School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD 4001, Australia.
Phys Chem Chem Phys. 2019 Jan 21;21(3):1110-1116. doi: 10.1039/c8cp07064d. Epub 2019 Jan 2.
N fixation is one of the most challenging tasks in chemistry. Recently, tremendous efforts have been devoted to transition metal-based materials. However, metal-free catalysts for N conversion have been rarely explored. Here, by using density functional theory, we predict, for the first time that a single B-atom decorated BN edge (B@BN) can act as a metal-free catalyst for the conversion of an N molecule to NH under ambient conditions. N fixation on the B@BN edge exhibits an extremely low overpotential of only 0.13 V through a distal mechanism. Moreover, fast removal of the produced NH molecule is observed with an uphill Gibbs free energy change of only 0.35 V, which is lower than those of ever-reported electrocatalysts such as Mo-doped BN and 2D Mxene. Our findings highlight a novel single atom metal-free catalyst for N fixation, providing a cost-efficient process for sustainable NH production.
固氮是化学领域最具挑战性的任务之一。最近，人们投入了大量精力研究基于过渡金属的材料。然而，对于转化氮的无金属催化剂的研究却很少。在这里，我们首次通过密度泛函理论预测，单原子硼修饰的 BN 边缘（B@BN）可以作为无金属催化剂，在环境条件下将 N 分子转化为 NH。B@BN 边缘上的固氮通过远程机制表现出极低的过电势，仅为 0.13V。此外，我们观察到所生成的 NH 分子的快速去除，其 uphill Gibbs 自由能变化仅为 0.35V，低于已报道的电催化剂，如 Mo 掺杂 BN 和二维 MXene。我们的研究结果突出了一种新型的单原子无金属固氮催化剂，为可持续 NH 生产提供了一种具有成本效益的方法。
