Descriptor-Based Screening of Dual-Atom Photocatalysts for Efficient Urea Synthesis from CO2 and N2

The development of efficient photocatalysts with high activity and selectivity for coreduction of N₂ and CO₂ under ambient conditions represents a highly promising but still challenging strategy for sustainable urea synthesis. In this study, using density functional theory (DFT) calculations, we present a comprehensive descriptor strategy integrating geometric, electronic, and energetic factors to screen Cu-metal dual-atom photocatalysts (CuM/CeO₂, where M = 27 transition metals) for urea synthesis. According to the screening of the catalyst stability, coadsorption capability of N₂ and CO₂, energy barriers of the rate-determining step (RDS), and urea desorption energies, CuMn/CeO₂ emerged as the most promising candidate photocatalyst. Through comprehensive analysis of the effects of the Cu-Mn interatomic distance on catalytic performance, a robust volcano-type relationship was established between the energy barrier for the RDS and the formation free energy of the key intermediate NCON (ΔG_NCON). This relationship was found to be independent of the support examined in this study.