On the nature of Con±/0 clusters reacting with water and oxygen

Bulk cobalt does not react with water at room temperature, but cobalt nanometals could yield corrosion at ambient conditions. Insights into the cobalt cluster reactions with water and oxygen enable us to better understand the interface reactivity of such nanometals. Here we report a comprehensive study on the gas-phase reactions of Con±/0 clusters with water and oxygen. All these Con±/0 clusters were found to react with oxygen, but only anionic cobalt clusters give rise to water dissociation whereas the cationic and neutral ones are limited to water adsorption. We elucidate the influences of charge states, bonding modes and dehydrogenation mechanism of water on typical cobalt clusters. It is unveiled that the additional electron of anionic Con– clusters is not beneficial to H2O adsorption, but allows for thermodynamics- and kinetics-favourable H atom transfer and dehydrogenation reactions. Apart from the charge effect, size effect and spin effect play a subtle role in the reaction process. The synergy of multiple metal sites in Con– clusters reduces the energy barrier of the rate-limiting step enabling hydrogen release. This finding of water dissociation on cobalt clusters put forward new connotations on the activity series of metals, providing new insights into the corrosion mechanism of cobalt nanometals. Cobalt-based materials have a wide range of applications from information storage to electromagnetic absorbers in aerospace manufacturing, but the corrosion of cobalt nanosurfaces is poorly explored. Here, the authors combine mass spectrometry and DFT to study gas-phase reactions of Con±/0 (n = 1–30) with water and oxygen and find that only anionic cobalt clusters give rise to water dissociation, whereas the cationic and neutral ones are limited to water adsorption.