Lithium sulfur batteries with high energy densities are promising next-generation energy storage systems. However, shuttling and sluggish conversion of polysulfides to solid lithium sulfides limit the full utilization of active materials. Physical/chemical confinement is useful for anchoring polysulfides, but not effective for utilizing the blocked intermediates. Here, we employ black phosphorus quantum dots as electrocatalysts to overcome these issues. Both the experimental and theoretical results reveal that black phosphorus quantum dots effectively adsorb and catalyze polysulfide conversion. The activity is attributed to the numerous catalytically active sites on the edges of the quantum dots. In the presence of a small amount of black phosphorus quantum dots, the porous carbon/sulfur cathodes exhibit rapid reaction kinetics and no shuttling of polysulfides, enabling a low capacity fading rate (0.027% per cycle over 1000 cycles) and high areal capacities. Our findings demonstrate application of a metal-free quantum dot catalyst for high energy rechargeable batteries.

Nanoscale resistance-switching cells that operate via the electrochemical formation and disruption of metallic filaments that bridge two electrodes are among the most promising devices for post-CMOS electronics. Despite their importance, the mechanisms that govern their remarkable properties are not fully understood, especially for nanoscale devices operating at ultrafast rates, limiting our ability to assess the ultimate performance and scalability of this technology. We present the first atomistic simulations of the operation of conductive bridging cells using reactive molecular dynamics with a charge equilibration method extended to describe electrochemical reactions. The simulations predict the ultrafast switching observed in these devices, with timescales ranging from hundreds of picoseconds to a few nanoseconds for devices consisting of Cu active electrodes and amorphous silica dielectrics and with dimensions corresponding to their scaling limit (cross-sections below 10 nm). We find that single-atom-chain bridges often form during device operation but that they are metastable, with lifetimes below a nanosecond. The formation of stable filaments involves the aggregation of ions into small metallic clusters, followed by a progressive chemical reduction as they become connected to the cathode. Contrary to observations in larger cells, the nanoscale conductive bridges often lack crystalline order. An atomic-level mechanistic understanding of the switching process provides guidelines for materials optimization for such applications and the quantitative predictions over an ensemble of devices provide insight into their ultimate scaling and performance.

Nanolaminate membranes made of two-dimensional materials (2D) such as graphene oxide (GO) are promising candidates for molecular sieving via size-limited diffusion in the 2D capillaries, but high hydrophilicity makes these membranes unstable in water. Here, we 25 report a nanolaminate membrane based on covalently functionalized molybdenum disulfide (MoS 2 ) nanosheets. The functionalized MoS 2 membranes demonstrate >90% and ~ 87% rejection for micropollutants and NaCl respectively when operating under reverse osmotic conditions. The sieving performance and water flux of the functionalized MoS 2 membranes are attributed to both control of the capillary widths of the nanolaminates and 30 control of the surface chemistry of the nanosheets. We identified small hydrophobic 20 12 References

The conversion of CO2 into desirable multicarbon products via the electrochemical reduction reaction holds promise to achieve a circular carbon economy. Here, we report a strategy in which we modify the surface of bimetallic silver-copper catalyst with aromatic heterocycles such as thiadiazole and triazole derivatives to increase the conversion of CO2 into hydrocarbon molecules. By combining operando Raman and X-ray absorption spectroscopy with electrocatalytic measurements and analysis of the reaction products, we identified that the electron withdrawing nature of functional groups orients the reaction pathway towards the production of C2+ species (ethanol and ethylene) and enhances the reaction rate on the surface of the catalyst by adjusting the electronic state of surface copper atoms. As a result, we achieve a high Faradaic efficiency for the C2+ formation of ≈80% and full-cell energy efficiency of 20.3% with a specific current density of 261.4 mA cm−2 for C2+ products.

