Regulating surface state of ZnIn2S4 by gamma-ray irradiation for enhanced photocatalytic hydrogen evolution

Surface vacancy has been demonstrated to be an active site in photocatalytic hydrogen evolution reaction (HER) over sulfide and oxide. In this work, surface S vacancy was regulated by high-energy...

Free Energy Surfaces and Barriers for Vacancy Diffusion on Al(100), Al(110), Al(111) Reconstructed Surfaces

Metadynamics is a popular enhanced sampling method based on the recurrent application of a history-dependent adaptive bias potential that is a function of a selected number of appropriately chosen collective variables. In this work, using metadynamics simulations, we performed a computational study for the diffusion of vacancies on three different Al surfaces [reconstructed Al(100), Al(110), and Al(111) surfaces]. We explored the free energy landscape of diffusion and estimated the barriers associated with this process on each surface. It is found that the surfaces are unique regarding vacancy diffusion. More specically, the reconstructed Al(110) surface presents four metastable states on the free energy surface having sizable and connected passage-ways with an energy barrier of height 0.55 eV. On the other hand, the reconstructed Al(100)/Al(111) surfaces exhibit two/three metastable states, respectively, with an energy barrier of height 0.33 eV. The findings in this study can help to understand surface vacancy diffusion in technologically relevant Al surfaces.

On the Role of Solvent in the Formation of Vacancies on Ibuprofen Crystal Facets

Surface defects play a crucial role in the process of crystal growth, as the incorporation of growth units generally takes place on under-coordinated sites on the growing crystal facet. In this work, we use molecular dynamics simulations to obtain information on the role of the solvent in the roughening of three morphologically-relevant crystal faces of form I of racemic ibuprofen. To this aim, we devise a computational strategy based on combining independent Well Tempered Metadynamics with Mean Force Integration. This approach enables us to evaluate the energetic cost associated with the formation of a surface vacancy for a set of ten solvents, covering a range of polarities and hydrogen-bonding ability. We find that both the mechanism of defect formation on these facets and the work associated with the process are indeed markedly solvent-dependent. The methodology developed in this work has been designed with the aim of capturing solvent effects at the atomistic scale while maintaining the computational efficiency necessary for implementation in high-throughput computational screenings of crystallization solvents.

A First-Principles Study on Na and O Adsorption Behaviors on Mo (110) Surface

Molybdenum-rhenium alloys are usually used as the wall materials for high-temperature heat pipes using liquid sodium as heat-transfer medium. The corrosion of Mo in liquid Na is a key challenge for heat pipes. In addition, oxygen impurity also plays an important role in affecting the alloy resistance to Na liquid. In this article, the adsorption and diffusion behaviors of Na atom on Mo (110) surface are theoretically studied using first-principles approach, and the effects of alloy Re and impurity O atoms are investigated. The result shows that the Re alloy atom can strengthen the attractive interactions between Na/O and the Mo substrate, and the existence of Na or O atom on the Mo surface can slower down the Na diffusion by increasing diffusion barrier. The surface vacancy formation energy is also calculated. For the Mo (110) surface, the Na/O co-adsorption can lead to a low vacancy formation energy of 0.47 eV, which indicates the dissolution of Mo is a potential corrosion mechanism in the liquid Na environment with O impurities. It is worth noting that Re substitution atom can protect the Mo surface by increasing the vacancy formation energy to 1.06 eV.

Optical Sensing of Molecular Oxygen (O2) via Metal Oxide Photoluminescence: A Comparative Study of TiO2, SnO2 and ZnO

A comparative study is presented on the photoluminescence (PL) response toward molecular oxygen (O2) in tin dioxide (SnO2), zinc oxide (ZnO) and titanium dioxide (TiO2) nanoparticles. The findings show that both PL enhancement and PL quenching can be observed on different materials, arguably depending on the spatial localization of the defects responsible for the PL emission in each different oxide. No significant results are evidenced for SnO2 nanoparticles. ZnO with red/orange emission shown an O2-induced PL enhancement, suggesting that the radiative emission involves holes trapped in surface vacancy oxygen centers. While the ZnO results are scientifically interesting, its performances are inferior to the ones shown by TiO2, which exhibits the most interesting response in terms of sensitivity and versatility of the response. In particular, O2 concentrations in the range of few percent and in the range of a few tenths of a part per million are both detectable through the same mixed-phase TiO2 sample, whose rutile phase gives a reversible and fast response to larger (0.4–2%) O2 concentration while its anatase phase is usable for detection in the 25–75 ppm range. The data for rutile TiO2 suggest that its surfaces host deeply trapped electrons at large densities, allowing good sensitivities and, more notably, a relatively unsaturated response at large concentrations. Future work is expected to improve the understanding and modeling of the photophysical framework that lies behind the observations.

The Surface-Vacancy Model—A General Theory of the Dissolution of Minerals and Salts

The kinetics of the dissolution of salts and minerals remains a field of active research because these reactions are important to many fields, such as geochemistry, extractive metallurgy, corrosion, biomaterials, dentistry, and dietary uptake. A novel model, referred to as the surface-vacancy model, has been proposed by the author as a general mechanism for the primary events in dissolution. This paper expands on the underlying physical model while serving as an update on current progress with the application of the model. This underlying physical model envisages that cations and anions depart separately from the surface leaving a surface vacancy of charge opposite to that of the departing ion on the surface. This results in an excess surface charge, which in turn affects the rate of departing ions. Thus, a feedback mechanism is established in which the departing of ions creates excess surface charge, and this net surface charge, in turn, affects the rate of departure. This model accounts for the orders of reaction, the equilibrium conditions, the acceleration or deceleration of rate in the initial phase and the surface charge. The surface-vacancy model can also account for the effect of impurities in the solution, while it predicts phenomena, such as ‘partial equilibrium’, that are not contemplated by other models. The underlying physical model can be independently verified, for example, by measurements of the surface charge. This underlying physical model has implications for fields beyond dissolution studies.