We employed machine learning-augmented density functional theory (DFT) thermodynamic calculations to assess the stability of different AgO x structures under catalytic ethylene epoxidation reaction conditions. We found that there are multiple AgO x surface motifs that could co-exist under the relevant conditions. These included Ag surface oxides (e.g., AgO_p(4 × 4) and Ag 1.83 O) and atomic oxygen-covered Ag(111) surfaces. Furthermore, we employed DFT calculations to evaluate the energetics of different reaction mechanisms by which ethylene and oxygen can react on these surfaces. These studies revealed several energetically viable reaction pathways for ethylene epoxidation. Microkinetic modeling analyses, based on the DFT-calculated reaction pathways, showed that ethylene epoxidation can proceed on all surfaces and that multiple pathways, including those involving Langmuir−Hinshelwood and Eley−Rideal mechanisms, could be involved in selective and unselective reactions. The diversity of mechanisms that we discovered in the context of the relatively simple ethylene epoxidation reaction on Ag suggests that the richness and complexity of surface chemistry are most likely a rule rather than an exception in heterogeneous catalytic chemical transformations on metal surfaces and that the concept of a single or even a dominant mechanism and reaction intermediates might need to be revisited for many reactions.
In recent decades, plenty of nanomaterials have been investigated as electrocatalysts for the replacement of the expensive platinum (Pt) counter electrode in dyesensitized solar cells (DSSCs). The key function of the electrocatalyst is to reduce tri-iodide ions to iodide ions at the electrolyte/counter electrode interface. The performance of the electrocatalyst is usually determined by two key factors, i.e., the intrinsic heterogeneous rate constant and the effective electrocatalytic surface area of the electrocatalyst. The intrinsic heterogeneous rate constant of the electrocatalyst varies by different types of materials, which can be roughly divided into five groups: non-Pt metals, carbons, conducting polymers, transition metal compounds, and their composites. The effective electrocatalytic surface area is determined by the nanostructure of the electrocatalyst. In this chapter, the nanostructural design and engineering on different types of Pt-free electrocatalysts will be systematically introduced. Also, the relationship between various nanostructures of electrocatalysts and the pertinent physical/electrochemical properties will be discussed.
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