Rational design of bimetallic MBene for efficient electrocatalytic nitrogen reduction.

Electrocatalytic nitrogen reduction reaction (NRR) is one of the most promising approaches to achieving green and efficient NH ₃ 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 M ₃ B ₄ type MBenes have been initially investigated for efficient N ₂ activation and reduction to NH ₃ via first-principles calculations. We highlight that Cr ₃ B ₄ 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 M ₂ M'B ₄ MBenes. As a result, 5 promising candidates including Ti ₂ YB ₄ , V ₂ YB ₄ , V ₂ MoB ₄ , Nb ₂ YB ₄ , and Nb ₂ CrB ₄ 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 NHNH ₂ ** and NH ₂ NH ₂ **, 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.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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