Construction of pH-universal hydrogen evolution freeway in MoO3-MoNi4@Cu core-shell nanowires via synergetic electronic and geometric effect

Both the adsorption/dissociation of water molecules and hydrogen intermediate (H*) are the major limitations to hydrogen evolution reaction (HER). Herein, the modulation of electronic structure and geometric configuration are combined to design one-dimensional electrocatalyst with outstanding HER activity in a wide pH range. The catalyst was composed of molybdenum trioxide doped molybdenum nickel alloy supported by copper nanowires (MoO3-MoNi4@Cu NWs). As revealed by the experimental characterizations and theoretical calculations, Cu NWs act as the electron donator to MoNi4, resulting in up shift of the d-band center in MoNi4, thus expediting H2O adsorption and dissociation. Moreover, the introduction of amorphous MoO3 sets up a unique geometric configuration on MoNi4 for the accelerated H* transfer via hydrogen-bond and hydrogen spillover. This work provides a synergetic route for constructing HER freeway and promotes further investigations on more versatile electrocatalysis involving H2O or H*.

Automated summary

In this study, a one-dimensional electrocatalyst with excellent hydrogen evolution reaction (HER) activity in a wide pH range was designed through the modulation of electronic structure and geometric configuration. The catalyst, composed of molybdenum trioxide doped molybdenum nickel alloy supported by copper nanowires (MoO3-MoNi4@Cu NWs), showed enhanced H2O adsorption and dissociation due to the up shift of the d-band center in MoNi4 facilitated by electron transfer from Cu NWs. Additionally, the introduction of amorphous MoO3 created a unique geometric configuration on MoNi4 for accelerated H* transfer via hydrogen-bond and hydrogen spillover. This work provides a synergistic approach for constructing HER pathways and promotes further investigations in versatile electrocatalysis involving H2O or H*.