Electrochemical Stability of Metastable Materials

We present a first-principles-based formalism to provide a quantitative measure of the thermodynamic instability and propensity for electrochemical stabilization, passivation, or corrosion of metastable materials in aqueous media. We demonstrate that this formalism can assess the relative Gibbs free energy of candidate materials in aqueous media as well as their decomposition products, combining solid and aqueous phases, as a function of pH and potential. On the basis of benchmarking against 20 stable as well as metastable materials reported in the literature and also our experimental characterization of metastable triclinic-FeVO₄, we present quantitative estimates for the relative Gibbs free energy and corresponding aqueous regimes where these materials are most likely to be stable, form inert passivating films, or steadily corrode to aqueous species. Furthermore, we show that the structure and composition of the passivating films formed on triclinic-FeVO₄ are also in excellent agreement with the Point Defect Model, as proposed by the corrosion community. An open-source web application based on the formalism is made available at https://materialsproject.org

Atom Probe Tomography Analysis of Ag Doping in 2D Layered Material (PbSe)₅(Bi₂Se₃)₃

Impurity doping in two-dimensional (2D) materials can provide a route to tuning electronic properties, so it is important to be able to determine the distribution of dopant atoms within and between layers. Here we report the tomographic mapping of dopants in layered 2D materials with atomic sensitivity and subnanometer spatial resolution using atom probe tomography (APT). APT analysis shows that Ag dopes both Bi₂Se₃ and PbSe layers in (PbSe)₅(Bi₂Se₃)₃, and correlations in the position of Ag atoms suggest a pairing across neighboring Bi₂Se₃ and PbSe layers. Density functional theory (DFT) calculations confirm the favorability of substitutional doping for both Pb and Bi and provide insights into the observed spatial correlations in dopant locations

Discovery of Manganese-Based Solar Fuel Photoanodes via Integration of Electronic Structure Calculations, Pourbaix Stability Modeling, and High-Throughput Experiments

The solar photoelectrochemical generation of hydrogen and carbon-containing fuels comprises a critical energy technology for establishing sustainable energy resources. The photoanode, which is responsible for solar-driven oxygen evolution, has persistently limited technology advancement due to the lack of materials that exhibit both the requisite electronic properties and operational stability. Efforts to extend the lifetime of solar fuel devices increasingly focus on mitigating corrosion in the highly oxidizing oxygen evolution environment, motivating our development of a photoanode discovery pipeline that combines electronic structure calculations, Pourbaix stability screening, and high-throughput experiments. By applying the pipeline to ternary metal oxides containing manganese, we identify a promising class of corrosion-resistant materials and discover five oxygen evolution photoanodes, including the first demonstration of photoelectrocatalysis with Mn-based ternary oxides and the introduction of alkaline earth manganates as promising photoanodes for establishing a durable solar fuels technology

van der Waals Epitaxial Growth of Graphene on Sapphire by Chemical Vapor Deposition without a Metal Catalyst

van der Waals epitaxial growth of graphene on <i>c</i>-plane (0001) sapphire by CVD without a metal catalyst is presented. The effects of CH₄ partial pressure, growth temperature, and H₂/CH₄ ratio were investigated and growth conditions optimized. The formation of monolayer graphene was shown by Raman spectroscopy, optical transmission, grazing incidence X-ray diffraction (GIXRD), and low voltage transmission electron microscopy (LVTEM). Electrical analysis revealed that a room temperature Hall mobility above 2000 cm²/V·s was achieved, and the mobility and carrier type were correlated to growth conditions. Both GIXRD and LVTEM studies confirm a dominant crystal orientation (principally graphene [10–10] || sapphire [11–20]) for about 80–90% of the material concomitant with epitaxial growth. The initial phase of the nucleation and the lateral growth from the nucleation seeds were observed using atomic force microscopy. The initial nuclei density was ∼24 μm^–2, and a lateral growth rate of ∼82 nm/min was determined. Density functional theory calculations reveal that the binding between graphene and sapphire is dominated by weak dispersion interactions and indicate that the epitaxial relation as observed by GIXRD is due to preferential binding of small molecules on sapphire during early stages of graphene formation