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Abstract: The electrochemical synthesis of hydrogen peroxide (H2O2) via a two-electron (2e-) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. However, the development of efficient electrocatalysts is still facing lots of challenges like insufficient understanding of active sites. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst (PCC) for H2O2 electrochemical production. The optimized PCC900 exhibits unprecedented activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.

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Abstract: The surface chemistry of alcohol synthesis from CO2 hydrogenation has been investigated using kinetic testing, ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and DFT calculations over a multicomponent system, where Pt and ceria nanoparticles coexisted on a titania template, Pt/CeOx/TiO2(110). Due to its high ability to bind and activate CO2, not seen for typical Cu–ZnO catalysts, the Pt–CeOx–TiO2 interface is excellent for the hydrogenation of CO2 to methanol, with some ethanol also being produced (21% selectivity). The results of AP-XPS and DFT calculations indicate that the active state involves a mixture of Ti4+/Ti3+, Ce3+, and Pt0/Pt+. A fast pathway for the formation of CH3O species is only plausible when Ce3+ and Pt are present. The addition of water to the reaction feed facilitates the first hydrogenation of CO2 and substantially enhances the surface coverage of C-containing species (CH3O, HCOO, CO3, CHx), facilitating the formation of C–C bonds and the production of ethanol (38% selectivity).

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Abstract: Photoelectron spectroscopy is a powerful characterisation tool for semiconductor surfaces and interfaces, providing in principle a correlation between the electronic band structure and surface chemistry along with quantitative parameters such as the electron affinity, interface potential, band bending and band offsets. However, measurements are often limited to ultrahigh vacuum and only the top few atomic layers are probed. The technique is seldom applied as an in situ probe of surface processing; information is usually provided before and after processing in a separate environment, leading to a reduction in reproducibility. Advances in instrumentation, in particular electron detection has enabled these limitations to be addressed, for example allowing measurement at near-ambient pressures and the in situ, real-time monitoring of surface processing and interface formation. A further limitation is the influence of the measurement method through irreversible chemical effects such as radiation damage during X-ray exposure and reversible physical effects such as the charging of low conductivity materials. For wide-gap semiconductors such as oxides and carbon-based materials, these effects can be compounded and severe. Here we show how real-time and near-ambient pressure photoelectron spectroscopy can be applied to identify and quantify these effects, using a gold alloy, gallium oxide and semiconducting diamond as examples. A small binding energy change due to thermal expansion is followed in real-time for the alloy while the two semiconductors show larger temperature-induced changes in binding energy that, although superficially similar, are identified as having different and multiple origins, related to surface oxygen bonding, surface band-bending and a room-temperature surface photovoltage. The latter affects the p-type diamond at temperatures up to 400 °C when exposed to X-ray, UV and synchrotron radiation and under UHV and 1 mbar of O2. Real-time monitoring and near-ambient pressure measurement with different excitation sources has been used to identify the mechanisms behind the observed changes in spectral parameters that are different for each of the three materials. Corrected binding energy values aid the completion of the energy band diagrams for these wide-gap semiconductors and provide protocols for surface processing to engineer key surface and interface parameters.

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Abstract: As a key component in many industrial heterogeneous catalysts, the surface structure and reactivity of ceria, CeO2, has attracted a lot of attention. In this topical review we discuss some of the approaches taken to form a deeper understanding of the surface physics and chemistry of this important and interesting material. In particular, we focus on the preparation of ultrathin ceria films, nanostructures and supported metal nanoparticles. Cutting-edge microscopic and spectroscopic experimental techniques are highlighted which can probe the behaviour of oxygen species and atomic defects on these model surfaces.

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Abstract: Using a combination of two surface-sensitive spectroscopy techniques, the chemical state of the Ag(111) surface and the nature of the adsorbed species in the presence of ethylene and oxygen gases are identified. In the 10 mbar pressure range and 25–200 °C studied here, Ag(111) remains largely metallic even in O2-rich conditions. The only adsorbed molecular species with a low but discernible coverage is surface carbonate, which forms due to further oxidation of produced CO2, in a similar manner to its formation in ambient air on Ag surfaces. Its formation is also pressure-dependent, for instance, it is not observed when the total pressure is in the 1 mbar pressure range. Production of carbonate, along with carbon dioxide and water vapor as the main gas-phase products, suggests that an unpromoted Ag(111) surface catalyzes mainly the undesired full oxidation reaction.