Photoinduced Cross-Metal Charge Transfer over Dual-Atom Z‑Scheme Catalysts Governing Cooperative Urea Synthesis from...

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.