Photoinduced Cross-Metal Charge Transfer over Dual-Atom Z-Scheme Catalysts Governing Cooperative Urea Synthesis from CO 2 and N 2

High Resolution Image Download MS PowerPoint Slide Photocatalytic urea synthesis from CO 2 and N 2 is limited by the simultaneous requirement for inert-molecule activation and selective C–N coupling. Herein, we theoretically designed a dual-atom-loaded C 7 N 6 /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 CO 2 and N 2 . 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 CO 2 and elongating N 2, into geometries inaccessible under thermal conditions. While competing pathways to CO or NH 3 are suppressed, the critical coupling barriers under explicit solvent are substantially reduced: the initial C–N coupling (*CO + *N 2 → *NCON) to 0.66 eV and the final urea formation step (*CO + *NH 2 NH 2 → *NH 2 CONH 2 ) 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.