Interfacial Electron Regulation of Rh Atomic Layer-Decorated SnO 2 Heterostructures for Enhancing Electrocatalytic Nitrogen Reduction.

Ammonia (NH 3 ), which serves as a fertilizer supply, is struggling to satisfy the ever-growing population requirements over the world. The electrocatalytic nitrogen reduction to NH 3 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 SnO 2 heterostructure catalyst through the interfacial engineering strategy, simultaneously achieving the highest NH 3 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 SnO 2 - 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 SnO 2 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 N 2 reduction.