Supplementary Discussion: To evaluate the activity of the edges, we calculated the free energies of H adsorption on TaS 2 and NbS 2 edges. Although the structures of TaS 2 and NbS 2 edges at working condition are unknown, and very likely they keep changing during the reaction as the materials are broken into small pieces, we take the most common structure of the MoS 2 edge at HER condition (as shown in the Supplementary figure 18 below) 1,2 , as a representative model for TaS 2 and NbS 2 edges.Our calculations show that the free energies of H adsorption on this specific type of edges are -0.13 eV/H for TaS 2 and -0.26 eV/H for NbS 2 . Compared with the free energies of H adsorption on the basal plane, 0.17 eV/H for TaS 2 and 0.01 eV/H for NbS 2 , this specific type of edges likely does have some level of activity. However, we point out that these edges are less active than the MoS 2 edge (0.05 eV/H; A closer-to-zero free energy suggests a higher activity, see the main text), which suggests that the better overall performance of NbS 2 and TaS 2 compared to MoS 2 must have significant contributions from other factors. The most likely explanation is basal-plane activity, as our calculations indicate.

Knowledge and foundational understanding of phenomena associated with the behavior of materials at the nanoscale is one of the key scientific challenges toward a sustainable energy future. Size reduction from bulk to the nanoscale leads to a variety of exciting and anomalous phenomena due to enhanced surface-to-volume ratio, reduced transport length, and tunable nanointerfaces. Nanostructured metal hydrides are an important class of materials with significant potential for energy storage applications. Hydrogen storage in nanoscale metal hydrides has been recognized as a potentially transformative technology, and the field is now growing steadily due to the ability to tune the material properties more independently and drastically compared to those of their bulk counterparts. The numerous advantages of nanostructured metal hydrides compared to bulk include improved reversibility, altered heats of hydrogen absorption/desorption, nanointerfacial reaction pathways with faster rates, and new surface states capable of activating chemical bonds. This review aims to summarize the progress to date in the area of nanostructured metal hydrides and intends to understand and explain the underpinnings of the innovative concepts and strategies developed over the past decade to tune the thermodynamics and kinetics of hydrogen storage reactions. These recent achievements have the potential to propel further the prospects of tuning the hydride properties at nanoscale, with several promising directions and strategies that could lead to the next generation of solid-state materials for hydrogen storage applications.

Li 2 B 12 H 12 , Na 2 B 12 H 12 , and their closo-borate relatives exhibit unusually high ionic conductivity, making them attractive as a new class of candidate electrolytes in solid-state Li-and Na-ion batteries. However, further optimization of these materials requires a deeper understanding of the fundamental mechanisms underlying ultrafast ion conduction. To this end, we use ab initio molecular dynamics simulations and density-functional calculations to explore the motivations for cation diffusion. We find that superionic behavior in Li 2 B 12 H 12 and Na 2 B 12 H 12 results from a combination of key structural, chemical, and dynamical factors that introduce intrinsic frustration and disorder. A statistical metric is used to show that the structures exhibit a high density of accessible interstitial sites and site types, which correlates with the flatness of the energy landscape and the observed cation mobility. Furthermore, cations are found to dock to specific anion sites, leading to a competition between the geometric symmetry of the anion and the symmetry of the lattice itself, which can facilitate cation hopping. Finally, facile anion reorientations and other low-frequency thermal vibrations lead to fluctuations in the local potential that enhance cation mobility by creating a local driving force for hopping. We discuss the relevance of each factor for developing new ionic conductivity descriptors that can be used for discovery and optimization of closo-borate solid electrolytes, as well as superionic conductors more generally.

