We report novel PtW solid-solution nanoparticles (NPs) produced through electrochemical cleaning of core/shell PtW@WO 3 NPs. The resulting PtW NPs achieved a record hydrogen evolution reaction (HER) performance as a class of Pt-based solid-solution alloys. A current density of 10 mA cm −2 was reached with an overpotential of 19.4 mV, which is significantly lower than that of a commercial Pt catalyst (26.3 mV). The PtW NPs also exhibited long-term stability. Theoretical calculations revealed that negatively charged Pt atoms adjacent to a W atom provide favorable hydrogen adsorption energies for the HER, realizing significantly enhanced HER activity.

As an initial step towards understanding the mechanism behind photocatalysis in graphitic carbon nitride (g-C3N4), we present a first-principles density functional theory (DFT) study of H2O molecular adsorption on the tri-s-triazine-based structure. The optimization of the system determined that the most stable configuration would be on top of the two-coordinated nitrogen atom in an orientation where one O–H bond is parallel to the surface and the other one is pointing to the surface. The adsorption energy at the most stable configuration was found to be 0.82 eV with a barrier energy of ∼0.02 eV. Partial density of states (PDOS) and charge density distribution analysis show that, primarily, the bonding occurs between the hydrogen atom of the water molecule and the two-coordinated nitrogen atom of g-C3N4. Results of this study would be useful not only to better understand the mechanism behind H2O molecule adsorption but also to give insight into the role of the catalyst in the photocatalytic process.

First-principles calculations based on density functional theory were performed to investigate the co-doping effects of Sm and Gd in ceria on its oxygen ion conduction. The focus of this study is on the interactions between the cation dopants and an oxygen vacancy within the two adjacent tetrahedral sites of fluorite structure surrounding the oxygen migration path. Vacancy formation energies, dopant-vacancy association energies, and migration energies were calculated to elucidate the doping effects on oxygen ion conduction. The migration energies show remarkable dependences on the ionic radii of the cations located at the edges of the migration path. A simple relation between migration energy and vacancy formation energy is proposed. This work provides an informative insight into vacancy diffusion that could be useful in optimizing doping materials for improving oxygen ion conductivity in doped ceria.

The decomposition of methane (CH4) is a catalytically important reaction in the production of syngas that is used to make a wide spectrum of hydrocarbons and alcohols, and a principal carbon deposition pathway in methane reforming. Literatures suggest that stepped Ni surface is uniquely selective toward methane decomposition to atomic C, contrary to other catalysts that favor the CH fragment. In this paper, we used dispersion-corrected density functional theory-based first principles calculations to identify the electronic factors that govern this interesting property of stepped Ni surface. We found that the adsorption of atomic C on this surface is uniquely characterized by a 5–coordinated bonding of C with Ni atoms from both the surface and subsurface layers. Comparison with Ru surface indicates the importance of the subsurface atoms of stepped Ni surface on its selectivity toward methane decomposition to atomic C. Interestingly, we found that substituting these subsurface atoms with other elements can dramatically change the reaction mechanism of methane decomposition, suggesting a new approach to catalyst design for hydrocarbon reforming applications.

The absorption of lithium in montmorillonite [LiSi8(Al3Mg)O20(OH)4] was investigated using Density Functional Theory (DFT). The final position of lithium after absorption was found to be in good agreement with an experimental observation where lithium atom migrated from the interlayer into the vacant octahedral site of montmorillonite. The lithium absorbed on montmorillonite was held together by a very strong attraction between ions and exhibited an insulating behavior as depicted from the density of states curve. Due to the presence of lithium in the octahedral site of montmorillonite, the OH group reoriented itself perpendicular to the ab plane and an electron of lithium was transferred in order to compensate the existing net charge of montmorillonite caused by isomorphous substitutions. Relative small charge transfer was observed between lithium and montmorillonite.