Hot Carrier Controlled Nitrogen Fixation Reaction in Metal-Free Boron-Anchored Aza-COF: Insight from Nonadiabatic Molecular Dynamics Simulation.

Designing highly efficient photocatalysts for the production of renewable energy is a challenging task that necessitates simultaneous control of chemical activity and photocarrier dynamics for a particular reaction. To this end, we have investigated the catalytic mechanism and real-time photocarrier dynamics of the nitrogen reduction reaction (NRR) at the metal-free boron-functionalized 2D aza-COF (B-aza-COF), an inexpensive and environmentally friendly semiconductor. By employing density functional theory (DFT) and time-dependent ab initio nonadiabatic molecular dynamics simulation, we have investigated the electronic structure, light harvesting ability, free energy change, and dynamics of photoexcited carriers. Our calculated results reveal that the gas phase N molecule can be effectively reduced into NH on B-aza-COF under UV-visible light. Therefore, our investigation on the design of efficient photocatalysts for the nitrogen reduction reaction (NRR) provides a cost-effective opportunity for the sustainable production of NH.