Alteration of Electronic Band Structure via a Metal-Semiconductor Interfacial Effect Enables High Faradaic Efficiency...

The interface engineering strategy has been an emerging field in terms of material improvisation that not only alters the electronic band structure of a material but also induces beneficial effects on electrochemical performances. Particularly, it is of immense importance for the environmentally benign electrochemical nitrogen reduction reaction (NRR), which is potentially impeded by the competing hydrogen evolution reaction (HER). The main problem lies in the attainment of the desired current density at a negotiable potential where the NRR would dominate over the HER, which in turn hampers the Faradaic efficiency for the NRR. To circumvent this issue, catalyst development becomes necessary, which would display a weak affinity for H-adsorption suppressing the HER at the catalyst surface. Herein, we have adopted the interfacial engineering strategy to synthesize our electrocatalyst NPG@SnS₂, which not only suppressed the HER on the active site but yielded 49.3% F.E. for the NRR. Extensive experimental work and DFT calculations regarded that due to the charge redistribution, the Mott-Schottky effect, and the band bending of SnS₂ across the contact layer at the interface of NPG, the d-band center for the surface Sn atoms in NPG@SnS₂ lowered, which resulted in favored adsorption of N₂ on the Sn active site. This phenomenon was driven even forward by the upshift of the Fermi level, and eventually, a decrease was seen in the work function of the heterostructure that increased the conductivity of the material as compared to pristine SnS₂. This strategy thus provides a field to methodically suppress the HER in the realm of improving the Faradaic efficiency for the NRR.