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Electrocatalytic N2O Reduction Catalyzed by Carbon-Supported Metal-Bis(diaryldithiolene) Complexes in Water
Masaru Kato1,2, Naoto Kuwamura3, Zhengwei Ma2
1Faculty of Environmental Earth Science, Hokkaido University, N10W5, Kita-ku, Sapporo 060-0810, Japan.
None:
We report the electrocatalytic nitrous oxide reduction reaction (N2ORR) activity of iron, cobalt, and nickel complexes with a noninnocent ligand of diaryldithiolene in alkaline media. At -0.3 V vs RHE, the cobalt complex on a carbon black of Ketjenblack (CoL2/KB) showed the highest N2ORR activity with a turnover frequency (TOF) of (3.6 ± 0.5) × 102 h-1, 98% Faradaic efficiency to N2 and almost no degradation over 24 h. At -0.6 V vs RHE, CoL2/KB exhibited a TOF of (8.6 ± 1.1) × 102 h-1, surpassing those of previously reported molecular-based electrocatalysts for the N2ORR. X-ray absorption spectroscopy and density functional theory calculations revealed that the square-planar CoI-S4 coordination environment with high Co-S covalency serves as the active site with high N2ORR activity. This work will guide us in designing and developing precious metal-free electrocatalysts with high N2ORR activity.
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