Photocatalytic urea synthesis from CO2 and N2 is limited by the simultaneous requirement for inert-molecule activation and selective C–N coupling. Herein, we theoretically designed a dual-atom-loaded C7N6/CTF Z-scheme catalyst to uncover that the photoinduced cross-charge transfer between heteronuclear Ti–V atoms dynamically facilitates the simultaneous activation and coupling of CO2 and N2. Specifically, nonadiabatic molecular dynamics (NAMD) combined with real-time time-dependent density functional theory (RT-TDDFT) identifies a near-spin-symmetric shallow trap state at the Ti–V site that accelerates weak electron–hole annihilation yet sustains high-energy carriers, ultimately enabling a photoinduced directional electron flux across the metals. The resultant femtosecond-scale charge redistribution synchronously preactivates both substrates, bending CO2 and elongating N2, into geometries inaccessible under thermal conditions. While competing pathways to CO or NH3 are suppressed, the critical coupling barriers under explicit solvent are substantially reduced: the initial C–N coupling (*CO + *N2 → *NCON) to 0.66 eV and the final urea formation step (*CO + *NH2NH2 → *NH2CONH2) to 0.27 eV, clarifying the origin of high catalytic selectivity for urea synthesis. Generally, heteronuclear dual-atom Z-scheme heterojunctions represent a promising design for regulating photocatalytic states to achieve cooperative activation and selective C–N coupling.
Lin et al. (Wed,) studied this question.