Nanoporous adsorbents are a diverse category of solid-state materials that hold considerable promise for vehicular hydrogen storage. Although impressive storage capacities have been demonstrated for several materials, particularly at cryogenic temperatures, materials meeting all of the targets established by the U.S. Department of Energy have yet to be identified. In this Perspective, we provide an overview of the major known and proposed strategies for hydrogen adsorbents, with the aim of guiding ongoing research as well as future new storage concepts. The discussion of each strategy includes current relevant literature, strengths and weaknesses, and outstanding challenges that preclude implementation. We consider in particular metal-organic frameworks (MOFs), including surface area/volume tailoring, open metal sites, and the binding of multiple H 2 molecules to a single metal site. Two related classes of porous framework materials, covalent organic frameworks (COFs) and porous aromatic frameworks (PAFs), are also discussed, as are graphene and graphene oxide and doped porous carbons. We additionally introduce criteria for evaluating the merits of a particular materials design strategy. Computation has become an important tool in the discovery of new storage materials, and a brief introduction to the benefits and limitations of computational predictions of H 2 physisorption is therefore presented. Finally, considerations for the synthesis and characterization of hydrogen storage adsorbents are discussed. IntroductionStorage of hydrogen with sufficient gravimetric and volumetric capacity for vehicular use remains a significant obstacle to the widespread adoption of hydrogen fuel cell electric vehicles (FCEVs). Several FCEV models are now commercially available in limited locations around the world, and in these vehicles hydrogen is stored as a gas at room temperature with a fill Table 1 along with the current performance of 700 bar systems. These values pertain to the entire storage system, which includes the mass and volume of hydrogen in addition to the tank and associated balance-ofplant (BOP) components. Notably, it is physically impossible to meet the 2025 and ultimate volumetric capacity target with pressurized gas, as the density of H 2 gas at 700 bar and room temperature is just 40 g L À1 without accounting for the BOP.The search for solid-state H 2 storage materials that can supplant compressed gas systems has been ongoing for at least two decades. The development of a viable storage material Broader contextThe widespread use of hydrogen as a clean, sustainable energy carrier has the potential to provide several significant benefits, including a reduction in oil dependency and emissions, improved energy security and grid resiliency, and substantial economic opportunities across many sectors. Hydrogen-fueled vehicles are already appearing internationally, and one of the critical enabling technologies for increasing their availability is on-board hydrogen storage. Stakeholders in developing a hydrogen in...

Polyborane salts based on B12H12 2–, B10H10 2–, CB11H12 –, and CB9H10 – demonstrate high Li and Na superionic conductivity that makes them attractive as electrolytes in all-solid-state batteries. Their chemical and structural diversity creates a versatile design space that could be used to optimize materials with higher conductivity at lower temperatures; however, many mechanistic details remain enigmatic, including reasons why certain known modifications lead to improved performance. We use extensive ab initio molecular dynamics simulations to explore the dependence of ionic conductivity on cation/anion pair combinations for Li and Na polyborane salts. Further simulations are used to probe the influence of local modifications to chemistry, stoichiometry, and composition. Carbon doping, anion alloying, and cation off-stoichiometry are found to favorably introduce intrinsic disorder, facilitating local deviation from the expected cation population. Lattice expansion likewise has a positive effect by aiding anion reorientations that are critical for conduction. Implications for engineering polyboranes for improved ionic conductivity are discussed.

We investigate the structure, topology, and dynamics of liquid water at the interface with natively hydroxylated (001) surfaces of InP and GaP photoelectrodes. Using ab initio molecular dynamics simulations, we show that contact with the semiconductor surface enhances the water hydrogen-bond strength at the interface. This leads to the formation of an ice-like structure, within which dynamically driven water dissociation and local proton hopping are amplified. Nevertheless, the structurally similar and isovalent InP and GaP surfaces generate qualitatively different interfacial water dynamics. This can be traced to slightly more covalent-like character in the binding of surface adsorbates to GaP, which results in a more rigid hydrogen-bond network that limits the explored topological phase space. As a consequence, local proton hopping can give rise to long-range surface proton transport on InP, whereas the process is kinetically limited on GaP. This allows for spatial separation of individual stages of hydrogen-evolving, multistep reactions on InP(001). Possible implications for the mechanisms of cathodic water splitting and photocorrosion on the two surfaces are considered in light of available experimental evidence.

Using density-functional theory calculations on a variety of model surfaces, we demonstrate that the low theoretical quantum capacitance of graphene-based electrodes can be significantly improved by altering local structural and morphological features. Common point defects, dopants, strain, and surface rippling are considered, as well as differences between locally single-layer and multilayer configurations. Local curvature is particularly effective at improving quantum capacitance, as is the inclusion of certain point defects and substitutional dopants at sufficiently high concentrations. We also show that single-layer graphene exhibits poor screening behavior of the double-layer potential when compared with multilayer samples, which suggests that higher area-specific capacitance can be obtained with samples a few layers thick. Overall, our results demonstrate the viability of local structural engineering as a tool to optimize graphene derivatives for use as supercapacitor electrodes, potentially increasing their theoretical charge storage capacity by severalfold.

water electrolyzers performed in acidic media, such as lower cost cell components, which has led to their commercialization at the megawatt level. [1] In addition, performing electrolysis under alkaline conditions can improve the purity of the generated hydrogen gas, [2] and, importantly, the less corrosive environment allows the use of most nonplatinum group metal catalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). [3] However, commercial AWS electrolyzers operate at relatively low current densities (<400 mA cm −2) and voltage efficiencies (<80%), [4] compared to PEM electrolyzers. Therefore, increasing the operational current density and voltage