Interface charge density modulation of a lamellar-like spatially separated Ni9S8 nanosheet/Nb2O5 nanobelt heterostructure catalyst coupled with nitrogen and metal (M = Co, Fe, or Cu) atoms to accelerate acidic and alkaline hydrogen evolution reactions

The creation of heterostructures based on non-precious metals with platinum-like hydrogen evolution reaction (HER) performance remains a challenge for hydrogen fuel technologies. Motivated by the fascinating properties of heterostructures, we establish here an effective approach to fabricate the heterostructured M-N-Ni9S8/Nb2O5 (M = Co, Fe, or Cu) catalysts using spatially separated Ni9S8 nanosheet/Nb2O5 nanobelts that are coupled with nitrogen (N) and metal atoms. Due to its improved intrinsic activity, interface-rich structure, abundant active sites, and large surface area the Co-N-Ni9S8/Nb2O5 heterostructure achieved a low acidic HER overpotential of-171 mV at-10 mA cm(-2), thereby performing better than existing heterostructures. Moreover, for the alkaline HER, the Cu-N-Ni9S8/Nb2O5 heterostructure required a low overpotential of-109 mV at-10 mA cm(-2), which is close to the performance of Pt/C catalyst. Density functional theory (DFT) predictions indicate that the local charge distribution and electronic properties at the heterointerface of Ni9S8/Nb2O5 can be significantly modulated by co-doping of metals with N atoms, resulting in optimal adsorption energy and reduced water dissociation barrier; thereby accelerating the acidic and alkaline HER activity. This work, therefore, provides a new design principle to create advanced heterostructured catalysts.

Automated summary

The construction of heterostructures based on non-precious metals with platinum-like performance in the hydrogen evolution reaction (HER) is a challenge in hydrogen fuel technology. In this study, heterostructured M-N-Ni9S8/Nb2O5 (M = Co, Fe, or Cu) catalysts were successfully fabricated using spatially separated Ni9S8 nanosheets/Nb2O5 nanobelts coupled with nitrogen (N) and metal atoms. The Co-N-Ni9S8/Nb2O5 heterostructure achieved a low acidic overpotential of-171 mV at-10 mA cm(-2) and outperformed existing heterostructures due to its improved intrinsic activity, interface-rich structure, abundant active sites, and large surface area. The Cu-N-Ni9S8/Nb2O5 heterostructure required a low alkaline overpotential of-109 mV at-10 mA cm(-2), approaching the performance of Pt/C catalyst. Density functional theory (DFT) predictions showed that the local charge distribution and electronic properties at the heterointerface of Ni9S8/Nb2O5 can be modulated by co-doping of metals with N atoms, leading to optimal adsorption energy and reduced water dissociation barrier, thereby enhancing the acidic and alkaline HER activity. This work provides a new design principle for advanced heterostructured catalysts.