site as postulated by Lunsford. From temperature-programmed oxidative coupling reactions of methane (OCM), we conclude that the same sites are responsible for the activation of CH4 on both Li-doped MgO and pure MgO catalysts. For a MgO catalyst prepared by sol-gel synthesis, the activity proved to be very different in the initial phase of the OCM reaction and in the steady state. This was accompanied by substantial morphological changes and restructuring of the terminations as transmission electron microscopy revealed. Further calculations on cluster models showed that CH4 binds heterolytically on Mg(2+)O(2-) sites at steps and corners, and that the homolytic release of methyl radicals into the gas phase will happen only in the presence of O2.

One-Dimensional Oxide Nanostructures Possessing Reactive Surface Defects Enabled a Lithium-Rich Region and High-Voltage Stability for All-Solid-State Composite Electrolytes.

The development of highly safe and low-cost solid polymer electrolytes for all-solid-state lithium batteries (ASSLBs) has been hindered by low ionic conductivity, poor stability under high-voltage conditions, and severe lithium-dendrite-induced short circuits. In this study, Li-doped MgO nanofibers bearing reactive surface defects of scaled-up production are introduced to the poly(ethylene oxide) (PEO)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) system. The characterizations and density functional theory calculations reveal that TFSI- is strongly adsorbed on the nanofibers based on the electrostatic interactions of surface oxygen vacancies and the formation of Li-N and Li-O bonds derived from the exposed Li. Additionally, the introduced Li exposed near oxygen vacancies may be liberated from the lattice and engage in the formation of Li-rich domains. Therefore, a high ionic conductivity of 1.48 × 10-4 S cm-1 for the solid electrolyte at 30 °C and excellent cycling stability for the assembled battery, with a discharge capacity retention of 85.2% after 1500 cycles at 2C, can be achieved. Furthermore, the increased coordination of EO chains in the Li-rich region and chemical interactions with nanofibers substantially improve the antioxidant stability of the solid electrolyte, endowing the LiNi0.8Co0.1Mn0.1O2/Li battery with a long lifespan of more than 700 cycles. The results of this study suggest that the surface defects of 1D oxide nanostructures can substantially improve the Li+ diffusion kinetics. This study provides insight into the construction of Li-rich regions for high-voltage ASSLBs.