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5 V. X-ray photoelectron spectra and Mn L-edge X-ray absorption spectra of the cathode powders reveal a Li+ deficiency and a partial reduction of Mn ions on the surface of the acid-treated material. More interestingly, although the irreversible oxygen evolution is greatly suppressed through the surface treatment, O K-edge resonant inelastic X-ray scattering shows that the lattice O-redox behavior is largely sustained. The acidic treatment, therefore, only optimizes the surface of the Li-rich material and almost eliminates the irreversible gas evolution, leading to improved cycling and rate performance. This work therefore presents a simple yet effective approach to passivate cathode surfaces against interfacial instabilities during high-voltage battery operation.With the development of microscopy and sensor techniques, it becomes evident that nonswelling clays show swelling behavior under CO2-water mixture environments at high pressures and temperatures. The examples include Illite, muscovite, and kaolinite-rich rock samples. Here, we investigated the underlying mechanisms of kaolinite swelling induced by CO2 and water using molecular simulations and low-pressure gas adsorption experiments. The results suggest the cooperative adsorption behavior of CO2 and water on contact with kaolinite micropores, which have distinct wettabilities on the two adjoining interlayer surfaces. Even if clay-bound water exists, CO2 can enter the micropores to induce swelling. The measured micropore volume, simulated equilibrium stable interlayer distance with pure water, and that with CO2-water mixture were used in the swelling estimation, which shows good agreement with our experiments. The CO2 and water molecule distributions inside the interlayer micropores verify the importance of the wettabilities of the kaolinite surfaces in this cooperative adsorption behavior. The result extends the traditional understanding of the swelling mechanism, i.e., cation hydration and subsequent osmotic processes. In addition to earlier observations of kaolinite swelling behavior with potassium acetate, our study indicates the significance of the subtle balance of the noncovalent interactions between CO2, water, and the kaolinite Janus surfaces.Cathodes based on layered LiMO2 are the limiting components in the path toward Li-ion batteries with energy densities suitable for electric vehicles. Introducing an overstoichiometry of Li increases storage capacity beyond a conventional mechanism of formal transition metal redox. However, the role and fate of the oxide ligands in such intriguing additional capacity remain unclear. This reactivity was predicted in Li3RuO4, making it a valuable model system. A comprehensive analysis of the redox activity of both Ru and O under different electrochemical conditions was carried out, and the effect of Li/Ru ordering was evaluated. Li3RuO4 displays highly reversible Li intercalation to Li4RuO4 below 2.5 V vs Li+/Li0, with conventional reactivity through the formal Ru5+-Ru4+ couple. In turn, it can also undergo anodic Li extraction at 3.9 V, which involves O states to a much greater extent than Ru. This reaction competes with side processes such as electrolyte decomposition and, to a much lesser extent, oxygen loss. Although the associated capacity is reversible, reintercalation unlocks a different, conventional pathway also involving the formal Ru5+-Ru4+ couple despite operating above 2.5 V, leading to chemical hysteresis. This new pathway is both chemically and electrochemically reversible in subsequent cycles. This work exemplifies both the challenge of stabilizing highly depleted O states, even with 4d metals, and the ability of solids to access the same redox couple at two very different potential windows depending on the underlying structural changes. It highlights the importance of properly defining the covalency of oxides when defining charge compensation in view of the design of materials with high capacity for Li storage.The Haber-Bosch (HB) process combining nitrogen (N2) and hydrogen (H2) into ammonia (NH3) gas plays an essential role in the synthesis of fertilizers for food production and many other commodities. However, HB requires enormous energy resources (2% of world energy production), and the high pressures and temperatures make NH3 production facilities very expensive. Recent advances in improving HB catalysts have been incremental and slow. To accelerate the development of improved HB catalysts, we developed a hierarchical high-throughput catalyst screening (HHTCS) approach based on the recently developed complete reaction mechanism to identify non-transition-metal (NTM) elements from a total set of 18 candidates that can significantly improve the efficiency of the most active Fe surface, Fe-bcc(111), through surface and subsurface doping. Surprisingly, we found a very promising subsurface dopant, Si, that had not been identified or suggested previously, showing the importance of the subsurface Fe atoms in N2 reduction reactions. Then we derived the full reaction path of the HB process for the Si doped Fe-bcc(111) from QM simulations, which we combined with kinetic Monte Carlo (kMC) simulations to predict a ∼13-fold increase in turnover frequency (TOF) under typical extreme HB conditions (200 atm reactant pressure and 500 °C) and a ∼43-fold increase in TOF under ideal HB conditions (20 atm reactant pressure and 400 °C) for the Si-doped Fe catalyst, in comparison to pure Fe catalyst. Importantly, the Si-doped Fe catalyst can achieve the same TOF of pure Fe at 200 atm/500 °C under much milder conditions, e.g. at a much decreased reactant pressure of 20 atm at 500 °C, or alternatively at temperature and reactant pressure decreased to 400 °C and 60 atm, respectively. find more Production plants using the new catalysts that operate under such milder conditions could be much less expensive, allowing production at local sites needing fertilizer.Gold (Au) has been considered catalytically inert for decades, but recent reports have described the ability of Au nanoparticles to catalyze H2O2 decomposition in the Haber-Weiss cycle. Herein, the design and demonstration of a flow-through electro-Fenton system based on an electrochemical carbon nanotube (CNT) filter functionalized with atomically precise Au nanoclusters (AuNCs) is described. The functionality of the device was then tested for its ability to catalyze antibiotic tetracycline degradation. In the functional filters, the Au core of AuNCs served as a high-performance Fenton catalyst; while the AuNCs ligand shells enabled CNT dispersion in aqueous solution for easy processing. The hybrid filter enabled in situ H2O2 production and catalyzed the subsequent H2O2 decomposition to HO·. The catalytic function of AuNCs lies in their ability to undergo redox cycling of Au+/Au0 under an electric field. The atomically precise AuNCs catalysts demonstrated superior catalytic activity to larger nanoparticles; while the flow-through design provided convection-enhanced mass transport, which yielded a superior performance compared to a conventional batch reactor.