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.

Nanoporous NiSb to Enhance Nitrogen Electroreduction via Tailoring Competitive Adsorption Sites

“…Moreover, molecular N 2 on NiSb surface is coordinated with Ni sites in side‐on configuration while end‐on manner of N 2 interaction is observed on Ni and Sb surfaces, indicating enhanced electron backdonation to the antibonding orbital of N 2 to activate the N≡N triple bond on NiSb. [ 32 ]…”

Spin-state reconfiguration induced by alternating magnetic field for efficient oxygen evolution reaction

“…The EIS were recorded under the following conditions: AC potential perturbation 5 mV, frequency ranges 100 kHZ to 0.01 Hz, and open circuit. To determine the double-layer capacitance ( C dl ), the cyclic voltammograms were tested at various scan rates (10, 20, 40, 60, 80, 100 mV s −1 ) between 1.06 V and 1.10 V (vs. RHE) 25 , 37 .…”

Electrochemical ammonia synthesis: Mechanistic understanding and catalyst design

“…In situ Raman spectroscopy has been employed to distinguish intermediates at molecular level and to further uncover the N 2 reduction pathway over Re 2 MnS 6 (Figure 12A). 89 A pronounced Raman mode at 658 cm À1 was visualized for Re 2 MnS 6 (Figure 12B), the signal of which increased with increasing overpotential and reached a maximum at À0.30 V. In contrast, only a weak Raman peak was discernible for ReS 2 which blue-shifted to 709 cm À1 (Figure 12C). 12F).…”