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 N₂ molecule can be effectively reduced into NH₃ 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 NH₃.

中文翻译：

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无金属硼锚定 Aza-COF 中热载流子控制的固氮反应：非绝热分子动力学模拟的见解

设计用于生产可再生能源的高效光催化剂是一项具有挑战性的任务，需要同时控制特定反应的化学活性和光载流子动力学。为此，我们研究了无金属硼功能化的二维氮杂COF（B-aza-COF）上氮还原反应（NRR）的催化机制和实时光载流子动力学，这是一种廉价且环保的半导体。通过采用密度泛函理论（DFT）和时间相关的从头算非绝热分子动力学模拟，我们研究了光激发载流子的电子结构、光捕获能力、自由能变化和动力学。我们的计算结果表明，在紫外可见光下，B-aza-COF 上的气相 N ₂分子可以有效地还原为 NH ₃ 。因此，我们对氮还原反应（NRR）高效光催化剂设计的研究为NH ₃的可持续生产提供了具有成本效益的机会。