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In situ soft X-ray absorption spectroscopy (XAS) was employed to study the adsorption and dissociation of carbon monoxide molecules on cobalt nanoparticles with sizes ranging from 4 to 15 nm. The majority of CO molecules adsorb molecularly on the surface of the nanoparticles, but some undergo dissociative adsorption, leading to oxide species on the surface of the nanoparticles. We found that the tendency of CO to undergo dissociation depends critically on the size of the Co nanoparticles. Indeed, CO molecules dissociate much more efficiently on the larger nanoparticles (15 nm) than on the smaller particles (4 nm). We further observed a strong increase in the dissociation rate of adsorbed CO upon exposure to hydrogen, clearly demonstrating that the CO dissociation on cobalt nanoparticles is assisted by hydrogen. Our results suggest that the ability of cobalt nanoparticles to dissociate hydrogen is the main parameter determining the reactivity of cobalt nanoparticles in Fischer-Tropsch synthesis.

Catalysts used for heterogeneous processes are usually composed of metal nanoparticles dispersed over a high-surface-area support. In recent years, near-ambient pressure techniques have allowed catalyst characterization under operating conditions, overcoming the pressure gap effect. However, the use of model systems may not truly represent the changes that occur in real catalysts (the so-called material gap effect). Supports can play an important role in the catalytic process by providing new active sites and may strongly affect both the physical and chemical properties of metal nanoparticles. We used near-ambient pressure x-ray photoelectron spectroscopy to show that the surface rearrangement of bimetallic (rhodium-palladium) nanoparticles under working conditions for ethanol steam reforming with real catalysts is strongly influenced by the presence of a reducible ceria support.

Sunlight plays a critical role in the development of emerging sustainable energy conversion and storage technologies. Light-induced CO2 reduction by artificial photosynthesis is one of the cornerstones to produce renewable fuels and environmentally friendly chemicals. Interface interactions between plasmonic metal nanoparticles and semiconductors exhibit improved photoactivities under a wide range of the solar spectrum. However, the photo-induced charge transfer processes and their influence on photocatalysis with these materials are still under debate, mainly due to the complexity of the involved routes occurring at different timescales. Here, we use a combination of advanced in situ and time-resolved spectroscopies covering different timescales, combined with theoretical calculations, to unravel the overall mechanism of photocatalytic CO2 reduction by Ag/TiO2 catalysts. Our findings provide evidence of the key factors determining the enhancement of photoactivity under ultraviolet and visible irradiation, which have important implications for the design of solar energy conversion materials.