We develop a model based on density functional theory calculations to describe trends in catalytic activity for CO2 electroreduction to CO in terms of the adsorption energy of the reaction ...intermediates, CO and COOH. The model is applied to metal surfaces as well as the active site in the CODH enzymes and shows that the strong scaling between adsorbed CO and adsorbed COOH on metal surfaces is responsible for the persistent overpotential. The active site of the CODH enzyme is not subject to these scaling relations and optimizes the relative binding energies of these adsorbates, allowing for an essentially reversible process with a low overpotential.
Li2B12H12, Na2B12H12, 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 Li2B12H12 and Na2B12H12 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.
Methanol, an important chemical, fuel additive, and precursor for clean fuels, is produced by hydrogenation of carbon oxides over Cu‐based catalysts. Despite the technological maturity of this ...process, the understanding of this apparently simple reaction is still incomplete with regard to the reaction mechanism and the active sites. Regarding the latter, recent progress has shown that stepped and ZnOx‐decorated Cu surfaces are crucial for the performance of industrial catalysts. Herein, we integrate this insight with additional experiments into a full microkinetic description of methanol synthesis. In particular, we show how the presence or absence of the Zn promoter dramatically changes not only the activity, but unexpectedly the reaction mechanism itself. The Janus‐faced character of Cu with two different sites for methanol synthesis, Zn‐promoted and unpromoted, resolves the long‐standing controversy regarding the Cu/Zn synergy and adds methanol synthesis to the few major industrial catalytic processes that are described on an atomic level.
Revealing the mechanism: CO and CO2, on copper, can be hydrogenated to methanol, but not at the same time. The former reaction is poisoned by CO2 and requires a carbophilic Cu step, whereas the latter reaction requires a Zn promoter and proceeds as an oxophilic Cu/Zn step.
We reported the growth of (AlGa)2O3 layers on (1010̅) α-Al2O3 substrates using cold-wall metalorganic chemical vapor deposition, and the electrical characterization of Si-doped (AlGa)2O3 layers. In ...the Ga2O3 growth, the α phase was dominant at low growth temperature, achieving the growth rate of 2.4 μm h−1 at 650 °C. Sheet resistance and electrical conductivity of the Ga2O3 layers with a Si concentration of 3 × 1020 cm−3 were 1 × 104 Ω/square and 8.3 S cm−1, respectively, at the measurement temperature of 500 °C. The Al composition in the (AlGa)2O3 layers was controlled from 0% to 74%. In our initial attempts, we obtained electrically conductive α-(AlGa)2O3 layers by Si doping (2 × 10−9 S cm−1 in the sample with an Al composition of 56%). Hybrid functional calculations suggest the conductivities are limited by compensation of Si through cation vacancy complexes, and not by the significant amounts of co-incorporated C and N that are predicted to be electrically passivated by hydrogen.
Point defects largely determine the observed optical and electrical properties of a given material, yet the characterization and identification of defects has remained a slow and tedious process, ...both experimentally and theoretically. We demonstrate a computationally-cheap model that can reliably predict the formation energies of cation vacancies as well as the location of their electronic states in a large set of II–VI and III–V materials using only parameters obtained from the bulk primitive unit cell (2–4 atoms). We apply our model to ordered alloys within the CdZnSeTe, CdZnS, and ZnMgO systems and predict the positions of cation vacancy charge-state transition levels with a mean absolute error of < 0.2 eV compared to the explicitly calculated values, showing useful accuracy without the need for the expensive and large-scale calculations typically required. This suggests the properties of other point defects may also be predicted with useful accuracy from only bulk-derived properties.
High-performance p-type transparent conducting materials (TCMs) are needed in a wide range of applications ranging from solar cells to transparent electronics. p-type TCMs require a large band gap ...(for transparency), low hole effective mass (for high mobility), and hole dopability. It has been demonstrated that oxides have inherent limitations in terms of hole effective masses making them difficult to use as a high-performance p-type TCM. In this work, we use a high-throughput computational approach to identify novel, non-oxide, p-type TCMs. By data mining a large computational data set (more than 30,000 compounds), we demonstrate that non-oxide materials can lead to much lower hole effective masses but to the detriment of smaller gaps and lower transparencies. We propose a strategy to overcome this fundamental correlation between low effective mass and small band gap by exploiting the weak absorption for indirect optical transitions. We apply this strategy to phosphides and identify zinc blende boron phosphide (BP) as a very promising candidate. Follow-up computational studies on defects formation indicate that BP can also be doped p-type and potentially n-type as well. Our work demonstrates how high-throughput computational design can lead to identification of materials with exceptional properties, and we propose a strategy to open the design of TCMs to non-oxide materials.
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