Interfacial Electron Regulation of Rh Atomic Layer-Decorated SnO₂ Heterostructures for Enhancing Electrocatalytic...

Ammonia (NH₃), which serves as a fertilizer supply, is struggling to satisfy the ever-growing population requirements over the world. The electrocatalytic nitrogen reduction to NH₃ production is highly desired but shows the extremely poor activity and selectivity of reported electrocatalysts. In this work, we rationally design a novel Rh atomic layer-decorated SnO₂ heterostructure catalyst through the interfacial engineering strategy, simultaneously achieving the highest NH₃ yield rate (149 μg h^-1 mg_cat^-1) and Faradaic efficiency (11.69%) at -0.35 V vs the reversible hydrogen electrode. This result is superior to the optimum response of previously reported SnO₂- or Rh-based catalysts for electrochemical nitrogen reduction. Both X-ray absorption spectra characterization and density functional theory calculations reveal the strong electron interaction between the Rh atomic layer and the SnO₂ heterostructure, which effectively regulated the interfacial electron transfer and d-band center. The downshift of the d-band center results in the greatly reduced H adsorption energy and the highly accelerated reaction kinetics for nitrogen reduction. This work endows a new insight into the interfacial electron regulation for weakening H adsorption and further enhancing the electrocatalytic N₂ reduction.