The decomposition of oxygenates in the presence of water finds various applications in chemical processes, such as biomass conversion. The presence of co-adsorbates and solvents affects both the reaction rate and selectivity. In this study, we used NAP-XPS and DFT to investigate the decomposition of acetic acid on Pd(111) as a model system for the decomposition of small oxygenates in the absence and presence of water. The decomposition of acetic acid occurs through two main reaction pathways, decarboxylation, and decarbonylation, forming CO₂ or CO, respectively. Our DFT calculations indicate that the two pathways have similar barriers without water. However, in the presence of water, the decarboxylation path becomes. Similarly, our AP-XPS experiments show an increase in the CO₂/CO ratio as well as a decrease in the CO/acetate-acetic acid and acetic acid/acetate ratios when water is present. The shift in selectivity is not due to a single reaction step, but rather the decreasing barrier in general for OH scissoring and the increasing barrier for C-O scissoring. This shift favors the formation of CO₂, as demonstrated by our microkinetic model.

Chemical processes occurring at solid-gas, solid-liquid, and solid-solid interfaces critically determine the performance and durability of hydrogen production and storage technologies. While directly probing behavior of these interfaces under actual operating conditions remains challenging, modern surface science approaches such as ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) can provide insight into the evolution of surface chemistry in approximate environments. However, interpretation of these spectra can be complicated: standards for complex surface chemical moieties are often unavailable, and bulk standards can be unreliable. First-principles computations are emerging as an important companion approach, offering the ability to directly compute spectroscopic fingerprints. This has the advantage of aiding interpretation of the experiments, while simultaneously using the experiment-theory comparison to inform construction of more accurate interface models. In this talk, I will show how computation has been combined with laboratory-based AP-XPS measurements to understand the evolving chemistry of complex native surface oxides. Two examples will be drawn from activities within the U.S. Department of Energy HydroGEN and HyMARC consortia, which focus on renewable hydrogen production and materials-based hydrogen storage, respectively. First, I will discuss the application to surface oxidation of III-V semiconductors for photoelectrochemical hydrogen production, which demonstrates transitions between kinetically and thermodynamically controlled oxidation regimes with implications for device performance. Second, I will also show how the same approach has been applied to understand the rate-determining role of surface oxides in the dehydrogenation performance of NaAlH₄ for solid-state hydrogen storage.

This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

The availability of laboratory-based NAP XPS creates novel interface research opportunities for scientific disciplines and technology areas that deal with materials incompatible with traditional ultra-high vacuum XPS. This is, for example, the case for many organic and/or pharmaceutical materials and formulations, whose characterization by XPS has hitherto been restricted by their vapour pressures. NAP XPS permits for the first time systematic and detailed analysis of the light element photoemission lines (expecially C/N/O 1s) in these materials. In conjunction with elemental analysis by survey XP spectra they provide quantitative information on composition and speciation both in the bulk and at the surfaces of pure organic solids, in their formulations with other components and in solutions. Especially of interest are studies of the solid/liquid interface with water, which is of high relevance for understanding and controlling drug release profiles from tablets. To illustrate these points I will present various examples of research on pharmaceutical materials. Moreover, near-ambient pressure core level spectroscopy turns out to be an extremely powerful probe for the structure and dynamics of hydrogen bonding and proton transfer in materials, both in the solid state and in solutions. NAP XPS measurements provide unique insight into proton dynamics in noncrystalline solids and liquids, where traditional characterisation by crystallography and nuclear magnetic resonance fails or provides ambiguous information on proton locations.