Dual-metal-driven Selective Pathway of Nitrogen Reduction in Orderly Atomic-hybridized Re₂MnS₆ Ultrathin Nanosheets.

Abstract

The future of sustainable fertilizers and carbon-free energy carrier demands innovative breakthroughs in the exploitation of efficient electrocatalysts for synthesizing ammonia (NH₃) from nitrogen (N₂) in mild conditions. Understanding and regulating the reaction intermediates that form on the catalyst surface through careful catalyst design could bypass certain limitations associated with ambiguous adsorbate evolution mechanism. Herein, we propose ternary intermetallic Re₂MnS₆ ultrathin nanosheets that include orderly hybridized Mn-Re dual-metal sites through strong Hubbard e-e interaction, demonstrating a promising selectivity toward reaction process from N₂ to NH₃. The ordered inclusion of Mn sites leads to a structural phase transition and appearance of nonbonding semimetal states, in which the rate-limiting activation energy barrier is significantly decreased through a conversion in reaction pathway. As a result, the performance of N₂ reduction in Re₂MnS₆ is increased about 6.6 times compared to the single-metal ReS₂.