The durability and long-term applicability of catalysts are critical parameters for the commercialization and adoption of fuel cells. Even though a few studies have been conducted on hollow carbon spheres (HCSs) as supports for Pt in oxygen reduction reactions (ORR) catalysis, in-depth durability studies have not been conducted thus far. In this study, Pt/HCSs and Pt/nitrogen-doped HCSs (Pt/NHCSs) were prepared using a reflux deposition technique. Small Pt particles were formed with deposition on the outside of the shell and inside the pores of the shell. The new catalysts demonstrated high activity (>380 μA cm−2 and 240 mA g−1) surpassing the commercial Pt/C by more than 10%. The catalysts demonstrated excellent durability compared to a commercial Pt/C in load cycling, experiencing less than 50% changes in the mass-specific activity (MA) and surface area-specific activity (SA). In stop-start durability cycling, the new materials demonstrated high stability with more than 50% retention of electrochemical active surface areas (ECSAs). The results can be rationalised by the high BET surface areas coupled with an array of meso and micropores that led to Pt confinement. Further, pair distribution function (PDF) analysis of the catalysts confirmed that the nitrogen and oxygen functional groups, as well as the shell curvature/roughness provided defects and nucleation sites for the deposition of the small Pt nanoparticles. The balance between graphitic and diamond-like carbon was critical for the electronic conductivity and to provide strong Pt-support anchoring.

The atomic arrangement of the terminating facets on spinel Co 3 O 4 nanocrystals is strongly linked to their catalytic performance. However, the spinel crystal structure offers multiple possible surface terminations depending on the synthesis. Thus, understanding the terminating surface atomic structure is essential in developing high-performance Co 3 O 4 nanocrystals. In this work, we present direct atomic-scale observation of the surface terminations of Co 3 O 4 nanoparticles supported on hollow carbon spheres (HCSs) using exit wavefunction reconstruction from aberration-corrected transmission electron microscopy focal-series. The restored high-resolution phases show distinct resolved oxygen and cobalt atomic columns. The data show that the structure of {100}, {110}, and {111} facets of spinel Co 3 O 4 exhibit characteristic active sites for carbon monoxide (CO) adsorption, in agreement with density functional theory calculations. Of these facets, the {100} and {110} surface terminations are better suited for CO adsorption than the {111}. However, the presence of oxygen on the {111} surface termination indicates this facet also plays an essential role in CO adsorption. Our results demonstrate direct evidence of the surface termination atomic structure beyond the assumed stoichiometry of the surface.

The hydrogenation of cinnamaldehyde is usually performed in the liquid phase in batch mode. In this study, a vapour phase flow system has been used to evaluate the use of cobalt catalysts supported inside and outside hollow carbon spheres (HCSs). The influence of temperature, hydrogen flow rate and catalyst mass on the hydrogenation reaction was investigated. The catalysts generally showed modest conversion to the required products, hydrocinnamaldehyde, 3-phenyl propanol, cinnamyl alcohol together with formation of various decomposition products. The data revealed that the Co@HCS showed better conversion and product selectivity compared to the Co/HCS. The catalysts with smaller particle sizes (ca. 6 nm) were more efficient than big particles (30 – 40 nm). An increase in reaction temperature (200 – 300°C) resulted in a lower cinnamaldehyde conversion and a poor product selectivity. TPR studies revealed that the Co@HCSs had a stronger metal-support interaction than the Co/HCSs catalysts. Catalyst recycling studies revealed that only the Co/HCSs could be regenerated (4 cycles) and post reaction analysis of the catalysts revealed that this was due to HCS pore blockage and not Co sintering.