电催化氮还原反应(NRR)是实现绿色高效NH3生产的最有前途的方法之一。然而,具有高活性和选择性的高效NRR催化剂的设计仍然受到NRR中间体吸附能之间固有的线性缩放关系的严重阻碍。在这里,已初步研究了十种M3B4型MBenes的特性,以通过第一性原理计算将N2有效活化并还原为NH3。我们强调Cr3B4MBene具有显着的NRR活性,具有创纪录的低极限电位(-0.13V)。然后,这项工作提出了基于描述符的设计原则,可以有效地评估MBenes的催化活性,已进一步用于设计双金属M2M\'B4MBenes。因此,从20个双金属MBenes中提取了5个有希望的候选物,包括Ti2YB4,V2YB4,V2MoB4,Nb2YB4和Nb2CrB4,具有优异的NRR性能。进一步的分析说明,构建双金属MBenes可以选择性地调节NHNH2**和NH2NH2**的吸附强度,并打破它们的吸附能之间的线性比例关系,使它们成为NRR的理想选择。这项工作不仅开创了MBenes作为高效NRR催化剂的应用,而且还提出了提高其催化性能的合理设计原则。
Electrocatalytic nitrogen reduction reaction (NRR) is one of the most promising approaches to achieving green and efficient NH3 production. However, the designs of efficient NRR catalysts with high activity and selectivity still are severely hampered by inherent linear scaling relations among the adsorption energies of NRR intermediates. Herein, the properties of ten M3B4 type MBenes have been initially investigated for efficient N2 activation and reduction to NH3via first-principles calculations. We highlight that Cr3B4 MBene possesses remarkable NRR activity with a record-low limiting potential (-0.13 V). Then, this work proposes descriptor-based design principles that can effectively evaluate the catalytic activity of MBenes, which have been further employed to design bimetallic M2M\'B4 MBenes. As a result, 5 promising candidates including Ti2YB4, V2YB4, V2MoB4, Nb2YB4, and Nb2CrB4 with excellent NRR performance have been extracted from 20 bimetallic MBenes. Further analysis illuminates that constructing bimetallic MBenes can selectively tune the adsorption strength of NHNH2** and NH2NH2**, and break the linear scaling relations between their adsorption energies, rendering them ideal for NRR. This work not only pioneers the application of MBenes as efficient NRR catalysts but also proposes rational design principles for boosting their catalytic performance.