Successful doping of single-layer transition metal dichalcogenides (TMDs) remains a formidable barrier to their incorporation into a range of technologies. We use density functional theory to study doping of molybdenum and tungsten dichalcogenides with a large fraction of the periodic table. An automated analysis of the energetics, atomic and electronic structure of thousands of calculations results in insightful trends across the periodic table and points out promising dopants to be pursued experimentally. Beyond previously studied cases, our predictions suggest promising substitutional dopants that result in p-type transport and reveal interesting physics behind the substitution of the metal site. Doping with early transition metals (TMs) leads to tensile strain and a significant reduction in the bandgap. The bandgap increases and strain is reduced as the d-states are filled into the mid TMs; these trends reverse are we move into the late TMs. Additionally, the Fermi energy increases monotonously as the d-shell is filled from the early to mid TMs and we observe few to no gap states indicating the possibility of both p-(early TMs) and n-(mid TMs) type doping. Quite surprisingly, the simulations indicate the possibility of interstitial doping of TMDs; the energetics reveal that a significant number of dopants, increasing in number from molybdenum disulfide to diselenide and to ditelluride, favor the interstitial sites over adsorbed ones. Furthermore, calculations of the activation energy associated with capturing the dopants into the interstitial site indicate that the process is kinetically possible. This suggets that interstitial impurities in TMDs are more common than thought to date and we propose a series of potential interstitial dopants for TMDs relevant for application in nanoelectronics based on a detailed analysis of the predicted electronic structures.where E(nM X 2 + D I ) is the energy of the TMD sample with n formula units including an interstitial dopant. We note that the formation energy for an adsorbed atom is defined following Eq. 2 as well. It is clear from Eqs. 1 and 2 that the formation energies depend on the chemical potential of the species involved, which are determined by growth conditions. The chemical potentials for the metal and chalcogen atoms are typically considered between two limits: metal rich and chalcogen rich. Under metal-rich conditions {µ M −rich M ,µ M −rich X }, the chemical potential of the metal is set by its ground state crystal structure and that for the chalcogen is set such that the TMD is in equilibrium with the metal source.In chalcogen-rich conditions {µ X−rich M ,µ X−rich X }, the chemical potential of the chalcogen is obtained from

We introduce electrochemical dynamics with implicit degrees of freedom (EChemDID), a model to describe electrochemical driving force in reactive molecular dynamics simulations. The method describes the equilibration of external electrochemical potentials (voltage) within metallic structures and their effect on the self-consistent partial atomic charges used in reactive molecular dynamics. An additional variable assigned to each atom denotes the local potential in its vicinity and we use fictitious, but computationally convenient, dynamics to describe its equilibration within connected metallic structures on-the-fly during the molecular dynamics simulation. This local electrostatic potential is used to dynamically modify the atomic electronegativities used to compute partial atomic changes via charge equilibration. Validation tests show that the method provides an accurate description of the electric fields generated by the applied voltage and the driving force for electrochemical reactions. We demonstrate EChemDID via simulations of the operation of electrochemical metallization cells. The simulations predict the switching of the device between a high-resistance to a low-resistance state as a conductive metallic bridge is formed and resistive currents that can be compared with experimental measurements. In addition to applications in nanoelectronics, EChemDID could be useful to model electrochemical energy conversion devices.

We derive an analytical expression of the density functional theory (DFT)-broken-symmetry (BS) estimation J(BS) of the singlet-triplet gap at the "3 sites-4 electrons" level, that is, two S = (1)/(2) metallic sites + one diamagnetic bridge orbital. As originally designed by Noodleman and Davidson (Chem. Phys.1986, 109, 131), J(BS) contains the residual ferromagnetic contribution, single ligand-to-metal and metal-to-metal charge-transfer terms, but no double ligand-to-metal charge-transfer terms or intra/interligand spin-polarization terms. As revealed by the present analysis, the triplet and BS states computed by DFT differ, not only perturbatively (as expected) because of the various physical mechanisms involved (i.e., differential charge-transfer terms) but mainly because of a spurious and unphysical symmetry breaking of the bridge orbitals in the BS state. We examine the consequences of such a difference by deriving two analytical expressions of the exchange coupling constant, one from the BS orbitals designed to match J(BS) and another one from triplet orbitals only. Following and extending on the first paper in the series (J. Phys. Chem. A 2010, 114, 6149), we propose a simple procedure to extract appropriate parameters filling in our analytical expressions. Moreover, we derive the equivalent "3 sites-4 electrons" exchange coupling constant in the configuration-interaction approach, J(CI), for the purpose of comparison. These analytical expressions have been applied to various copper dimers and compared to experimental values.

We use density functional theory (DFT) to study the thermodynamic stability and migration of copper ions and small clusters embedded in amorphous silicon dioxide. We perform the calculations over an ensemble of statistically independent structures to quantify the role of the intrinsic atomic-level variability in the amorphous matrix affect the properties. The predicted formation energy of a Cu ion in the silica matrix is 2.7±2.4 eV, significantly lower the value for crystalline SiO 2 . Interestingly, we find that Cu clusters of any size are energetically favorable as compared to isolated ions; showing that the formation of metallic clusters does not require overcoming a nucleation barrier as is often assumed. We also find a broad distribution of activation energies for Cu migration, from 0.4 to 1.1 eV. This study provides insights into the stability of nanoscale metallic clusters in silica of interest in electrochemical metallization cell memories and optoelectronics.