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This paper establishes the chemical nature of Pd nanoparticles protected by alkanethiolates that were prepared through a ligand place-exchange approach and the two-phase method, firstly developed for Au nanoparticles by Brust and Schiffrin. After ten years since the first study on this kind of Pd nanoparticles was published, the surface composition of the particles is a matter of debate in the literature and it has not been unambiguously assessed. The nanoparticles were studied by means of several techniques: UV-visible spectroscopy, scanning transmission electron microscopy (STEM), Fourier-transform infrared spectroscopy (FTIR), extended X-ray absorption fine structure (EXAFS) and X-ray photoelectron spectroscopy (XPS). The experimental data, obtained for the 3 nm diameter Pd particles, prepared by both synthetic routes, are consistent with nanoparticles composed by Pd(0) cores surrounded by a submonolayer of sulfide species, which are protected by alkanethiolates. Also, we unambiguously demonstrate that the chemical nature of these particles is very similar to that experimentally found for alkanethiolate-modified bulk Pd. The results from this paper are important not only for handling thiolate-protected Pd nanoparticles in catalysis and sensing, but also for the basic comprehension of metallic nanoparticles and the relation of their surface structure whit the synthesis method.

The photoreactivity of single particles with atmospheric interest was studied by using an acoustic levitation system coupled to Raman microspectrometry. Both, inorganic and organic single particle phototransformation has been investigated without any surface contact. The Raman microspectrometry has suitably provided the identification, the chemical heterogeneity as well as the formation rates of products. Complex surface limited processes are demonstrated for photolysis of both nitrate‐rich and sulfur‐rich droplets. Copyright © 2017 John Wiley & Sons, Ltd.