Dual-site adsorption regulation on a bcc/fcc heterophase PdCuIn metallene for efficient urea electrosynthesis

Abstract

Electrochemical co-reduction of CO2 and nitrate to produce urea is a sustainable alternative to the Bosch–Meiser process, yet its practical application is impeded by slow C–N coupling kinetics and limited urea selectivity. Here, we design a bcc/fcc hetero-phase PdCuIn metallene catalyst for urea electrosynthesis from CO2 and nitrate. The resultant b/f-PdCuIn-ene catalyst achieves an urea yield rate of 2096.2 μg h⁻¹ mgcat.⁻¹ and a Faradaic efficiency of 37.7% at a low potential of –0.3 V vs. reversible hydrogen electrode, along with good stability. Attenuated total reflection Fourier transform infrared spectroscopy verifies the genaration of *CO and *NH2 key intermediates during the CO2/nitrate co-reduction process. Density functional theory calculations reveal that the bcc/fcc hetero-phase structure could blance the adsorption of *CO and *NH2 intermediates and promte the C–N coupling reaction for urea synthesis. This study provides an effective crystal phase engineering strategy for tailoring metallene catalysts toward urea electrosynthesis.