Non-Stoichiometry Induced Exsolution of Metal Oxide Nanoparticles via Formation of Wavy Surfaces and their Enhanced Electrocatalytic Activity: Case of Misfit Calcium Cobalt Oxide.

Most heterogeneous catalytic reactions demand high density and yet spatially separated nanoparticles that are strongly anchored on the oxide surfaces. Such nanoparticles can be deposited or synthesized in situ via nonstoichiometric methods. To date, nanoparticles have been exsolved from perovskite oxide surfaces using nonstoichiometric processes. However, the density of the space-separated nanoparticles on the oxide surfaces is still low. And less attention is paid toward the changes that happen to the host during the nanoparticle exsolution process. In this work, we demonstrated in situ exsolution of ultrafine nanoparticles (∼5 nm) of either Co3O4 or Ca(OH)2 via judicious control of nonstoichiometry in a misfit Ca3Co4O9 (CCO). The nanoparticle density over the CCO surface reached as high as 8500/μm2, which is significantly higher than previously reported values. High-resolution electron microscopy studies reveal the formation mechanism of Co3O4 nanoparticles over CCO, and the formation takes palace via the formation of wavy surfaces on the CCO. Defects caused by the nonstoichiometric synthesis created microstrain within the host CCO, resulting in making the new density of states near the Fermi energy. Further, the exsolution process turned the inert host (CCO) into electrocatalytically active toward water splitting. The nonstoichiometric samples obtained by shorter annealing times showed high electrocatalytic behavior for the hydrogen evolution (HER) and oxygen evolution (OER) reactions. The catalytic activity is further enhanced (reaching overpotential of 320 mV and 410 mV for HER and OER respectively, for a current density of 10 mA/cm2) by removing the surface nanoparticles. The observation indicates that the active sites that are produced during the nonstoichiometric synthesis also present in the bulk of the CCO (host). We believe that similar nonstoichiometric synthesis can be applied to a wide variety of tricomponent systems, and they could endow the hosts with novel properties for applications such as catalysis and thermoelectrics.