We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquid and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt2+ and Pt4+ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.

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Where oxide and metals meet: The activation of an efficient associative mechanistic pathway for the water-gas shift reaction by an oxide-metal interface leads to an increase in the catalytic activity of nanoparticles of ceria deposited on Cu(111) or Au(111) by more than an order of magnitude (see graph). In situ experiments demonstrated that a carboxy species formed at the metal-oxide interface is the critical intermediate in the reaction

These authors contributed equally to the work. MFL, SH and MHR contributed to the design, execution, and analysis of the experiment; EJC was critical in the design, building and testing of the end station that allows atmospheric pressure XPS data collection on a solution under potentiostatic control. ‡ Corresponding authors:

The role of the interface between a metal and oxide (CeO x −Cu and ZnO−Cu) is critical to the production of methanol through the hydrogenation of CO 2 (CO 2 + 3H 2 → CH 3 OH + H 2 O). The deposition of nanoparticles of CeO x or ZnO on Cu(111), θ oxi < 0.3 monolayer, produces highly active catalysts for methanol synthesis. The catalytic activity of these systems increases in the sequence: Cu(111) < ZnO/Cu(111) < CeO x /Cu(111). The apparent activation energy for the CO 2 → CH 3 OH conversion decreases from 25 kcal/mol on Cu(111) to 16 kcal/mol on ZnO/Cu(111) and 13 kcal/mol on CeO x /Cu(111). The surface chemistry of the highly active CeO x −Cu(111) interface was investigated using ambient pressure X-ray photoemission spectroscopy (AP-XPS) and infrared reflection absorption spectroscopy (AP-IRRAS). Both techniques point to the formation of formates (HCOO −) and carboxylates (CO 2 δ−) during the reaction. Our results show an active state of the catalyst rich in Ce 3+ sites which stabilize a CO 2 δ− species that is an essential intermediate for the production of methanol. The inverse oxide/metal configuration favors strong metal−oxide interactions and makes possible reaction channels not seen in conventional metal/oxide catalysts.

High-pressure X-ray photoelectron spectroscopy, mass spectrometry, and density functional theory calculations have been combined to study methane oxidation over Pd(100). The measurements reveal a high activity when a two-layer PdO(101) oriented film is formed. Although a one-layer PdO(101) film exhibits a similar surface structure, no or very little activity is observed. The calculations show that the presence of an oxygen atom directly below the coordinatively unsaturated Pd atom in the two-layer PdO(101) film is crucial for efficient methane dissociation, demonstrating a ligand effect that may be broadly important in determining the catalytic properties of oxide thin films.

Work function is a fundamental property of a material's surface. It is playing an ever more important role in engineering new energy materials and efficient energy devices, especially in the field of photovoltaic devices, catalysis, semiconductor heterojunctions, nanotechnology, and electrochemistry. Using ambient pressure X-ray photoelectron spectroscopy (APXPS), we have measured the binding energies of core level photoelectrons of Ar gas in the vicinity of several reference materials with known work functions (Au(111), Pt(111), graphite) and PbS nanoparticles. We demonstrate an unambiguously negative correlation between the work functions of reference samples and the binding energies of Ar 2p core level photoelectrons detected from the Ar gas near the sample surface region. Using this experimentally determined linear relationship between the surface work function and Ar gas core level photoelectron binding energy, we can measure the surface work function of different materials under different gas environments. To demonstrate the potential applications of this ambient pressure XPS technique in nanotechnology and solar energy research, we investigate the work functions of PbS nanoparticles with various capping ligands: methoxide, mercaptopropionic acid, and ethanedithiol. Significant Fermi level position changes are observed for PbS nanoparticles when the nanoparticle size and capping ligands are varied. The corresponding changes in the valence band maximum illustrate that an efficient quantum dot solar cell design has to take into account the electrochemical effect of the capping ligand as well.

Au-Pd bimetallic model catalysts were synthesized as alloy clusters on SiO2 ultrathin films under ultrahigh vacuum (UHV) conditions. The surface composition and morphology were characterized with low energy ion scattering spectroscopy (LEIS), infrared reflection absorption spectroscopy (IRAS), and temperature programmed desorption (TPD). Relative to the bulk, the surface of the clusters is enriched in Au. With CO as a probe, IRAS and TPD were used to identify isolated Pd sites at the surface of the supported Au-Pd clusters. Ethylene adsorption and dehydrogenation show a clear structure-reactivity correlation with respect to the structure/composition of these Au-Pd model catalysts.