Ni Triple-Atom Doped Cu₂O Electrocatalysts for Efficient Electrochemical Urea Synthesis: A Theoretical Study

Chemical C–N coupling from CO 2 and N 2 toward urea synthesis is an appealing approach for Bosch–Meiser urea production. However, this process faces significant challenges, including the difficulty of N 2 activation, high energy barriers, and low selectivity. In this study, we theoretically designed a Ni triple-atom doped Cu 2 O catalyst, Ni TAC@Cu 2 O, which exhibits exceptional urea synthesis performance. Using density functional theory and the constant potential method, we show that the superior catalytic performance of Ni TAC@Cu 2 O stems from synergistic metal–support interactions (MSIs) between Ni atoms and Cu 2 O. Cu 2 O serves as an anchoring substrate and actively participates in CO 2 activation via strong Cu–O bonding, whereas Ni serves as the pivotal active center for N 2 activation. Ni TAC@Cu 2 O achieves a moderate N 2 adsorption energy and a limiting potential ( U L ) of −0.60 V, overperforming Ni single-atom (Ni SAC@Cu 2 O, U L = −0.85 V) and Ni double-atom (Ni DAC@Cu 2 O, U L = −0.88 V) catalysts. The third Ni atom enhances electron donation, reducing the energy barrier of the rate-determining step (*CO + *N 2 + H + + e – → *CONNH), while O atoms in Cu 2 O regulate Ni’s electronic structure through MSIs. Additionally, Ni TAC@Cu 2 O demonstrates thermodynamic, electrochemical, and acid–base stability and effectively suppresses competing side reactions. This work underscores the importance of Cu 2 O-supported MSIs in multiatom catalysts for enhanced performance and provides insights for advanced electrocatalyst design.